EnergyChem 3 (2021) 100061

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EnergyChem
journal homepage: www.sciencedirect.com/journal/energychem

Recent research progress in PEM fuel cell electrocatalyst degradation and

mitigation strategies
Xin Wei a, Ru-Zhi Wang a, *, Wei Zhao b, Ge Chen c, Mao-Rong Chai b, Lei Zhang d, Jiujun Zhang e, *
a
Institute of New Energy Materials and Devices, Faculty of Materials and Manufacturing, Key Laboratory of Advanced Functional Materials of Education Ministry of
China, Beijing University of Technology, Beijing 100124, China
b
State Power Investment Corporation Hydrogen Energy Company, Limited, Beijing 102209, China
c
Beijing Key Laboratory for Green Catalysis and Separation, College of Environmental & Energy Engineering, Beijing University of Technology, Beijing 100124, China
d
Energy, Mining & Environment, National Research Council of Canada, Vancouver V6T 1W5, Canada
e
Institute for Sustainable Energy/College of Sciences, Shanghai University, Shanghai 200444, China

A R T I C L E I N F O A B S T R A C T

Keywords: The performance degradation of proton exchange membrane fuel cells (PEMFCs) is one of the most critical
Degradation challenges in their practical applications. Degradations of electrocatalysts for oxygen reduction reaction (ORR) at
Mitigation strategies cathode and hydrogen oxidation reaction (HOR) at the anode are the major contributors to PEMFC degradation,
Contamination tolerance catalyst
which are mainly induced by fuel/air impurities, unintentional harmful species during the preparation and use of
Proton exchange membrane fuel cells
the catalysts, as well as catalyst decomposition during the operation. This review summarizes the recent research
on PEMFC performance degradation and the progress in developing mitigation strategies for avoiding the
degradation. Several aspects are emphasized as follows: the understanding of catalyst poisoning phenomena,
influencing factors, and general degradation mechanisms. Several technical challenges are analyzed and the
corresponding future research directions are proposed to facilitate the further research and development of
mitigation strategies for PEMFC catalyst degradation.

1. Introduction
The energy and environment have become two of the most important
topics in today’s world. In order to reduce the dependency on fossil fuels
for energy and their associated environmental impact, it is necessary to
develop clean and sustainable energy sources such as solar, wind,
waterfall, geothermal, etc., and their associated electricity energy stor­
age and conversion technologies. Electrochemical energy technologies
including fuel cells, batteries, supercapacitors, water electrolysis to
produce hydrogen, CO2 reduction to produce low-carbon fuels, etc. have
been recognized as feasible, efficient, and practicable options for elec­
trical energy storage and conversion [1-3]. Fuel cells, in particular,
hydrogen-fed proton exchange membrane fuel cells (PEMFCs) can
convert the chemical energy of hydrogen and oxygen (air) into electric
energy directly, possessing the advantages of fast refueling, high power
density, and zero-emission [4]. The timetable of significant events in the
development of PEMFCs is shown in Scheme 1 [4-8].
Even though PEMFCs show great promise in future energy conver­
sion systems, their high cost due to the expensive components and
fabrication as well as the related functional system has hindered the real
commercialization. Particularly, the scarce and expensive platinum (Pt)-
based electrocatalysts are required for speeding up the kinetically-
sluggish oxygen reduction reaction (ORR) at the cathode to a practical
rate. From the performance point of view, the Pt-based electrocatalysts
are sensitive to operating conditions such as hydrogen fuel impurity and
air contaminants [9-10]. In previous researches, comprehensive reviews
were introduced regarding the degradation of Pt-based catalysts caused
by contamination [11].
In recent years, many researchers introduced the ligand/strain effect
to electrocatalysts to prevent degradation or improve ORR activity by
adding non-precious metals [12]. Discussions were commonly focused
on the nanostructure, morphology, and composition of Pt and Pt-based
metal (PtM) alloy electrocatalysts [13-15]. Among them, fabricating
Pt-based alloys by adding a second or third metal to stabilize Pt lattices,
or controlling morphology to obtain novel structures, like one dimen­
sional (1D) nanodendrites exposing high-index facets, nanoframes, and
nanocages with threedimensional (3D) edges, core-shell structures that
improve Pt utilization, has shown effectiveness in optimizing catalytic

* Corresponding authors.
E-mail addresses: wrz@bjut.edu.cn (R.-Z. Wang), jiujun@shaw.ca (J. Zhang).

https://doi.org/10.1016/j.enchem.2021.100061
Received 19 June 2021; Received in revised form 29 August 2021; Accepted 30 August 2021
Available online 23 September 2021
2589-7780/© 2021 Elsevier Ltd. All rights reserved.
X. Wei et al. EnergyChem 3 (2021) 100061

properties [16-18]. Some researchers were also prospecting support

materials with low cost, high specific surface area, pore structure,
adjustable conductivity, and good electrochemical corrosion resistance
to achieve uniform Pt dispersion [19-20]. Nonprecious metal catalysts
(NPMCs) such as transition metal-C-N(M-C-N) structure and non-metal
(N, S, etc.) doped carbon and single-atom catalysts have also been
studied [21-25].
However, most researchers are focusing on how to prepare catalysts
with higher performance or stability, but few on the catalyst contami­
nation issues caused by the catalyst synthesis precursors, catalyst com­
ponents leaching out in the actual operation, and catalyst poisoning
from gaseous contaminants, etc. [26]. Furthermore, certain groups, like
–COOH introduced from the support materials through functionaliza­
tion or pre-processing could accelerate catalyst decomposition in the
durability test. Fe2+and Co2+cation shedding, generation of
oxygen-containing species, and even unstable support decomposition
could not only deactivate the catalyst to varying degrees but also pose a
threat to other parts of the PEMFCs assembly. The sensitivity of the
catalyst to the impurities in the fuel, eg. CO [27], CO2, H2S [28], SO2
[29], etc. [30]. and air pollutants, eg.SO2 [31-32], requires that the
interference of these species should be avoided as much as possible
during the operation.
Fig. 1. Pollutants, impurities, or decomposition products produced during the
In this paper, the degradation or poisoning of PEMFC catalyst per­ preparation and use of the electrocatalysts for proton exchange membrane
formance induced by reactants or residual impurities or treatment fuel cells.
methods are comprehensively reviewed from three aspects of catalyst
preparation, catalyst use, and external pollutants, and the underlying
saturation after a while, and then the corrosion process makes the per­
mitigation strategies are also presented as schematically summarized
formance decline slowly. Platinum dissolved during corrosion can be
Fig. 1 and listed in Table 1. To facilitate the research of catalyst
redeposited on the surface of the catalyst [81]. Except for Pt/C, chloride
degradation and development of mitigation strategies for reducing the
ions could poison the active sites of Pt-based alloy catalysts to accelerate
degradation, several technical challenges are analyzed and the corre­
the dissolution and dealloying of non-precious metals [82]. For PtNi
sponding future research directions for overcoming the challenges are
alloys, the dealloying phenomenon was particularly obvious at the
also proposed in this review.
initial cycle stage. The subsequent formation of Pt-skin could prevent
further nickel dissolution from the electrode, but a small amount of
2. Synthesis induced catalyst degradation
chlorine was sufficient to dissolve most of the non-precious metals in the
alloy [82]. Elemental analysis of the catalysts composed of Pt75Ni25 and
2.1. Cl− residue induced catalyst degradation
Pt10Ni90 showed that in the absence of Cl− , there were 17 and 58 atom%
Ni remained after 15 CV cycles, while 14 and 22 atom% Ni were found in
I− [74], Br− [75,76], and Cl− [77] are commonly used reagents,
the presence of Cl− . According to Jayasayee et al.’s research, ORR po­
which may be retained in the catalyst during the synthesis process.
larization curves after 1000 CVs for both Pt and its Ni alloys showed a
Particularly Cl− may also adsorb on the catalyst through the catalyst
considerable extent deactivate indicating that the alloy could not
precursor (chloroplatinic acid hexahydrate, H2PtCl6•6H2O) or the salt in
effectively alleviate the dissolution of Pt in the presence of Cl− 82 Given
the air, and a small amount of Cl− residue can cause great harm to the
the inevitable use of chloride-containing precursors and their damage to
PEMFC performance [78]. Taking the reduction of H2PtCl6•6H2O with
both Pt and Pt alloy catalysts, it is necessary to learn the factors that
ethylene glycol(EG) as an example, reaction (1) occurs:
influence damage levels and mitigation measures.
PtCl2−6 + CH2 OH − CH2 OH →Pt + CHO − CHO + 4H+ + 6Cl− (1) Considering the difficulty of quantifying anionic residues in the
preparation process, relatively high concentrations of impurities (ppm)
To understand the degradation mechanism of Pt catalyst in PEMFC are often injected into the system to induce damage tests for Pt disso­
and identify its prevention methods, the chlorine-contaminated Pt was lution. The quantitative description of Pt dissolution can be fulfilled by a
simulated by adding different Cl− sources (e.g. NaCl, KCl, HCl, Cl279) series of integrated experimental and characterization techniques,
and controlling the chloride ion concentration (0.1–1000 ppm). including analysis of the content of the dissolved platinum in the elec­
Poisoning of Pt with different shapes deposited on different supports (e. trolyte after cyclic voltammetry(CV) scanning for accelerated degrada­
g. carbon fibers[80]) in the presence of Cl− has been studied, as listed in tion tests. Typically, electrochemical surface area (ECSA) loss of Pt could
Tables 1 and 2. Numerous studies show almost similar observations: at be obtained by CV curve through measuring the charge quantity under
the beginning of chloride ion pollution, the PEMFC performance de­ hydrogen adsorption/desorption peaks or the charge quantity under the
clines rapidly. Pt corrosion rate is extraordinarily high and reaches

Scheme 1. Timeline of the development of PEMFCs.

2
 Table 1

X. Wei et al.
Common challenges and their coping strategies for catalyst degradation issues of PEMFCs.
Project Catalyst type Source Negative impact Mitigation strategies Effect Limitations References

Cl− residue Pt H2PtCl6•6H2O (i)The formation of Use other Pt sources like Pt(acac)2 to replace Avoid the occurrence of Result in higher costs [33]
PtCl62− and PtCl42− H2PtCl6•6H2O Cl− from the source−
complexes block the Pt Prepare a nitrogen-doped reduction graphene oxide/ With more pyridinic and Cl− cannot be completely [34]
site. (ii) Cl− reduces the platinum electrocatalyst that is resistant to Cl− corrosion pyrrolic groups, KOH removed
corrosion potential of Pt. activated N-doped GO
showed the highest
resistance to Cl−
corrosion
Washing: one-time washing with 0.1 M NaOH followed by A convenient method to – [35]
repeated washing with deionized water and finally tested remove Cl−
by AgNO3
Anneal treatment in gaseous NH3 at 400 ◦ C for 1 h and in The content of total Pt NPs may re- [35]
H2 (5%) and Ar after the temperature is 190 ◦ C Cl− is low agglomerate at high
temperature
Surfactants/ capping agents Pt PVP, CTAB Occupy the active site of Simply filter/centrifugal with ethanol, hexane, DI water The operation is simple There are residuals [36]
Pt resistant to removal.
Pt oleylamine (OAm) Chemical washing: disperse in pure acetic acid (HAc) at OAm is easier to wash Some non-precious [37]
75 ◦ C for 10 h off ascribed to the loses metals may leach out
of the strong affinity when the treatment is
between residues and conducted in the air
metal surfaces
Pt PA Leave Pt colloidal suspension with two NaOH pellets and Obtain the clean sample Strong alkali washing [38]
then wash with ultra-pure water for 3–4 times. may not be suitable for
some NPMC catalysts
PtM (PtNi) 1,2- Immerse Pt-Pd particles in the mixed solution of NaBH4 Sodium borohydride Two-step washing creates [39]
hexadecanediol, and TBA for 30 min, and then use ethanol/acetone solution produces hydrides that a cumbersome process
OAm to remove the residual amine are readily attached to
3

metal surfaces to
replace adsorbents
PtM (PtPdCu) OAm and Stir PtPdCu NPs in HAc for 24 h with carbon support to Acetic acid plays roles The extent of chemical [40]
oleic acid avoid the aggregation both in the dealloying etching needs to be
and removal of surface controlled
residues
Pt TTAB, PVP Remove capping layers with UV-ozone (O3) Ozone and ultraviolet Partially oxidize surface [41]
light are responsible for atoms
oxidizing carbon-
containing species into
CO2 and water
Pt PVP or OAm/oleic Electrochemical potential cycles in 0.5 M NaOH Remove surfactants Operation is complex [42]
without defects on the
surface of the Pt cube
Pt OAm Thermal anneal in a tubular furnace for 5 h at 185 ◦ C in the Decompose capping Cause particles to [37]
air agent by heat treatment agglomerate and shape
change
Anion Pt Halogen ions Seriously inhibit the In-situ potentiostatic at 0.1 M NaOH solution, ~0.03V Restore the active Limited to laboratory [43]
activity of the geometric surface area without level operations
surface changing the shape
Pt Tetrahedral Surface design with adsorbed cyanide addition layer, Block the sites necessary Complex catalyst [44]

EnergyChem 3 (2021) 100061

sulfuric acid and marked as Pt(111) CNad for the adsorption of modification
phosphate anions
NPMCs (Fe-C- CN− (in the (SCN− and CN− ) easy to Heat treatment at 300 ◦ C in Ar Anion is removed Half of the performance is [45]
N) alkaline form complexes with Fe loss
electrolyte)
SCN− (in the acidic Encapsulated mental components with graphitic layer Graphitic layers tailored – [46]
electrolyte) (G@Fe) by one-step high-pressure pyrolysis. by temperature and
(continued on next page)
 Table 1 (continued )

X. Wei et al.
Project Catalyst type Source Negative impact Mitigation strategies Effect Limitations References

atmosphere dominate
ORR activity
Cation PtM TMs Catalyst migrates and Improve the degree of alloying by controlling composition Compared with V and The relation between [47,48]
grows, and the ligand (as Au and Mo doping), structure, and size Ni, Co/Cr /Au/Mo are particle size and [49,50]
effect disappears. more stable while dissolution rate requires a
alloying with Pt lot of experiments as well
as verification and is not
universal.
PtM TMs (Fe) Coat Pt-Fe nano-alloy with graphene nanopores Carbon shell thickness Block part of the active [51,52]
should be less than 1 nm site
to keep its performance
PtM TMs (Ni) Acid leach Treated with 20 mL 0.1 M HClO4 and Pt-rich shells can After preliminary acid [53-55]
and post- following annealed at 400 ◦ C protect base metals from treatment, there is a
anneal leaching possibility of mental loss
PtM TMs (Ni) (dealloy) Mixe catalyst with (1)1 M NHO3 at 70 ◦ C Milder H2SO4 facilitate Sometimes damage the [56]
(named as P1-NA) or (2) 0.5 M H2SO4 at the formation of Pt skin structure of the catalyst
80 ◦ C in nitrogen (named as P2-SA) and of good quality than the
stir them for 24 h in air NHO3
Non-reactive oxygenates Pt and PtM OHad Block the Pt/ PtM site. Pt-IL IL [MTBD-NTf2] acts as a viscous fluid IL can protect Pt from Complex operation [57-58]
composite intercalation phase to prevent metal oxidation process
catalyst from contacting water
Pt 1‑butyl‑3-methylimidazolium bis There is lower ORR [59]
(trifluoromethanesulfonyl) imide onset potential.
([C4C1im][NTf2])
Air/fuel containments Pt, PtM CO The competitive Alloy catalyst PtRu/C Reduce the voltage at [60]
adsorption of air/fuel PtMo/C which CO is oxidized [61]
containments with O2/ PtSn/C [62]
H2 results in the Graphene nanosheets (GNS) was modified with PFSA The sulfonic (-SO3− ) CO poisoning cannot be [63]
4

occupation of the active groups introduced by completely avoided

site PFSA promote the
oxidation of CO to CO2
SO2 Preparation of alloy catalyst like Pt6Ru1/C Greatly improve the SO2 SO2 poisoning cannot be [64]
Choose appropriate supports like Pt-CeO2 tolerance. completely avoided [65]
CO and H2S Modify the surface with organic molecule 2,6-diacetyl­ Weaken the adsorption [66]
pyridine (DAcP y) of CO and H2S
Support decomposition carbon carbon Promote the shedding Surface functionalization with milder surface modifiers Improve activity – [67]
support and growth of Pt NPs like thiolated CNTs (SH–CNTs) without decreasing
stability
Preparation of metal oxide supports like TiO2, IrO2 Get better corrosion Possess low electro- [68,69]
resistance catalytic activity
Preparation of composite materials like MCNT-SCNT Improve the stability of – [70]
Preparation of composite supports like CNT@TiO2 the catalyst The activity may be lower [71]
than that of carbon
materials
Corrosion of WO3 WO3 decompose into Awaiting further study [72]
carbon HxWO3 and WO3-y.
support metal ITO ITO forms hydroxides [73]
oxide support with poor conductivity
and dissolves under

