energies

Review
A Review of Hydrogen Leak Detection Regulations
and Technologies
Mohammed W. Qanbar 1,2, * and Zekai Hong 1,2

1 Department of Mechanical Engineering, University of Ottawa, Ottawa, ON K1N 6N5, Canada;

zekai.hong@nrc-cnrc.gc.ca
2 National Research Council Canada, Ottawa, ON K1A 0R6, Canada
* Correspondence: mw.qanbar@uottawa.ca

Abstract: Hydrogen (H2 ) is positioned as a key solution to the decarbonization challenge in both the
energy and transportation sectors. While hydrogen is a clean and versatile energy carrier, it poses
significant safety risks due to its wide flammability range and high detonation potential. Hydrogen
leaks can occur throughout the hydrogen value chain, including production, storage, transportation,
and utilization. Thus, effective leak detection systems are essential for the safe handling, storage,
and transportation of hydrogen. This review aims to survey relevant codes and standards governing
hydrogen-leak detection and evaluate various sensing technologies based on their working principles
and effectiveness. Our analysis highlights the strengths and limitations of the current detection
technologies, emphasizing the challenges in achieving sensitive and specific hydrogen detection.
The results of this review provide critical insights into the existing technologies and regulatory
frameworks, informing future advancements in hydrogen safety protocols.

Keywords: hydrogen; leak; detectors; sensors; regulations; codes and standards

1. Introduction
Hydrogen is gaining significant attention as an energy carrier due to its great potential
in the transition to a low-carbon economy. As the most abundant element in the universe,
Citation: Qanbar, M.W.; Hong, Z. A
hydrogen can be produced from various sources, including fossil fuels, biomass, and
Review of Hydrogen Leak Detection
electrolysis of water using renewable energy. When used as a fuel, hydrogen produces only
Regulations and Technologies.
water as the product, making it a natural zero-carbon fuel option [1,2].
Energies 2024, 17, 4059. https://
In Canada, hydrogen holds particular importance due to the country’s vast renewable
doi.org/10.3390/en17164059
energy resources, including hydroelectric power and wind energy. The Canadian gov-
Academic Editor: Vladislav A. ernment has recognized the potential of hydrogen in achieving its climate-change goals,
Sadykov including the commitment to net-zero greenhouse gas emissions by 2050 [3]. By leveraging
Received: 18 July 2024
its renewable energy capacity, Canada aims to become a global leader in the production,
Revised: 4 August 2024
distribution, and utilization of clean hydrogen. The use of hydrogen as a power source in
Accepted: 9 August 2024 Canada offers several key benefits. First, it enables the decarbonization of various end-use
Published: 15 August 2024 sectors—transportation, in particular. For example, hydrogen can be used as a fuel for
fuel-cell electric vehicles (FCEVs), providing long-range and quick refueling capabilities,
while emitting zero tailpipe emissions. Additionally, hydrogen can replace fossil fuels in
industrial processes, such as steelmaking or chemical production, reducing carbon dioxide
Copyright: © 2024 by the authors. emissions significantly. Furthermore, hydrogen can be utilized for heating applications in
Licensee MDPI, Basel, Switzerland. residential and commercial buildings, contributing to the shift away from fossil fuel-based
This article is an open access article heating systems.
distributed under the terms and Hydrogen leak detection is of utmost importance in Canada’s hydrogen economy.
conditions of the Creative Commons While hydrogen is a clean and versatile energy carrier, it poses safety risks due to its
Attribution (CC BY) license (https://
wide flammability range and great potential for explosion. The flammability range of
creativecommons.org/licenses/by/
hydrogen is between 4 and 75 vol% in air, and it becomes explosive within a wide range of
4.0/).

Energies 2024, 17, 4059. https://doi.org/10.3390/en17164059 https://www.mdpi.com/journal/energies

Energies 2024, 17, 4059 2 of 25

concentrations (18–59%) at standard atmospheric conditions [4]. Hydrogen leaks can occur
in various stages of the hydrogen value chain, including production, storage, transportation,
and utilization. Effective hydrogen leak-detection systems and protocols are essential to
ensure the safe handling, storage, and transportation of hydrogen. Early detection of
leaks is critical for preventing accidents, protecting workers and the public, and avoiding
potential damage to infrastructure. Hydrogen leak-detection systems employ technologies
such as sensors, detectors, and monitoring equipment to identify leaks promptly. These
systems can detect leaks in various settings, including hydrogen production facilities,
storage tanks, pipelines, and refueling stations.
In Canada, the importance of hydrogen leak detection is amplified by the country’s
ambition to develop a robust hydrogen infrastructure. Investments are being made to
establish hydrogen production hubs, build hydrogen refueling stations, and integrate
hydrogen into existing energy systems. With these developments, ensuring the safety
of hydrogen infrastructure and operations becomes vital. By prioritizing hydrogen leak
detection, Canada can build public confidence in hydrogen technologies and maintain a
strong safety record. Moreover, robust leak detection measures contribute to the long-term
viability and sustainability of the hydrogen sector.
Furthermore, when it comes to the storage of hydrogen, subsurface formations such
as natural gas reservoirs, salt caverns, and saline aquifers offer a substantial potential due
to their established infrastructure, geological stability, and capacity to store large volumes
of gas. By repurposing these formations for hydrogen storage, the energy industry can
leverage existing expertise and infrastructure, thereby accelerating the deployment of
hydrogen as a mainstream energy solution. One notable advantage of subsurface hydrogen
storage is its potential to enhance energy reliability and grid stability. Hydrogen storage can
bridge the gap between variable renewable energy production and demand fluctuations
by allowing excess energy to be stored during periods of high generation and released
during periods of high demand. This capability can contribute to a more resilient energy
system and facilitate the effective integration of intermittent renewable sources like wind
and solar into the grid. Moreover, utilizing existing subsurface storage fields for hydrogen
offers a sustainable and cost-effective approach, minimizing the need for building entirely
new infrastructure.

2. Review of Codes and Standards

There are several codes and standards for hydrogen systems that aim to ensure the
safety, reliability, and performance of these technologies. Some of the most widely used
codes and standards are developed by organizations such as the International Organization
for Standardization (ISO), the American Society of Mechanical Engineers (ASME), the
National Fire Protection Association (NFPA), and the International Electrotechnical Com-
mission (IEC). It is important to differentiate between mandatory and voluntary documents
that are used to define safety and quality requirements for goods and services, as defined
by the Standards Council of Canada [5]:
• Code: A code is broad in scope and is intended to carry the force of law when adopted
by a provincial, territorial, or municipal authority. Codes may include references to a
number of standards.
• Standard: A standard is a document that provides a set of agreed-upon rules, guide-
lines, or characteristics for activities or their results. Standards establish accepted
practices, technical requirements, and terminologies for diverse fields.

2.1. Requirements for General Hydrogen Systems and Technologies

Table 1 lists some of the standards, codes, and relevant documents concerning general
hydrogen systems and technologies. These documents cover various aspects of hydrogen
systems, such as design, installation, operation, maintenance, testing, and inspection.
However, most of these documents do not provide guidance on handling potential hazards,
such as leakage mitigation.
Energies 2024, 17, 4059 3 of 25

Table 1. Standards, codes, and relevant documents for general hydrogen systems and technologies.

Designation Title Publication Date

Basic considerations for the safety of
ISO/TR 15916 2015
hydrogen systems
CAN/BNQ 1784-000 Canadian Hydrogen Installation Code 2022
ASME B31.12 Hydrogen Piping and Pipelines 2019
NFPA 2 Hydrogen Technologies Code 2023

ASME B31.12, for example, establishes a procedure according to which leakage indica-
tions of flammable gas can be graded and controlled [6]. Grade 1 leaks are of the highest
level of threat and represent situations in which the leak poses an immediate hazard to
persons or properties and requires immediate intervention. Grade 2 leaks represent situa-
tions in which the leak is non-hazardous at the time of detection but could lead to a future
hazardous event, thus requiring a scheduled repair. Finally, grade 3 leaks are considered
non-hazardous at the time of detection and can be reasonably expected to remain so for
the foreseeable future. This classification is shown in Table 2, with examples and reading
ranges expressed in percentages of the lower explosive limit (LEL), which is 4 vol% H2
in air.
Table 2. ASME B31.12 leak-grade classification.

Leak Grade Readings Examples

Grade 1
• Any readings at the outside wall of a • Escaping gas that has ignited
building or where gas would likely migrate • Gas that has migrated into or under
to an outside of a building a building or a tunnel
• Readings of ≥80% LEL in enclosed spaces
or small substructures from which gas
would likely migrate to the outside wall of
a building
Grade 2
• Readings of ≥40% LEL under a sidewalk in • Leaks requiring action ahead of
a wall-to-wall paved area ground freezing or other adverse
• Readings of ≥100% LEL under a street in a changes in venting conditions
wall-to-wall paved area that has significant • Leaks that, under frozen or other
gas migration adverse conditions, would likely
• Readings of <80% LEL in small migrate to a building
substructures from which gas would likely
migrate, creating probable future hazards
• Readings of ≥20% LEL and ≤80% LEL in
enclosed spaces
Grade 3
• Readings of ≤20% LEL in enclosed spaces • Any outdoor readings where it is
unlikely that the gas could migrate
to a building

2.2. Sensor Testing Requirements

Table 3 lists codes and standards that specify requirements and recommendations on a
range of scenarios concerning hydrogen leak detection, including sensor selection/installation,
calibration/testing, and response/notification protocols in the event of a hydrogen release.
The purpose of these codes and standards is to ensure that gas detection systems are reliable;
effective; and capable of protecting personnel, facilities, and the environment from the hazards
associated with hydrogen gas. These documents present testing requirements applicable
to a product standard for hydrogen detection apparatus, and are intended to be used by
manufacturers to assess and certify their products.
Energies 2024, 17, 4059 4 of 25

Table 3. Standards, codes, and relevant documents for hydrogen- and combustible-gas-detection
instruments.

