Showcasing research from the Institute of Photonics As featured in:

Technology, Jinan University, Guangzhou, China.

Volume 11 Number 34 14 September 2019 Pages 15671–16144

High-sensitivity and fast-response fiber-tip Fabry–Pérot

hydrogen sensor with suspended palladium-decorated graphene
Nanoscale
rsc.li/nanoscale

The safe utilization of hydrogen as a clean fuel and industry

material requires the reliable detection of a gas leakage. Here,
we report a sensitive and fast-response fiber-tip Fabry–Pérot
hydrogen sensor by integrating an optical fiber with a suspended
palladium (Pd)-decorated graphene. In addition to providing a
compact and all-optical solution to sensitive and fast hydrogen
detection, the rationally-designed sensor can be employed for
diverse chemical/gas sensing applications by replacing Pd with
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High-sensitivity and fast-response fiber-tip

Cite this: Nanoscale, 2019, 11, 15821
Fabry–Pérot hydrogen sensor with suspended
palladium-decorated graphene†
Jun Ma, Yanglin Zhou, Xue Bai, Kai Chen and Bai-Ou Guan*

Received 19th May 2019,
Accepted 25th June 2019
DOI: 10.1039/c9nr04274a
rsc.li/nanoscale
The safe utilization of hydrogen as a clean fuel and industry material requires the reliable detection of a
gas leakage; thus, hydrogen sensors with high sensitivity and fast response are in urgent demand. Among
various hydrogen detection techniques, optical hydrogen sensors are especially attractive because of
their intrinsic safety. Herein, by integrating an optical fiber with a suspended palladium (Pd)-decorated
graphene, we demonstrate a fiber-optic hydrogen sensor with fast-response that is sensitive, compact
and capable of remote detection. The suspended Pd-decorated graphene, attached to the optical fiber
tip with an air cavity, forms a flexible Fabry–Pérot interferometer. Upon hydrogen absorption, the ultrathin
Pd film facilitates a fast hydrogen dissociation and the ultrathin graphene enables an effective conversion
of the Pd lattice expansion to Pd/graphene film displacement, which can be readily measured by fiber-
optic interferometery. With a hybrid film of ∼5.6 nm-thick Pd and ∼3 nm-thick suspended graphene, a
low detection limit of ∼20 parts per million ( ppm) and a short response time of ∼18 s have been achieved.
In addition to providing a compact and all-optical solution to sensitive and fast-response hydrogen detec-
tion, the rationally-designed sensor can be used for diverse chemical/gas sensing applications by repla-
cing Pd with other functional materials.

1. Introduction ity.8 By using Pd films with the thickness of tens of nano-

Hydrogen gas (H2) has widespread applications in petroleum,
chemical and aerospace industries, and is also regarded as a
clean energy source to alleviate the global warming problem
associated with fossil fuel consumption.1,2 The utilization of
H2 is, however, inevitably accompanied by safety problems
because H2 has a low ignition temperature and can easily form
an explosive mixture with air over a wide concentration range
from 4% to 75%. H2 is also light-weight and highly soluble in
many metals, which greatly increases the risk of leakage.3 To
ensure the safety in H2 usage, transportation and storage, the
development of a sensitive H2 detection method with fast-
response is of great importance. In the past decades, a range
of H2-sensors based on electrochemical, microelectromechani-
cal, resistive, and optical mechanisms have been developed.4–7
Among these sensors, palladium (Pd) is frequently used as the
catalyst due to its high affinity towards H2 and good reversibil-
Guangdong Provincial Key Laboratory of Optical Fiber Sensing and Communications,
Institute of Photonics Technology, Jinan University, Guangzhou 511443, China.
E-mail: tguanbo@jnu.edu.cn; Fax: +86 020 37336640; Tel: +86 020 37336640
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c9nr04274a
meters, a low H2 detection limit down to parts per billion
( ppb) level can be achieved.9 However, their long response
time, typically tens of seconds or even minutes,5,7,9 impedes
the instantaneous detection of H2 leakage in order to prevent
explosions without delay.
With the rapid development of nanotechnology and nano-
materials, Pd nanostructures in the forms of nanofilms, nano-
wires and nanoparticles, featuring a large surface-to-volume
ratio, have been exploited to shorten the surface dissociation
and/or diffusion time of H2 molecules.10–19 For example,
F. Favier et al. deposited a Pd mesowire array onto a graphite
film and reduced the sensor response time to 75 ms.10 The Pd
nanogaps between the mesowires close immediately upon H2
absorption due to the Pd lattice expansion, leading to a rapid
drop in the electrical resistance of the array. This mesowire-
array-based sensor, however, works in a switch mode and is
only sensitive to H2 concentrations above a certain threshold.
To enable fast and low-concentration H2 detection, Y. Sun
et al. decorated carbon nanotubes (CNTs) with Pd nano-
particles.12 By recording the electrical resistance change in the
CNTs, a minimum detectable concentration of as low as 30
parts per million ( ppm) and a short response time of ∼1.5 s at
1% H2 concentration were achieved. In addition to CNTs, gra-