EnergyChem 3 (2021) 100061

highly acidic conditions
X. Wei et al.
Table 2
The effect of chloride ion on the cell performance.
Species Concentration Time
HCl 30 mM 50h
KCl 10 ppm 1h
AlCl3 9.5 mM 48h
FeCl3 9.5 mM 48h
CrCl3 9.5 mM 48h
MgCl3 14.25 mM 48h
NiCl2 14.25 mM 48h
CaCl2 9391 ppm – 0.6 mg cm− 2
NaCl 10043 ppm operat for 12 h then stop for 12 h
adsorbed CO oxidation peak [83]. Using electrochemical quartz crystal
microbalance (EQCM), which consists of an oscillation circuit, a fre­
quency counter, and a potentiostat controlled by a personal computer, to
detect nanoscale mass changes, the Pt dissolution can be studied and
measured even during dynamic treatment [84-85]. The content of Pt
that inductively coupled plasma mass spectrometry (ICP-MS) can detect
in an experiment depends on the ratio between dissolved Pt diffused into
the electrolyte and the dissolved Pt redeposited. Coupling electro­
chemical flow cell (EFC) directly to ICP-MS can lead to a new under­
standing of the dissolution mechanism of Pt [86]. Besides, most of the
available surface sensitive techniques, including Fourier transform
Infrared (FTIR) have also been used to illustrate the adsorption coverage
and structure of Pt-based catalysts.
2.1.1. Factors affecting the extent of Cl− contamination
The effect of Cl− pollution with different Cl− concentrations, tem­
peratures, voltages, and other operating conditions has been studied
extensively. As observed, when the cathode was exposed to Cl− with a
concentration as low as 1 ppm, the cell suddenly suffered a performance
loss and but stabilized with the prolonged pollution time [26]. At a Cl−
concentration of 0.1 ppm, the cell performance showed a fairly stable
attenuation, faster than the uncontaminated attenuation. With
increasing the current density and chloride ion concentration increase
and decreasing reactants, the level of pollution was even worse. The
generation of hydrogen peroxide in the chlorine-comprising solution
could be divided into two states as a function of the electrode potential:
at a potential less than 0.2 V, peroxide formation did not appear to be
affected by Cl− , when the potential was greater than 0.2 V, the amount
of peroxide generated was increased with increasing Cl− concentration,
which was consistent with the higher coverages [87]. Regarding the
effect of temperature, when the temperature was declined from 80 ◦ C to
60 ◦ C, there was a slight voltage drop. However, when the temperature
was further declined from 60 ◦ C to 40 ◦ C, a sudden drop in cell voltage
appeared, showing a complicated influence [26]. The performance
degradation of PEMFC exposed to 4 ppm HCl in the air was studied when
the battery voltage was 0.4, 0.5, and 0.6 V, and the most obvious Cl
poisoning at 0.6 V was observed [88]. Interestingly, in the stability
experiment, regardless of the presence of chloride ions, Pt experienced
less dissolution, which was interpreted as the formation of surface ox­
ides [78]. It was also observed that the constant potential stress test was
much less damaged than the constant potential dynamic test (less Pt was
removed). This was because a large amount of transmission could
greatly enhance corrosion. The experiment of rotating disk electrodes in
the sulfuric acid at 1600 rpm showed that the dynamic corrosion rate
was increased by 5 times compared with the stagnant state [89]. It can
be concluded that higher voltage, chloride ion concentration, and dy­
namic environment can accelerate catalyst poisoning.
At a working voltage of 0.6 V, after the anode and cathode were
respectively polluted with 100 ppm Cl2, the performance losses of
approximately 94% (anode) and 82% (cathode) were observed accord­
ing to Unnikrishnan et al. [79]. When their cell was operated at 0.1 V,
EnergyChem 3 (2021) 100061
Subjects Effect (Performance drop) Ref.
− 2
Pt thin film electroplated onto a gold 80 mV@0.3A •cm , 30%ECSA loss [98]
substrate
10 wt.% 1% mass loss [80]
Pt/nanofibre
0.4 mg cm− 2 80 mv@1 Acm− 2 40.16% ECSA loss [99]
0.4 mg cm− 2 60 mV@1 Acm− 2 34.53%ECSA loss [99]
0.4 mg cm− 2 30 mV@1 Acm− 2 35.22%ECSA loss [99]
0.4 mg cm− 2 15 mV@1 Acm− 2 10.8 %ECSA loss [99]
0.4 mg cm− 2 15 mV@1 Acm− 2 11.4% ECSA loss [99]
3.446 mV h − 1@ 1 Acm− 2 [100]
0.6 mg cm− 2 1.082 mV h − 1@ 1 Acm− 2 [100]
the degradation could be completely recovered with the recovery times
of anode and cathode were 2 h and 4 h, respectively. In other words, the
anode was easier to contaminate and easier to recycle. It was observed
that Cl− was adsorbed on two different surfaces of Pt(100) and Pt(111),
namely. The employed characterization techniques were low energy
electron diffraction (LEED) and auger electron spectroscopy (AES) for
studying H underpotential deposition (Hupd) and OH adsorption (Had)
regions, and the obtained results showed that the potential of Cl− ions
adsorbed on the surface of Pt(100) was lower than that of Pt (111)
surface, indicating that the former was more sensitive to Cl− ion
poisoning [90]. If the Pt/Vulcan catalyst was composed of 4 nm cubic
octahedral nanoparticles with 63% of Pt atom being (111) surface, 12%
being the (100) surface, and 25% being the edges and corners, the
observed Cl− adsorbed on the (111) plane as a site-blocking species did
not promote the production of H2O2, and the Cl− attached to the (100)
plane could hinder the breaking of O–O bonds, thus enhancing the 2e−
reduction pathway. These results above suggest that the ORR pathway
can be understood as the superposition of the ORR characteristics of Cl−
adsorption on Pt(111) and Pt(100), respectively [87].
Since protons are the reactants of ORR to water and platinum cat­
ions, it is easy to understand that Cl− dissolution increases with
decreasing pH [89]. In addition to acidic electrolytes, studies of Pt/C in
alkaline electrolytes containing anions (F− , Cl− , Br− , I− , CO32− , SO42− ,
SO32− and S2− ) found that although the ORR activity and durability
were lower than those of acidic electrolytes, the impact of anions on the
catalyst was less [91].
2.1.2. Contamination mechanism
In addition to blocking the Pt site, the increase of Cl− concentration
can also accelerate the corrosion by reducing the corrosion potential of
Pt [86]. CV and EQCM were utilized to test the dissolution of Pt
contaminated with Cl− . The EQCM displayed quantity increase as the
PtO began to be produced during the positive-going scanning and a
decrease of mass was ascribed to the electroreduction of PtO during the
reverse scan. At 100 and 1000 ppm Cl− , a mass loss was particularly
evident after 1.1 V during the positive-going scan. Both the saturated
solution with PtCl62− and the one with 10 ppm PtCl62− were analyzed
with an ultraviolet (UV) spectroscopy Fig. 2a) [85]. There is only a
strong absorption band at 250 nm in the standard solution, indicating
the presence of PtCl62− , but two bands at 250 and 325 nm correspond to
PtCl62− and PtCl42− , qualitatively showing that PtCl62− and PtCl42−
complexes could be formed after Pt dissolved, as expressed by Eqs. (2)
and ((3) [86]:
Pt + 4Cl− →PtCl2−4 + 2e− E0 = 0.758V (vs. SHE) (2)
Pt + 6Cl− →PtCl2−6 + 4e− E0 = 0.742V (vs. SHE) (3)
Eqs. (4) and (5) can be used to describe mechanism of platinum
oxidation in an acidic medium. The chemical bonds of water break and
combine with Pt to generate PtO releasing two electrons and two pro­
tons as Eqs. (4) and (5) [92-93]:
5
X. Wei et al. EnergyChem 3 (2021) 100061

Pt + H2 O→PtOH + H+ + e− (4) extent of the poisoning of Pt (110) crystal plane was more serious than
that of Pt (111). It could be reasonably inferred that by controlling the
PtOH→PtO + H+ + e− (5) movement of Pt crystal face to Pt(111), the adsorption of Pt by Cl− could
be partially inhibited [90]. In many cases, to liberate Pt sites from the
However, when the catalyst was contaminated in a sulfuric acid
anion and boost ORR/HER, adding a second atom type seemed to be an
environment, the process could be largely different. At low potential
effective method. However, research on the structure of PtNi alloy
(0–0.4 V, vs. RHE), Cl− could move to the surface of Pt while
showed that the second mental Ni was not conductive to resist Cl−
HSO4− •2H2O hydrated anions were formed in the uncontaminated
pollution [82].
sulfuric acid electrolyte solution. Cl− •3H2O was formed on the surface
Various post-treatment methods, like washing with large amounts of
of the contaminated Pt continuously in the potential range of 0.4–1.06
deionized water with the assistance of AgNO3, have also been used to
V, vs. RHE. Then, as the voltage was increased, only oxides (PtO are
move Cl− residue. Using impregnation and microwave-assisted polyol
PtO2) were formed on the uncontaminated Pt surface, and the amount of
preparation method, Pt was profitably deposited onto carbonaceous
oxides were increased with an increasing amount of dissolved Pt.
support by Kaluža et.al [35]. Both NaOH and NH3 were used for
However, after a thin protective oxide layer was present on the surface,
dechlorination. Compared with NH3 dechlorination, NaOH was a
only chemical dissolution of PtO or PtO2 and a small amount of oxida­
nontoxic and cleaner method, resulting in lower Cl− residue.
tion of the metal/oxide interface could happen at the oxide/electrolyte
High-temperature treatment was also projected as an effective way.
interface. Then, the contaminated Pt underwent a dissolution reaction,
For example, using H2PtCl6 as the metal precursor, the catalyst was
forming a chloride complex, as shown by Eqs. (2)-(3). In other words,
synthesized by the strong electrostatic adsorption (SEA) method [97].
the corrosion effect could be accelerated by delaying the production of
The Cl− content in the catalyst was turned by changing the gas atmo­
platinum oxide. Ptn+ could be formed when the electrode potential was
sphere and the time of reduction step. Since the high temperature could
less than 1.2 V, while PtCl62− was formed when the potential was more
cause the gasification of the carbon support, the reduction time needed
than 1.2 V [94]. The simplified interpretation is shown in Fig. 2b [89].
to be long enough. It was observed that a trace of Cl− even after calci­
nation in a pure hydrogen atmosphere at 450 ◦ C for 5 h. The residual
2.1.3. Mitigation strategies
amount of Cl− was monitored by ion liquid chromatography and
Both precursor selection and processing methods can affect the Cl−
neutron activation method. It was found that NH3 calcination and
content of the product. Therefore, some proper post-treatment should be
dichlorination (Pt/CBx(NH3) catalyst) could result in lower total Cl−
used to reduce the residual amount of Cl− for mitigating its effect on the
content, but higher hydrolyzable Cl− content, thus, poor electro­
catalysts.
chemical performance [35].
To avoid the poisoning of Cl− , many other Pt sources (e.g. Pt(acac)2
[33], Pt(NH3)2(NO2)2[95]) have been used to replace H2PtCl6•6H2O.
2.2. Roles of surfactants/capping agents
However, Pt(NH3)2(NO2)2 can cause an unpleasant exothermic effect in
the reduction process, which seemed unsuccessful. The price of Pt
Most industrial catalysts tend to be nanoparticles uniformly
(acac)2 is five times higher than that of H2PtCl6•6H2O, making it diffi­
dispersed on the solid supports because most metals possess catalytic
cult being used commercially. Therefore, it is necessary to study how to
activity generally at the nanoscale. Due to their abnormal adsorption
remove the residual Cl− derived from H2PtCl6•6H2O as a relatively
capacity and chemical reaction capacity, nanoparticles with high sur­
low-cost Pt precursor. Studies showed that at low Cl− concentration, the
face energy are easy to form secondary particles spontaneously. There­
reversible performance degradation rate of the catalyst was related to
fore, controlling the nucleation process is the principal step for
the entire surface area, and the poisoning rate and level of different
preparing nanoparticles with good dispersion and controllable shape
catalysts might be dissimilar [96]. When the PtCoMn nanostructured
and size [101]. As identified, the overgrowth of nanocatalysts can be
thin-film catalyst (NSTFC) was poisoned with 20 µM HCl, the reversible
suppressed in the presence of certain organics or polymers, which can be
performance degradation decreased sequentially with
attached to the surface of the nanoparticles as a stabilizer and are usu­
0.2mg-Pt•cm− 2PtCoMn/NSTF>
ally named as the organic/inorganic capping agents, surfactants, or li­
0.2mg-Pt•cm− 2Pt/C>0.4mgPt•cm− 2Pt/C [96].
gands. They have the primary role as the ligands in the preparation of
The modification of the catalyst support can also affect Cl− corrosion.
catalysts. They can stabilize the nanoparticles through electrostatic or
The study found that if there were more pyridyl and pyrrolyl groups in
space exclusion interactions, preventing further growth or agglomera­
N-doped graphene and Pt-containing nanoparticle composite materials,
tion, and thus control the particle size. The adsorption capacity of the
the catalysts would have the highest Cl− corrosion resistance [34]. The
capping ligand on the nanoparticle surface is proportional to the

Fig. 2. (a) UV spectrum of the standard solution of 10 ppm PtCl62− (red line) analyzed with an ultraviolet (UV) spectrometer along with an HCl solution in which Pt
is polarized potentiostatically at 1.1 V (blue line). Reproduced with permission [85]. Copyright 2007, Elsevier Ltd.. (b) Schematic illustration of the suggested
dissolution mechanism. With the participation of H and Cl− , Pt dissolves and forms oxides (step II), and further dissolution is inhibited. Under the reducing con­
ditions, oxides are mainly reduced from the oxide/electrolyte interface (step III). Reproduced with permission [89]. Copyright 2015, Elsevier Ltd..