Designation Title Publication Date

Hydrogen detection
ISO 26142 2010
apparatus—Stationary applications
Explosive atmospheres—Part 29-1: Gas
CSA C22.2 No. 60079-29-1:17 detectors—Performance requirements of 2017
detectors for flammable gases
UL 2075 Gas and Vapor Detectors and Sensors 2013
Characterization of On-Board Vehicular
SAE J3089 2018
Hydrogen Sensors

ISO 26142, for example, is an international standard prepared by the Technical Com-
mittee ISO/TC 197 that was published in 2010 and was last reviewed and confirmed in
2021 [7]. Intended to be used for product certification purposes, the standard defines the
performance requirements of hydrogen-detection apparatuses designed to measure and
monitor hydrogen concentrations in stationary applications based on certain testing criteria.
The standard covers the hydrogen-detection apparatuses used to achieve single and/or
multilevel safety operations, such as nitrogen purging, ventilation, and/or system shut-off
corresponding to the hydrogen concentration. The standard sets out the requirements
applicable to a product standard for hydrogen-detection apparatuses, such as precision,
response time, stability, measuring range, selectivity, and poisoning. The appendices also
present two testing methods commonly used in the industry: the chamber test method
and the flow-through test method. Both test procedures are described to determine the
time of response and recovery, and the advantages and disadvantages of each method are
presented. Similar testing procedures are also documented in the SAE J3089 Technical Infor-
mation Report (TIR) and were derived from methods originally developed by researchers
at the NREL Hydrogen Safety Test Laboratory [8]. The UL 2075 is another standard that is
commonly referred to and is considered a complete product assembly performance listing
standard that applies to fixed, portable, and transportable toxic and combustible gas and
vapor detectors and sensors [9]. Another standard is CSA C22.2 No. 60079-29-1:17, which
is a national standard of Canada published by the CSA group adopted from an IEC stan-
dard [10]. It specifies general requirements for construction, testing, and performance. It
also describes the test methods which apply to portable, transportable, and fixed equipment
for the detection of flammable gas or vapor concentrations in the air. Table 4 compares
some of the testing requirements specified in these standards.
Table 4. Detector-testing requirements.

Metric ISO 26142 UL 2075 CSA C22.2 No. 60079-29-1:17

Measurement range At least 1 order of magnitude N/A According to manufacturer
Temperature range 15 ◦ C to 25 ◦ C, ±2 ◦ C variation −40 ◦ C to 66 ◦ C 15 ◦ C to 25 ◦ C, ±2 ◦ C variation
Relative humidity range 20% to 80%, ±10% variation 7.5% ± 0.5% to 95% ± 4% 20% to 80%, ±10% variation
Response time <30 s N/A According to manufacturer
Accuracy According to manufacturer N/A According to manufacturer
Lifetime N/A Tested for a min of 1 year N/A

2.3. Specific Requirements for Hydrogen Leak-Detection Instruments

Depending on the target application, the sensor-performance requirements could vary.
However, the U.S. Department of Energy (DOE) identified in their 2007 Multi-Year Program
Plan (MYPP) several key target performance metrics for hydrogen sensors for the purposes
of research and development [11]. These metrics displayed in Table 5 are rather general and
do not account for different usage scenarios. It was later recognized that different applica-
tions can have significantly different requirements. In 2011, the U.S. National Renewable
Energy Laboratory (NREL) organized a sensor workshop where a panel of researchers and
Energies 2024, 17, 4059 5 of 25

industry experts agreed upon sensor requirements for various usage scenarios [12]. Some
of these applications included on-board deployment for light-duty road vehicles and indus-
trial trucks, indoor fueling-facility monitoring and in-dispenser deployment, residential
applications, production plants, battery backup systems, and hydrogen storage applica-
tions, both indoors and outdoors. For example, in indoor hydrogen storage applications, a
required linear measuring range was determined to be 0–4 vol% H2 , but an extension up to
10% was identified to be useful or even required by a local Authority Having Jurisdiction
(AHJ). Other analytical parameters include sensor drift, which is required to be less than
10% of the alarm level and output no false positives or negatives. In addition, the sensor
must be stable in temperatures ranging from 0◦ to 40 ◦ C for most applications but can go
as low as −25 ◦ C for refrigerated spaces. The operating relative humidity range must also
be between 25% and 95% RH at the prevailing temperature in an unregulated facility. The
sensor is also required to be selective and not show cross-sensitivity behaviors towards CO,
H2 S, or other application-specific gases and chemicals. It is also required to have a response
time of at least 30 s at 1 vol% H2 or the alarm level. There are other operational and deploy-
ment requirements, such as being commercially mature and purchasable off-the-shelf and
having a lifetime of at least 5 years.
Table 5. Target performance metrics for hydrogen sensors extracted from the 2007 DOE MYPP.

Metric Target Performance

Measurement range 0.1–10%
Operating temperature −30 ◦ C to 80 ◦ C
Relative humidity range 10% to 98%
Response time <1 s
Accuracy 5% of full scale
Lifetime 10 years
Selectivity Interference resistant (e.g., hydrocarbons)

3. Review of Sensor Performance Metrics

An expanded compilation of potential performance metrics with brief definitions
is presented in Table 6. These specifications encompass a wide spectrum, ranging from
analytical metrics to operational and deployment logistical parameters. While some of
these metrics are covered by standards, it is worth noting that there is no one-size-fits-all
technology for hydrogen sensing. As such, the values and significance of each parameter
are specific to the application, and the relative importance of a particular parameter will
vary significantly across different use cases.
Energies 2024, 17, 4059 6 of 25

Table 6. Key performance metrics used to parameterize hydrogen sensor performance.

Metric Type Metric Information

Analytical metrics Selectivity The ability of the sensor to specifically detect and respond to a particular target substance or stimulus while
minimizing interference from other substances or factors present in the environment.
Response time The time taken by a gas sensor to reach a specified percentage of its final output after exposure to the target gas.
Recovery time The time required for a gas sensor to return to its baseline measurement after exposure to the target gas is removed.
Lower detection limit (LDL) The minimum concentration of the target gas that a gas sensor can reliably detect and quantify.
Reversibility The capability of a gas sensor to return to its initial state after exposure to the target gas is ceased.
Repeatability The ability of a gas sensor to produce consistent results when exposed to the same concentration of the target gas
under the same conditions.
Analytical resolution The smallest detectable change in concentration that a gas sensor can discern.
Environmental effects The influence of external factors (e.g., temperature, humidity, and pressure) on the performance of a gas sensor.
Signal drift The gradual change in the gas sensor’s output over time, leading to a shift in measurements.
Linear and dynamic range The range of gas concentrations over which a gas detector/sensor provides accurate and proportional measurements.
Limits of quantitation The lowest and highest concentrations of the target gas that a gas sensor can measure with acceptable precision
and accuracy.
Logistic–operational Operational lifetime The duration for which a gas sensor can reliably function before it needs replacement.
parameters Calibration and maintenance requirements The regular procedures needed to ensure the accuracy and proper functioning of the gas sensor.
Orientation effects The impact of the gas sensor’s positioning or orientation on its performance or operation.
Warm-up time The time needed for the gas sensor to stabilize and provide accurate readings after being turned on.
Signal management The processing and handling of the signal generated by the gas sensor.
Matrix requirements Considerations for the type of sample or environment in which the gas sensor will be used.
Sample size The volume or amount of the gas sample required for analysis.
consumables Additional consumable materials or components needed for the gas sensor to function (e.g., calibration gases
and filters).
Logistic–deployment Capital cost The initial cost of purchasing the gas-sensor equipment.
parameters Installation cost The expenses associated with setting up and integrating the gas sensor into a system or environment.
Physical size The dimensions and form factor of the gas sensor.
Power requirements The energy demands of the gas sensor for its operation.
Shelf life The duration for which the gas sensor can be stored and remain functional before it needs to be used or replaced.
Placement The optimal location or positioning of the gas sensor for effective gas monitoring.
Electronic interface The means of communication and data transfer between the gas sensor and external devices or systems.
Control circuitry The internal circuitry responsible for managing the gas detector/sensor’s operation and output.
Pneumatic connections The connections used to transport gas to the gas sensor for analysis.
Government regulations The compliance requirements and standards set by regulatory bodies for gas detectors/sensors.
Maturity/availability The level of development and accessibility of the gas detector/sensor technology in the market.
 Energies 2024, 17, 4059 7 of 25

4. Review of Hydrogen Sensing Technologies

There are numerous mechanisms that H2 sensors use to detect and quantify hydrogen
leakage. This section provides an overview of sensing mechanisms, emphasizing their
working principles and performance characteristics. Throughout, the advantages and
disadvantages of each sensor technology are evaluated and discussed here to provide a
comprehensive overview of their respective strengths and limitations.

4.1. Electrochemical Sensors

Electrochemical sensors function by detecting the change in charge transport or elec-
trical characteristics resulting from electrochemical reactions taking place at a sensing
electrode. These sensors are highly reconfigurable and can be used to detect a wide range
of combustible gases at different performance targets. There are two primary embodiments
of electrochemical sensors: the amperometric and potentiometric types.

4.1.1. Amperometric Type

The amperometric-type electrochemical sensors function at a constant applied voltage
and rely on measuring a current proportional to the concentration of diffused hydrogen
in the working electrolyte. They typically consist of three major constituents, as seen
in Figure 1: the electrodes, the electrochemical cell, and the gas-permeable layer. The
electrodes consist of a working (or sensing) electrode and a counter electrode. They can also
include a reference electrode coupled with a potentiostat to keep the voltage constant across
both ends. The electrodes are typically constructed of a noble metal, such as platinum
or palladium, which acts as a catalyst, facilitating the hydrogen oxidation reaction on the
surface. In addition, the electrochemical cell contains an electrolyte, which can be of a liquid
or a solid nature, allowing for the transfer of hydrogen ions between the two electrodes.
Finally, the gas-permeable layer limits the amount of gas that is passing through to the
working electrode. This layer is typically composed of a perfluorinated polymer, such as
Teflon, and can also act as a filter to reduce the passthrough of other gases, thus increasing
selectivity. When a target analyte interacts with the working electrode, it undergoes
an electrochemical reaction, which leads to the generation or consumption of electrons
according to the equation H2 → 2H+ + 2e− [13]. This results in a change in the current
flowing between the two electrodes. At the counter electrode, the reduction of oxygen takes
Energies 2024, 17, x FOR PEER REVIEW place according to the equation ½ O2 + 2H+ + 2e− → H2 O. A meter is connected between 8 of 27
the two electrodes that measures the electric current proportional to the concentration of
the analyte gas according to Faraday’s law of electrolysis [14].