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Paper
phene has also been widely exploited for H2-sensing because
of its large surface-to-volume ratio, high carrier mobility
and inherent low electrical noise.20–27 Decoration of Pd
nanoparticles on a multilayer-graphene nanoribbon network
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can realize a H2 concentration detection limit on the ppm
level and a short response time of 6 s at 8000 ppm H2
concentration.22
The abovementioned nanosensors rely on the detection of
an electrical resistance change caused by a Pd hydride for-
mation after the reaction of Pd with H2. Considering the low
ignition energy of H2, there exists a potential risk of explosion
triggered by electrical sparks generated during the signal
readout process. Therefore, optical H2-sensors with intrinsic
safety have attracted much attention,28–33 such as the nanoan-
tenna-excited single Pd nanoparticle28 and Pd nanorod-coated
silica microfiber.29 H2 absorption or release modifies the
dielectric function of the Pd nanoparticle, giving rise to the
change in optical scattering or localized surface plasmon reso-
nance (LSPR) of the nanoparticle. However, the complicated
excitation and detection schemes, such as the nanoantenna or
whispering-gallery-mode (WGM) supported microfiber are
necessary to cope with the weak LSPR signals. The free-space
light delivery and collection are also bulky and sensitive to
environmental vibration/motion, which is undesirable for on-
site H2-sensing. In addition to the optical refractive index
change, the H2 absorption can also induce mechanical stress
in the Pd films.34 This mechanism has been exploited to
develop an interesting eye-readable H2-sensor based on the Pd-
coated Janus nanofibers (H-NFs), exhibiting fast response
times as short as 5.1 s.35 The H2-absorption-induced stress
effect can be also applied to develop fiber-optic H2-sensors,
which are compact, easy to handle and intrinsically safe.
Decoration of Pd films onto the surfaces of a capillary-based or
a femtosecond laser-carved Fabry–Pérot cavity has enabled sen-
sitive H2 detection by measuring the stress-induced cavity
length change.36–38 To achieve high sensitivity, a thick Pd film
is necessary to stretch the fiber structure with a diameter of
roughly 100 μm. Even when a much thinner silica cantilever
was used to construct the Fabry–Pérot cavity,39 a 150 nm-thick
Pd film was still needed, which significantly slowed down the
sensor response.
Herein, we demonstrated a miniature fiber-optic H2-sensor
with a Pd-decorated multilayer graphene (MLG). The Pd/MLG
film covered the air cavity at the optical fiber tip, forming a
flexible Fabry–Pérot (FP) interferometer. The expansion of the
Pd lattices after H2 absorption stretches and deforms the sus-
pended MLG film, whose displacement can be readily resolved
using high-precision fiber-optic interferometry. By depositing
a ∼5.6 nm-thick Pd film onto a ∼3 nm-thick MLG film, a detec-
tion limit of ∼20 ppm and a response time of ∼18 s were
achieved. Through the integration of Pd/graphene nano-
materials and fiber-optic sensing technology, we have show-
cased a compact, sensitive and fast-response H2-sensor, which
is also intrinsically safe toward electrical discharge and
capable of remote sensing in hazardous or space-limited
environments.
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2. Principle
The schematic of the suspended Pd/MLG film-based H2-sensor
is shown in Fig. 1. The Pd/MLG film and the fiber end facet,
separated by a section of silica capillary, act as two partially
reflective mirrors and form a low-finesse Fabry–Pérot cavity.
When exposed to H2, the Pd/MLG film adsorbs and dissociates
the H2 molecules at its surface. The dissociated hydrogen atoms
diffuse into the Pd film and form PdHx until reaching equili-
brium.40 The Pd-to-PdHx transition causes the expansion of the
Pd lattice, which stretches and deflects the Pd/MLG film. The
deflection of the Pd/MLG inward to the air cavity reduces the
Fabry–Pérot cavity length defined by the separation between the
Pd/MLG film and the fiber end facet. The reduction in the
cavity length (ΔL) results in the wavelength shift (Δλ) of the
cavity reflection spectrum, following the simple relationship as
Δλ/λ = ΔL/L, where λ is the wavelength of the traced interference
valley and L is the length of the cavity. Consequently, the H2
concentration encoded in the Pd/MLG film deflection can be
extracted by directly measuring the wavelength shift of the
reflection spectrum.41 If the Pd film and MLG film are con-
sidered as thin and elastic, the cavity length (ΔL) upon H2
absorption or the deflection of the Pd/MLG film (h), is related
to the strain in the film (εc) caused by the Pd lattice expansion
1=2
by h ∼ εc ,42 where εc can be described as,
EPd tPd
εc ¼ εPd ð1Þ
EPd tPd þ EG tG
In eqn (1), εPd is the strain in the Pd film and relates to the
H2 content of the Pd film (CH) by εPd = 0.026·CH,9 and EPd, tPd
(EG, tG) are the Young’s modulus and thickness of the Pd
(MLG) film, respectively. The relationship between the deflec-
tion of the Pd/MLG film (h) and the H2 partial pressure ( p) can
then be derived as,
pffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
6 4 0:026 EPd tPd
h R0 p ð2Þ
2 K EPd tPd þ EG tG
where R0 is the radius of the suspended Pd/MLG film and K is
the Sievert’s coefficient (K = 350 Torr1/2). A detailed derivation
Fig. 1 Schematic of a fiber-optic H2-sensor with Pd-decorated MLG
film.
This journal is © The Royal Society of Chemistry 2019