6
X. Wei et al.
additional rate of the corresponding plane, which can be intended for
controlling the growth rate to synthesize catalysts with different mor­
phologies by adding different ligands [102]. The stabilizers/surfactants
have the ability to precisely customize the size [103], shape, composi­
tion[104] of the nanoparticle catalysts. For example, Miyabayashi et al.
[105] modified the surface of Pt with octylamine and alkylamine with
pyrene group (PA) to obtain Pt nanoparticles supported on carbon black
(CB), and obtained a negligible ECSA decrease by adjusting the ratio of
octylamine and PA. Also, the surfactant could make the Pt nanoparticles
firmly fixed on the catalyst support, resulting in a material with narrow
particle distribution [106].
2.2.1. Choice of surfactant/capping agent
Appropriate adsorption of surfactant on catalyst is crucial in deter­
mining whether the growth of highly active crystal surface of nano­
particles can be promoted. However, the extremely strong adsorption
strength makes it too difficult to complete removal, which will prevent
the reactant molecules from approaching the surface atoms, thus greatly
reducing the active sites of the electrocatalytic reaction. Another sig­
nificant adverse effect is that the capping agent is reactive during cat­
alytic progress, which not only consumes other reactive substances but
also results in its structural destruction [107].
In the preparation of catalysts, selecting surfactants should be care­
ful. Although the same catalyst shape could be generated by different
catalysts, nanoparticles with different properties could be obtained due
to different reaction paths and different effects on the active sites [108].
For example, the ORR activity of Pt nanoparticles could even be
manipulated deliberately by selecting organic coating ligands. Poly­
vinylpyrrolidone (PVP) and tetradecyl trimethyl ammonium bromide
(TTAB) were simultaneously used as the surfactants to obtain the Pt
nanocubes (NCs) and found that TTAB covered fewer active sites than
PVP, thus had a cleaner surface and better catalytic performance [109].
Alkylphenol polyoxyethylene (9) (NP9) and TTAB were added during
the catalyst preparation to test the catalyst performance without
removing the surfactant. Among them, the activity of the electrocatalyst
using TTAB was greatly deteriorated, whereas the electrocatalyst using
NP9 was comparable with commercial Pt/C, emphasizing the signifi­
cance of accurately surfactant choosing in catalyst synthesis [110].
Carbonyl groups are usually added in non-hydrolyzed media for the
reason of typically dirtless decomposition products in the course of heat
treatment, which helps control the reaction kinetics of the colloid
synthesis.
2.2.2. Removal of surfactants/capping agents
Due to the detrimental effect of surface capping agents on catalytic
activity, most previous studies have focused on the removal of surfac­
tants. Among them, washing and centrifugation with mixed solvent is a
conventional method in the laboratory. The mixed solvent usually
contains strong and weak parts. Slightly larger nanoparticles are initially
dispersed in an elegant solvent, and the capping agent can be completely
dissolved, allowing them to be easily separated from the nanoparticle
surface. However, nanoparticles smaller than 5 nm are difficult to pre­
cipitate at regular centrifugation. By adding a weak solvent, the
stretched encapsulated molecules can contract on the surface of the
particle, forming a denser compound that precipitates at the bottom of
the centrifuge tube for easy separation. This can be roughly explained
mathematically in previous reviews [101].
To remove the remaining capping agent, the post-treatment methods
like UV-ozone [41], calcination [111], acid and alkali washing [112],
and electrochemical potential cycling [42] have been utilized. The
characteristics of these methods and their shortcomings are shown in
Table 1. Li et al. [37] found that compared with UV-ozone and acid
treatment, low-temperature heat treatment was a suitable cleaning
method. On the contrary, excessively high temperatures could cause the
agglomeration of surface atoms. According to Alipour et.al. [113], due
to the migration and growth of Pt or PtM nanoparticles on the support
7
EnergyChem 3 (2021) 100061
during the thermal annealing, its dynamic behavior was significantly
different from the corresponding macroscopic alloys. Luo et al. [39]
added TTBA to NaBH4 washing solution. The substituted PVP was easy
to be dissolved in TTBA solution, which overcame the re-absorption
problem, so it could greatly remove the PVP on the surface of Pt/Pd
nanocubes. The improved method did not require heat treatment and
retained the catalytic properties of nanocubes. Contaminated Pt nano­
particles containing PVP were added to the mixture of H2O2 and H2SO4
for centrifugation to physically remove the surfactant by the oxygen
bubbling that decomposed from H2O2 [114]. As a widely used surfac­
tant, PVP had been reviewed from preparation[115] to removal [116].
2.2.3. Surfactant-free catalyst
The processes of removing surfactants inevitably cause changes in
the shape of nanocrystals[117] and are environment-harmful [118]. The
use of small absorbents as stabilizers for the synthesis of nanoparticles
would be a more direct way to produce well-defined nanoparticles for
improving electrochemical catalytic ORR performance. For example,
some Pt clusters could be successfully synthesized by surfactant-free
method [116], including nanodendrites[119] and nanopolyhedral
[120].
By controlling the kinetic conditions of nucleation and growth, Pt
alloy catalysts with different shapes can be obtained experimentally. For
example, Tang et al. [121]. synthesized polyhedral nanoparticles
through the complexation reaction between palladium ions and
ammonia and the control of the Pd/Pt ratio. Guo et al. [122]. directly
assembled the generated PtFe nanostructure on graphene using ultra­
sonic waves instead of using an auxiliary agent. The G/FePt nano­
particles presented roughly no activity change after 10,000 potential
sweeps. Light-induced substitution of surfactants was also used to pre­
pare structurally controlled PdPt@Pt core-shell structures [123]. The
octahedral PtNi/C was prepared by simply impregnating the Pt/Ni with
acetylacetonate on the carbon carrier by a solid-phase synthesis method
of burning for 1 hour in 200 ◦ C under the flow of 120/5 cm3 min− 1
CO/H2 [124].
A one-step reduction of ethanol was developed to synthesizing
numerous ‘‘clean’’ and small (4 nm) three-dimensional (3D) Pt nano­
flowers (PtNFs) by controlling the composition of the original precursors
[125]. A water-assisted method was designed by Sharma et al. [123]. to
control the size of Pt nanoparticles by varying either the H2O volume
percent or the Pt precursor (NH4)2PtCl6 concentration during the syn­
thesis. The appropriate H2O/EG content could turn the particle size
between 2 and 6 nm through controlling the nucleation and growth of Pt
nanoparticles.
In summary, electrocatalysts prepared without surfactants are the
green and pollution-free methods with the least impact on performance.
However, Pt-based nanoparticles with controllable shapes can be ob­
tained by using surfactants as the stabilizers and capping agents to avoid
aggregation and shape distortion. The characteristics of capping agents
in the catalytic process play an irreplaceable role in achieving high-
performance catalysts. Choosing less harmful surfactants seems to be a
more practical approach. Changes in the use of surfactants are often
faced with differences in the performance of catalysts obtained, and the
search for real alternatives is still a long way off. Future researches may
mainly devote to the removal and use of capping agents to satisfy the
specialized demands of the catalysts.
3. Catalysis process-induced degradation
In the process of catalyst performance, some generated impurities,
including dissolved base metals and produced oxygen-containing spe­
cies, could damage the structure of the catalyst and accelerate its
dissolution.
X. Wei et al.
3.1. Catalyst dissolution
Catalyst dissolution includes Pt dissolution, preferential leaching of
active metal elements in Pt-based alloy nanoparticles, and metal
element dissolution in non-noble metal catalysts. As we knew, relatively
stable platinum is not completely insoluble in harsh corrosive environ­
ments. The aging mechanism of common pure Pt catalysts is shown in
Fig. 3, which usually involves: (a) particle detachment. This phenome­
non could be explained by the weak binding strength between the
catalyst and matrix and/or carbon support deterioration; (b) coales­
cence. This can be triggered by the occurrence of unfirm bond for matrix
and particles; (c) dissolution. Dissolution is mainly responsible for per­
formance degradation due to the loss of the active site; (d) precipitation/
growth. Smaller nanoparticles dissolved previously in the electrolyte
could redeposit on larger ones; and (e) electrochemical Ostwald
ripening. The difference in chemical potentials between nanoparticles
with different sizes results in Ostwald ripening [126].
Gibbs free energy difference (ΔGpbx) is typically used to evaluate the
dissolution trend of a metal. a ΔGpbx smaller than 0.5 eV atom− 1 is
required to against corrosion. Pt has a higher dissolution potential of
about 0.8 V and tends to form solid oxide while Fe, Co, Ni, Cu tends to
form soluble ions corresponding to the lower potential at 0.1, − 0.2,
− 0.5, and 0.3 V (vs. NHE) [127]. Cationic decomposition or leaching out
from the Pt alloy catalyst not only causes irreversible ORR activity but
also enters the feed of the reagent, which can contaminate the flow
channel and membrane electrode assembly (MEA) membrane, thereby
degrading performance, reducing lifespan, and hindering the normal
operation of PEM fuel cells.
As an experiment showed, 5 ppm Fe3+ could cause a 174 mV po­
tential shift in 191 h, while the same content of Al3+ causes 65 mV
voltage attenuation in 282 h [128]. Li et al. [129] studied that in the
presence of 5 ppm Co2+, a single PEM fuel cell with a current density of
1.0 A had a voltage loss of 15% in 230 h. Although the introduction of
10 ppm Mg2+ for 11 h resulted in negligible power loss, increasing the
Mg2+ concentration to 100 ppm could reduce the peak power density to
30% in the 10-hour test [130]. 10 ppm Fe2+, Al3+, Cr3+ and Ni2+ at a
constant voltage of 0.6 V led to of approximately 70%, 90%, 65%, and
69% performance losses, respectively [131]. In contrast, Ba2+ and Ca2+
hardly caused voltage attenuation (~1.74 mV h − 1) [132].
Expect base catalyst metals are prone to decomposition due to poor
thermodynamic stability, demetallization is also a noteworthy factor for
the loss of metal active centers of non-precious metal catalysts. Kumar
et al. [133] tested the performance attenuation of M-CN (M: metal)
catalysts after 10,000 cycles of accelerated stress tests (AST), and the
results showed that metal ion sites (M-NxCy) had less loss of initial ORR
activity than metal embedded in the carbon matrix (M-@NC) catalysts,
which were 10–20% and 60–100% respectively.
3.1.1. Cation dissolution
Generally, for Pt-based catalysts, the reasons for the dissolution of
base metals in a solution as a more complex degradation problem can be
summarized as follows:(i) the acidity (pH is approximately zero) and
oxygen-filled environment of PEMFC make it difficult for most non-
noble metal components in the Pt alloys to be stable. The Pourbaix di­
agram shows that almost all transition metals (TMs) such as Co and Cr
Fig. 3. Schematic representation of degradation mechanisms of Pt nanocatalysts embedded within a C support. Reproduced with permission [126]. Copyright
2020, ACS.
8
EnergyChem 3 (2021) 100061
can be dissolved when the potential is located in 0.3~1 V (vs. SHE)
when the service condition is a strong acid[134], (ii) the working po­
tential of the PEMFC cathode is much higher than the dissolution po­
tential of TMs. Although Pt also begins to dissolve at a potential above
0.8 V, and (iii) in the ORR process, the oxygenated intermediates can
interact directly with the subsurface of the alloy to promote the segre­
gation of the alloyed TMs.
For the purpose of understanding the mechanism of non-precious
metal leaching, a FePc catalyst with the active center recognized as
the coordination of Fe with nitrogen in the phthalocyanine was syn­
thesized [135]. The heat treatment process was avoided to maintain the
original structure of FePc. By using in-situ infrared reflectance spec­
troscopy, the authors were able to find that two protons could replace Fe
sites to form H2Pc with low ORR activity. It was worth noting that this
loss was obvious in O2 but almost not evident in argon. Some researchers
believed that this was because Fe2+ could be oxidized to Fe3+ through
Eq. (6) [136]:
FePc + 2H+ →H2 Pc + Fe3+ (6)
Regarding this, the demethylation of Fe in certain potential ranges
was explored. The results showed that iron could experience leaching at
a potential lower than 0.7 V vs. RHE, while the carbon began to be
oxidized at 0.9 V vs. RHE [137].
3.1.2. Mitigation strategies
Improving the stability of PEMFCs, which largely rely on catalysts, is
an important task for commercial application. Mitigation measures can
be summarized as follows: controlling the size, composition, and
morphology of catalyst to prevent coalescence; physical constraints by
Surface modification; formating of Pt-skin structure to inhibit the
dissolution.
3.1.2.1. Control of catalyst size, composition, and morphology. For metals
with a low degree of alloying between TMs and Pt characterized by the
composition, structure, size, etc., cations have a thermodynamic trend to
dissolution. Studies on the decomposition resistance of Pt-TM alloys in
acidic environments found that the type of TMs could affect their solu­
bility. For example, Pt-V, Pt-Ni, and Pt-Fe tended to decompose, while
Pt-Cr and Pt-Co had better durability [47-48]. Hunsom et al. [138]
studied the stability of three alloys formed by adding Co, Ni, and Cr to
the Pt lattice and found that Pt-Cr was the most prominent catalyst. It
was demonstrated that the formation heat of the two early transition
metal oxides, Pt3Y and Pt3Sc, could give better stable structures through
affecting dynamic stability rather than thermodynamic stability. How­
ever, Pt3Sc was easier to agglomerate than Pt3Y, which was attributed to
the formation of scandium oxide on the surface [139-140]. Particularly,
the sputter-cleaned polycrystalline Pt5Gd exhibited impressive resis­
tance behavior at 1.6 V(vs. RHE) [141]. In addition to the decrease in the
d-band center, the more negative alloy heat which could create a higher
barrier to the atoms dissolution could be used to explain the increased
stability. However, it was a challenge to prepare nanostructured Pt3Y,
Pt3Sc, and Pt5Gd with the commonly used preparation method.
In terms of the structure-activity-stability relationship of the Pt-Co
alloy, the stability was found to increase accordingly when the
carbonization temperature rose from 600 ◦ C to 950 ◦ C. In the
X. Wei et al.
carbonization catalyst, the dissolution rate was decreased with
increasing carbonization temperature within a certain range [142],
appealing that the catalytic performance could be stimulated by tuning
the promising fabrication condition.
Normally, the smaller Pt particle size has more oxygen-loving
property than that of larger particle size. However, due to the electro­
chemical dissolution and reduced driving force, the large Pt particles can
exhibit enhanced durability [143-144]. Large particles exhibit low Gibbs
Thomson energy and therefore dissolve slowly, while small particles
with higher energy can dissolve at a lower potential. This dissolution law
is also applicable to the alloy cases. But due to the difference in alloy
composition, the relationship between particle size and dissolution rate
is more complicated. In particular, large alloy particles have an
enhanced dynamic tendency to form nanopores, leading to rapid loss of
non-noble metals [145]. However, when Pt is too thick, the formation of
bulk Pt will reduce the activity due to the decrease in surface energy.
Therefore, it is important to find the most suitable particle size for both
activity and stability.
Relative to the Pt concentration in the alloy, the leaching content of
base metals increases with Pt concentration, which experimentally
corresponds to the lower activity loss of Pt: M (1:1) than Pt: M (3:1)
during the cycling process [146]. Various characterization techniques
showed that a disordered layer of 1~2 nm thickness of pure Pt could be
formed on the surface of Pt alloy. In the preparation process of the alloy
catalyst, the suitable acid treatment caused the non-noble metal atoms
to be instantly dissolved from the near-surface region of the platinum
alloy and left the vacancies. Therefore, the rapidly diffused platinum
atoms continuously enriched the surface, while the underground parti­
cles were largely unaffected. Pt with high defects was enriched on the
surface to form a "Pt framework". The increased activity of Pt framework
particles was based on the concentration of less precious metals in the
subsurface and the degree of low coordination of Pt surface atoms
[147-148]. Pt had lower surface energy than TMs, providing a tendency
for the formation of "Pt skin". Stamenkovic et.al evaluated the stability of
these near-surface structures in HClO4 and found that the surface of Pt
skin was much more stable than the surface containing Pt framework
[147].
Due to the superior stability of the ordered Pt coating on Pt alloys,
some core-shell structures composed of Pt shells and a considerable
proportion of other precious metals like Ir cores have been synthesized.
The low activity of Au is found to be catalytically active when served as
the shell. In terms of surface segregation, the core composed of pure Ag,
Ir, and Au is basically stable. Alloys based on Co[149] and Ni[150] with
Pt shell have also been studied. In addition, the ternary core-shell
structure, e.g., PdFe/C, PdCo/C, and PdNi/C coated with Pt, was
further used to reduce the concentration of precious metals while
increasing stability [151-153].
3.1.2.2. Physical constraints. Another way to modify the surface of the
alloy to increase stability is to encapsulate the metal in a carbon shell to
make electrons transferred from the encapsulated metal nanoparticles to
carbon [154]. Characterized by the transmission electron microscopy
(TEM) images, the metal could be wrapped in a graphite shell and would
not be leached under acidic conditions. Some studies observed that the
surface carbon layer only served as a protective shell and could not
participate in the catalytic reaction, while others believed that electrons
transferred from the metal could activate the surface carbon layer [133,
155-156]. Graphitized shells have the advantage of reduced adsorption
energy, especially shells with heterologous copolymers [157]. Consid­
ering that carbon shell could hinder the active site to a certain extent,
the shell thickness of the prepared catalyst was controlled at about 1 nm
to obtain good activity and prevent leaching [51]. Zhong et al. fabri­
cated a favorable "double nanopore" structure of Pt-Fe nano-alloys
through in-situ etching and acid leaching. Their results showed that the
presence of graphene nanopores could hinder alloy aggregation and
9
EnergyChem 3 (2021) 100061
dissolution. In addition to having an important effect on stability, the
presence of graphene nanopores could also reduce the d-band center
[52]. The medium/macroporous nitrogen-doped carbon structure with
nanocrystalline Fe3C particles completely wrapped in the graphite layer
was also found to be an effective and stable catalyst material for ORR
[158]. Furthermore, some metal-organic framework (MOF) as a pre­
cursor and self-sacrificing template was used to introduce Co in pre­
paring Pt2Co8/N–C catalyst. It was found that abundant N atoms could
increase the adhesion between alloy and the carbon support to prevent
shedding [52]. In addition, non-noble metal, Cu-Co nanoalloys
embedded in zeolitic imidazolate frameworks (ZIF)-derived carbon
(CuCo@NC) were prepared by pyrolyzing ZIF-67 and Cu(OH)2 nano­
wires, and the obtained results showed that Cu ions were uniformly
restricted in the pores of ZIF-67, which could effectively prevent
self-aggregation and Cu was not easy to dissolve [159].
3.1.2.3. Dealloying. By investigating stable operating voltage windows
and operating strategies to prevent base metal leaching, one of the
strategies was found to be dealloying before using the alloy catalysts in
PEMFC [54-55]. Using an acid leaching protocol, most unstable mental
species can be preliminarily removed. For example, Pt–Ni core nano­
particle with Pt surface (≈3 monolayers) acting as the protective
“armor” to prevent interior Ni atoms was prepared by leaching the
minor nickel atoms (shown in Fig. 4) [160]. Han et al. [161] prepared
PtNi3 nanoparticles as precursors and treated them in nitric acid at 70 ◦ C
in the air (denoted as P2-NA) and sulfuric acid at 80 ◦ C under nitrogen
atmosphere (denoted as P2-SA) for 24 h, respectively. TEM images
coupled with energy dispersive spectrometer (EDS) data showed the
changes in Ni content and revealed that compared with nitric acid,
sulfuric acid was more capable of removing non-precious metals while
retaining a Pt-rich skin structure. Gan et al. [162] suggested that
oxygen-free acid could inhibit the nanoporosity created during the
leaching of metals, thus compact the structure of the products.
Post-acid-treatment annealing to P2-SA (P2-SA-AN) could further pro­
mote the production of relatively dense-Pt shells and improve base metal
retention. Reducing low-coordinated surface sites to obtain Pt-rich
passivation layers could lead to exceptional activity and durability.
Nevertheless, this metal-removing, due to high overpotential and/or
peroxide oxidative attack or straightforward metal shedding in acidic
solution, still possibly produced metal loss [137] [163].
The dissolution of base metals is a long-term issue of electrocatalysts.
Although many methods such as controlling the size of alloy particles,
encapsulating the alloy with a carbon shell, choosing an appropriate
pyrolysis temperature, and preparing a core-shell structure can alleviate
the dissolution of non-noble metals to a certain extent, it is difficult to
have both stability and activity. Researches are still needed to under­