Figure
Figure 1. Schematic
1. Schematic of of
anan amperometricelectrochemical
amperometric electrochemicalsensor.
sensor.

Sulfuric acid is the most used liquid electrolyte [15]. However, solid electrolytes
Sulfuric acid is the most used liquid electrolyte [15]. However, solid electrolytes have
have been utilized more recently due to their mitigation of problems such as leakage
been utilized more recently due to their mitigation of problems such as leakage and cor-
and corrosion. For example, Nafion perfluoro sulfonic acid (PFSA) membranes are used
rosion. For example, Nafion perfluoro sulfonic acid (PFSA) membranes are used in elec-
in electrochemical cells, functioning as cation-conducting solid electrolytes [16,17]. In
trochemical cells, functioning as cation-conducting solid electrolytes [16,17]. In another
recent study, Gao et al. [18] developed an advanced amperometric hydrogen sensor fea-
turing a unique “sandwich” structure comprising a titanium foam electrode loaded with
platinum nanoparticles (Pt-NPs) and a solid polymer electrolyte. This design enables di-
rect gas diffusion to the active interface, significantly enhancing the sensor’s electrochem-
Energies 2024, 17, 4059 8 of 25

another recent study, Gao et al. [18] developed an advanced amperometric hydrogen sensor
featuring a unique “sandwich” structure comprising a titanium foam electrode loaded with
platinum nanoparticles (Pt-NPs) and a solid polymer electrolyte. This design enables direct
gas diffusion to the active interface, significantly enhancing the sensor’s electrochemical
performance. The sensor demonstrated high sensitivity, stability, and a low detection limit
for hydrogen, making it highly effective for real-time monitoring, especially in applications
like lithium-ion battery safety. Table 7 lists some of the advantages and disadvantages of
amperometric-type electrochemical sensors.
Table 7. Advantages and disadvantages of amperometric-type electrochemical sensors.

Advantages Disadvantages
• Can be used in the temperature range from −20 to 80 ◦ C, • Oxygen is required to be present for the counter electrode
provided the electrolyte does not freeze within this reaction to proceed.
range [19]. • Ambient humidity may have an influence on the sensor
• Easy to reconfigure for specific applications and signal due to its effect on the water content of the
performance targets. electrolyte and therefore on its proton conducting
• Low detection limit. ability [19].
• Low power consumption. • Exhibit cross-sensitivity to various species, including
• Low cost and easy to use. some hydrocarbons.
• Lifetime of 5 years or more. • Slow response time.

4.1.2. Potentiometric Type

In contrast to amperometric-type electrochemical sensors, potentiometric sensors
typically operate at a close-to-zero current, and the potential difference is related to the
amount of gas measured. The structure of potentiometric sensors is similar to that of their
amperometric counterpart, consisting of two electrodes with an electrolyte in between.
Similarly, the electrodes are constructed of noble metals, such as palladium, platinum, gold,
or silver [20,21]. As for the electrolyte, proton conducting solids are typically used, such as
alpha-alumina [22], phosphoro-silica glass [23], NASICONs [24], and many others.
In a recent publication, Yi et al. introduced a high-performance potentiometric hydro-
gen sensor utilizing a hierarchical porous, hollow SnO2 nanofiber sensing electrode [25].
This innovative electrode features a three-dimensional scaffold architecture that provides
high porosity, a large pore size, and excellent pore interconnectivity, significantly enhanc-
ing gas transport. The sensor demonstrated a remarkable performance, with a response
time of 5 s for 1000 ppm H2 at 450 ◦ C, outperforming similar sensors with nanoparticle-
based electrodes. The sensor also exhibited excellent selectivity, repeatability, and stability.
This superior performance is attributed to the unique morphology of the hierarchical
nanofibers, facilitating faster gas diffusion and a higher hydrogen concentration at the
boundary. Table 8 lists some of the advantages and disadvantages of potentiometric-type
electrochemical sensors.
Table 8. Advantages and disadvantages of potentiometric-type electrochemical sensors.

Advantages Disadvantages
• Can measure low concentrations of hydrogen. • Logarithmic response curve resulting in lower accuracy at
• Measured signal is nearly independent of sensor size and higher concentrations, compared to the more linear
geometry [19]. response of amperometric type [17].
• Can detect hydrogen in gas mixtures, aqueous solutions, • Lower sensitivity compared to amperometric type [27].
or molten metal [26]. • Less market availability compared to the
• Can operate at temperatures up to 1300 ◦ C [22]. amperometric type.

4.2. Catalytic Sensors

Catalytic sensors operate on the reactionary principle of catalytic behavior. In the case
of a hydrogen sensor, H2 reacts with O2 on the catalytic sensor surface, producing heat.
The production of heat can be quantized and related to the concentration of hydrogen,
 4.2. Catalytic Sensors
Catalytic sensors operate on the reactionary principle of catalytic behavior. In the
case of a hydrogen sensor, H2 reacts with O2 on the catalytic sensor surface, producing
Energies 2024, 17, 4059
heat. The production of heat can be quantized and related to the concentration of9 of 25
hydro-
gen, which has a standard heat of combustion of 141.9 kJ/g. There are two main types of
catalytic-based sensors: the pellistor type and the thermoelectric type.
which has a standard heat of combustion of 141.9 kJ/g. There are two main types of
catalytic-based sensors: the pellistor type and the thermoelectric type.
4.2.1. Pellistor Type
4.2.1. As seen in
Pellistor TypeFigure 2, pellistor-type hydrogen gas sensors are composed of two ele-
ments: a detector
As seen in Figureand2,apellistor-type
compensatorhydrogen
element.gasEach element
sensors is a platinum
are composed of twocoilelements:
embedded
aindetector
a palletand
or ceramic bead. These
a compensator coilsEach
element. haveelement
a double is afunction
platinumsincecoil they act as in
embedded both
a a
heater and a resistance thermometer. The bead surface of the detector
pallet or ceramic bead. These coils have a double function since they act as both a heater element is activated
withaaresistance
and catalytic thermometer.
material, usually Theabead
noble metal,ofsuch
surface as platinum
the detector or palladium,
element is activatedwhilewith the
compensator bead is inert. A Wheatstone bridge circuit is typically
a catalytic material, usually a noble metal, such as platinum or palladium, while the formed using both
elements, in which
compensator bead isa inert.
variable resistor is adjusted
A Wheatstone to balance
bridge circuit the bridge
is typically circuit
formed in clean
using bothair,
without combustible
elements, gases. During
in which a variable resistorthe operation
is adjusted to of the sensor,
balance an external
the bridge circuit inpower
cleansource
air,
drives acombustible
without current throughgases.a heating
During theelement, causing
operation of the ansensor,
increase an in the temperature
external power source of the
drives a current through a heating element, causing an increase in
sensing bead to values typically above 300 °C [19]. At such elevated temperatures, hydro-the temperature of
the ◦
gensensing
moleculesbead to values typically
chemisorbed above 300
on the catalyst C [19].
sensing bead Atreact
suchwith
elevated temperatures,
the adsorbed oxygen.
hydrogen
This reactionmolecules
is of anchemisorbed
exothermicon the catalyst
nature, raising sensing bead react with
the temperature of the thesensing
adsorbed bead,
oxygen. This reaction is of an exothermic nature, raising the temperature
which in turn increases the resistance of the detector element, creating an imbalance in the of the sensing
bead,
bridgewhich in turn
circuit. Thus,increases the resistancegases
when combustible of theare
detector
present, element, creating
an output an imbalance
voltage signal pro-
in the bridge circuit. Thus, when combustible gases are
portional to the concentration of the combustible gases is produced. present, an output voltage signal
proportional to the concentration of the combustible gases is produced.

Figure 2. Schematic of a pellistor-type catalytic sensor.

In a recent study, Ivanov et al. developed a highly selective low-temperature cat-

alytic hydrogen sensor [28]. This sensor utilizes a Wheatstone bridge circuit and a divider
circuit to measure responses to hydrogen and various hydrocarbons. The sensor oper-
ates effectively at temperatures between 66 and 130 ◦ C, demonstrating high sensitivity
(25–35 mV/%) and low power consumption (approximately 8.6 mW). The Wheatstone
bridge circuit provided superior selectivity and sensitivity, making this sensor a promising
tool for detecting hydrogen in the range of pre-explosive concentrations (0.1–2 vol%) with
minimal energy requirements. There has also been a focus on miniaturizing pellistor-type
catalytic sensors to reduce power consumption and enhance response and recovery times.
Lee et al. reported an integrated catalytic combustion hydrogen sensor utilizing MEMS
technology [29]. The sensor, which consists of two sensing and two reference elements
on a 5.76 mm2 chip, was fabricated using silicon wafers with silicon dioxide and nitride
films, patterned through photolithography and electroplating. It detects hydrogen at con-
centrations as low as 20 ppm, with a low power consumption of 55.68 mW. The sensor also
boasts fast response and recovery times of 0.36 and 1.29 s, respectively, to 1000 ppm H2
at an operating voltage of 1 V. Table 9 lists some of the advantages and disadvantages of
pellistor-type catalytic sensors.
Energies 2024, 17, 4059 10 of 25

Table 9. Advantages and disadvantages of pellistor-type catalytic sensors.

Advantages Disadvantages
• Fast response time. • Generally not selective for hydrogen and will respond to
• Typically used for hydrogen concentrations up to 4 vol%. other combustible gases, such as hydrocarbons and
• Claimed lifetime of 3–5 years. carbon monoxide.
• Wide market availability. • Requires oxygen to operate (minimum of between 5% and
10% oxygen in the gas mixture for the oxidation reaction).
• Can be affected by variations in operating temperature
and humidity.
• Performance is affected following exposure to inhibitors
(e.g., halogen-containing hydrocarbons), which have a
reversible effect, or poisons (e.g., organic silicon and
phosphorous-containing compounds), which have an
irreversible effect [19].
• High power consumption.

