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Platinum single-atom catalysts: a comparative

Cite this: Catal. Sci. Technol., 2019,
review towards effective characterization
9, 4821
Qing Liu *a and Zailei Zhang *b
Published on 15 July 2019. Downloaded by Virginia Tech on 3/24/2021 3:53:34 PM.

Received 26th May 2019,
Accepted 14th July 2019
DOI: 10.1039/c9cy01028a
rsc.li/catalysis
Single-atom catalysis is a new frontier in the heterogeneous catalysis field due to its high activity and selec-
tivity for various catalytic reactions. However, decades ago, single-atom catalysts could not be clearly visu-
alized and characterized due to limitations associated with instrument resolution. In recent years, with the
rapid development of characterization techniques, high-resolution scanning tunneling microscopy (STM),
high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), extended X-ray
absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), diffuse reflectance infrared
Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and other characteriza-
tion techniques have been used to accurately represent single-atom catalysts. In this review, we discuss in
depth these characterization techniques for Pt single-atom catalysts and focus on Fourier transformed
EXAFS spectroscopy to study the coordination environment of Pt–M (M = Cl, O, C, N, S, Pt, Cu, Pd, Ni, Fe)
for atomically dispersed Pt catalysts on diverse supports. We believe that this review will lead to better un-
derstanding of the effective characterization of Pt single-atom catalysts and promote further research on
Pt single-atom catalysis in the future.

1. Introduction years as a new frontier in the heterogeneous catalysis field.3

Single-atom catalysis is catalysis by a “single-atom catalyst”
(SAC), which is a catalyst that contains only isolated single
atoms dispersed on a support.1,2 This term was first proposed
in 2011 and has attracted considerable attention in recent
a
Key Laboratory of Low Carbon Energy and Chemical Engineering, College of
Chemical and Environmental Engineering, Shandong University of Science and
Technology, Qingdao, Shandong, 266590, China. E-mail: qliu@sdust.edu.cn
b
CAS Center for Excellence in Nanoscience, Beijing Institute of Nanoenergy and
Nanosystems, Chinese Academy of Sciences, Beijing 100083, China.
E-mail: zhangzailei@binn.cas.cn
The most important structural property of SACs is the iso-
lated metal particles at the single-atom level dispersed on the
support, which not only maximizes the atomic efficiency of
the metal but also provides more uniform, well-defined active
sites compared with common nanocluster and nanoparticle
catalysts that contain various kinds of active sites.4–15 A vari-
ety of noble16–19 and transition metals20–22 can be prepared
as SACs over various supports using different preparation
methods, such as the wetness impregnation method, atomic
layer deposition method, high-temperature vapor transport
method, galvanic replacement method and photochemical

Qing Liu started his Ph.D. stud-
ies in Materials Science in 2012
at the Institute of Process Engi-
neering, Chinese Academy of Sci-
ences in China under the super-
vision of Prof. Fabing Su. After
completing his studies in 2015,
he became a professor at Shan-
dong University of Science and
Technology. His research focuses
on energy catalysis and porous
materials.
Qing Liu
Zailei Zhang is an assistant pro-
fessor at Beijing Institute of
Nanoenergy and Nanosystems,
Chinese Academy of Sciences.
His research focuses on single-
atom catalysis and energy
storage.
Zailei Zhang