Nanoscale
can be found in the ESI.† Based on eqn (2), the Pd/MLG film
experiences a larger strain and thus a larger Pd/MLG film
deflection at the same H2 concentration for a thinner MLG
film. If the H2 sensitivity of the sensor is defined as the ratio
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of the wavelength shift to the H2 concentration, a thinner MLG
film provides a higher H2 sensitivity. Therefore, we chose gra-
phene, arguably the strongest two-dimensional (2D)
material,43 as a free-standing membrane to firmly support the
Pd film. Its atomic thickness can greatly increase the sensi-
tivity and its superior mechanical strength simplifies its trans-
fer onto the fiber tip and subsequent Pd deposition. Its unpar-
alleled elastic stiffness and low mass per unit area also make it
especially attractive for nanomechanical systems (NEMS) and
serving as reinforcing agents in composites,44 which is critical
to the repeatable conversion of Pd expansion into the Pd/MLG
film displacement. Here, MLG (6–8 layers), instead of single or
few-layer graphene, is used because of its easy manipulation,
as well as large optical reflectivity for high fringe contrast of
the sensor interference spectrum. According to eqn (1), the
utilization of thicker Pd films is another alternative method to
improve the H2 sensitivity, albeit at the expense of the
response speed.45 This has been proven by the follow-up
experimental result, which suggests an optimum Pd thickness
of ∼5 nm. A detailed theoretical analysis regarding the H2 sen-
sitivity of the sensor can be found in Fig. S1 (ESI†).
3. Sensor preparation
The sensor fabrication process is as follows: first, a section of
silica capillary with a bore diameter of 25 μm (Polymicro,
TSP025150) was spliced to a conventional single-mode fiber
(SMF) by a fusion splicer (Fujikura FSM-45PM, slicing para-
meters: 50 bit, 150 ms) and was cleaved at a distance of L to
the splicing joint using a standard fiber cleaver under micro-
scope. This distance defines the initial cavity length and can
be adjusted within a range from 20 to 60 μm. A MLG film was
then transferred onto the capillary to form a microcavity, with
the detailed transfer process shown in Fig. 2. The MLG film
grown on a copper (Cu) foil with a thickness of 20 μm (ACS
Material) by chemical vapor deposition (CVD) was first
detached from the Cu foil by immersing the MLG/Cu sample
into a 0.05 g mL−1 FeCl3 solution (Step 1). After the Cu foil was
Fig. 2 Schematic of the preparation process of a Pd-decorated MLG-
based optical H2-sensor.
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etched off, the MLG film was moved to deionized (DI) water
using a clean glass slide and the process was repeated three
times to wash out the residual ions (Step 2). The clean MLG,
floating on the water surface, was then transferred onto the
fiber-tip microcavity by a dip-coating process (Step 3). During
the coating process, the fiber was mounted onto a mechanical
stage with its tip facing the water and slowly moved towards
the MLG floating on the water. Once the fiber tip touched the
MLG, the fiber tip was immediately pulled up. The MLG,
together with residual water, was then stuck onto the fiber tip
due to the surface tension of water. As the water evaporated,
the MLG remained firmly attached to the fiber-tip end facet as
a result of van der Waals force and suspended over the micro-
cavity (Step 4).46 Finally, the surface of the MLG was coated
with a thin layer of Pd by magnetron sputtering (JGP-450, SKY
Technology Development) (Step 5). The fiber was fixed inside
the sputtering chamber with the tip facing the Pd source. The
Pd thickness was controlled by the splicing time of the sputter
(SKY Technology Development, JGP-450).
Fig. 3(a) shows the sideview of the sensor structure com-
prised of a SMF and a short piece of silica capillary. Fig. 3(b)
and 3(d) show the scanning electron microscopy (SEM) images
of the MLG-covered end facet of the fiber-tip before and after
Pd coating, respectively, and Fig. 3(c) and (e) are the close-up
images of the suspended films.
The surface of the Pd/MLG film exhibits a continuous mor-
phology as observed from the atomic force microscopy (AFM)
image shown in Fig. 3(g). We have further characterized the
thickness of the Pd and MLG films by transferring them onto
Fig. 3 (a) Sideview of the sensor structure comprising a piece of capil-
lary attached to a SMF end. (b–e) Scanning electron microscopy (SEM)
images of the fiber tip end facet before (b) and after (d) being coated
with Pd; (c) and (e) are the close-up images of (b) and (d), respectively.
(f ) Photograph of the sensor protype. (g) Atomic force microscopy
(AFM) image of the morphology of the Pd-coated MLG. (h) and (i) are
the height profiles of Pd and MLG films, respectively; the insets show
AFM images of the Pd and MLG films on silicon (Si) wafers.
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silicon wafers, and the thickness estimated from Fig. 3(h) and
(i) are ∼5.6 nm and ∼3.1 nm, respectively. Compared with
silicon-substrate based graphene devices,20 the fiber-tip struc-
ture has a small form-factor (Fig. 3(f )) and is well suited for
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The wavelength shift exhibits a nonlinear correlation to the
H2 concentration since the fraction of the Pd surface sites
occupied by the hydrogen atom is proportional to the square
root of H2 partial pressure, according to the Langmuir adsorp-
tion isotherm theory.12 It needs to be noted that the unit