4.2.2. Thermoelectric Type

The first thermoelectric-type catalytic sensor was reported in 1985 by McAleer et al. [30].
Similar to the pellistor-type sensor, thermoelectric catalytic sensors also rely on the catalyzed
exothermic oxidation reaction of hydrogen. However, instead of relying on an increase in
resistance as temperature rises, the Seebeck effect occurs when there is a temperature gradient
between two areas of a conductor or a semiconductor, producing a measurable voltage
difference [31]. Usually, catalytic hydrogen sensors of the thermoelectric type are composed
of a thermoelectric film divided into two halves deposited on an insulating substrate material.
Half of the film is coated with a catalytic material, usually platinum, due to its high catalytic
reactivity at lower temperatures, while the other half is left uncoated. The chosen material for
the substrate is typically glass, alumina, or magnesium oxide [32].
Recently, Panama and Lee demonstrated a catalytic thermoelectric hydrogen sensor
using a CoSb3 thermopile fabricated by single-step deposition on bare and textured glass [33].
The sensor features a Co-In-Sb stack with a SiO2 capping layer, which was deposited via an
e-beam evaporator. The combination forms a thermoelectric pair through thermal activation.
This innovative method allows for the simultaneous creation of p-type CoSb3 on bare glass
and n-type CoSb3 on textured glass. The resulting sensor, incorporating 41 thermoelectric
pairs, has a thermoelectric sensitivity of 1.6 mV/K and demonstrates a steady-state voltage
of 13 mV for 1% H2 in air at room temperature. Table 10 lists some of the advantages and
disadvantages of thermoelectric-type catalytic sensors.
Table 10. Advantages and disadvantages of thermoelectric-type catalytic sensors.

Advantages Disadvantages
• Can detect low hydrogen concentrations up to the LEL. • Long response time but can be decreased by increasing the
• Can operate at relatively lower or slightly elevated measured gas flow rate [34].
temperatures compared to the pellistor type (room • Not commercially available to the knowledge of
temperature to <100 ◦ C) [19]. the author.
• Have low cross-sensitivity to other combustible gases.
• Can be micro-fabricated to reduce power consumption.

4.3. Resistance-Based Sensors

4.3.1. Semiconducting Metal-Oxide Type
Resistance-based semiconducting metal oxide (MOS)-type sensors detect the concen-
tration of various types of reducing gases by measuring the resistance change in the metal
oxide due to the adsorption of reducing gases. Typically, a metal oxide film is applied on
an insulating substrate between two electrodes, coupled with a heating element placed on
the reverse side. The substrate material of choice is usually aluminum oxide due to its high
thermal stability and electrical resistance, while allowing the effective adherence of metal
Energies 2024, 17, 4059 11 of 25

oxides to it. When the sensor is in operation, the film is typically heated to temperatures
between 180 and 450 ◦ C, depending on the specific metal oxide chosen [19]. At such elevated
temperatures, the reaction with the reducing gas is enhanced, and the trace amount of water
resulting from the reaction is removed. A wide range of semiconductor oxides can be used to
detect hydrogen, including but not limited to tin, zinc, and iron oxides [35].
The working principle of resistance-based metal oxide sensors is based on the change in
the surface electron depletion region when hydrogen reacts with the chemisorbed oxygen on
the surface of the semiconductor. As seen in Figure 3, oxygen molecules have the ability to
be adsorbed onto the semiconductor’s surface in the presence of an air atmosphere, where
they can draw electrons from the conduction band, forming oxygen ions. This results in the
creation of an electron-depletion region close to the surface, leading to a significant increase
in resistance caused by the reduction in the net carrier density. When the sensor is exposed
to a hydrogen atmosphere, the hydrogen molecules undergo an exothermic redox reaction
with the adsorbed oxygen species, leading to the rapid desorption of the resulting water
molecules. The freed electrons diminish the thickness of the depletion region, leading to a
decrease in the semiconductor resistance. When the sensor is returned
Energies 2024, 17, x FOR PEER REVIEW 12 of 27 to a hydrogen-free
atmosphere, the depletion-region thickness increases again, thereby increasing the resistance
of the semiconductor.

Figure
Figure3. Semiconducting metal oxide-type
3. Semiconducting sensor undersensor
metal oxide-type air and hydrogen atmospheres.
under air and hydrogen atmospheres.
Recently, there has been a need for small-sized, low-power-consumption MOS sen-
Recently, there has been a need for small-sized, low-power-consumption MOS sensors that
sors that utilize micro-electro-mechanical systems (MEMSs). Gorokh et al. described the
utilize micro-electro-mechanical
development systemsgas
of a micropowered chemoresistive (MEMSs). Gorokh
sensor utilizing etalumina
a thin al. described
na- the development
of a micropowered
noporous membrane andchemoresistive
a three-component gas sensor utilizing
nanocomposite a thin
structure basedalumina nanoporous membrane
on Sn-O/Bi-
O/Mo-O metal oxides [36]. Thenanocomposite
and a three-component sensor’s design leverages
structurethe based
high specific surface area and
on Sn-O/Bi-O/Mo-O metal oxides [36].
ordered structure of the anodic alumina matrix, combined with the sensitivity of the nano-
The sensor’s design leverages the high specific surface area and ordered structure of the anodic
composite structure to hydrogen gas. The sensor reportedly operates efficiently at a low
alumina
power matrix, combined
consumption of 10 mW and with
showsthea sensitivity
sensitivity of of the
0.22 andnanocomposite
0.40 for hydrogenstructure
con- to hydrogen gas.
The sensor
centrations of reportedly
5 and 40 ppm, operates efficiently
respectively, at 250 at
°C.a Other
low power consumption
high-performance of 10 mW and shows a
flexible
room-temperature
sensitivity of 0.22 MOS
andsensors
0.40 have been heavilyconcentrations
for hydrogen explored recentlyof[37], including
5 and 40 ppm,thoserespectively, at 250 ◦ C.
based on MOS modified with noble metal nanoparticles [38,39], organic polymers [40],
Other high-performance flexible room-temperature MOS sensors have been heavily explored
and carbon-based materials [41], among others. Table 11 lists some of the advantages and
recently [37],
disadvantages of including those
semiconducting based
metal on MOS
oxide-type modified with noble metal nanoparticles [38,39],
sensors.
organic polymers [40], and carbon-based materials [41], among others. Table 11 lists some of the
Table 11. Advantages and disadvantages of semiconducting metal oxide-type sensors.
advantages and disadvantages of semiconducting metal oxide-type sensors.
Advantages Disadvantages
Table 11. Advantages and disadvantages of semiconducting metal oxide-type sensors.
• Fast response time. • Low selectivity: cross-sensitive to other reducing and hydro-
• Low detection range. gen-containing compounds such as carbon monoxide, me-
• Advantages
Exhibit no sensitivity towards CO at thane, and alcohols. Disadvantages
• concentrations
Fast response time. up to 0.3% [19]. • Require• theLow
presence of oxygen
selectivity: in the ambienceto
cross-sensitive to other
work. reducing and
• Low• detection
Wide market availability.
range. • High operation temperature.
hydrogen-containing compounds such as carbon monoxide,
• • Response ismethane,
Exhibit no sensitivity towards CO at concentrations influencedand
by variations
alcohols.in the oxygen concentra-
up to 0.3% [19]. tion. • Require the presence of oxygen in the ambience to work.
• Temperature and humidity have a strong influence on the
• Wide market availability. • High operation temperature.
sensor response in the presence of hydrogen but have no in-
• Response is influenced by variations in the oxygen concentration.
fluence on the sensor response in air [19].
• Temperature and humidity have a strong influence on the sensor
• Sensors tend to overestimate the hydrogen concentration, and
response in the presence of hydrogen but have no influence on the
their responses saturate at low concentrations [19].
sensor response in air [19].
• Sensors
4.3.2. Metallic-Resistor Type (Thin-Film tend to overestimate the hydrogen concentration, and
Resistor)
their responses saturate at low concentrations [19].
Metallic-resistor hydrogen sensors operate on the principle that the electrical resis-
tivity of certain metals and alloys undergoes significant changes upon the absorption of
hydrogen gas. Among these metals, palladium stands out due to its high solubility to hy-
drogen, and the interaction between them is also selective, making palladium the metal of
choice for this type of sensor. The detection mechanism in metallic-resistor hydrogen sen-
sors relies on detecting the increase in electrical resistivity that occurs when hydrogen is
absorbed from the surrounding environment. This increase in resistivity is attributed to
the higher electrical resistance of palladium hydride compared to pure palladium. As hy-
Energies 2024, 17, 4059 12 of 25

4.3.2. Metallic-Resistor Type (Thin-Film Resistor)

Metallic-resistor hydrogen sensors operate on the principle that the electrical resistivity
of certain metals and alloys undergoes significant changes upon the absorption of hydrogen
gas. Among these metals, palladium stands out due to its high solubility to hydrogen, and
the interaction between them is also selective, making palladium the metal of choice for
this type of sensor. The detection mechanism in metallic-resistor hydrogen sensors relies
on detecting the increase in electrical resistivity that occurs when hydrogen is absorbed
from the surrounding environment. This increase in resistivity is attributed to the higher
electrical resistance of palladium hydride compared to pure palladium. As hydrogen
molecules are absorbed, the electrical resistance of the palladium film changes, providing
a measurable signal indicative of the hydrogen concentration in the environment. To
fabricate metallic-resistor sensors, a thin film of the metal (e.g., palladium) is deposited onto
a substrate using techniques such as vacuum evaporation, electrodeposition, sputtering, or
pulsed laser deposition [19]. The substrate, commonly made of silicon, acts as a support
structure for the metal film and is placed between two electrical contacts. These contacts
allow for the measurement of the electrical resistance changes in the palladium film when
exposed to hydrogen gas.
Recently, Gong et al. reported the development of a MEMS-based resistive hydrogen
sensor utilizing a palladium–gold alloy thin film [42]. The sensor was fabricated using
DC magnetron sputtering deposition, followed by annealing at various temperatures.
Integrated onto a patterned silicon substrate with heating and temperature detection
resistances, the sensor exhibited an optimal performance at a working temperature of 60
◦ C and can detect hydrogen at concentrations ranging from 5 ppm to 30,000 ppm, with

response and recovery times of 22 and 160 s, respectively, at 30,000 ppm. The sensor also
showed excellent repeatability, long-term stability, low power consumption, and high
selectivity for hydrogen. Other attempts were also made to miniaturize and decrease power
consumption of thin film resistive sensors [43–46], which makes this technology promising
for applications with power and weight constraints. Table 12 lists some of the advantages
and disadvantages of metallic resistor-type catalytic sensors.
Table 12. Advantages and disadvantages of metallic resistor-type sensors.