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Fig. 1 (a) High-resolution STM image of a 0.01 ML Pt/Cu(111) single atom alloy surface. Scale bar, 1.5 nm. Adapted with permission from ref. 57.
Copyright 2018 Macmillan Publishers Limited, part of Springer Nature. (b) High-resolution STM of 0.5% monolayer Pt coverage on ‘29’ copper ox-
ide after adding CO and annealing at 250 K. Scale bar: 5 nm. Adapted with permission from ref. 56. Copyright 2018 Macmillan Publishers Limited,
part of Springer Nature.
method.14,23–32 Among these, Pt SACs have been prepared
using different methods and applied in many reactions, in-
cluding hydrogenation,33,34 dehydrogenation,35 CO oxida-
tion,36 the water–gas shift,37,38 NO reduction,39 photo-
catalysis,40 selective electrochemical reactions,41,42 the
hydrogen evolution reaction (HER),43,44 benzene combus-
tion,45 catalytic reforming,46 diboration of alkynes and al-
kenes,47 and the Suzuki coupling reaction.48
Characterization techniques are of great importance for
SAC research because the supported single-atom level active
species cannot be observed by conventional characterization
methods due to limitations associated with instrument reso-
lution.49 Considerable efforts have been made worldwide to
develop characterization techniques for SACs, and great prog-
ress has been made in recent years. Due to these powerful
characterization techniques, it has been possible to obtain di-
rect observations and analyses on the structural transforma-
tion of different types of SACs to provide insight into their
physical–chemical essence and the mechanism of the pro-
cess. In the year 2010, Flytzani-Stephanopoulos et al. reported
that partially oxidized Pt–alkali–OxIJOH)y in the presence of
atomically dispersed Pt species was the active site for the
low-temperature water–gas shift reaction, and HAADF-STEM
images showed that subnanometer Pt clusters and atoms
were abundant, with a proportion as high as 65%.7 In 2011,
Zhang and co-workers synthesized pure Pt1/FeOx SACs with
excellent stability and high activity for CO oxidation and
presented several characterization techniques for atomically
dispersed Pt catalysts.3 In the years 2012 and 2013, the
Flytzani-Stephanopoulos group and the Zhang group
reviewed SACs for heterogeneous catalysis.14,50 Since then,
many researchers have prepared various Pt SACs and charac-
terized them using various techniques, such as high-
resolution STM, HAADF-STEM, EXAFS, XANES, DRIFTS, XPS,
temperature-programmed reduction (TPR), H2–O2 titration,
and inductively coupled plasma spectrometry (ICP).
Various noble metals (Pt, Au, Ru, etc.)16–19 and transition
metals (Cu, W, Ni, etc.)20–22 as well as non-metal51 single-
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atom catalysts have been reported, and their systematic char-
acterization has provided crucial evidence of the successful
construction of these single-atom structures. Considering the
wide application of Pt SACs as well as the universality of the
related characterization techniques for different types of
SACs, we will only focus on Pt SACs in this review; the tech-
niques discussed can also be applied to other metal SACs.
Here, we provide an overview of the recent developments and
future outlook of characterization techniques for Pt SACs,
which will be helpful to achieve better understanding of the
effective characterization of atomically dispersed Pt catalysts.
2. Characterization techniques for Pt
single-atom catalysts
In order to systematically characterize Pt SACs, various tech-
niques have been used, such as high-resolution STM,
HAADF-STEM, EXAFS, XANES, DRIFTS, XPS, temperature-
programmed reduction (TPR), H2–O2 titration, and induc-
tively coupled plasma spectrometry (ICP). These techniques
can be classified into two categories: STM, HAADF-STEM and
EXAFS can be classified as ‘techniques to provide direct evi-
dence’ because they provide direct evidence of the successful
construction of SACs; meanwhile, XANES, DRIFTS, XPS and
other techniques reveal the necessary physicochemical prop-
erties of SACs and can be denoted as ‘techniques to provide
indirect evidence’.
2.1 Characterization techniques to provide direct evidence
2.1.1 STM. A scanning tunneling microscope (STM) is an
instrument used to image surfaces at the atomic level with a
lateral resolution of 0.1 nm and a depth resolution of 0.01
nm (10 pm). Individual atoms within materials can be rou-
tinely imaged and manipulated by conducting tips under
many working conditions, such as ultra-high vacuum, air, wa-
ter, and various other liquid or gas atmospheres at tempera-
tures ranging from near 0 to over 1273 K.52 STM can be used
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Fig. 2 (a) HRSTEM Z-contrast image of Pt on γ-Al2O3. Some of the clusters can be seen to be resolved into single atoms. Adapted with permission
from ref. 24. Copyright 1996 The American Association for the Advancement of Science. (b) Pt single atoms are seen to be uniformly dispersed on
the FeOx support and occupy the exact positions of the Fe atoms. Adapted with permission from ref. 3. Copyright 2011 Macmillan Publishers Lim-
ited, part of Springer Nature. (c) Densely and homogeneously dispersed Pt single atoms on mesoporous carbon. Scale bar, 2 nm. Adapted with per-
mission from ref. 61. Copyright 2017 Macmillan Publishers Limited, part of Springer Nature. (d) Atomic-resolution HAADF-STEM images for Pt-
GDY1. Adapted with permission from ref. 62. Copyright 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (e) Representative aberration
corrected-TEM images of Pt/CeO2. Adapted with permission from ref. 63. Copyright 2017 The American Association for the Advancement of Sci-
ence. (f) High-resolution STEM Z-contrast images of used 0.2% Pt/α-MoC catalyst. Adapted with permission from ref. 64. Copyright 2017 Macmil-
lan Publishers Limited, part of Springer Nature. (g) HAADF-HRSTEM image of Pt@MCM-22, where the two enlarged images show the square re-
gions marked in green (#1) and yellow (#2). In these two areas, several single atoms have been highlighted. Scale bar, 2 nm. Corresponding
intensity profiles obtained on the two zoomed areas. Adapted with permission from ref. 65. Copyright 2017 Macmillan Publishers Limited, part of
Springer Nature. (h) HAADF-STEM image of 0.2Pt/m-Al2O3–O2, with enlargements of the regions marked by a circle and square and line-scanning
intensity profiles obtained for the enlarged areas. Scale bar, 2 nm. Adapted with permission from ref. 34. Copyright 2017 Macmillan Publishers Lim-
ited, part of Springer Nature.