stand the mechanisms to obtain a suitable method to improve the PtM
catalysts for their real use in PEMFCs.
3.2. Oxygen-containing species/product during ORR
When oxygen-containing intermediate produced in the ORR process
is strongly bound to the surface of the catalyst, its active sites will be
blocked. This section mainly discusses the production of these in­
termediates and how to avoid their harm to the catalyst. In addition, the
ORR reaction product H2O2 not only reduces the utilization efficiency of
precious metal catalysts but also causes the poisoning of NPMCs. Un­
derstanding the redox potential of metal cations can help choose
appropriate catalysts.
3.2.1. The effect of oxygen-containing species/product
In PEMFCs, the most desirable ORR is to produce water through a
four-electron pathway, rather than to produce hydrogen peroxide
(H2O2) through a two-electron pathway. In reality of the ORR, oxygen
may generate H2O through a four-electron mechanism, or H2O2 through
X. Wei et al.
a two-electron mechanism, which can be described as the following
steps under acidic conditions [164-165]:
Four-electron mechanism:
O2 (g) + ∗→O∗2
O∗2 + ∗→2O∗
2O∗ + 4H+ + 2e− →2OH∗
2OH∗ + 2H+ + 2e− →2H2 O(l) + 2∗
Two-electron mechanism:
O2 (g)+∗ →O2 ∗
H+ + O∗2 →OOH∗
H+ + OOH∗ →H2 O2
H2 O2 + ∗→2OH∗
2OH∗ + 2H+ →2H2 O(l) + 2∗
where “*” stands for an active site on the surface of the electrocatalyst.
Both four-electron and two-electron path generates oxygen-
containing species like O*, OOH*, and OH*. The weak combination
between catalyst and oxygen is not conducive to the transfer of electrons
and protons from the catalyst to oxygen. However, when this combi­
nation is too strong, the surface oxygen-containing intermediates and
anions cannot be removed immediately, which will negatively affect the
subsequent oxygen adsorption and reduction reaction [166]. All of the
Pt-based electrocatalyst materials involved can encounter difficulties in
overcoming approximately 300 mV overpotential of ORR, which will
lead to the thermal efficiency of the entire PEMFC being much lower
than the thermodynamic limit [47]. The distribution of highly unreac­
tive oxygen-containing species on Pt can induce sluggish ORR kinetics,
especially in the low overpotential region [167].
Fig. 4. Pt–Ni@PtD/G catalyst before (middle) and after (right) acid treatment. Reproduced with permission [160]. Copyright 2020, John Wiley and Sons.
EnergyChem 3 (2021) 100061
In addition, H2O2, the product of the two-electron path, induced
chemical degradation of the PEMs is one of the most serious issues for
fuel cell durability. The most common perfluorosulfonic acid such as
Nafion could be attacked by free radicals decomposed by H2O2. For the
(7)
catalyst itself, the production of H2O2 not only reduces the utilization
efficiency of the precious metal catalyst but also accelerates the degra­
(8)
dation of NPMCs, especially the oxidation of carbon and/or activity site
(9) [168]. Taking metal phthalocyanine as an example, the weakening of C
and N bond cooperation can easily take place with the oxidative attack
(10) in presence of O2 or H2O2, corresponding to the immediate drop of the
cell voltage during a short time [169]. To test the effect of H2O2, The
catalyst of carbon-supported iron(III) tetramethoxyphenylporphyrin
(11) chloride (FeTMPP− Cl) treated with H2O2 was compared with the un­
treated one. It was found that the degradation rate of the catalyst after
(12) treatment was significantly higher than that untreated one [170].
Lefevre et al. [163]. observed that the performance loss of iron-based
(13) catalysts treated by peroxide varied with the Fe content and pyrolysis
temperature. At 900 ◦ C pyrolysis temperature, the catalyst with the most
(14) iron content was least affected by peroxide.
There are two possible mechanisms for H2O2 to attack NPMCs: (i)
(15) Directly oxidized by H2O2 and (ii) attacked by the intrusive hydroxyl
radical, which is the decomposition product of H2O2 [163]. The process
by which Fe2+ promotes the decomposition of H2O2 into highly active
radicals is known as the Fenton reaction (Eq. (16)). The iron impurity
concentration levels from 0 to 1000 ppm are a key parameter in the
simulation. The oxidation intensity of these species follows the order
OH*> H*> OOH*> H2O2 [171].
Fe2+ + H2 O2 + H+ →Fe3+ + OH− + H2 O (16)
Therefore, it is needed to find ways to further avoid the harmful
effects of oxygen-containing intermediates on ORR and the production
of H2O2.
3.2.2. Mitigation strategies
The main sources of oxygen-containing species are water and oxy­
gen, which, to a large extent, increase the probability of blockage of Pt
10
X. Wei et al.
sites. However, water is both a reaction medium and a reaction product,
which makes it is uneasy to perform catalyst modification. By preparing
the alloy structure, the d-band center of Pt can be reduced, and the
interaction between surface Pt and inactive oxidizing substances can be
weakened, thereby unlocking the active sites for ORR.
The concept of ionic liquid (IL) was applied to heterogeneous cata­
lysts, and the term SCILL (Supported Catalyst With Ionic Liquid Layer)
was employed for the treatment and modification of catalysts [176]. To
a certain extent, IL as a substitute for water can impregnate the surface
with a second phase with higher oxygen solubility than the aqueous
phase to increase the availability of O2 to the catalyst. Restricting oxy­
gen to the pore size (~2 nm) of the catalytic surface can promote the
frequency of interaction with the substrate, thereby making the catalyst
system be fully exploited [59,172]. By controlling the accessibility of
water molecules derived from the product as well as the electrolyte, the
catalyst surface can create a hydrophobic microenvironment, which
would help protect the active center from being poisoned by the highly
non-reactive oxygenates OHad, and at the same time facilitate the
adsorption of decoupling reactants (O2) to reduce the ORR
overpotential.
Zheng et al. [58] impregnated graphene-supported Pt nanoparticles
with IL ([MTBD][bmsi]) to prepare a Pt-IL composite catalyst and found
that the catalyst had optimal compatibility. Their results proved the
pronounced potential of IL modification to enhance the activity of
non-commercial Pt for ORR. The researchers [57] also impregnated
different contents of IL [MTBD-NTf2] into the narrow gaps of the Pt/C
catalyst and changed the content of IL filling to achieve changeable ORR
activity and stability. It was worth noting that the Pt/C-SCILL with
50% hole-filling had an optimal mass activity of 0.56A•mg− 1Pt at
0.9 V (Fig. 5a-b). Hydrophobic ionic liquid (IL) containing a certain
amount of isopropanol, 1‑butyl‑3-methylimidazolium bis(tri­
fluoromethanesulfonyl) imide ([C4C1im][NTf2]) was also used as a
dispersant, and the surface of Pt/C (20wt%) was modified to be hy­
drophobic with lower ORR onset potential [59]. The activity promotion
mechanism observed with the introduction of ionic liquids can be
summarized as follows: Pt at defect sites are prone to oxidation due to
their higher reactivity (Fig. 5c). The introduction of hydrophobic IL has
dramatic effects on avoiding oxidation of vulnerable parts without
repelling reactants (Fig. 5d). Moreover, such a surface modification
technique is desired to decouple the adsorption of non-reactive species
and reactants and correspondingly free up more space for the redox
reaction. Considering the diversity of ILs, there is assuredly much po­
tential for performance improvement of majority catalysts by reasonably
controlling the cation and/or anion structure of ILs.
As for the unpleasant product H2O2, Gubler et al. [173] reported that
by measuring the relative redox potential of metal cations, the ability of
the catalyst to withstand the Fenton reaction could be predicted. Spe­
cifically, only when the redox couple of the designated cation was lower
relative to the H2O2/OH, the metal cation could be used as Fenton’s
reagent. The potential of H2O2 forming •OH was 0.88 V, which was
greater than that of Fe3+ reducing to Fe2+ (0.77 V), on the contrary, less
than that of Co3+ generating Co2+ (1.92 V). Obviously, it is a thermo­
dynamically unfavorable reaction for H2O2 to oxidize Co2+while the
oxidation reaction of Fe2+ is undoubtedly just right in a suitable con­
dition. Therefore, this oxidative attack mechanism can present a
reasonable explanation for which Co base is more stable than Fe base.
Observing the degradation behaviors of FeN4 and CoN4 sited cata­
lysts and found that, in comparison with the continuous performance
decline of Fe-N-C catalyst, Co-N-C can be more stable. The degradation
of catalysts with different H2O2 content under in-situ contact was also
studied [174].The degree of degradation was more pronounced with
increasing H2O2 when Cr-N-C was used in comparison with those of
Fe-N-C and Co-N-C [174]. After treatment with a relatively large amount
of H2O2, Co-N-C, and Cr-N-C could only retain 40% and 60% of their
initial masses.
In order to produce as little H2O2 as possible, continuous efforts need
11
EnergyChem 3 (2021) 100061
to improve the selectivity of the catalyst to the four-electron pathway.
Four methods can be envisaged for the synthesis of M-N-C catalysts
[174]: (i) producing the least H2O2, (ii) improving graphitized structure,
(iii) choosing catalysts without forming radical oxygen species (ROS) if
H2O2 cannot be absent, and (iv) adding free radical scavenger. It seems
that a thicker catalyst layer can result in less quantitative peroxide
because it contributes to the further reduction of peroxide and the
production of water. Unfortunately, an ultra-thick layer can limit the
diffusion of water and reactive species [175].
3.3. Supporting materials decomposition
As the selected catalyst support, it needs to have particular properties
including (i) suitable porous structure to maximize the specific surface
area, (ii) high electrochemical stability, (iii) auspicious electronic con­
ductivity, (iv) stable chemical links at the catalyst-support interface, and
(v) good crystallinity [176]. In this regard, the environment-friendly and
availability of the carbon black materials, including Vulcan C, Ketjen C,
Black Pearls, etc., make them popularly employed among supporting
materials for Pt nanoparticle catalysts, which can be produced by
tailoring the synthesis parameters. In particular, graphene and carbon
nanotubes (CNTs), due to their inherent large surface area and fewer
defects, are consequently showing better durability in cell performance
than traditional carbon blacks. As identified, carbon may be more sus­
ceptible to corrosion through chemical or electrochemical processes,
which is pronounced especially at high potentials.
Carbon oxidation product-CO2 is one of the gasses that induce
PEMFC poisoning [177]. The decomposition of the carbon support
material will accelerate the detachment of the catalyst particles from the
support, thereby accelerating the performance degradation. For
example, Park et al. [178] observed 50% loss of the Pt surface area while
the AST of the MEA was conducted at 1.3 V for 50 h In addition, the
hydrophilic carbon surface species formed after carbon corrosion could
result in the reduced gas diffusion. The oxidation and decomposition of
the carbon support are not only related to its properties but also corre­
sponding to the type or pretreatment methods of the materials. Wang
et al. [179] evaluated corrosion resistance of Black Pearl 2000 and
Vulcan XC-72, a lower performance loss was observed for Pt/XC-72
during the durability test.
In addition, To get high corrosion resistance supports, some non-
carbon materials such as metal oxides, nitrides, and carbides have
been explored as catalyst support materials [180].
3.3.1. Decomposition mechanism
When carbons, such as Vulcan carbon, are used as support materials,
some of them contain defective surfaces and rich organic surface groups
(e.g., CO, COOH, CN) [181]. Surface defects can increase the activity by
dispersing the particles but promote catalysts to have serious corrosion
issues and eventually unsatisfactory thermochemical stability. Typi­
cally, carbon oxidation occurs through two paths of electron transfer: (i)
incomplete oxidation leading to the production of various groups; and
(ii) complete oxidation, owing to the destruction of the graphitic plane,
leading to the formation of gaseous CO2 from CO (Eqs. (17) − 19) [182].
Cs →C+ −
(17)
s +e
2C+ +
(18)
s + H2 O→2Cs O + 2H
Cs O + H2 O→CO2 (g) + 2H+ + 2e− (19)
where the "s" is referred to the surface groups.
As a typical transition metal oxide material, WO3, is not susceptible
to corrosion, making it a possible support material in acid media.
However, TEM observed that after 300 cycles at a potential range of
0.0~1.4 V, the average size of Pt on WO3 was changed from 3 nm
uniformly deposited Pt clusters to 20~50 nm large clusters,
X. Wei et al.
Fig. 5. (a) ORR polarization curves of Pt/C-SCILL with the different pore filling degree (O2-saturated 0.1 M HClO4 solution, scanning rate 10 mV s − 1). (b) Cor­
relation between the apparent specific activity for ORR and the pore-filling degree of the SCILL materials at 0.90 V. Reproduced with permission [57]. Copyright
2015, ACS. (c-d) a conceivable mechanism for IL to selectively locate at the defect sites and boost the activity of Pt/C catalysts. Reproduced with permission [59].
Copyright 2016, John Wiley & Sons Ltd..
accompanied by a significant decrease in electrochemical activity [183].
Research on its electrochemical process found that WO3 could react with
hydrogen to form stable hydrogen tungsten bronze (HxWO3) and sub­
stoichiometric oxide WO3-y according to Eqs. (20)-(22): [72]
xH+ + xe− + WO3 →Hx WO3 0 < x < 1
2yH+ + 2ye− + WO3 →WO3− y + yH2 O 0 < y < 3
PtHads + WO3 →Pt + Hx WO3
The tungsten bronze was slightly soluble in acidic electrolytes at a
slow dissolution rate, which could destroy the stability of the Pt/WO3
catalyst and force Pt clusters to leave the surface, resulting in perfor­
mance loss. Similar dissolution could be observed when WC acted as the
support. The possible explanation was that WC could be oxidized to WOx
when E>0.8 V, as shown in Fig. 6a.
The performance and stability of Pt/indium tin oxide (ITO) in MEA
during conventional fuel cell operation were also studied by Wang et al.
[73]. In performing XPS to characterize the degradation of Pt/ITO
electrode, the obvious hydroxyl groups were found on the surface of
indium oxide. The conductivity of this hydroxide layer was poor (in
contrast to ITO), which increased the electrode resistance and negatively
affected the performance of the MEA. The indium in the hydroxide layer
could be dissolved under strong acid conditions, resulting in the pene­
tration of In3+ into the membrane (and the ionomer in the electrode).
These would further increase cell resistance and reduce both ECSA and
mass activity (MA). In simulating fuel cell operating conditions, the
EnergyChem 3 (2021) 100061
in-situ ICP-MS was used by Hornberger et al. to track the structural
stability of the atomically composed catalyst Pt nanoparticles on the
ruthenium-titanium mixed oxide (RTO) support [184]. They observed
that owing to the strong metal-support interaction (SMSI), a thin (par­
tial) oxide layer could cover Pt nanoparticles, which was impenetrable
(20)
to oxygen and poisoned the Pt catalyst, as shown in Fig. 6b. The SMSI
triggered by heat treatment for TiO2 supported Pt catalyst was also
(21)
investigated by Hsieh et.al [185]. High-resolution TEM images of
(22) Pt/TiO2 calcined under hydrogen (abbreviation for Pt/TiO2–HT) at
200 ◦ C and 300 ◦ C were shown in Fig. 6c-d, respectively, demonstrating
that Pt nanoparticles are partially or completely covered by the reduced
TiO2-x.
3.3.2. Mitigation strategies
3.3.2.4. Functionalization of carbon supports. Supports with higher sur­
face inertia can increase the stability of the catalyst, but make it difficult
to combine with other catalysts, such as CNTs with a high curvature
radius [186]. Two conventional ways, including chemical activation and
thermal treatment, can be used to optimize the carbon supports. The
enhancement mechanism of heat treatment can be achieved by the
removal of metal or amorphous carbon at higher temperatures. The
oxidation treatment can be used to modify carbon through the addition
of some facilitating oxygen-containing groups in the presence of diverse
oxidants like nitric acid. Therefore, both thermal treatment and oxida­
tion treatment methods are beneficial to increase the catalyst’s ECSA
12
X. Wei et al.
and improve the dispersion on the support surface.
Based on spectral characterization, Kim et al. [187]. found that ox­
ygen functionalization at the interface of Pt/C was an interaction
enhancement strategy to improve the initial activity of ORR. Unfortu­
nately, electrons from Pt nanoparticles could be attracted by neigh­
boring oxygen atoms with strong electronegativity, motivating the
partial oxidize of Pt nanoparticles and initiating their dissolution. Due to
the corrosion of carbon, the agglomeration of Pt nanoparticles was
accelerated due to the weak interaction of anchoring sites which pro­
moting the happening of the Ostwald Ripening [100]. It is obvious that
oxygen-containing functional groups and defects have similar effects on
other nano-carbon materials like CNTs.A mild treatment method can be
expected to take advantage of the properties of oxygen-containing
functional groups for preserving structural stability. Chen et al. [67]
attached SH− groups to CNTs to obtain thiolated nanotubes (SH–CNTs).
Compared with COOH performed as anchor centers (Pt/COOH–CNTs),
sufficient SH groups could achieve high dispersion of Pt nanoparticles
with good corrosion resistance through inhibiting CNTs from being
oxidized and decomposed. As shown in Fig. 7a, the results show that
Pt/SH–CNTs can have better stability than that of Pt/COOH–CNTs
although Pt/COOH–CNTs have high initial activity, it presents signifi­
cant degradation under the same conditions. This observation indicates
the importance of selecting suitable functional materials for stability.
They also verified that the migration energy and oxidation resistance of
Pt/SH–CNTs were stronger than those of Pt/OH–CNTs as obtained
through density functional theory (DFT) calculations, induced by
maintaining the stable structure of CNTs instead of having an adverse
effect on it [188].
Carbon blacks can be coated with chitosan derivatives, which can not
only protect them from harsh acid environments but also provide metal
ions-attractive amine groups [189]. A typical property of these hybrid
materials is the ease of proton transfer if amine groups are introduced to
improve the interaction between Pt and support. However, CV results
exhibited the ECSA for 5 wt.% Pt/chitosan derivative-CB (49 m2 g − 1)
was not as high as commercially available catalyst Pt/C (84 m2g − 1).
Polyaniline (PANI) is also a milder surface modifier. For example, He
et al. [190] deposited Pt colloids on the surface of PANI-modified CNTs
to obtain a Pt-PANI/CNT catalyst, as illustrated in Fig. 7b. The free
electron pair of N at one end of the polyaniline molecule was complexed
with the space orbital of Pt and linked with the CNT at the other end
through π-π bonding [191]. The ECSA of Pt-PANI/CNT was decayed to
60% of the initial value after 6000 cycles, while Pt/CNT could only
experience 4000 cycles to reach such a degradation. The doping of
heteroatoms such as N, P, S, B, and F is considered an implementable
13
EnergyChem 3 (2021) 100061
way to achieve high Pt dispersion and adsorption on the surface of CNTs
[192]. Regardless of the electronegativity of the doping element, the
metal-support interaction can be significantly enhanced by changing the
electronic structure of carbon. This reduces the migration of Pt nano­
particles, thereby improving the stability of the catalyst.
To solve the corrosion of the supports in the harsh environment,
various materials have been used to modify the catalyst support.
Although the modified support can become a contributing component,
the introduction of some inappropriate impurities should be avoided to
avoid the negative effect on the long-term stability of the catalyst.
3.3.2.5. Preparation of hybrid support. In order to achieve both activity
and stability of carbon supports, searching for a synergistic combination
of carbon-carbon support materials to develop ideal scaffold support has
been carried out [176,193] Till now, electrostatic self-assembly [194],
chemical vapor deposition (CVD) [195], and partially exfoliated nano­
tubes[196] methods were used to synthesize CNT-graphene composite
materials. A single-wall nanotube-multiwall nanotube (SMWNT-MCNT)
hybrid structure was found to have an improved mass transport [70].
Xiong et al. [197] inserted carbon nanoparticles into nitrogen-doped
graphene and deposited Pt on it to form a catalyst. The graphene
acted as a barrier to retrieve the shed Pt particles. The MA of the ob­
tained Pt deposited nanocarbon wedged structure could retain 76.9%
during the 5000 cycles of accelerated durability tests (ADT), while
commercial Pt/C could only do 32.3%.
To obtain a suitable metal-support interaction, Hsieh et al. [185].
removed the TiO2-x covered on Pt with 0.5 M HF and exposed the active
sites of the activated Pt again. In this way, they could restore the MA
from 1.83 to 4.23 mA/mg Pt. (Fig. 6e). Normally, the addition of het­
eroatoms in TMOs can increase conductivity while forming stronger
M-Pt interactions. Ti3O5− Mo support was elaborated by modifying
commercial anatase TiO2 with Mo into Ti3O5− Mo suboxide initially
[198]. Subsequently, Esfahani et al. [199] dropped Mo and Si into ti­
tanium suboxide to obtain Ti3O5Mo0.2Si0.4 (TOMS) as new catalyst
support. Compared to commercial Pt/C, which lost more than 81% of its
ECSA over the 5000-cycle AST, the tailor-made catalyst lost only 10% of
its initial value. The synergistic effect between Si and Mo greatly
improved the electrical conductivity of TiO2 by effectively reducing the
bandgap of TiO2 and reducing Ti4+ to Ti3+ stoichiometrically.
Although noncarbonaceous supports generally have high corrosion
resistance and improved metal-support interactions, they face the
following challenges: (i) low conductivity is not conducive to electron
conduction, and (ii) limited specific surface area makes them difficult to
uniformly load catalysts like Pt, resulting in few active sites and poor
Fig. 6. (a) Description of the process of Pt ag­
gregation induced by WO3 support decomposi­
tion. Reproduced with permission [183].