Advantages Disadvantages
• Wide detection range. • Response time and resistance to poisoning are dependent
• Very low response time. on the method of film fabrication [19].
• Low power consumption. • Some variants are prone to poisoning effects from gases
• Some variants are resistant to poisoning effects from gases like carbon monoxide, sulfur dioxide, and hydrogen
like methane, oxygen, and carbon monoxide. sulfide [48].
• Can operate in the absence of oxygen [47]. • Limited market availability.

4.4. Thermal Conductivity Type

Thermal conductivity-based sensors are one of the earliest types of hydrogen sensors
used. The method is based on the discovery by Andrews in 1840 that changes in the com-
position of the gas surrounding a heated electrical wire result in changes in the resistivity
of the wire [49]. The technology then came into realization thanks to the efforts of Daynes
in 1933 [50]. These sensors rely on hydrogen’s relatively high thermal conductivity when
compared to air (0.174 vs. 0.026 W/m·K at 20 ◦ C, respectively) to measure the hydrogen
concentration in air by measuring heat loss from a hot body to the surrounding gas. There
are two main types of these sensors with similar working principles. The first one is com-
posed of two inert resistor beads, each containing an embedded thermoresistor. As seen in
Figure 4, one of the resistors is exposed to the measured gas (detector cell), while the other
one is insulated in a chamber that contains a reference gas (reference cell), which typically
is air. An analyte elutes and changes the thermal conductivity of the column effluent,
changing the thermoresistor temperature of the detector cell. The change in temperature
leads to a change in resistance, which is typically detected using a Wheatstone bridge
Energies 2024, 17, 4059 13 of 25

circuit by producing an imbalance that translates to a measurable voltage change. The other
type operates without a reference cell and consists of a hot and a cold element, maintained
at a constant temperature difference. Thermal conduction occurs through the monitored
gas, transferring heat from the hot to the cold element. The power consumption
Energies 2024, 17, x FOR PEER REVIEW 14 of to
27 keep
the hot element’s setting temperature directly relates to the thermal conductivity of the gas
being monitored, allowing for the detection of the gas composition.

Figure 4.
Figure Schematicofofa athermal
4.Schematic thermal conductivity-type
conductivity-type sensor.
sensor.

There have
There haverecently
recentlybeenbeenattempts
attemptsat at miniaturizing
miniaturizing thermal
thermal conductivity
conductivity sensors,
sensors,
makingthem
making themmore
morepower
power efficient,
efficient, while
while reducing
reducing fabrication
fabrication costs.
costs. In their
In their study,study,
Berndt Berndt
et al.
al. developed
developedaaMEMS-based
MEMS-based thermal
thermalconductivity
conductivity hydrogen
hydrogen sensor [51]. [51].
sensor The sensor
The sensor
employs
employsmicro-fabrication
micro-fabrication techniques
techniquesononsilicon wafers,
silicon creating
wafers, a micro-hotplate
creating a micro-hotplate with awith a
suspended heated filament. This design minimizes power consumption
suspended heated filament. This design minimizes power consumption by operating by operating in in
pulsed mode and ensures thermal decoupling from the substrate to prevent
pulsed mode and ensures thermal decoupling from the substrate to prevent heat loss. The heat loss. The
sensor
sensor has
has aa measurement
measurement rangerange from
from 500 ppm to
500 ppm to at
at least
least 44 vol%
vol% of of H in air,
H22 in air,with
withsuccessful
suc-
cessful measurements in ambient gas temperatures ranging
measurements in ambient gas temperatures ranging from −15 C to 84 C. TheThefrom −15
◦ °C to ◦84 °C. authors
authors havethat
have noted noted that humidity
humidity significantly
significantly affects affects the sensor’s
the sensor’s thermal
thermal conductivity,
conductivity, a factor
aaccounted
factor accounted for intheoretical
for in both both theoretical and experimental
and experimental analyses.
analyses. OtherOther thermal
thermal con-
conductivity
ductivity sensors
sensors were were proposed
proposed by Harumoto
by Harumoto et al. thatet utilize
al. thatsweep
utilize heating
sweep heating
insteadinstead of
of continuous
continuous or pulsed heating, which acquires more information at a lower working tem-
or pulsed heating, which acquires more information at a lower working temperature,
perature, without requiring complex machining or the usage of MEMS technology [52,53].
without requiring complex machining or the usage of MEMS technology [52,53]. Table 13
Table 13 lists some of the advantages and disadvantages of thermal conductivity-type sen-
lists some of the advantages and disadvantages of thermal conductivity-type sensors.
sors.
Table 13. Advantages and disadvantages of thermal conductivity-type sensors.
Table 13. Advantages and disadvantages of thermal conductivity-type sensors.
Advantages Disadvantages
Advantages Disadvantages
• •Wide detection
Wide rangerange
detection whichwhich
often often
coverscovers <1–H2 [19]. • • Poor
<1–100% Poor detectivityatatvery
detectivity verylow
lowHH2 2concentrations
concentrations (often
(often used
• Can100%
operate in the
H2 [19]. absence of oxygen [47]. in conjunction with other sensors) [19].
used in conjunction with other sensors) [19].
• Not affected by sensor poisoning. • Not selective: The presence of other gases with high
• Can operate in the absence of oxygen [47]. • Not selective: The presence of other gases with high
• Low signal drift. thermal conductivity, such as helium, argon, methane, or
• •Claimed
Not affected by sensor
long operating poisoning.
lifetime (>5 years). thermal
carbonconductivity,
monoxide, can such as helium,
influence argon,
sensor me-
output.
• Low signal drift. • thane, or carbon
Sensitive monoxide,
to changes in the can influence
ambient sensor out-
temperature
• Claimed long operating lifetime (>5 years). put.
and humidity.
• Sensitive to changes in the ambient temperature and
4.5. Work Function Sensors humidity.

Work function-based sensors typically have a triple-layer structure consisting of a

4.5. Work Function Sensors
hydrogen-sensitive catalytic metal deposited on an oxide (insulator) layer on top of a
Work function-based sensors typically have a triple-layer structure consisting of a
semiconductor layer. During their operation, hydrogen atoms diffuse through the metal
hydrogen-sensitive catalytic metal deposited on an oxide (insulator) layer on top of a sem-
and get adsorbed at the metal–insulator interface [54]. These positively charged atoms
iconductor layer. During their operation, hydrogen atoms diffuse through the metal and
create a dipole layer that causes a shift in the energy levels, thus changing the work function
get adsorbed at the metal–insulator interface [54]. These positively charged atoms create
of the metal. The work function is a fundamental property, measured in electron volts, that
a dipole layer that causes a shift in the energy levels, thus changing the work function of
is related to the energy required to detach one electron from the surface of a material [55].
the metal. The work function is a fundamental property, measured in electron volts, that
There aretothree
is related main types
the energy of work
required function-based
to detach one electronsensors,
from thenamely metal–semiconductor
surface of a material [55].
There are three main types of work function-based sensors, namely metal–semiconductor
diodes (Schottky type), metal–insulator–semiconductor transistors (MOSFET type), and
metal–insulator–semiconductor capacitors.
Energies 2024, 17, 4059 14 of 25

Energies 2024, 17, x FOR PEER REVIEW 15 of 27

diodes (Schottky type), metal–insulator–semiconductor transistors (MOSFET type), and
metal–insulator–semiconductor capacitors.
4.5.1. Metal–Semiconductor Diodes (Schottky Type)
4.5.1. Metal–Semiconductor Diodes (Schottky Type)
These types of sensors consist of a metal brought into contact with a semiconductor
or, in These types of sensors
other variations, with anconsist of a oxide
insulating metalmaterial
broughtininto contact
between, aswith
seen ainsemiconductor
Figure 5.
or, in other variations, with an insulating oxide material
When the metal is brought into contact with the semiconductor, the Fermi in between, as level
seen ofin the
Figure 5.
When the metal
semiconductor is brought
adjusts to theinto
Fermi contact
level with
of thethe semiconductor,
dominating metal. the
ThisFermi level of the
adjustment
semiconductor
amount adjusts
is governed by to
thethe Fermi level of the
Schottky-barrier dominating
height, which is metal. This
equal to theadjustment
difference amount
in
is governed
Fermi by the Schottky-barrier
levels between the two materials height, which
[56]. To is equal
detect to the difference
the presence of hydrogen, in Fermi
palla-levels
dium
betweenandtheplatinum are typically
two materials [56]. To used as the presence
detect catalytic metal. In an environment
of hydrogen, palladium and where
platinum
hydrogen
are typicallyis present,
used ashydrogen molecules
the catalytic metal.getInadsorbed onto the where
an environment surfacehydrogen
of the catalytic
is present,
metal and disassociate
hydrogen molecules get intoadsorbed
hydrogenonto atoms,thesome of which
surface of thediffuse into
catalytic the metal–oxide
metal and disassociate
interface, forming
into hydrogen a dipole
atoms, layerofinwhich
some between. This dipole
diffuse into thelayer changes theinterface,
metal–oxide work function
forming a
of the catalytic metal, which, in this case, is a change in the Schottky-barrier
dipole layer in between. This dipole layer changes the work function of the catalytic height [57].metal,
This change leads to a change in voltage when a constant bias current
which, in this case, is a change in the Schottky-barrier height [57]. This change leadsis run through the to a
Schottky diode.
change in voltage when a constant bias current is run through the Schottky diode.

Schottky-type
Figure5.5.Schottky-type
Figure sensor
sensor composition.
composition.