space-limited H2 detection.
ppm1/2 instead of ppm is used for the H2 concentration in
Fig. 5(a), which accounts for the nonlinear relationship
4. Results and discussion between the Pd/MLG film deflection h and the strain in the
1=2
film εc caused by the Pd lattice expansion as h ∼ εc .42 For the
Fig. 4 shows the reflection spectra of the Fabry–Pérot cavity
MLG coated with a 5.6 nm-thick Pd film, a H2 concentration of
covered with bare and Pd-decorated MLG films. A broadband
∼200 ppm induced a large wavelength shift of ∼50 pm, which
source (1200 nm–1700 nm) was used as the interrogation light.
corresponds to a H2 sensitivity of ∼0.25 pm ppm−1. During
The reflected light from the sensor head after travelling
20 minutes exposure of 0.5% H2, the wavelength fluctuation of
through an optical circulator was received by an optical spec-
the sensor reflection spectrum is ∼0.01 nm (see inset of
trum analyser. The length of the Fabry–Pérot cavity L can be
Fig. 5(a)). The temporal responses of the Pd/MLG sensor to
calculated according to the formula L = λ1λ2/4nair(λ2 − λ1),
several H2 concentrations were also measured and are sum-
where λ1 and λ2 are the adjacent valley wavelengths of the
marized in Fig. 5(b). The durations of the sensor exposed to
reflection spectrum, and nair is the air refractive index. The cal-
diluted H2 and pure N2 for each concentration test are 150 s
culated cavity length is ∼24 μm, close to the estimated value
and 300 s, respectively. The temporal wavelength fluctuation of
from the microscopic image in Fig. 3(a). By curve-fitting the
the sensor at steady H2 concentration is ∼5 pm (1σ). This noise
reflection spectra in Fig. 4, the reflectivity of the graphene film
level, in combination with the measured sensitivity, suggests a
is estimated to be 0.3% and increases to 1.1% after Pd depo-
limit of detection (LOD) of ∼20 ppm for the Pd/MLG sensor. At
sition. The higher reflectivity of the Pd/MLG film significantly
increases the fringe contrast of the reflection spectrum from
∼7 dB to ∼15 dB, which is favourable to improve the resolution
for measuring the wavelength shift of the reflection
spectrum.47
To investigate the H2 response of the Pd/MLG sensor, it was
placed inside a custom-built gas chamber as shown in Fig. S2
(ESI†). The H2 gas concentration in the chamber was con-
trolled by regulating the flow rate of a 3% N2-diluted H2 gas
and a pure N2 via two mass flow controllers. The total flow rate
of the gas mixture was fixed at 200 sccm during the test. After
the H2 concentration was set, we continuously recorded the
sensor reflection spectrum with a time interval of 2 seconds.
As shown in the inset of Fig. 5(a), the reflection spectrum of
the sensor shifts to shorter wavelengths as the H2 concen-
tration increases from 200 ppm to 20 000 ppm.