Copyright 2012, ACS. (b) After the degradation
process, thin oxides formed on the surface of
platinum prevented further contact between
both reactive oxygen or non-essential CO and
Pt. Reproduced with permission [184]. Copy­
right 2018, ACS. (c) After pure hydrogen
reduction at 200 ◦ C (Pt/TiO2–HT) and (d)
300 ◦ C (Pt/TiO2–300HT). (e) Linear sweep
voltammetry (LSV) curves of Pt/TiO2 before
and after 0.5 M HF treatment. Reproduced with
permission [185]. Copyright 2017, Elsevier
Ltd..
X. Wei et al.
Fig. 7. (a) Cyclic voltammograms of Pt/SH–CNTs, Pt/pristine-CNTs, and Pt/COOH–CNTs catalysts scanned between 0 and 1.2 V (vs. RHE) for 1500 cycles in N2-
saturated 0.5 M H2SO4. Reproduced with permission [67]. Copyright 2011, RSC. (b) Molecular diagram of Pt crosslinked with CNT modified by polyaniline.
Reproduced with permission [190]. Copyright 2011, ACS.
activity.
Generally, the combination of carbonaceous and noncarbonaceous
hybrid support will enable it to satisfy both stability and activity re­
quirements. On the one hand, the exophilic MOx phase can effectively
facilitate the cleavage of highly reactive oxygen species, which protects
both the active sites and carbon substrates from attack. On the other
hand, the nucleation of Pt on MOx/junctions of carbon and metal (oxide)
leads to improved corrosion resistance by restricting Pt ion migration
and/or Pt particles detachment from the support. Therefore, heteroge­
neous nanohybrids —consisting of carbon with other metal oxides (WO3
[200], TiO2 [71], and MnO2[201]) have shown particular promise in
realizing both acceptable conductivity and favorable corrosion resis­
tance. Xia et al. [65] grafted TiO2 nanosheets on the CNT backbone to
get a Pt/CNT@TiO2 structure by solvothermal and subsequently calci­
nation process. Their chronoamperometric measurements confirmed a
slower decline in the current density while CNTs were closely sur­
rounded by TiO2 support with good hydrophilicity and feather-like
structure. In contrast to a traditional two-step loading process that
preload MOx on carbon support followed by deposition of Pt nano­
particles, platinum-tin oxide hybrids supported on carbon black
(Pt-SnO2/C) was synthesized by air annealing PtSn alloy nanoparticles
on carbon black according Guan et.al. [202]. The author enlarged the Pt
interfacial region and found an obvious overlap of the lattice fringes of
the Pt (111) and SnO2 (200) planes in the vertical direction and the
strong interfacial interaction results in a lattice distortion of SnO2.
Therefore, the generated SnO2 act as a binder not only to prevent the
coalescence of Pt, but format a strong interaction with support due to the
charge redistribution between C 2p-derived states and the valence and
conduction bands in SnO2.
In summary, developing valuable catalyst supports is fairly impor­
tant in mitigating the degradation of Pt-based catalysts for PEMFCs.
Further investigation is required to clarify the mechanism of corrosion
resistance and to achieve more desirable catalysts.
3.4. Catalyst degradation caused by operation conditions
3.4.1. Operation events
During normal operation, all the reactive gas is sufficiently fed into
the anode and cathode of the battery, resulting in a uniform distribution
on the electrode surface. However, if uneven gas distribution is formed
within the fuel cell, oxygen or air from the cathode will be diffused from
the cathode through the membrane electrode to the anode under the
action of the concentration difference, thus forming a hydrogen-air
interface at the anode. Uneven gas distribution may cause by oper­
ating conditions like shut-down and start-up events, air starvation, cold-
start, etc.. In many fuel cell applications, start-up and shut-down (SU/
14
EnergyChem 3 (2021) 100061
SD) of the system have the most significant impact on cell durability due
to transient changes in load and gas feed, which poses a severe limitation
on the lifetime of the system. For example, the voltage increase of the
fuel cell occurs after the hydrogen and air supply is stopped, which leads
to the oxidation reaction and irreversible loss of performance of the
cathode catalytic layer [203].
3.4.2. Mitigation strategy
At present, there are three main strategies to suppress/avoid the
performance attenuation of fuel cells when hydrogen-air interface exists:
(i) search for corrosion-resistant catalyst support; (ii) Prepare catalysts
with high corrosion resistance; (iii) adopt the control strategy to restrain
or avoid the carbon corrosion on the cathode side. Lee et al. [204].
calculated the corrosion rates of various carbon carriers such as Vulcan
XC-72, graphite nano powder and carbon nanotubes by measuring the
concentrations of gasses such as CO2, CO and SO2 emitted from the
cathode outlet during fuel starvation in a PEM fuel cell cathode. The
carbon nanotube-supported Pt catalyst showed the best performance
according to their research. The research had revealed that carbons with
low BET surface such as graphite nanoparticles (GNP500, 100 m2 g− 1)
are less prone to degradation than ordered mesoporous carbon (OMC,
1000 m2g − 1) [205]. More strategies for improving catalyst durability
are introduced in Section 3.2. In addition, Ferreira-Aparicio et al. [206]
used catalysts with different Pt/C ratios to directly electrospray cathode
CL on the membrane, and prepared a membrane electrode assembly to
determine the effect of electrospraying morphology on the cell degra­
dation rate. The electrospraying morphology mitigates the deleterious
effects of local water accumulation in cells by improving the homoge­
neity of cell responses. In addition, the porous form of the catalyst layer
(CL) provides high hydrophobic characteristics, which makes the
corrosion kinetics unfavorable. The long-term degradation rate
increased with Pt/C ratio in the CL due to the catalytic effect of Pt on
carbon corrosion. Gas purge is one of the most practical methods to
shorten the time that the hydrogen - air interface exists at the anode.
Three operations, including (i) isolation of hydrogen with opening of the
PEMFC’s anodic compartment to the external atmosphere, (ii) stopping
the flow of air through the PEMFC’s cathodic compartment, and (iii)
tensile loading, are recommended to be performed in a period of long
time no-use [203]. For more information on the control of fuel cell
systems, readers interested can refer to the work of other researchers
[207-212].
X. Wei et al.
4. Catalyst degradation caused by external impurities
4.1. Anion adsorption
4.1.1. Anion species
Typically, the distribution of adsorbed hydrogen is affected by the
presence of halogen ions (Cl− , I− , Br− ) and organic species on the surface
of the Pt electrode, thus affecting the hydrogen underpotential deposi­
tion (Hupd) region [213]. For example, halide ions (I-, Br-, Cl− ) adding to
clean-surfaced Pt nanocubes (Pt-NC), Pt cuboctahedral (Pt-CO), or Pt
polycrystalline (Pt-PC) could decrease the area of Hud. When the ion
concentration was high enough, the obtained voltammogram could not
show any feature of hydrogen adsorption. Compared with I− , the
adsorption strength of Br− was relatively weak, corresponding to a weak
poisoning [43]. For most impurity ions, the pollution extent was almost
proportional to the adsorption strength of the ion to the catalyst because
the strong adsorption made surface pollution difficult to be removed.
In addition to halides, sulfides are the main induction factor for
performance degradation. As observed, under various high potentials,
the specific activity was inversely proportional to the logarithm of sul­
fate concentration [214]. Behm et al. [87] examined the ORR of typical
Pt/C catalyst in the presence of Cl− , HSO4− , ClO4− anions, and obtained
the order of the poisoning effect as the strong adsorption of Cl− > the
strong adsorption of HSO4− > the weak adsorption of ClO4− . In-situ
Fourier transform infrared spectroscopy (FTIR) as a research method
confirmed that the adsorption of (Bi) sulfate on the Pt surface, and the
extent of sulfur adsorption was reliant on the structural properties of the
Pt surface. As believed, (Bi) sulfate was adsorbed on Pt(111) surface
through three oxygen atoms which was consistent with the band present
at 1270 cm− 1 [214]. The morphology and the applied potential of Pt
could also affect the adsorption and removal of sulfate. Radiotracer
measurements showed that polycrystalline Pt had less adsorption of
sulfate than single crystals [215]. Sulfur could poison platinum through
the adsorption process. Compared with other low-value sulfur, H2SO4
has a weak adsorption capacity. The low-value sulfur is usually oxidized
to SO42- and HSO4− as water-soluble anions and can be desorbed from
the Pt nanoparticles by a potential cycle.
Phosphate and perchlorate ions as the electrolyte components or
impurities also have a weak effect on the Pt-based catalysts. The
adsorption of structure-sensitive anions can cause the blockage of re­
action sites, which seriously inhibits the activity of the geometric sur­
face. Under steady-state conditions, the ORR suppression caused by
anion adsorption was compared and found to follow this order of 0.75 M
H3PO4> 0.05 M H2SO4> 0.1 M HClO4 [216]. He et al. [200] Observed
the ORR on a single-crystal platinum electrode in H3PO4 solution, and
found that PO43− consumed three oxygen atoms on the surface of Pt
(111), while the number on the surface of Pt (100) and Pt (110) was
reduced to 1 or 2 [217]. This finding corresponded to the order of Pt
plane poisoning in phosphoric acid: Pt(111)> Pt(110) ~ Pt(100) [90,
217]. In aqueous solutions with a large pH range, phosphate anions
could prevent the reactants from reaching the catalyst surface by
occupying the adsorption sites of Pt, which in turn had a negative impact
on ORR [218-219]. When pH<5.8, the adsorption and deprotonation of
dihydrogen phosphate H2PO4− could give the adsorbed HPO42− . This
HPO42− was the main anions adsorbed on the Pt(111) site when the pH
was between 5.8 and 11. When a pH was greater than 11, OH− and
phosphate were co-adsorbed.
80% of the ORR activity of Pt catalyst may be inhibited by ionomers
(usually perfluorinated sulfonic acid polymers) containing anionic
components in the PEFCs catalyst layer [220]. Nafion® has been effi­
ciently utilized as a binder in the catalyst layer and to provide a proton
conductive path. ORR activities of Pt electrode in 0.1 M HClO4, a
Nafion®-coated Pt electrode in 0.1 M HClO4, and a Pt electrode in
HClO4/CF3SO3H solutions were examined and found that both of late
two were lower than that of Pt electrode in 0.1 M HClO4 solution, as
observed by Ohma et al. [221]. The formation of H2O2 and reduction of
15
EnergyChem 3 (2021) 100061
apparent activation energies in Nafion®-coated Pt could be interpreted
as the sulfonate anion adsorption. The O2 adsorption could be blocked
due to the anion species of Nafion® and CF3SO3H orientation to Pt
surface induced by water molecules.
As recognized, NPMCs are less stable under acidic conditions than
alkaline conditions. Therefore, Liu et al. [222-223] and Herranz et al.
[224] recently reported that the protonation of the active site was
responsible for the rapid initial decline in performance. The protonated
catalyst electrode was more likely to combine with anions, resulting in
the occupation of active sites, and the protonation was more likely to
occur under acidic conditions. Fig. 8 depicts that the protonation of the
initially passivated N site provides a location for subsequent anion
adsorption and ultimately leads to catalyst deactivation [224]. SCN−
and CN− were reported to have a strong metal affinity and are easy to
form complexes with iron that can make ORR poisoning [225]. In the
presence of potassium cyanide, the electrochemical performance of FePc
before and after pyrolysis was evaluated and found that the onset po­
tential of the two materials was significantly reduced by 200 mV, and
the diffusion limiting current was slightly decreased [226]. Previous
studies also found that when iron-based electrocatalysts were poisoned
by cyanide, the transition from four-electron to two-electron ORR
pathways occurred [225,227].
4.1.2. Mitigation strategies
For the contaminated electrode surface, an in-situ potentiostat
approach was designed to remove the absorbed halide ions from the Pt
surface [38]. Immersing the poisoned Pt electrode in 0.1 M NaOH so­
lution, ~0.03 V could effectively restore the active surface area without
changing the surface structure, as shown in Fig. 9a. The halogen ions on
the Pt surface can be replaced by OH− with strong adsorption capacity
produced by NaOH solution with the assistant of chronoamperometry.
This method is perceived to be a facile and effective way to remove
adsorbed halide ions without disturbing the original structure, espe­
cially for catalysts with specific morphologies [43,35].
Changing the number and geometry of adsorption sites by surface
design can prevent the sites from the adsorption of anions, providing
more free metal sites for chemical adsorption and allowing for maximum
utilization of active sites. Based on this idea, Markovic et al. [44]. pre­
pared an irreversibly adsorbed cyanide addition layer on the surface of
Pt(111) (Pt(111) CNad). The case of Pt(111) was particularly interesting
because Pt(111) could spontaneously form an ordered (2√3 × 2√3)
R30◦ inert structure when immersed in a cyanide container [228]. CNad
extended to the entire electrode surface and was attached to hexagonal
Pt surface atoms surrounding free Pt atoms. The adsorbed CN blocked
the reaction that required three closely arranged triangular Pt atoms to
exist at the same time [229]. Therefore, this stable structure could
prevent the adsorption of tetrahedral sulfuric acid and phosphate an­
ions, but could not prevent the adsorption of O2 and change the energy
of Pt-O2 or Pt-intermediate. The ORR activity of Pt(111)CNad could be
increased by 25 times in the presence of sulfuric acid anion, by 10 times
in the presence of phosphate anion, and had no effect in the presence of
perchlorate anion. Therefore, the influence of adsorbed CN on the
electronic properties and Pt catalytic ORR was negligible. Fig. 9b & c
shows that on the Pt(111) surface shielded with phosphorus/sulfuric
acid anions, reactive gasses like oxygen can only contact surface atoms
through a few holes in the adsorption anion layer. Due to the inhibition
of the adsorption of phosphoric acid/sulfuric acid anions on the surface
of Pt(111)CNad, more pores are required for O2 adsorption. The com­
bination of site blocking and electronic effects can be used as a funda­
mental to discover the true function between the activity and selectivity
of the Pt(111)CNad interface in an environment involving distasteful
HSO3− /PO43− . According to the energy calculated by DFT calculations,
the protonation reaction of CNad on Pt(111) was obviously superior to
that of Pt atoms, subsequently proved that when the CN covering layer
was 0.3 ML, the best activity could be obtained [230]. Similarly, the
adsorption of Pt(111) by phosphate decreased significantly with
X. Wei et al.
Fig. 8. A Fe/N/C catalyst containing N groups is protonated under acidic
conditions and then combines with anions. Reproduced with permission [224].
Copyright 2011, ACS.
increasing OAm surface coverage. Based on this viewpoint, direct syn­
thesis of OA-adsorbed Pt/C followed with the elimination of the OAm
adsorption step was developed by Chung et al. and the resulted catalyst
showed especially small ECSA but could resist phosphate ions [231].
These studies indicated that in order to effectively utilize the third-party
effect of ORR on the adsorption of specific anions, the modified organic
molecules should leave enough space for the O2 reactant to contact the
catalyst.
The zwitterionic L-cysteine molecule could be functionalized on the
Pt surface, producing the electrostatic interaction between charged
spectral ions, that could enhance the ORR activity in both KOH and
H3PO4 solutions [232]. The negatively charged L-cysteine could cover
the surface of Pt nanoparticles, being able to inhibit the excess OH− in
KOH, and the NH3+ of l-cysteine could also bind with phosphate oxygen
anions to protect the original Pt surface. It is worth noting that although
these surface adsorption methods were carried out only in phosphoric
acid electrolyte, it can be proved that the surface modification method
can prevent the desired sites of anion adsorption through steric hin­
drance, inspiring future researches.
The alloy catalyst can release more active sites through obvious
electronic effect or ligand effect to reduce the tendency of Pt anion
adsorption in acidic medium, thereby reducing phosphate ion poisoning
[217][233]. Δµ X-ray absorption spectroscopy analysis showed that the
potential of phosphate anion adsorption was higher on PtNi than on Pt,
which could inhibit the adsorption activation of water and release
enough sites for ORR. Different from simple alloy structure, Nb could not
only serve as the electronic and geometric properties of alloy component
adjustment but also as oxide support to avoid catalyst degradation
[234]. The hydration chemical method was used to synthesize the Pt-Nb
complex (PtNb/NbOx-C) with immunity to phosphate anion poisoning
[234]. Research on the non-Pt-based-MOF-supported iron-based
(FePen@MOF-ArNH3) catalyst found that the presence of HPO43− in the
electrolyte had no adverse effect on the carbon-based active sites based
on the ORR mechanism. The single-cell MEA steady-state polarization
test demonstrated that the catalyst had complete immunity to phosphate
ion poisoning [235].
Designing an effective interface structure over a catalyst layer to
avoid Nafion® poisoning was proposed by Zhou et al. [236]. In their
approach, commercial Pt/C catalyst powder was dispersed in a mixture
of Nafion® and isopropanol, and the sulfonate could detach from
Nafion® forming porous shells on the surface of Pt after annealing at
300 ◦ C. The thin porous layer derived from Nafion® retained access for
protons and O2 but separated catalyst and Nafion®.
The anion adsorption of NPMCs is usually initiated by protonation,
which should be avoided. The XPS was used to assess nitrogen-modified
carbon fiber catalysts (NMCCs) with the same synthesis method and
16
EnergyChem 3 (2021) 100061
different heat treatment temperatures under acidic conditions, and the
analysis results showed that NPMC treated at a temperature of 800 ◦ C
(marked as NMCC-800) had two ORR active centers (pyridine N and
graphitization) N), while NPMC treated at 1100 ◦ C (marked as NMCC-
1100) had a single ORR active site (graphitized N) [45]. It was diffi­
cult for protons to combine with the graphitized N lacking of a lone pair
of electrons for protonation to deactivate, which made NMCC-1100 had
higher stability than NMCC-800. Pickling, as a common method, is often
used to remove unstable non-precious metals. However, Juan et al.
[237] developed a Fe/N/C catalyst by pyrolysis in NH3 and found that
the acid treatment could cause an order of magnitude degradation of
ORR activity, which was only 1/20 of the original catalyst. The study
confirmed that the activity of the catalyst was mainly determined by the
FeN4 sites, and the turnover frequency of ORR could be accommodated
by the subtle surface structure control. The pyridine N group on the
surface was protonated at pH=1 and then combined with the HSO3−
anion to neutralize the active site, causing the activity to decay. Sub­
sequently, the acid-washed catalyst was reheated for 1 hour in argon,
and the temperature was changed between 200 and 950 ◦ C. At 300 ◦ C,
the anion was removed to obtain the maximum recovery of FeN4 active
sites, and half of the performance loss was irreversible. The authors also
found that using 0.1 M HClO4 instead of 0.1 M H2SO4 for pickling could
give the similar results. Different from H2SO4, the chemical reaction
between HClO4− and carbon support at around 150–350 ◦ C led to the
formation of chloride ions that were still bound to the surface during the
reheating treatment.
Ciapina et al. [220] prepared a FeNC-dry-0.5 as a model catalyst that
almost had a complete immunity to the electrochemical interferences of
bulk Fe and studied its catalytic ORR performance at different concen­
trations of KCN and KClO4. They found that the ORR activity of some
FeNxCy groups was irreversibly poisoned by CN− anions (the Fe sites
binding CN− strongly), while others were only moderately poisoned,
and the degree of poisoning was proportional to the KCN concentration.
The analysis of the activity reduction after exposure to different cyanide
concentrations and the activity recovery after water washing showed
that there were two ORR active FeNxCy species. The competitive
adsorption of oxygen molecules and cyanide anions determined whether
cyanide poisoning was reversible. The ferrous ions in the FeNxCy part
showed three spin states: low, medium, and high, respectively, which
was consistent with the previous research [238]. It was believed that the
low-spin FeNxCy groups could adsorb cyanide reversibly, while the
medium-spin FeNxCy groups irreversibly adsorbed cyanide. They sup­
posed that maximizing the use of low-spin Fe populations could help
retain higher resistivity to prevent poisoning [238].
Zhong et al. [239] prepared graphitized layer coated Fe nano­
particles (G@Fe) with a definite hollow and encapsulated structure by
various methods including high-pressure progress [46]. They compared
poisoning of three representative catalysts, G@Fe, commercially avail­
able Fe/N/C, and molecular iron phthalocyanine (FePc) in 10 mmol L− 1
KSCN electrolyte solution. All of these three catalysts showed perfor­
mance degradation, supported by negative shifts of LSV and decrease of
half-wave potential value. However, the encapsulated iron showed the
lowest shift value (78 mV) than Fe/N/C (109 mV) and FePc(153 mV), as
shown in Fig. 10 [239]. The encapsulated catalyst was prepared by
sandwiching FePc with monolayer graphene (MLG) and Si substrate,
marked as MLG/FePc/Si [240]. Unlike the exposed FePc, this coating
structure helped the ORR active center to transfer electrons from the
internal metal to the coated carbon surface. The degree of graphitization
of the surface carbon layer and activation of the surface carbon layer
could inevitably protect the catalyst from SCN-poisoning. Besides,
compared with FePc, G@Fe and Fe/N/C revealed relatively better sta­
bility, confirming the positive effect of high-temperature pyrolysis on
relieving cyanide poisoning.
X. Wei et al. EnergyChem 3 (2021) 100061