Shivaramanet
Shivaraman et al.,
al., in
in 1979,
1979,was
wasone oneofof
thethe
earliest to demonstrate
earliest to demonstrate thatthat
current transport
current
through Schottky
transport barriers formed
through Schottky barriersby palladium
formed on n-typeonsilicon
by palladium n-typewith a thin
silicon withoxide layer in
a thin
between
oxide is in
layer sensitive
betweentoishydrogen inhydrogen
sensitive to the ambient [58].
in the Since then,
ambient numerous
[58]. Since Schottky diode
then, numerous
sensors have
Schottky diodebeen
sensorsreported in thereported
have been literature
in [59–61]. Chen[59–61].
the literature et al. have
Chenrecently presented
et al. have re- a
Pd nanoparticle/Pt
cently presented a Pdthin film/GaN/AlGaN-based
nanoparticle/Pt sensor device for
thin film/GaN/AlGaN-based hydrogen
sensor devicedetection
for hy- [62].
drogen detection
The sensor [62].
exhibits The sensor
a response exhibits
time of 18as response time oftime
and a recovery 18 s of
and12asrecovery
at 1 vol%time
H2 inof air at
12 s ◦
at 1 vol% H in air at 300 °C. The sensor can detect hydrogen at concentrations
300 C. The sensor can detect hydrogen at concentrations as low as 1 ppm, showing high
2 as low
as 1 ppm, showing
selectivity towardshigh selectivity
hydrogen overtowards hydrogen
other gases, suchover other
as NH 3 , gases,
CH4 , Csuch
2 H5as NHand
OH, 3, CHNO4,
2.
C2H5OH, and NO2.
4.5.2. Metal–Insulator–Semiconductor Transistors (MOSFET Type)
4.5.2. These
Metal–Insulator–Semiconductor
types of sensors rely on Transistors (MOSFET
a field-effect transistorType)
(FET) to detect hydrogen by
These types
transforming theof work-function
sensors rely on change
a field-effect
into atransistor
measurable(FET)electrical
to detect signal.
hydrogen by
Similar to
transforming the work-function
the Schottky-type change into
sensors, a metallic a measurable
layer sensitive toelectrical
hydrogensignal. Similar to the
is deposited onto an
Schottky-type
oxide layer on sensors,
top ofa ametallic layer sensitive
semiconducting to hydrogen
layer, as seen inisFigure
deposited onto an oxide
6. Hydrogen-sensing
layer on top of a semiconducting layer, as seen in Figure 6. Hydrogen-sensing
MOSFET sensors have a triple-layer structure typically composed of palladium MOSFET
or platinum,
sensors have a triple-layer structure typically composed of palladium or
silicon dioxide, and silicon [19]. In contrast to Schottky-type sensors, two regions platinum, siliconof the
dioxide, and silicon [19]. In contrast to Schottky-type sensors, two regions
semiconducting layer are ion-implanted in MOSFET sensors to form a drain and a source. of the semicon-
ducting layer metal
The catalytic are ion-implanted
layer functionsin MOSFET sensors
as a gate and, to form a adrain
by applying andbias
positive a source. Theallows
voltage,
catalytic metal layer functions as a gate and, by applying a positive bias voltage, allows
the control of the conductivity between the source and the drain. When hydrogen is present,
the control of the conductivity between the source and the drain. When hydrogen is pre-
the molecules get adsorbed onto the metal surface and then disassociate into hydrogen
sent, the molecules get adsorbed onto the metal surface and then disassociate into hydro-
atoms that diffuse to the metal–insulator interface, forming a dipole layer that changes
gen atoms that diffuse to the metal–insulator interface, forming a dipole layer that changes
the work function of the metal. Thus, the concentration of hydrogen is determined by
the work function of the metal. Thus, the concentration of hydrogen is determined by
measuring the change in the voltage of the FET between the drain and the source when it is
measuring the change in the voltage of the FET between the drain and the source when it
operated
is operatedatataaconstant
constantcurrent.
current.
 Energies2024,
Energies
Energies 2024,17,
2024, 17,4059
17, xx FOR
FOR PEER
PEER REVIEW
REVIEW 16 of
16 of 27
2715 of 25

Figure
Figure 6.6.MOSFET-type
Figure6. MOSFET-type
MOSFET-typesensor
sensor composition.
composition.
sensor composition.

Lundströmet
Lundström
Lundström etetal.al.
al. inin
in 1975
1975
1975 was
was was
oneone
one of of the
of the
the earliest
earliest
earliest to report
to report
to report a hydrogen-sensitive
aa hydrogen-sensitive
hydrogen-sensitive MOS MOS
MOS
field-effect
field-effect transistor
field-effecttransistor
transistor [63]. The
[63].
[63]. The The sensor could
sensor
sensor couldcoulddetect 40 ppm
detect
detect 40 ppm
40 ppmof hydrogen
of hydrogen
of hydrogenin air
in airin
atair
at aa device
device
at a device
temperature
temperatureof
temperature ofof150
150
150°C,◦ C,
°C, with aa response
with
with response
a response time
time of 22of
time
of min. OneOne
2 min.
min. One drawback
drawback
drawback was the
was the requirement
wasrequirement
the requirement
of
ofaaahigh
of high device
highdevice temperature
devicetemperature
temperature to to
to accelerate
accelerate
accelerate response
response
responseandand
and enhance
enhance sensitivity.
sensitivity.
enhance Thereafter,
Thereafter,
sensitivity. Thereafter,
techniques
techniques to reduce power consumption have been reported
techniques to reduce power consumption have been reported in the literature, as
to reduce power consumption have been reported in
in the
the literature,
literature, such
such as
such as
modulated
modulated operation
operation temperature
temperature [64],
[64], selective
selective heating
heating of
of catalytic
catalytic
modulated operation temperature [64], selective heating of catalytic metal [65], suspended metal
metal [65],
[65], suspended
suspended
gates
gates [66],
gates[66], and
[66],and complete
andcomplete
complete heat
heat
heat isolation
isolation
isolation[67].
[67].
[67].

4.5.3.
4.5.3. Metal–Insulator–Semiconductor
4.5.3.Metal–Insulator–Semiconductor
Metal–Insulator–Semiconductor Capacitors
Capacitors
Capacitors
These
These types
Thesetypes ofof
typesof sensors
sensors
sensors areare
are very
very
verysimilar
similar
similar in principle
in principle to the
to
in principle the Schottky
to Schottky diodediode
diode
the Schottky type, type,
type, with with
with
the
the main
themain difference
maindifference being
differencebeing
beingaa thicker
thicker
a thickeroxide
oxide layer,
layer,
oxide as seen
as
layer, seen in Figure
in
as seen Figure 7. This
7.
in Figure This thicker
thicker
7. This insulating
insulating
thicker insulating
layer
layer causes
causesaaacharge
layercauses charge
charge buildup
buildup
buildup onon
on both
both sides
sides
both by by
by
sides preventing
preventing
preventing current
current conduction
conduction
current conduction between
between
between
the
the metal
metal and
and the
the semiconductor
semiconductor layers.
layers. Hydrogen
Hydrogen molecules
molecules
the metal and the semiconductor layers. Hydrogen molecules dissociate on the dissociate
dissociate on
on the
the Pt
Pt surface,
surface,
Pt surface,
and
and the
andthe resulting
theresulting hydrogen
resultinghydrogen
hydrogen atoms
atoms
atomsdiffuse
diffuse through
through
diffuse throughthe metal
the metal to be
to
the metal betoadsorbed
adsorbed at the
at
be adsorbed theatmetal–
metal–
the metal–
insulator interface,
insulator interface, forming
forming aa dipole
dipole moment
moment that that affects
affects the
the capacitance–voltage
capacitance–voltage (C-V) (C-V)
insulator interface, forming a dipole moment that affects the capacitance–voltage (C-V)
characteristics of
characteristics of the MOS
MOS structure
structure [19].
[19]. This
This interaction
interaction causes
causes aa voltage
voltage shift,
shift, which
which cancan
characteristics ofthe the MOS structure [19]. This interaction causes a voltage shift, which can
be measured
be measured to to determine
determine the the presence
presence of of hydrogen.
hydrogen. The The magnitude
magnitude of of the
the voltage
voltage shift
shift
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Figure 7.7.Metal–insulator–semiconductor
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capacitive sensor designed for hydrogen gas detection at room temperature [71]. The
sensor, fabricated on a p-type silicon substrate with a nanostructured titanium oxide layer
fabricated by thermal evaporation, demonstrates a high hydrogen gas response. The
Energies 2024, 17, 4059 16 of 25

sensor’s performance showed a maximum gas response of 84% using conductance and 65%
using capacitance when exposed to 4% hydrogen gas, with a significant response observed
around zero bias voltage. The overall advantages and disadvantages of work-function
sensors are listed in Table 14.
Table 14. Advantages and disadvantages of work-function sensors.

Advantages Disadvantages
• Low detection limit. • Slower response times (t90 > 60 s).
• No cross-sensitivity to other combustible gases. • Poor performance under anaerobic conditions [19].
• Small size and mass producible. • Susceptible to chemical poisoning.
• Long lifetime. • Exhibits drift and hysteresis and requires periodical calibration.
• Limited commercial availability.

4.6. Optical Sensors

These sensors leverage changes in optical properties to accurately detect the presence
and concentration of hydrogen gas. The concept of optical hydrogen sensors dates to 1984
when the first designs were proposed. The earliest design described by Butler utilized
an optical fiber coated with palladium which expanded upon exposure to hydrogen,
causing a measurable change in the fiber’s effective optical path length [72]. Subsequent
advancements have led to the development of various optical hydrogen sensors based
on different materials and principles. For instance, Ito et al. introduced a sensor design
involving an optical fiber coated with tungsten oxide, which underwent a palladium-
catalyzed reaction with hydrogen, leading to changes in reflectivity [73]. Over time, optical
hydrogen sensors have evolved, with many still relying on thin films of palladium or
chemochromic oxides coated onto optical fibers. Researchers have since explored various
materials and sensing mechanisms to enhance the sensitivity and reliability of these sensors.
In this section, we explore some of the most common types of optical sensors, such as
grating-based sensors, plasmonic sensors, and evanescent field-based sensors.