Fig. 4 Reflection spectra of a fiber tip cavity covered with a graphene
film before and after Pd decoration.
Fig. 5 (a) Wavelength shift and (b) temporal response of the Pd/MLG
sensor with a 5.6 nm Pd film for various H2 concentrations; upper inset
in (a): reflection spectrum at several H2 concentrations; bottom inset in
(a): signal stability to 0.5% H2. Inset in (b): enlarged temporal response at
0.5% H2.

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Fig. 6 Response times of the Pd/MLG sensor for different H2
concentrations.
0.5% H2 concentration, the sensor response time, defined as
the time interval for the sensor to reach 90% of its steady
response, is estimated to be 18 s. It needs to be mentioned
that the longer response time of our sensor, in comparison
with those of the Pd-decorated carbon nanotubes or graphene
nanoribbons, are mainly caused by the different definitions of
their response times, over which the sensor response reached
e−1 (ref. 12) or 50%22 of the steady value. Following the above
definitions, the response time of our sensor will have a similar
response time of as short as ∼3 s and ∼5 s, respectively.
The response time τ was also affected by the H2 concen-
tration, as plotted in Fig. 6. At the low H2 concentration stage,
the sensor response time is relatively long, ∼60 s at 200 ppm.
As the H2 concentration increases, the response time reduces
accordingly because the absorption rate, a reciprocal of the
response time τ, is linearly correlated to the H2 concentration.
When larger than 1%, the H2 concentration approaches the
saturation level. The increased amount of hydrogen atoms
occupies more available surface sites of the Pd,30 which pro-
longs the response time of the sensor at high H2 concen-
trations as shown in Fig. 6. In the future, Pd alloys such as Pd/
Au or Pd/Ni, which exhibit low hysteresis and fast response,
can be employed to further shorten the sensor response time.48
As we mentioned previously, thicker Pd films can improve
the H2 sensitivity, but at the expense of the response speed.45
To verify this, the temporal responses of the sensors with a Pd
thickness of ∼5.6 nm and ∼10 nm over three cycles of 0.5% H2
were measured and compared in Fig. 7. The sensor with a
∼10 nm-thick Pd film shows higher sensitivity but a longer
response time of ∼70 s. In contrast, the sensor with ∼5.6 nm-
thick Pd film exhibits a much shorter response time of 18 s,
which is attributed to the short dislocation and diffusion time
for the thinner Pd film. Further reduction of the Pd film was
also attempted, but the sensor showed a weak response
(Fig. S3, ESI†). The possible reason is the discontinuous Pd
film at such a small thickness, which hinders the effective con-
version of the Pd lattice expansion into the Pd/MLG out-of-
plane deflection.
Fig. 8 lists the performance of several types of fiber-optic
H2-sensors using pure Pd as the catalyst.9,30,49–51 A fiber-optic
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Fig. 7 Temporal response of the Pd/MLG sensor to the cyclic switching
of feed-in gas from 100% N2 and 0.5% H2.
Fig. 8 Comparison of sensing responses of different types of fiber-
optic H2-sensors employing pure Pd as the catalyst. SPR: surface plas-
monic resonance.
Mach–Zehnder interferometer, having its sensing arm coated
with a 2.5 μm-thick Pd film, demonstrated a LOD of as low as
20 ppb but a long response time of ∼2 min. In contrast, the
micromirror, SPR and nanofiber-based sensors using thinner
Pd films generally exhibit a faster response, but a much larger
LOD. Consequently, compared with the abovementioned
sensors, the Pd/MLG sensor reported in this work effectively
shortens the response time while simultaneously maintaining
the low LOD.
It needs to be mentioned that all of the above experiments
were conducted at room temperature. For field tests, the temp-
erature fluctuation may cause an expansion or contraction of
the Pd/MLG film. To evaluate the temperature influence on
the sensor performance, we monitored the evolution of the
sensor reflection spectra during continuous temperature rise
(see Fig. S4, ESI†). The sensor shows a temperature sensitivity
of 1.4 pm/°C. Based on the measured H2 sensitivity of 0.25 pm
ppm−1, the temperature cross-sensitivity is ∼5.6 ppm °C−1 at a
low H2 concentration. Turbulent gas flow can also induce a
pressure difference to deflect the graphene and cause the wave-
length shift of the sensor reflection spectrum (Fig. S5, ESI†).
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Such “false signals” can be removed by a reference sensor with
similar structure using H2-insensitive metals.
For the stability of the sensor, we tested its response to
0.5% H2 for up to ten cycles and no noticeable drift in the
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response baseline was observed (Fig. S6, ESI†). As a proof-of-