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Fig. 3 (a) EXAFS wavelet transform (WT) for the k 3-weighted EXAFS signal. Adapted with permission from ref. 74. Copyright 2018 The American
Association for the Advancement of Science. (b) WT spectra of Pt1δ+/TiO2 and Pt foil. Adapted with permission from ref. 75. Copyright 2018
American Chemical Society.
in modern surface science to explore conducting surfaces
and the adsorption processes on these surfaces.53,54 High-
resolution STM is able to detect single atoms, which opens
new aspects of science on the smallest scale currently accessi-
ble in surface science.55,56 For example, using high-resolution
STM, the Flytzani-Stephanopoulos and Sykes groups clearly
observed Pt single atoms on a Cu surface (Fig. 1a).57 In addi-
tion, individual adsorbates, including single molecule chem-
istry, can be observed by STM. In the above work,57 pure
methyl groups formed via pyrolysis of azomethane and some
individual iodine atoms to mark positions were observed to
be absorbed on Pt or Cu atoms. Furthermore, STM imaging
allows visualization of the atomic-scale structure of the sur-
face around the Pt sites during CO oxidation progress at low
temperatures (Fig. 1b), and a surface composed of Pt single
atoms with adsorbed CO can be clearly observed.56
2.1.2 HAADF-STEM. Several decades ago, due to limitations
associated with instrument resolution and the stability of ma-
terials under electron beams, the atomic level dispersion of Pt
was difficult to distinguish.58 With the rapid development of
transmission electron microscopy (TEM) techniques, high-
angle annular dark-field scanning transmission electron
microscopy (HAADF-STEM) can provide intuitive evidence for
the formation of SACs due to Z (atomic number)-contrast be-
tween the active metal atoms and their supports; it has been
widely used in single-atom catalysis.59,60 HAADF-STEM pro-
duces an annular dark field image formed by very high angles
which is highly sensitive to variations in the atomic number of
atoms in the sample (Z-contrast images). The higher the Z
values of the elements, the more electrons are scattered at
higher angles due to greater electrostatic interactions between
the nucleus and electron beam. As a result, a higher Z leads to
a brighter image. In 1996, some Pt clusters on a γ-Al2O3 sup-
port were observed by Pennycook et al. to be single Pt atoms
from an HRSTEM Z-contrast image (Fig. 2a).24 Importantly,
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Pt1/Fe2O3 catalysts that consisted of only isolated Pt single
atoms anchored to the surface of iron oxide were seen in the
HAADF-STEM images (Fig. 2b).3 Recently, densely and homo-
geneously dispersed Pt single atoms on mesoporous carbon
were observed by Wu et al. (Fig. 2c).61 The HADDF-STEM im-
ages for both Pt-GDY1 and Pt-GDY2 display isolated bright
dots (Fig. 2d), which can be attributed to the heavy Pt atoms
anchored on graphdiyne.62 Wang et al. synthesized single-
atom Pt/CeO2 catalysts for low-temperature CO oxidation, and
the atomic dispersion of Pt2+ was maintained on both Pt/
CeO2_S and Pt/CeO2 even after steam treatment at 800 °C, as
evidenced by aberration-corrected-STEM (Fig. 2e).63 Fig. 2f in-
dicates that a high density of atomic-level dispersed Pt species
was maintained over the fcc structure of the α-MoC surface for
the used Pt/α-MoC catalysts.64 Fig. 2g shows the Pt atoms in
Pt@MCM-22 based on the contrast of the intensity profiles;
the 12 member-ring sub-units of the external cups in MCM-22,
with diameters of approximately 0.7 nm, can be clearly seen
from the view of the c-axis.65 Zhang et al. demonstrated the ex-
istence of isolated Pt atoms with high number density in
0.2Pt/m-Al2O3-O2 catalysts (Fig. 2h), in which the Pt atoms were
firmly anchored on the internal surface of mesoporous Al2O3
and stabilized by coordinatively unsaturated pentahedral Al3+
centres.34 Furthermore, the rapid development of in situ TEM
techniques in recent years has enabled researchers to study
the dynamic structural evolution of nanoparticles under differ-
ent atmospheres. Liu et al. studied the evolution and stabiliza-
tion of subnanometric Pt species confined in MCM-22 zeolite
by in situ TEM; they found that Pt@MCM-22 catalyst can be
stabilized by this particular zeolite structure at a very high tem-
perature (>800 °C) during NO reduction with CO and H2.66
Therefore, the dynamic changes in the shapes of metal nano-
particles, the oscillatory behavior of metal particles, and the
interaction between the metal surface and substrate molecules
can been visualized by in situ TEM.
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Fig. 4 (a) Fourier transform of the Pt L3-edge EXAFS oscillations of Pt–CN, K2PtCl6, and Pt foil. Adapted with permission from ref. 76. Copyright
2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) FT k 3-weighted χ(k)-function of the EXAFS spectra for Al-TCPP-0.3Pt, Al-TCPP-0.1Pt,
K2PtCl4, and Pt foil. Adapted with permission from ref. 77. Copyright 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) The k 3-weighted
Fourier transforms of the EXAFS spectra derived from EXAFS of Pt foil, H2PtCl6, and PtO2, 0.2Pt/m-Al2O3–O2 and 0.2Pt/m-Al2O3–H2. Adapted with
permission from ref. 34. Copyright 2017 Macmillan Publishers Limited, part of Springer Nature. (d) FT k 3-weighted χ(k)-functions of the EXAFS
spectra for Pt foil, PtO2, H2PtCl6, and HNTM-Ir/Pt (Pt). Adapted with permission from ref. 78. Copyright 2018 Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim.