Fig. 9. (a) Time-current curve of the contaminated Pt electrode surface immersed in 0.1 M NaOH solution. Reproduced with permission [43]. Copyright 2017,
Electrochemical Society, Inc. (b-d) Proposed models for selective adsorption of spectator species and reactants and schematic presentation of the availability of Pt
surface atoms for adsorption of O2 molecules on CN-free and CN-covered Pt(111) [44]. (b) Phosphorus/sulfuric acid anions cover the surface of Pt(111), preventing
O2 from contacting surface atoms. (c) CNad inhibits the adsorption of two anions and facilitates the contact of O2 with the surface. (d) CNad− Mþ(H2O)x clusters are
formed in alkaline solution, which can obviously inhibit the adsorption of O2. Reproduced with permission [44]. Copyright Springer 2010, Nature.

4.2. Poisoning by CO pollutant at anodes
At normal operating temperature (<80 ◦ C), a small amount of carbon
monoxide in the fuel can enter PEMFC anode and cause performance
loss. The metal nanoparticle catalyst is inevitably coordinated with CO,
creating a solid barrier to fuel adsorption and oxidation. With respect to
this, the poisoning characteristics, mechanism, mitigation strategies,
and theoretical model of Pt-based electrocatalysts in PEMFCs have been
evaluated and the research on catalysts with CO tolerance can be sum­
marized as follows.
4.2.1. Poisoning mechanisms
For fundamental understanding of CO poisoning, DFT calculations
can be used as a favorable evaluation method to obtain energetics and
reaction elementary pathways to obtain the microscopic mechanism of
CO influence on H2 oxidation at Pt surface, which can also provide a
reasonable basis for the design of new anode electrocatalysts. As H2 is
used as fuel, the competitive adsorption of CO with H2 and the block of
Pt site can be described as Eqs. (23)-(26):
Dissociative chemisorption:
H2 + 2Pt→2Pt − Hads
CO + Pt→Pt − COads
2CO + 2Pt − Hads →2Pt − COads + H2
Electrooxidation reaction:
2Pt − Hads →2Pt + 2H+ + 2e−
Reaction (23) is a rate-limiting step in the electrochemical oxidation
of hydrogen, requiring two adjacent exposed platinum sites to make the
reaction start. On the contrary, the Volmer reaction (Eq. (26)) is a
relatively fast discharge step. CO and H2 are competitively adsorbed on
the Pt site [241], providing a barrier for Pt to adsorb hydrogen. CO is
more easily adsorbed on the surface of Pt than H2 (the heat of adsorption
of CO on Pt is 134 kJ mol− 1, while H2 is 87.9 kJ mol− 1). Excepting CO
adsorption at the exposed Pt sites, the hydride sites of Pt also adsorb CO
molecules. In other words, the adsorption and/or resorption of CO de­
termines the final surface coverage.
CO adsorbed on Pt surface can be removed by further oxidation:
Pt + H2 O→Pt − OHads + H+ + e− (27)
Pt − COads + Pt − OHads →2Pt + CO2 + H+ + e− (28)
It is difficult for water to directly adsorb on the Pt sites poisoned by
CO. Reaction (27) occurs at 0.5 V versus NHE to form oxygen-containing
substances while CO is converted to CO2 by Reaction (28) at a higher
electrode potential (about 0.6 V versus NHE). After the partial oxidation
of CO, the remaining CO on the surface is rearranged to form a more
strongly bonded CO layer with different surface structures [242-243].
4.2.2. Contamination mitigation
(23)
Generally, the binary or ternary electrocatalysts with CO tolerance
are elaborated by alloying Pt with second and/or third metals. To
(24)
explain the change in the sensitivity of carbon monoxide to H2 oxidation
(25) induced by platinum alloying, both bifunctional mechanism[244] and
electronic model[244-245] were proposed. The bifunctional mechanism
indicates that the second alloying metal (M) initially activates water
(26) accompanying the formation of M-OHad on exophilic sites, and then CO
oxidation is completed with the assistant of adjacent co-adsorbed Pt
atoms Eqs. (29)-((30)): [244]