4.6.1. Grating-Based Sensors

A fiber Bragg grating (FBG) is a portion of the optical fiber where the refractive index
is periodically modified along its length [74]. This modulation creates a wavelength-specific
reflector at a specific wavelength known as the Bragg wavelength, which is determined
by the period of the grating and the refractive index of the fiber. To sense the presence
of hydrogen, the FBG is coated with a sensing material that reacts with hydrogen, such
as palladium or platinum. The interaction between the hydrogen gas molecules and this
sensing material induces changes in the refractive index of the material, which can change
the effective refractive index of the grating region, causing a shift in the Bragg wavelength.
In 1999, Sutapun et al. implemented the first FBG hydrogen sensor by vaporizing
a 560 nm thick Pd layer on a fiber Bragg grating [75]. The sensor showed a linear sen-
sitivity for 0.3–1.8% hydrogen concentrations, with a sensitivity of 1.95 × 10−2 nm/1%
H2 . However, when exposed to hydrogen concentrations higher than 1.8%, the Pd coating
peeled off, and the sensor was irreversibly damaged. In 2015, Wang et al. introduced a FBG
hydrogen sensor based on co-sputtered Pd/Ni composite film. The results showed that the
wavelength shifted by 5, 12, 19, and 28 pm at respective hydrogen concentrations of 1%,
2%, 3%, and 4% at a response time of approximately 2 min [76]. Xian et al., since then, have
had numerous attempts to improve the sensitivity and decrease the response time of FBG
sensors, notably by incorporating a spiral microstructure and experimenting with different
alloy compositions for the sensing material [77–79].
One of the shortcomings of this sensing method is its temperature dependence. To
account for this, a hydrogen sensor based on a palladium-coated tapered FBG has been
proposed by Silva et al., in which a pair of FBGs in one fiber is constructed to improve
the sensitivity and compensate for the effect of temperature [80]. The tapered portion was
coated with a 150 nm thick Pd film for hydrogen sensing, while the other standard FBG
Energies 2024, 17, 4059 17 of 25

was left uncoated for temperature compensation. Most recently, Wang et al. demonstrated
a highly sensitive FBG hydrogen sensor based on hydrogen-doped Pt/WO3 nanomate-
rials [81]. Compared with non-doped Pt/WO3 , a 184-fold improvement in sensitivity is
achieved with a response time of 25 s to 2% of hydrogen. Temperature compensation was
also achieved by self-calibration through the detection of wavelength differences between
a pair of FBGs.
Another modified type of FBG is Long-Period Fiber Grating (LPFG), in which the core
mode beam encounters the first Long-Period Grating (LPG), causing some of its optical
power to be coupled to the cladding mode at a specific wavelength. A second LPG then
recouples a part of the cladding back to the core mode, creating an interference between the
core and the recoupled core modes. Thus, an interference fringe pattern is formed in the
transmission spectrum, which gets shifted upon hydrogen exposure [82]. When compared
to FBGs, LPFGs have a higher sensitivity to hydrogen and, thus, are influenced to a lesser
extent by variations in temperature [83].

4.6.2. Plasmonic Sensors

Surface plasmons are electromagnetic waves that travel parallel to a metal/dielectric
interface and are sensitive to alterations in the metal surface’s structure. Surface Plasmon
Resonance (SPR) occurs when incident light matches the resonant conditions for exciting
these surface plasmons at specific angles and wavelengths. In the context of hydrogen
detection, a metal-coated fiber, often made of an SPR-active metal like palladium, is exposed
to hydrogen gas. Hydrogen molecules interact selectively with the metal surface, causing
changes in the refractive index of the metal and the surrounding dielectric environment [84].
These alterations in the SPR support lead to detectable shifts in the resonant wavelength,
resonant angle, or intensity of reflected light, providing a reliable method for hydrogen
detection. Hosoki et al. have proposed a hetero-core sensor structure that includes short
single-mode fiber connected to multi-mode fibers on both ends [85]. The difference between
the core diameters causes the transmitted light in the fiber to leak into the single-mode
fiber’s cladding, generating evanescent waves at the cladding surface boundary via total
internal reflection. At the opposite end of the fiber, some light is recoupled into the multi-
mode fiber’s core, and if coated with a thin metal film, SPR waves can be induced in a
similar manner.

4.6.3. Evanescent Field-Based Sensors

Evanescent field-based hydrogen sensors utilize the phenomenon of the evanescent
field, which is an electromagnetic field occurring at the interface between different mediums,
such as the core and cladding of an optical fiber. In these sensors, the cladding of the fiber is
removed, and the core is coated with a hydrogen-sensitive layer. When hydrogen interacts
with this layer, it induces a change in the refractive index, resulting in an attenuation of
the evanescent field, detectable as a shift in transmittance [19]. The sensors operate based
on the alteration of the distribution of light field at the interface between materials with
varying refractive indices. This principle dictates that changes in the incident angle and
refractive index of the medium lead to variations in the effective penetration depth of the
transmitted wave, hence modifying the evanescent field’s depth. Evanescent field-based
hydrogen sensors come in various shapes and configurations to suit different applications.
These include D-Type Fiber Optical Hydrogen Sensors, Tapered Fiber Hydrogen Sensors,
Bare Core Fiber Optic Hydrogen Sensors, Core Mismatch Type Fiber Optic Hydrogen
Sensors, and Microstructure Fiber Optic Hydrogen Sensors. Each of these sensor types
utilizes the evanescent field principle in unique ways to detect hydrogen gas, offering
flexibility and versatility in their design and implementation. The main advantages and
disadvantages of optical sensors are listed in Table 15.
Energies 2024, 17, 4059 18 of 25

Table 15. Advantages and disadvantages of optical sensors.

Advantages Disadvantages
• Resistance to electromagnetic interference. • Some types are influenced by environmental factors such
• Fast response times. as temperature and humidity variations.
• Some types do not require the presence of oxygen. • Fragility and reduced mechanical strength.
• Highly sensitivity. • Limited upper detection limit.
• Wide area monitoring. • Unscalable fabrication methods.
• Miniaturization. • High cost and limited market availability.

4.7. Comparison between Sensor Types

The evaluation of a sensor technology’s advantages and disadvantages can be accom-
plished by comparing its performance metrics using various approaches. One such method
involves assigning a rating of either poor, acceptable, or good to assess its relative merits. As
such, Table 16 presents a qualitative comparison between the different sensor technologies.
Table 16. Qualitative comparison between sensor types.

Metric Electrochemical Catalytic Resistance Based Thermal Conductivity Work Function Optical
Selectivity Acceptable Acceptable Acceptable Poor Good Good
Response time Acceptable Good Acceptable Good Acceptable Good
Detection range Acceptable Acceptable Acceptable Good Good Poor
Lower detection limit Good Good Good Poor Good Good
Environmental sensitivity Acceptable Poor Poor Poor Acceptable Acceptable
Market availability Good Good Acceptable Acceptable Poor Poor
Operational lifetime Acceptable Poor Acceptable Good Good Good

When it comes to selectivity, electrochemical sensors are generally not very selective,
but can be customized and configured for specific gas detection scenarios. For example, the
material for the gas-permeable layer, which covers the inlet to the sensing electrode, can be
chosen in a way to allow the selective passage of the analyte, thus reducing interference
from other gases. As for catalytic sensors, they can respond to other combustible gases,
such as carbon monoxide and hydrocarbons. However, it has been reported that covering
the surface of a tin dioxide bead with a dense silica layer can increase the selectivity to
hydrogen of a pellistor-type catalytic sensor [86]. Semiconducting resistance-based gas
sensors are also cross-sensitive to several reducing or hydrogen-containing compounds,
such as alcohols, methane, and carbon monoxide. However, selectivity can be improved
by either doping the metal oxides with catalytic metals [87,88], depositing a thin filtering
layer on the metal oxide surface [89], or optimizing the operating temperature [90]. When
it comes to metallic resistor-based sensors, detection is selective to hydrogen, but poisoning
effects can be noticed from gases such as carbon monoxide and hydrogen sulfide. Thermal
conductivity sensors have poor selectivity since the presence of other gases with high ther-
mal conductivity influences the sensor output [19]. On the other hand, work function-based
sensors are generally hydrogen selective and are not sensitive to other combustible gases,
depending on the composition of the sensor and the selection of the catalytic metal. Optical
sensors are also selective to hydrogen by utilizing specific coatings or fiber configurations.
As for response time, it is defined as the time taken by a gas sensor to reach a specified
percentage of its final output after exposure to the target gas, with the value usually being
90%. Amperometric electrochemical hydrogen sensors have a response time in the range
of 20–50 s, while the potentiometric type has a typical response time of 10–100 s [16,17].
Catalytic-type hydrogen sensors typically have response times of less than 30 s for the
pellistor type and less than 60 s for the thermoelectric type, with some variants having
response times of less than a second. For resistance-based sensors, they have been reported
to have response times of anywhere between 10 s and a few minutes. Thermal conductivity-
type sensors usually have a response time of less than 20 s, with other configurations being
significantly lower at less than 4 s [91]. Work function sensors have a response time often
Energies 2024, 17, 4059 19 of 25

in the range of 30–60 s, with some variants taking up to several minutes to respond. Finally,
optical sensors generally have a rapid response time, with some being in the sub-1 second
mark [84].
When it comes to the detection range, different amperometric-type electrochemical
sensors have been reported to be able to detect hydrogen in the range of 5 ppm in argon
up to the LEL, depending on the configuration [15,17]. Catalytic-type sensors are also
typically used to detect hydrogen in concentrations up to the LEL. As for metal oxide-based
resistive sensors, they are typically used to detect hydrogen in the range of 10 ppm to
2% [19], while metallic resistor-type sensors can boast a wide detection range of 0.1–100%
of the LEL [92]. Meanwhile, thermal conductivity-type sensors have a very wide detection
range of 1–100 vol% H2 , but cannot detect very low concentrations. Thus, they are typically
used with other types of sensing technologies. Work function-based sensors have a good
detection range, typically up to 100% H2 , while optical sensors typically suffer from a low
upper detection limit in exchange for a high sensitivity at the lower detection limit.
When it comes to environmental effects, the performance of electrochemical sensors is
highly dependent on variations in temperature. Thus, an external temperature sensor is
typically implemented with an electrochemical sensor. Amperometric-type electrochemical
sensors typically have an operating temperature range between −20 and 80 ◦ C. Ambient
humidity can also affect the reading due to the alterations in the water content of the elec-
trolyte, thus affecting the proton conducting ability. It is worth noting that potentiometric
electrochemical sensors with solid proton conducting electrolytes can operate at more
extreme temperatures since the electrolyte does not freeze at extremely low temperatures
or evaporate at elevated temperatures. Catalytic sensors are also affected by variations in
the operating temperature and humidity, and always require the presence of oxygen to
operate. Pellistor-type catalytic sensors typically operate at temperatures ranging from −20
to 70 ◦ C and a relative humidity range of 5–95%. Thermoelectric-type catalytic sensors,
however, can operate at lower or slightly elevated temperatures compared to the pellistor
type. Resistance-based semiconducting metal oxide-type sensors also require the presence
of oxygen in the ambient to operate, and their response is strongly affected by variations in
temperature and humidity [19]. Similarly, variations in the ambient temperature on the
thermal conductivity-type sensors’ readings must be considered due to the temperature
dependence of the working principle. Work function-based sensors usually perform poorly
under anaerobic conditions but are generally not influenced by temperature or humidity
variations. On the other hand, some types of optical sensors are influenced by temperature
and humidity variations, but they do not necessarily require the presence of oxygen.
Regarding market availability, electrochemical and catalytic-type sensors are the most
abundant. The lifetime of these is 5 years or more for electrochemical sensors and 3–5 years
for catalytic-type sensors. Resistance-based sensors are not abundantly present for com-
mercial applications, while thermal conductivity-type sensors have been in use for many
decades but are commonly only used in conjunction with other types of sensors. Mean-
while, no commercial work function or optical hydrogen sensors were found in the market
to the best of the author’s knowledge. Some of the commercially available sensors from a
market survey are presented in the next section.