concept demonstration, we did not test the lifetime of the
device. As pure Pd is employed here, the sensor may face a
degradation issue similar to other Pd-based sensors. It has
been reported that using other materials such as Pd alloy45
and/or adding a protective material can improve the device
lifetime. Such kinds of materials can be readily integrated into
our sensors in the future.
5. Conclusions
In summary, a miniature fiber-optic H2-sensor with a low
detection limit of ∼20 ppm and a short response time of 18 s
was demonstrated using a suspended Pd-decorated graphene.
The Pd/MLG with nanoscale thickness and large surface-to-
volume ratio facilitates fast H2 dissociation as well as effective
conversion of the Pd lattice expansion into optical output.
Compared with the Pd-decorated graphene ribbons or CNTs
that convert the H2 concentration change into electrical
signals, our sensor integrates the Pd-coated graphene with an
optical fiber capable of providing a compact and all-optical
solution to the safe measurement of H2 concentration in
hazardous or space-limited environments. Furthermore, by
decorating different functional materials on graphene, the pro-
posed sensor structure can serve as a platform for diverse
chemical/gas measurements in the future.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Natural
Science Foundation of China (No. 61705082, U1701268) and
Natural Science Foundation of Guangdong Province (No.
2017A030313361).
References
1 M. Momirlan and T. N. Veziroglu, The properties of hydro-
gen as fuel tomorrow in sustainable energy system for a
cleaner planet, Int. J. Hydrogen Energy, 2005, 30, 795–802.
2 G. Nicoletti, N. Arcuri, G. Nicoletti and R. Bruno, A techni-
cal and environmental comparison between hydrogen and
some fossil fuels, Energy Convers. Manage., 2015, 89, 205–213.
3 P. M. Ordin, Safety Standard for Hydrogen and Hydrogen
Systems, Guidelines for Hydrogen Systems Design, Materials
Selection, Operations, Storage, and Transportation, NSS,
15826 | Nanoscale, 2019, 11, 15821–15827
View Article Online
Nanoscale
1740.16, Office of Safety and Mission Assurance,
Washington, DC, 1997, p. 20546.
4 R. Bouchet, S. Rosini, G. Vitter and E. Siebert, Solid-state
hydrogen sensor based on acid-doped polybenzimidazole,
Sens. Actuators, B, 2001, 76, 610–616.
5 D. R. Baselt, B. Fruhberger, E. Klaassen, S. Cemalovic,
C. L. Britton Jr., S. V. Patel, T. E. Mlsna, D. McCorkle and
B. Warmack, Design and performance of a microcantilever-
based hydrogen sensor, Sens. Actuators, B, 2003, 88, 120–
131.
6 A. Katsuki and K. Fukui, H2 selective gas sensor based on
SnO2, Sens. Actuators, B, 1998, 52, 30–37.
7 P. Tobiska, O. Hugon, A. Trouillet and H. Gangnaire, An
integrated optic hydrogen sensor based on SPR on palla-
dium, Sens. Actuators, B, 2001, 74, 168–172.
8 E. Antolini, Palladium in fuel cell catalysis, Energy Environ.
Sci., 2009, 2(9), 915–931.
9 M. A. Butler and D. S. Ginley, Hydrogen sensing with palla-
dium-coated optical fibers, J. Appl. Phys., 1988, 64(7), 3706–
3712.
10 F. Favier, E. C. Walter, M. P. Zach, T. Benter and
R. M. Penner, Hydrogen Sensors and Switches from
Electrodeposited Palladium Mesowire Arrays, Science, 2001,
293(5538), 2227–2231.
11 J. Kong, M. G. Chapline and H. Dai, Functionalized Carbon
Nanotubes for Molecular Hydrogen Sensors, Adv. Mater.,
2001, 13(18), 1384–1386.
12 Y. Sun and H. H. Wang, High-Performance, Flexible
Hydrogen Sensors That Use Carbon Nanotubes Decorated
with Palladium Nanoparticles, Adv. Mater., 2007, 19(19),
2818–2823.
13 Y. Hu, D. Perello, U. Mushtaq and M. Yun, A single palla-
dium nanowire via electrophoresis deposition used as a
ultrasensitive hydrogen sensor, IEEE Trans. Nanotechnol.,
2008, 7(6), 693–699.
14 K. J. Jeon, M. Jeun, E. Lee, J. M. Lee, K. I. Lee, P. Von
Allmen and W. Lee, Finite size effect on hydrogen gas
sensing performance in single Pd nanowires,
Nanotechnology, 2008, 19(49), 495501.
15 R. K. Joshi, S. Krishnan, M. Yoshimura and A. Kumar, Pd
Nanoparticles and Thin Films for Room Temperature
Hydrogen Sensor, Nanoscale Res. Lett., 2009, 4(10), 1191.
16 J. F. Patton, S. R. Hunter, M. J. Sepaniak, P. G. Daskos and
D. B. Smith, Rapid response microsensor for hydrogen
detection using nanostructured palladium films, Sens.
Actuators, A, 2010, 163(2), 464–470.
17 J. S. Noh, J. M. Lee and W. Lee, Low-Dimensional
Palladium Nanostructures for Fast and Reliable Hydrogen
Gas Detection, Sensors, 2011, 11(1), 825–851.
18 X. Q. Zeng, M. L. Latimer, Z. L. Xiao, S. Panuganti, U. Welp,
W. K. Kwok and T. Xu, Hydrogen gas sensing with networks
of ultrasmall palladium nanowires formed on filtration
membranes, Nano Lett., 2011, 11(1), 262.
19 Y. Pak, N. Lim, Y. Kumaresan, R. Lee, K. Kim, T. H. Kim,
S. Kim, J. T. Kim, H. Lee, M. Ham and G. Y. Jung,
Palladium Nanoribbon Array for Fast Hydrogen Gas
This journal is © The Royal Society of Chemistry 2019