17
X. Wei et al. EnergyChem 3 (2021) 100061

1
Fig. 10. LSVs of G@Fe (a), Fe/N/C (b), FePc (c) with adding 10 mmol L − KSCN into the electrolyte solution and histogram of shifts of half-wave potential (d).
Reproduced with permission [239]. Copyright 2018, Science China Press.

M + H2 O→M − OHads + H+ + e− (29) Pt-related catalysts have been recognized. The electronic structure
modification of Pt could be interpreted as the electronic donation from
Pt − COads + M − OHads →Pt + M + CO2 + H+ + e− (30) CO2 to unoccupied metal orbitals or back-donation in an opposite di­
rection, which was mainly contributing to the stabilization of the co­
The bifunctional mechanism and ligand effect or combination of two
ordination bond [244]. The added elements could donate electrons from
was studied to explain the promotion of rationally engineering other
the Pt D-band to nearby promoter atoms, causing a downward shift in the
metals to Pt [246]. It was believed that the added M could facilitate CO
Fermi level, thereby increasing the vacant d orbitals and leading to
oxidation and removal by activating water to form well-dispersed oxy­
higher activity than pure Pt. Therefore, the electronic properties of the
gen-containing species (OH) and inducing electrosorption of OH on the
electrocatalyst nanoparticles could be modified, thereby reducing the
surface of PtM, making the onset potential of CO oxidation shifted to
strength of the Pt-CO bond and promoting hydrogen oxidation on
lower values. The formation of hydroxide could be intuitively reflected
Pt-based catalysts, resulting in the improved catalytic performance in
from the adsorption performance of the catalyst surface for water (the
the CO coverage area.
adsorption performance of oxygen). Fig. 11 shows metal-oxygen bond
Fig. 12 shows the anode overpotential with the addition of 100 ppm
dissociation energy in diatomic molecules as a function of group in the
CO as a function of Pt D-band vacancy (Fig. 12a) and D-band center
period.270 A systematic study showed that an outstanding CO-tolerance
(Fig. 12b) for a series of Pt–M electrocatalysts. It can be seen that PtMo/
catalyst could be achieved through alloying Pt with the second mental
C has a moderate CO tolerance, indicating that the bifunctional mech­
with the M-O bond energy similar to Pt-CO (590 kJ/mol). This supported
anism dominates the electronic performance. The CO tolerances of PtNi/
the hypothesis that Pt-Sn, Pt-Re, Pt-Mo, and Pt-Ru were ideal binary
C and PtCo/C are similar to that of PtRu, but the bifunctional mechanism
alloy catalysts because they were optimized by suitable components.
is not obvious, indicating the advantage of the electronic effect in the
The added metal to Pt could change the electronic structure of Pt by
situations of PtNi/C and PtCo/C [61].
weakening Pt-CO, promoting the activation of Pt-H2O and making it
possible to directly oxidize CO on the Pt site [247]. Through FEFF8
4.2.2.6. Pt-base alloy catalysts. Various catalysts were achieved by
calculation, in-situ X-ray absorption spectroscopy (XAS) analysis and
adding transition metals or certain oxidants to traditional Pt/C.
electrochemical test [61], the effect of the electronic effect of Pt and