5. Commercially Available Hydrogen Sensors

Most of the commercially available hydrogen sensors in the market are either of the
electrochemical or the catalytic type. In some cases, devices manufactured by different
vendors with nearly identical basic design features exhibit dramatically different response
behaviors. Thus, several sensors with similar working principles are examined below from
a market search. The sensor types, models and approximate price ranges are also listed
in Table 17. The selection of an appropriate hydrogen sensor for a specific application
depends on the user’s needs and preferences. It is also important to note that the sensing
elements of those detectors are also optimized to detect gases other than hydrogen, making
Energies 2024, 17, 4059 20 of 25

it necessary to review and verify with the manufacturer the detector’s ability to respond to
hydrogen while satisfying the performance requirements.

5.1. Electrochemical Sensors

These are currently the most commonly used types of sensors to detect hydrogen. They
are widely employed for hydrogen detection due to their high sensitivity, rapid response,
and relatively low cost. Honeywell (Charlotte, NC, USA), for example, has a large lineup
of industrial sensors and monitors, such as the Sensepoint XCD and the XNX Universal
Transmitter, which can be configured to detect a wide range of combustible and toxic gases
in potentially explosive atmospheres, including hydrogen. The XNX can be equipped with
different types of electrochemical sensors having different measuring ranges and response
times. The lower configuration has a default range of 1000 ppm, an accuracy of less than
+/− 8 at 100 ppm, and a response time of less than 90 s. On the other hand, the high-range
configuration has a default range of 10,000 ppm and a faster response time of less than
30 s at the cost of lower accuracy at +/− 150 at 1000 ppm. The operating temperature
ranges from −20 ◦ C to 55 ◦ C, and the humidity ranges from 15% to 90% RH. Similar to
other electrochemical sensors, the sensing element has a lifespan of around 24 months.
ATO (Diamond Bar, CA, USA) is another international supplier of industrial au-
tomation products. They offer several portable and fixed combustible gas detectors. The
ATO-GAS-H2, for example, is a portable hydrogen gas detector that draws the gas via
a micro pump towards an electrochemical sensing element. It can be configured for dif-
ferent applications with varying measurement ranges, down to as low as 0–10 ppm. The
ATO-GAS-H2-A, on the other hand, is a fixed hydrogen gas detector that is compatible
with various control systems and remote monitors. The sensing element is also electro-
chemical, and the lowest detection range configuration is 0–1000 ppm. Both configurations
have a response time of less than 10 s; an accuracy of less than +/− 3% full scale; and
an operating temperature and humidity range from −20 ◦ C to 50 ◦ C and from 0% to 95%
RH, respectively.
IGD (Stockport, UK) offers another electrochemical sensor, the TOC-750X-H2, with a
detection range of 0–1000 ppm, an accuracy of +/− 2% of full scale, and a response time of
less than 30 s. Like other electrochemical sensors, its operating temperature and humidity
range from −20 ◦ C to 55 ◦ C and from 0% to 95% RH, respectively.
Dräger (Lübeck, Germany) is another company that offers both electrochemical and
catalytic H2 sensors. Its Polytron® 6100 EC WL is a wireless transmitter for continuous
monitoring of toxic gases and oxygen that can be installed for fixed applications and
interlinked to create a monitoring network. It can be equipped with the Electrochemical
DrägerSensor® H2 , with a hydrogen detection range from 15 to 3000 ppm. It can also
be equipped with a selective A2F filter A2F to improve reading accuracy and reduce
cross-sensitivity effects.

5.2. Catalytic Sensors

In addition to electrochemical sensors, Dräger also offers the Polytron® 8200 CAT,
which is an explosion-proof transmitter for the detection of combustible gases in the lower
explosion limit (LEL). It can be equipped with the Catalytic Bead DrägerSensors Ex LC M,
which contains PR pellistors that allow for the detection of very low gas concentrations in
the range from 0% to 10% LEL. The operating temperature and humidity range from 40 ◦ C
to 70 ◦ C and from 5% to 95% RH, respectively. However, no selective filters are available
for use with the catalytic sensor and the sensitivity of the catalytic bead sensor to hydrogen
and methane is almost the same (1.1 mV/% LEL vs. 1.0 mV/% LEL). To solve this issue,
the catalytic sensor can be coupled with an infrared sensor, which is totally insensitive to
hydrogen. Depending on the readings of both detectors, it could be determined whether
the alarm is caused by the presence of methane (both sensors will output close values) or
hydrogen (there would only be a reading on the catalytic bead unit).
Energies 2024, 17, 4059 21 of 25

The Sensitron S2157H2 (Cornaredo, Italy) is another catalytic option for hydrogen
detection. The sensing element has a longer lifespan than typical electrochemical sensors at
about 4 to 5 years, and it can detect 0–100% LEL at a response time of less than 60 s. The
operating temperature and humidity range from −40 ◦ C to 60 ◦ C and from 20% to 90%
RH, respectively.

5.3. Resistance-Based Sensors

Semiconductive sensors are another low-cost option for the detection of hydrogen.
They offer advantages such as high sensitivity, low power consumption, and high linearity.
However, they suffer from low selectivity and are cross-sensitive to other reducing and
hydrogen-containing chemicals. The Hanwei MQ range (Zhengzhou, China), for example,
includes semiconductor metal oxide-based sensors composed of a micro aluminum oxide
tube coupled with a tin dioxide sensitive layer. The variant that detects hydrogen is the
MQ-8, which is highly sensitive to hydrogen, with a low sensitivity to alcohol, Liquefied
Petroleum Gases (LPGs), and cooking fumes. They have a typical detection range of
100–10,000 ppm, an operating temperature range from −10 ◦ C to 50 ◦ C, and an operating
humidity of less than 95% RH.
The HY-ALERTA™ range of area monitors by H2scan (Valencia, CA, USA) identifies
hydrogen presence in the air by utilizing a distinctive solid-state sensor technology. These
thin-film resistive sensors offer continuous real-time hydrogen detection without being
influenced by other gases in the surrounding environment. They operate without the need
for reference gases, ensuring reliable and precise hydrogen detection with good response
times. H2scan employs a durable hydrogen-specific palladium-nickel solid-state sensor
that guarantees longevity, reduces false alarms, and measures hydrogen concentrations
ranging from 10% to 125% LEL at a response time not exceeding 60 s.
Table 17. Approximate prices for commercially available hydrogen sensors ($ = up to CAD 100, $$ = up
to CAD 1000, and $$$ = more than CAD 1000).

Sensor Type Sensor Make and Model Price Range

Electrochemical Honeywell Sensepoint XCD $$$
Honeywell XNX Universal Transmitter $$$
ATO-GAS-H2 $$
ATO-GAS-H2-A $$
IGD TOC-750X-H2 $$
Dräger Polytron 6100 EC WL $$$
Catalytic Dräger Polytron 8200 CAT $$$
Sensitron S2157H2 $$
Resistance-Based Hanwei MQ-8 $
H2scan HY-ALERTA 600B $$$

6. The Future of Hydrogen Detection

The adoption of hydrogen as a clean energy carrier holds significant promise for
addressing climate change and fostering a transition to a low-carbon future, particularly in
countries like Canada, with abundant renewable energy resources. However, ensuring the
safety and reliability of hydrogen infrastructure and operations is paramount to realizing
this potential. Hydrogen leak detection is critical in maintaining safety throughout the
hydrogen value chain, from production to utilization.
Reviewing existing standards reveals a comprehensive framework established by
organizations such as ISO, ASME, NFPA, and IEC to govern various aspects of hydrogen
systems and technologies, including leak detection. These standards provide guidelines for
the design, installation, operation, maintenance, and testing of hydrogen systems, empha-
sizing the importance of safety and reliability. However, it is important to acknowledge a
notable gap in the existing standards’ landscape, particularly regarding standards specifi-
cally focused on hydrogen leak detection. While current standards provide comprehensive
Energies 2024, 17, 4059 22 of 25

guidelines for various aspects of hydrogen systems and technologies, including safety
considerations, there is a lack of dedicated standards solely focused on the intricacies of
hydrogen leak detection. This gap highlights an opportunity for further research and devel-
opment to comprehensively address this aspect of hydrogen safety. Developing specialized
standards tailored to the unique characteristics and challenges of hydrogen leak detection
could further enhance the reliability and effectiveness of detection systems, ultimately
bolstering the safety and sustainability of hydrogen infrastructure.
Additionally, it is crucial to recognize the ongoing advancements in sensing technolo-
gies, particularly the emergence of novel approaches such as work function solid-state
sensors and optical sensors. These novel sensor technologies offer promising capabilities
in detecting hydrogen leaks with enhanced precision, speed, and reliability. As research
and development efforts progress, there is a concerted focus on aligning sensor capabilities
with the stringent requirements outlined by organizations such as the U.S. Department of
Energy (DOE), and the exploration of new sensing modalities and the refinement of existing
technologies signify a dynamic landscape in hydrogen leak detection, characterized by
continuous innovation and improvement.

Author Contributions: Conceptualization, Z.H.; methodology, Z.H.; formal analysis, M.W.Q.; in-
vestigation, M.W.Q.; resources, Z.H.; writing—original draft preparation, M.W.Q.; writing—review
and editing, Z.H.; visualization, M.W.Q.; supervision, Z.H.; project administration, Z.H.; funding
acquisition, Z.H. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by Natural Resources Canada’s Office of Energy Research and
Development (OERD), grant number NRC-22-306 through National Research Council Canada’s
Advanced Clean Energy Program (ACE).
Conflicts of Interest: The authors declare no conflicts of interest.

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