Nanoscale
Sensing with Ultrahigh Sensitivity, Adv. Mater., 2015,
27(43), 6945–6952.
20 W. Yuan and G. Shi, Graphene-based gas sensors, J. Mater.
Chem. A, 2013, 1(35), 10078–10091.
Published on 28 June 2019. Downloaded by Missouri University of Science and Technology on 11/22/2022 11:07:55 PM.
21 S. S. Varghese, S. Lonkar, K. K. Singh, S. Swaminathan and
A. Abdala, Recent advances in graphene based gas sensors,
Sens. Actuators, B, 2015, 218, 160–183.
22 J. L. Johnson, A. Behnam, S. J. Pearton and A. Ural,
Hydrogen sensing using pd-functionalized multi-layer gra-
phene nanoribbon networks, Adv. Mater., 2010, 22(43),
4877–4880.
23 R. Kumar, D. Varandani, B. R. Mehta, V. N. Singh, Z. Wen,
X. Feng and K. Müllen, Fast response and recovery of
hydrogen sensing in Pd-Pt nanoparticle-graphene compo-
site layers, Nanotechnology, 2011, 22(27), 275719.
24 U. Lange, T. Hirsch, V. M. Mirsky and O. S. Wolfbeis,
Hydrogen sensor based on a graphene–palladium nano-
composite, Electrochim. Acta, 2011, 56(10), 3707–3712.
25 R. Kumar, S. Malik and B. R. Mehta, Interface induced
hydrogen sensing in Pd nanoparticle/graphene composite
layers, Sens. Actuators, B, 2015, 209, 919–926.
26 M. G. Chung, D. H. Kim, D. K. Seo, T. Kim, H. U. Im,
H. M. Lee, J. Yoo, S. Hong, T. J. Kang and Y. H. Kim,
Flexible hydrogen sensors using graphene with palladium
nanoparticle decoration, Sens. Actuators, B, 2012, 169(8),
387–392.
27 J. Yi, S. H. Kim, W. W. Lee, S. S. Kwon, W. N. Sung and
W. I. Park, Graphene meshes decorated with palladium
nanoparticles for hydrogen detection, J. Phys. D: Appl.
Phys., 2015, 48(47), 475103.
28 N. Liu, M. L. Tang, M. Hentschel, H. Giessen and
A. P. Alivisatos, Nanoantenna-enhanced gas sensing in a
single tailored nanofocus, Nat. Mater., 2011, 10(8), 631–636.
29 F. Gu, L. Zhang, Y. Zhu and H. Zeng, Free-space coupling
of nanoantennas and whispering-gallery microcavities with
narrowed linewidth and enhanced sensitivity, Laser
Photonics Rev., 2015, 9(6), 682–688.
30 N. R. Fong, P. Berini and R. N. Tait, Hydrogen sensing with
Pd-coated long-range surface plasmon membrane wave-
guides, Nanoscale, 2016, 8(7), 4284–4290.
31 S. J. McKeown and L. L. Goddard, Reflective Palladium
Nanoapertures on Fiber for Wide Dynamic Range
Hydrogen Sensing, IEEE J. Sel. Top. Quantum Electron.,
2017, 23(2), 6.
32 N. Zhang, H. Peng, X. Qian, Y. Zhang, G. An and Y. Zhao,
Recent advancements in optical fiber hydrogen sensors,
Sens. Actuators, B, 2017, 244, 393–416.
33 J. Dai, L. Zhu, G. Wang, F. Xiang, Y. Qin, M. Wang and
M. Yang, Optical fiber grating hydrogen sensors: A review,
Sensors, 2017, 17(3), 577.
34 B. Xu, Z. Tian, J. Wang, H. Han, T. Lee and Y. Mei, Stimuli-
responsive and on-chip nanomembrane micro-rolls for
enhanced macroscopic visual hydrogen detection, Sci. Adv.,
2018, 4, eaap8203.
35 H. Han, S. Baik, B. Xu, J. Seo, S. Lee, S. Shin, J. Lee,
J. H. Koo, Y. Mei and C. Pang, Bioinspired Geometry-
This journal is © The Royal Society of Chemistry 2019