18
X. Wei et al.
Although none of the catalysts developed could avoid suffering from the
damaging effects of CO poisoning on the performance of PEMFCs, many
alloying experiments were indicative of beneficial effects [248].
Ru is currently the most extensively researched and practically
applied for anti-CO poisoning catalysts. With the aim of enhancing the
durability and improving the combination with support, a Ti4O7-sup­
ported Ru@Pt core-shell catalyst was prepared by microwave pyrolysis
method [249]. In the presence of a certain content of CO, the durability
of the PtRu/C catalyst was unquestionably lower than that of the
Ru@Pt/Ti4O7 catalyst. Wang et al. [250] located a PtRu shell on the
outmost layer of PtNi/C core through an annealing process, created the
spontaneous segregation of Pt and Ru. The PtRu in the shell could pro­
tect Ni from dissolving in acidic medium. Although PtNi/C initially
showed high performance but got worse in the presence of 30 ppm CO.
Kim et al. [251] used carbonized polydopamine as the protective coating
of Pt-Ru. Ozone was employed effectively to convert the polydopamine
on the surface into CO2 and inhibit the sintering of the catalyst particles.
Modification of the catalyst surface by metal groups could promote
catalytic activity in some cases [251]. Dubau et al. [252] demonstrated
that Ru-modified Pt/C had a better CO tolerance than Pt/Ru alloys
prepared by co-reduced metal salts. They believed that two metals could
show real synergistic effects only when they interacted strongly.
The activity of PtSn on HOR is comparable to that of widely used Pt/
C. For example, PtSn/C was less sensitive to CO poisoning for which Sn
could donate electrons to Pt adsorption sites [62]. DFT calculations
[253] found that AuSn and PdSn catalysts were also less sensitive to CO
poisoning than Pt, but had no suitable activity for HOR. Herranz et al.
[254] used SnEt4 to control the surface modification of Pt/C to study
which crystal structure of the PtSn intermetallic phase could eliminate
CO poisoning. Both Pt3Sn with a face center cubic (FCC) phase and PtSn
with a hexagonal close packed (HCP) phase were developed. In inves­
tigation of methanol electrooxidation in the presence of CO, the current
density of Pt3Sn catalytic phase was found to be better than that of the
PtSn HCP phase.
For the Pt skin/PtCo core catalyst, alloy composition and particle size
were two important parameters that could be optimized with respect to
HOR activity and durability. Studies found that when the Co atom
content was 30–50%, HOR had the best CO poisoning resistance. In the
range of 2.2–3.3 nm, the relative activity had a weak dependency on the
particle size, which was inversely proportional to mass activity (MA).
When the particle size was 2.2 nm, the MA was the largest, which might
provide some reference for Pt-Co alloy research [248].
When the 100 ppm CO was induced to the hydrogen feed, PtMo/C
had the best CO tolerance as indicated by the bifunctional mechanism
[61]. The CO oxidation at a lower potential could be attributed to the
effective Mo (IV/VI) redox and the formation of hydroxides with
Fig. 11. Metal-oxygen bond dissociation energy in diatomic molecules as a
function of group in the period. Reproduced with permission [270]. Copyright
1997, Electrochemical Society, Inc.
19
EnergyChem 3 (2021) 100061
uniform distribution. The CO tolerance and short-term stability of
Pt0.8Mo0.2 alloy and MoO@Pt core-shell anode electrocatalysts were
also studied. Because of the influence of the residual surfactants during
the morphology-controlled synthesis process on the catalyst-ionomer
interface, the MoOx@Pt core-shell electrocatalyst could show high ac­
tivity in 1000 ppm CO of H2 but performed relatively poor in the MEA
test [255]. The ternary alloys formed by adding Mo into the commercial
PtRu/C and PtFe/C catalysts, and the quaternary alloy PtMoRuFe/C
showed better CO poisoning resistance [256,257].
Similar to Mo, W-containing materials can not be only used as cat­
alysts and auxiliary catalysts, but also used as catalyst supports [258].
The diversity of oxidation states of tungsten ranging from W1+ to
W6+can provide convenience for its application in various aspects. For
example, Dai et al. [259] studied Pt-W nanoalloys with different atomic
ratios from Pt3W to PtW2 and found that they had nearly 4 times
increased exchange current density and remarkable enhanced CO
tolerance than those of Pt/C and PtRu/C. Regarding W oxides, the H2O2
could cover the WO3 surface in Pt-WO3 catalyst, the Pt-WO3 electrode
showed active in the oxidation of CO and other poisons [260]. It was
observed that the changes of W oxidation state could provide the type of
oxygen required to remove CO [261]. Impregnation of Pt/C electrode
with WO3 could further increase the resistance to CO [262].
In addition to the above, the activity of the platinum-based electro­
catalyst modified by the (hydro)oxide species could be affected by the
content of the promoter. For example, the promotion for CeO2 to Pt/C
was somewhat dependent on CeO2 content while it was used as the
modifying agent [263]. The results showed that a moderate content of
cerium (20%) could effectively promote the oxidation of CO, while an
excessive percentage could reduce the activity via blocking the active
site of Pt. Cao et al. [264] exploited the atomic layer deposition (ALD)
method to selectively deposit Fe1(OH)x on silica-supported Pt nano­
particles and realized the precise control of the covering layers (denoted
as xcFe-Pt/SiO2). The mass-specific reaction rates were increased
initially with Fe loading but showed a decreasing trend when x>5,
indicating that this reaction occurred in Pt – FeOx interface. It should be
worth mentioning that non-noble metal oxide catalysts as CoO/C and
SnO2/C had the ability to oxidize CO at low potentials [265].
4.2.2.7. Catalysts support. The support materials can make a contribu­
tion to the dispersion of active components and the CO tolerance of the
catalyst. For example, He et al. [63] reduced Pt precursor on graphene
nanosheets (GNS) modified with perfluorosulfonic acid (PFSA). It was
found that the introduction of PFSA could increase the interaction be­
tween the uniformly deposited Pt and graphene. Furthermore, it could
also promote the absorption of CO on the catalyst and the formation of
active oxygen compounds of Pt-OH, which was conducive to oxidation
of CO to CO2, thereby improving the tolerance of CO. Narischat et al.
[266] studied the role of carbon support pores in catalyst CO tolerance.
The results showed that the highest CO tolerance could be obtained on
mesopores with modal size as large as 50 nm.
TiO2 as noncarbonaceous support showed high stability in acidic and
oxidizing environments [267]. However, its electronic conductivity was
not as high as carbonaceous supports, which could be improved by
adding heterovalent cations. Using an improved multi-step sol-gel-based
synthesis technology assisted with thermal annealing, Pt nanoparticles
loaded on Ti0.8Mo0.2O2-–C were synthesized by Vass et al. [268]
Compared with PtRu/C, the oxidation of CO on Pt/Ti0.8Mo0.2O2–C was
observed at a relatively lower potential (ECO, Onset = 50 mV).
Nilekar et al. [269] used both DFT calculations and CV tests to assess
the performance of Pt-M (M=Ir, Pd, or Ru) monolayer loaded on non-Pt
metals. According to their results, the catalyst could exhibit a better CO
tolerance and might be suitable for use for the anode side of PEMFCs.
DFT was used to calculate the ligand effects on Ir(111), Ru(001), and Pd
(111) surfaces deposited with a Pt monolayer and obtained a reduced
CO binding energy at 1/4 ML coverage (− 1.27, − 1.25, and-1.87 eV) in
X. Wei et al.
Fig. 12. Anode over-potential versus the Pt d-band vacancies of the indicated catalysts in the presence of (a) 50% molar ration CO2 in the hydrogen feed for current
densities of 0.25, 0.5, 0.75, and 1 Å cm− 2. (b) 100 ppm CO in the hydrogen feed for current densities of 0.25 and 0.5 Å cm− 2. Reproduced with permission [61].
Copyright 2013, Elsevier Ltd..
comparison to pure Pt(− 1.82 eV). The weak binding energy of CO was
attributed to the repulsive interactions between adsorbed CO on
designed surfaces according.
4.3. Poisoning by SO2 pollutant at cathode
Air pollutants can enter predominantly from the PEMFC cathode,
causing performance degradation. In particular, sulfur-containing spe­
cies have the most notorious effect. They can occupy the active sites and
obstruct ORR, leading to inactivated Pt and resulting performance
degradation [271]. It was reported that when the coverage of
sulfur-containing species reached 14%, the catalytic ORR activity loss
could be as high as 95% [272].
4.3.1. Poisoning mechanisms
The adsorption mechanism of SO2 has been extensively studied,
suggesting that sulfur chemisorbs as a SOx species, according to Reaction
(31): [31-32]
Pt + SO2 →Pt − SOx
In the laboratory, Na2SO3 was generally used to decompose for
producing SO2 to simulate its poisoning effects [273-274]. If the elec­
trode potential was ranging from 0.05 to 0.4 V, sulfur could convert from
other valence states to zero valence state. When the potential reached to
0.8~1.4 V, the sulfur species could oxidize to the form of SO42− . The
actual oxidation state and properties were actually controversial and
needed to confirm when the potential was between 0.4 and 0.8 V.
Although numerous researches hold the view that sulfur species exist in
the form of zero-valent sulfur [274], sulfur with a valence of − 2 valence
was existed as a Pt sulfide.
As observed by Park et al. [275], the impact of sulfur-containing
species was related to sulfur coverage. When sulfur coverage was low
(~0.16 layer), a small amount of sulfide adsorption could not reduce
ORR but promoted it, which was identified by the higher half-wave
potential of ORR on the Pt surface with sulfur modification. However,
too much sulfur could make such an enhancement disappeared. Whether
the O = O bond was broken is usually determined by observing whether
H2O is produced by a 4-electron reaction or H2O2 is produced by a
2-electron reaction. As the coverage of sulfide is increased, more H2O2
can be produced, indicating that the effect of sulfur adsorption on
electrocatalyst was electronic/chemical interaction instead of simple
physical shielding. However, the ORR enhancement recognized in the
presence of an appropriate amount of sulfur was likely due to a
compromise between competing factors. In contrast, too much coverage
on the Pt site can weaken the O-Pt interaction, making the O = O bond
difficult to dissociate and leading to the generation of H2O2. The low
EnergyChem 3 (2021) 100061
sulfide coverage has a weak effect on the adsorption of O on Pt, leading
to the dissociation of O2 on the surface and resulting in the enhanced
ORR activity [276].
4.3.2. Contamination mitigation
After a MEA of PEMFC was inactivated by sulfur, the oxidation of
sulfur adsorbed on Pt to water-soluble sulfate at a potential greater than
0.8 V could be carried out to remove sulfur electrochemically from the
surface to restore PEMFC performance [277-279]. With the desorption
of sulfate from the electrode surface, the catalyst performance could be
partially restored. The removal of sulfur along with the formation of
sulfate could also be accomplished with the assistant of a redox process
with Pt oxide (or Pt hydroxide) and water [280]. One possible oxidation
mechanism is as follows [65]:
Pt − S0 + 4H2 O→SO2−4 + 8H+ + 6e− + Pt(x) (32)
PtO + Ptn − SO2 + H2 O→SO2−4 + 2H+ + (n + 1)Pt (33)
y
(31) PtOy + S0∗ → SO∗2 + Pt (34)
2
SO∗2 + PtO→Pt − SO3 (35)
The slow rate of performance recovery could be traced to the for­
mation of intermediate species, like HSO3+, Sx, and SO during oxidation
[281]. According to Fu et al. [282], the scanning potential played an
important role in the severity of the poisoning. Awad et al. [283].
compared the effects of two potential scanning modes, a narrow po­
tential range (NPR, 0 to 0.8 V vs. Ag/AgCl/KCl (sat.)) and a wide po­
tential range (WPR, − 0.2 to 1.3 V) on the recovery of poisoned
electrodes. They found that the WPR mode was more effective in
recovering poisoned cathode than the NPR mode, and analogous current
recovery in polycrystalline Pt (poly-Pt) electrode was observed. The
removal of sulfur from Pt catalyst required a high potential to adsorb the
required O/OH to assist in the oxidation of SO2. The effect of such a
process was inferior on the edge and (100) plane but effective on the
(111) plane [284].
Compared to CO, SO2 has a more serious impact on Pt-based cata­
lysts, because the adsorption of SO2 on the surface of Pt can be multi­
layered. This requires a more positive potential, even greater than 1.5 V
(vs. RHE), to oxidize the adsorbed SO2 [272]. This electrode potential is
much higher than the working potential of PEMFC cathode (0.6–0.9 V).
Therefore, it is necessary to prepare a catalyst with anti-poisoning
ability in the actual application process. The Pt-OH and Pt-S bonds
can be weakened by the metal ligand in the alloy catalyst PtM, which
does not facilitate -OH adsorption but is conducive to the oxidation of
20
X. Wei et al.
SO2 to SO3/SO4 at a relatively low potential. The SO2 can be cleaned by
circulating PtM alloy cathode in the air at about 0.9 V, which can
remove more sulfur species than pure Pt [284].
As identified, SO2 could not be adsorbed on the Ru/C catalyst. Based
on this observation, the catalyst can be obtained by incorporating fea­
tures of Pt with high catalytic activity and Ru with strong SO2 tolerance
to achieve these two advantages. Experimental studies have also
confirmed that Ru can reduce the adsorption energy of SO2 by changing
the electronic structure according to the bifunctional mechanism of Pt in
the initial stage, and accelerate the oxidation of toxic SO2 to form SO42−
in the subsequent reaction [64]. Similar to Ru, theoretical and experi­
mental studies on other alloy catalysts with SO2 tolerance such as Pt3Co
[285], Pt3Ni [286], and PtMo[287] have also been carried out, ener­
getically proving their role in inhibiting poisoning. For example, a
minimum of 8 scans were required to remove sulfur from Pt/VC, while
only 3 scans were required for Pt3Co/VC. Recent studies demonstrated
that the performance of Pt3Co/VC was not only faster but also easier to
recover. The Pt3Co/VC cathode could be recovered completely while
Pt/VC cathode was recovered only 57% of its initial performance (0.1 A
cm− 2) when the electrode polluted in 1 ppm SO2 and cycled between ~
0.9~0.5 V. The platinum load was also liable for the properties of the
alloy catalysts. As evidenced, under SO2 poisoning, 30 wt.% Pt3Co/VC
catalyst was more sensitive than 50 wt.% Pt3Co/VC although the ac­
tivity was easier to recover [288].
The local oxygen concentration on the catalyst surface can be
adjusted by switching Ce between the oxidation state (Ce4+) and the
reduction state (Ce3+) [289]. Xu et al. [65] used CeO2 as a substrate on
which Pt particles were deposited to prepare a carbon-supported and
Pt-modified CeO2 catalyst. The abundant Pt-CeO2 interface facilitated
the migration of oxygen, reduced the coverage of SO2, and made the
main adsorption state of SO2 on the Pt surface changed from SO2
multilayer to SO4*. Studies also showed that the catalysts with CeO2
content of 10 and 20 wt.% had the best performance. Different from
calcination at high temperature to obtain crystalline cerium, modifying
Pt/C with 2 wt% amorphous CeO2 at low temperature could also in­
crease the diffusion and overflow of oxygen through its high concen­
tration of surface vacancies to obtain SO2 resistant catalysts [290-291].
Similarly, The Pt-MoO3/C composite obtained by depositing MoO3 on
carbon and then nucleating Pt nanoparticles on the surface of MoO3
exhibited anti-poisoning properties similar to PtMo predicted by DFT
[287,292].
Research on the effects of different supports on SO2 poisoning had
shown that Pt/G (G: graphene) had a smaller sulfur coverage area
compared with Pt/C [293]. The membrane electrode of the Pt/G catalyst
was completely recovered by the continuous polarization method,
which achieved better results compared to the traditional Pt/C catalyst.
The positive effect could be ascribed to the indirect removal of the sulfur
ions from Pt by removing the OH− ions. Since carbon tended to increase
the corrosion of the catalyst, the mesoporous Pt particles without sup­
porting materials were conducted by the hard template method [294].
The electrochemical assessment showed that the total sulfur coverage of
Meso-Pt was 38% of ECSA, and the Pt/C was 58%, which proved the
valuable SO2 resistant catalyst.
4.4. Other pollutants
Other pollutants entering PEMFCs from cathode air and anode fuel,
including but not limited to HN3 [295-298], H2S [299-300], CO2 [301],
and COS [277], etc., can also poison PEMFC catalysts although the
mechanisms of some of them are not very clear yet. Among them, CO2
and NH3 may come from both air or fuel. In addition to CO, H2S is a
typical pollutant in the fuel reforming process and the influence of ni­
trogen oxides (NO2/NO) as air pollutants cannot also be ignored.
4.4.1. Poisoning mechanisms
It is speculated that the combination of ammonium and the adsorbed
21
EnergyChem 3 (2021) 100061
OH intermediate could produce a nitrogen-comprising adsorbent, which
might enhance the surface binding of ammonium and OH, thereby
increasing the electrode overpotential. Another hypothesis is that
ammonia on the Pt electrode could form a blocking surface poison NO in
the form of an adsorbent at low potential (gas-phase NO at a formation
potential higher than 1.2 V) [302]. Under acidic conditions, ammonia
could be oxidized [303] by Pt/C or react with water or protons to form
ammonium ions (following the ammonia-ammonium balance (Reaction
(36)), which might be further transported to the cathode [304]. The
presence of NH3+ could affect the performance of PEMFC by reducing
the proton conductivity of the Nafion® membrane [305], increasing the
overpotential of the half-cell charge transfer, and affecting the ECSA of
the catalyst [297] [306].
NH3 (aq) + H+ ⇌NH+
4 (aq) K b = 1.96∗10
9
(36)
CO2 may affect PEMFC performance by diluting hydrogen (Reaction
(37)) and reducing it to CO (Reaction (38)) in the presence of Pt:
[307-308]
2Pt + CO2 − Hads →Pt − COads + H2 O + Pt (37)
2Pt + CO2 + H+ + e− →Pt − COads + Pt − OHads (38)
The S-containing species adsorb to the active center of the catalyst,
occupying the polyatomic center, preventing the reactants (including
oxygen and hydrogen) from adsorbing on the surface of the catalyst.
The effect of a significant number of other airborne contaminants,
organic species (e.g. methyl acetate, acetaldehyde, etc.) on PEMFC
catalysts have been documented, but comprehensive mitigation strate­
gies need to be further studied and developed [309].
4.4.2. Contamination mitigation
The effect of reactivity of CO2 and the adsorbed reducing agents on
PEMFC performance were studied. It was found that the CO2 could be
easily reduced at the Pt/C, Pt0.5Ru0.5/C, and Pt0.4Ru0.6/C electro­
catalysts at 0.06–0.30 V (vs. DHE) at which the anode reaction of the
PEMFC took place [301]. The Pt0.4Ru0.6/C obtained by controlling the
content of Ru was the most suitable anode catalyst, which could easily
desorb CO2 reductant [301]. The reduction of CO2 on PtWO3/C led to
the formation of adsorbents on the Pt site, which was CO. At 0.1 V, the
accumulation rate of adsorbate on PtWO3/C was lower than that on pure
Pt/C. When the PtWO3/C electrode was exposed to a CO2 saturated
solution for a long time, the Pt site and the adsorbate might be
completely poisoned at room temperature [310].
In general, the tolerance of H2S is related to the catalyst loading,
higher anodic catalyst loadings are more tolerant toward catalyst con­
taminants [300]. Lopes et al. [311-312] conducted sulfur poisoning
experiments on Pd85Cu15/C catalyst, and found the relative relieve of
H2S was dependent on the concentration of Cu. PEMFC overpotential
and durability tests showed that the sulfur resistance of the catalyst
could be enhanced with increasing of copper atom content. Pre-leaching
the catalyst in hot sulfuric acid solution could remove oxides, incom­
pletely alloyed copper, and most of the copper from the surface, and
generated a catalyst with low H2S tolerance [311].
As mentioned above, the modification of Pt surface with cyanide
could produce some isolated Pt atoms, preventing the damage of anions
such as PO43− and SO42− . This modification using functional molecules
to construct local steric hindrance of noble metal surface active sites to
prevent the absorption of toxic substances such as CO and H2S without
affecting H2 is a promising but challenging method to solve the
poisoning reaction of PEMFC anode [66]. The strong covalent interac­
tion between CO/H2S and the Pt surface is capable to resist modified
functional molecules. The diameter of CO and H2S molecules is as low as
2–5A, allowing them to be adsorbed on the isolated metal atoms created
by the molecular structure. Therefore, the interaction between the mo­
lecular structure and the surface needs to be strong enough to compete
X. Wei et al.
with CO/ H2S. The organic molecule 2,6-diacetylpyridine (DAcPy) can
be fixed on the surface of Pt to construct a coronal molecular structure.
The pyridine ring of DAcPy was tilted, providing protection for the Pt
atom under the ring. This highly restricted space is only suitable for
smaller volumes of H2, but not for larger volumes of H2S and CO. DAcPy
can be strongly adsorbed on Pt surface through tridentate coordination
(two Pt-C bonds and one Pt-N bond), which weakened the adsorption of
CO and H2S [66].
Non-noble metal catalysts for ORR appear to have better tolerance to
pollutants. CNx catalysts were prepared by cracking carbon and nitrogen
sources (e.g., acetonitrile) on the growth medium [313]. Generally, the
support is an oxide (aluminum oxide, silicon, magnesium oxide), either
used alone. or doped with a transition metal (Fe or Co). These materials
are then washed with strong acids or strong bases to obtain graphitic
carbons with different nano-geometry and high nitrogen content. The
remaining transition metals are encapsulated in C and do not interact
with CO, H2S, or CNx. Some studies have even shown that H2S treatment
not only had no negative effects on CNx catalyst but also improved its
performance [313]. Fe/C/N catalysts are usually prepared by supporting
macrocycles on carbon supports, which have a metal center. Some of
these materials undergo pyrolysis in an inert or nitrogen-containing
environment, but there are no washing steps to remove metals during
the preparation process. DFT calculations confirmed that the Fe/N/C
cathodes exposed to 2 and 10 ppm SO2 did not cause any performance
decline and current redistribution due to the weak absorption of SO2 by
Fe-NxCy sites, but the performance loss caused by NO2 was obvious. The
adsorption energy of NO2 and NO was greater than the adsorption en­
ergy of molecular oxygen, which corresponded to the observed
poisoning [314].
A FeNx/C catalyst derived from polymetaphenylene diamine
(PmPDA-FeNx/C) was reported. The ORR activity of PmPDA-FeNx/C
was not sensitive to CO and NOx, but could be significantly inhibited
by halide ions (e.g. Cl− , F− and Br− ) and low-valence sulfur-containing
species (e.g. SCN− , SO2 and H2S) [315]. They also carried out DFT
calculations on transition metal composite carbon materials and found
that these materials had pleasurable contamination resistance. When the
iron clusters were encapsulated in a C60 cage, a Fen@C60 (n = 1–7)
catalyst with a larger energy gap between the highest occupied molec­
ular orbital and the lowest unoccupied molecular orbital than C60 was
synthesized. Fen@C60 catalyst had superior poisoning resistance to SO2,
H2S, CO, NO, NH3. This was due to the unstable physical adsorption
between these species and the Fen@C60, which was completely
different from the easily poisoned Pt catalyst [316]. Through DFT cal­
culations, several FeSx/C catalysts, e.g., FeS2/C, FeS3/C, FeS4/C, and
FeS6/C, were selected for ORR. As identified, O2 molecules were first
chemically adsorbed on FeS2 active sites in a stable side-on mode, and
then gradually reduced to H2O through a 4e− pathway, maintaining its
original planar structure. In addition, compared with Pt(111) surface,
FeS2/C was also resistant to impurities such as sulfur compounds (SO2,
H2S), carbon compounds (CO), and nitrogen compounds (NO, NH3).
Unfortunately, although non-noble metal catalysts have universal
poisoning resistance, the rapid degradation and ionomer oxidation can
lead to a decrease in the performance during the cycle process.
Despite the low levels of pollutants in the air, catalysts with tolerance
ability should also be thoroughly studied. Understanding and clarifying
the mechanisms by which they affect PEMFCs can help prepare miti­
gation strategies to minimize their destructive effects.
Conclusion
Various structures and preparation methods enable some catalysts
for PEMFCs to reach or exceed the required performance (US energy
goals). However, performance degradation induced by catalyst
contamination is the main challenge of PEMFCs. Among them, the re­
sidual ions or auxiliaries in the catalyst preparation process, oxygen-
containing intermediates generated in the ORR process, decomposition
22
EnergyChem 3 (2021) 100061
products of the catalyst in a highly acid medium, fuel impurities, and air
pollutants are responsible for the performance degradation. We have
herein systematically analyzed possible harmful impurities from the
aspects of catalyst preparation and use, identified the mechanisms by
which PEMFCs are affected and some valuable mitigation methods, and
summarized the up-to-date progress in the studies of pollutants with
emphasis on the conventional and advanced methods for fabricating
novel electrocatalysts or manipulating the M-support interaction to
obtain mitigation approaches. In view of the impurities or residues
generated in the catalyst preparation process, the selection of more
stable or harmless precursors/auxiliaries, the control of the catalyst
structure (for example, the Pt(110) crystal plane has better anti-
poisoning ability than Pt(110) crystal plane), and appropriate post-
processing methods are reviewed. The impurities induced by the
decomposition of the catalyst body or the formation of intermediate
products during the use of the catalyst should be avoided by preparing a
more stable alloy catalyst or a C-metal oxide composite support. As for
the impurities brought by fuel and gaseous pollutants, in addition to
preparing catalysts with anti-poisoning ability, it is also possible to
prevent impurities from entering the PEMFCs by preparing purer
hydrogen or manufacturing excellent air purifiers. The major impurities
and corresponding mitigation strategies are summarized in Table 1.
We believe that this review will benefit peer researchers by avoiding
the use of unstable metals/supports, removing residual ions or organic
solvents, and preparing catalyst resistant to fuel/air pollutants to meet
the requirements of the new-generation electrocatalysts.
In developing the mitigating strategies for overcoming catalyst
degradation of PEMFCs, there are still several technical challenges as
summarized as follows:
(i) PtM intermetallic catalysts with special morphology often get
better performance. However, the changes of Pt and PtO chemical
states induced by the constant changes of the cell potential during
operation make the surface structure difficult to maintain
stability.
(ii) Some strategies for mitigating catalyst degradation are limited to
the laboratory level (e.g., the effects of IL on oxygenated species)
and lack experimental validation for MEA level. Some mitigation
ideas or strategies are even contrary to the practical application.
(iii) Studies on the poisoning resistance of catalysts often focus on a
single substance, and more comprehensive and in-depth studies
are needed to simulate the tolerance of multiple poisons in
practical application.
To overcome the challenges in catalyst degradation, the following
several research directions may be proposed as follows:
(i) The doping of the third metal or nonmetallic element can further
stabilize the alloy structure and alleviate the degradation of the
morphology control catalyst.
(ii) Except for rotating disk electrode technique, cell test was further
required to confirm activities. It is possible to combine the opti­
mization of catalyst composition with the control system of
limiting potential variation to find suitable conditions for the use
of materials.
(iii) Future work needs to combine calculation and experimental data
to simulate a more accurate pollution/poisoning model, so as to
find a better way to alleviate performance degradation.
Author contributions
Ruzhi Wang and Jiujun Zhang proposed the topic of the review. Xin
Wei, Wei Zhao, Ge Chen, Mao-Rong Chai, Lei Zhang and Jiujun Zhang
contributed to investigating the literature and wrote the manuscript. All
the authors discussed and revised the manuscript.
X. Wei et al.
Declaration of Competing Interest
The authors declare no conflict of interest.
Acknowledgments
This work was financially supported by the National Natural Science
Foundation of China (NSFC) (Grant No. 11774017), the Beijing
Municipal Science and Technology Foundation (Grant No.
Z191100004719006).
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28
X. Wei et al.
Wei Zhao is a director at Research Department of catalyst,
State Power Investment Corporation Hydrogen Energy Com­
pany. He received his Ph.D. from Beijing University of Tech­
nology in 2012. His-main research interests include polymer
electrolyte fuel cell, water electrolysis, and catalysis.
Ge Chen received his B.S., M.S. from University of Science &
Technology, Beijing in 1997 and 2000, respectively, and Ph.D.
from Beijing University of Technology in 2010. He is now a full
professor in the College of Environmental and Energy Engi­
neering, Beijing University of Technology. His-research group
interests are focused on developing novel electrocatalysts to­
wards energy conversion.
Maorong Chai is a technical director at State Power Invest­
ment Corporation Hydrogen Energy Company. He received his
Ph.D. degree from Kyushu University in 1994. His-main
research interests include hydrogen energy, fuel cell, catal­
ysis, and petrochemistry.
29
EnergyChem 3 (2021) 100061
Lei Zhang is a Research Council Officer at National Research
Council of Canada Institute for FuelCellInnovation. She
received her first MSc majoring in Materials Chemistry from
Wuhan University. China in1993 and her second MSc in Ma­
terials/PhysicalChemistry from Simon Fraser University Can­
ada in 2000. Ms. Zhang’s main research interests include PEM
fuel cell electrocatalysis, metal-air batteries and
supercapacitors.
Jiujun Zhang is a professor in College of Sciences/Institute for
Sustainable Energy at Shanghai University, a former Principal
Research Officer (Emeritus) at National Research Council of
Canada (NRC). Dr. Zhang received his B.S. and M.Sc. in Elec­
trochemistry from Peking University in 1982 and 1985,
respectively, and his Ph.D. in Electrochemistry from Wuhan
University in 1988. Dr. Zhang’s expertise areas are electro­
chemistry, electrocatalysis, fuel cells, batteries, super­
capacitors, water/CO2 electrolysis.