View Article Online
Paper
Switchable Janus Nanofibers for Eye-Readable H2 Sensors,
Adv. Funct. Mater., 2017, 27, 1701618.
36 J. S. Zeakes, K. A. Murphy, A. Elshabini-Riad and
R. O. Claus, Modified extrinsic Fabry Perot interferometric
hydrogen gas sensor, in Proc. IEEE Laser in Electro Optics
Society Annual Meeting LEOS’94, 1994, vol. 2, pp. 235–236.
37 Z. Yang, M. Zhang, Y. Liao, Q. Tian, Q. Li, Y. Zhang and
Z. Zhuang, Extrinsic Fabry–Perot interferometric optical fiber
hydrogen detection system, Appl. Opt., 2010, 49, 2736–2740.
38 M. Wang, M. Yang, J. Cheng, G. Zhang, C. R. Liao and
D. N. Wang, Fabry–Pérot Interferometer Sensor Fabricated
by Femtosecond Laser for Hydrogen Sensing, IEEE
Photonics Technol. Lett., 2013, 25, 713–716.
39 D. Innnuzzi, S. Deladib, M. Slamana, J. H. Rectora,
H. Schreudersa and M. C. Elwenspoekb, A fiber-top cantile-
ver for hydrogen detection, Sens. Actuators, B, 2007, 121,
706–708.
40 T. B. Flanagan and W. Oates, The palladium-hydrogen
system, Annu. Rev. Mater. Sci., 1991, 21(1), 269–304.
41 J. Ma, W. Jin, H. L. Ho and J. Y. Dai, High-sensitivity fiber-
tip pressure sensor with graphene diaphragm, Opt. Lett.,
2012, 37(13), 2493–2495.
42 R. J. Nicholl, H. J. Conley, N. V. Lavrik, I. Vlassiouk,
Y. S. Puzyrev, V. P. Sreenivas, S. T. Pantelides and
K. I. Bolotin, The effect of intrinsic crumpling on the
mechanics of free-standing graphene, Nat. Commun., 2015,
6, 8789.
43 C. Lee, X. Wei, J. W. Kysar and J. Hone, Measurement of
the elastic properties and intrinsic strength of monolayer
graphene, Science, 2008, 321(5887), 385–388.
44 D. G. Papageorgiou, I. A. Kinloch and R. J. Young, Prog.
Mater. Sci., 2017, 90, 75–127.
45 N. Javahiraly, Review on hydrogen leak detection: compari-
son between fiber optic sensors based on different designs
with palladium, Opt. Eng., 2015, 54(3), 030901.
46 J. S. Bunch, S. S. Verbridge, J. S. Alden, A. M. Van Der
Zande, J. M. Parpia, H. G. Craighead and P. L. McEuen,
Impermeable atomic membranes from graphene sheets,
Nano Lett., 2008, 8(8), 2458–2462.
47 I. M. White and X. Fan, On the performance quantification
of resonant refractive index sensors, Opt. Express, 2008,
16(2), 1020–1028.
48 F. A. A. Nugroho, R. Eklund, S. Nilsson and
C. Langhammer, A fiber-optic nanoplasmonic hydrogen
sensor via pattern-transfer of nanofabricated PdAu alloy
nanostructures, Nanoscale, 2018, 10(44), 20533–20539.
49 M. A. Butler, Fiber optic sensor for hydrogen concen-
trations near the explosive limit, J. Electrochem. Soc., 1991,
138(9), L46–L47.
50 K. Schroeder, W. Ecke and R. Willsch, Optical fiber Bragg
grating hydrogen sensor based on evanescent-field inter-
action with palladium thin-film transducer, Opt. Lasers
Eng., 2009, 47(10), 1018–1022.
51 J. Villatoro and D. Monzón-Hernández, Fast detection of
hydrogen with nano fiber tapers coated with ultra thin
palladium layers, Opt. Express, 2005, 13(13), 5087–5092.
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