2.1.3 EXAFS. X-ray absorption spectroscopy (XAS) is the
measurement of transitions from the core electronic states of
a metal to the excited electronic states and the continuum;
the spectral region extending the energy range from the ab-
sorption edge to 30 to 50 eV is known as X-ray absorption
near-edge structure (XANES) spectroscopy, while that in the
range of 50 to 1000 eV or more is called extended X-ray ab-
sorption fine structure (EXAFS) spectroscopy.67 EXAFS is an
extremely useful way to determine the chemical states of
practically important species which occur in very low abun-
dance or concentration. The EXAFS technique studies the
fine structures in absorption at energies greater than the
threshold for electron release, which provides information on
the number of different coordinating species and their dis-
tances from the absorber atom, the angles between chemical
bonds, and thermal disorder.67–69 To investigate the coordi-
nation conditions of Pt centers, wavelet transform (WT) anal-
ysis can provide radial distance resolution and resolution in
the K space.70 WT analysis can discriminate atoms at similar
distances.71–73 Pt–C/N/O bonds with similar scattering param-
eters to their neighboring positions in the periodic table of
elements can be distinguished using WT analysis. However,
its applications in distinguishing the Pt–O, Pt–C and Pt–N
bonds in Pt SACs remain virtually unexplored. Fig. 3a shows
that a WT intensity maximum near 5.5 Å−1 arising from the
light atom coordinator is well resolved for Pt@PCM, whereas
the intensity maximum at ∼8.5 Å−1 associated with Pt–Pt co-
ordination is not detected; this confirms the successful load-
ing of isolated Pt atoms in the carbon matrix.74 In the WT
contour plots of Pt1δ+/TiO2, there is only one intensity maxi-
mum at about 5.3 Å−1 from the Pt–O contributions, whereas
no intensity maximum near 8.5 Å−1 indexed to the Pt–Pt path

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Fig. 5 (a) Pt K-edge EXAFS in R space for atomically dispersed Pt/MoS2 with different Pt loadings and Pt nanoparticles/MoS2. Pt foil was used as a
reference. The dashed lines are the corresponding fitted curves. Adapted with permission from ref. 79. Copyright 2018 Macmillan Publishers Lim-
ited, part of Springer Nature. (b) Fourier transforms of k 3-weighted Pt LIII-edge EXAFS, confirming that the Pt species in Pt/HSC exhibit only Pt–S
coordination (CN = 3.8) without significant Pt–Pt coordination. Adapted with permission from ref. 80. Copyright 2016 Macmillan Publishers Lim-
ited, part of Springer Nature. (c) EXAFS spectra of Pt/NiS@Al2O3 and Pt foil at the Pt K-edge for comparison. Adapted with permission from ref. 81.
Copyright 2018 Royal Society of Chemistry. (d) The k 2-weighted EXAFS spectra of Pt–MoS2 in comparison to Pt foil and commercial 40% Pt/C.
Adapted with permission from ref. 82. Copyright 2015 Royal Society of Chemistry.

is detected (Fig. 3b).75 As illustrated by the WT contour plots,
the intensity maxima at 5.3 to 5.5 Å−1 and 8.5 Å−1 are ascribed
to the Pt–O and Pt–Pt contributions, respectively.
Fig. 4a shows that the Fourier transformed (FT) EXAFS
peak for the Pt–Cl bond in K2PtCl6 is at about 2.0 Å and that
for the Pt–Pt bond in Pt foil is at about 2.61 Å.76 Fig. 4b indi-
cates that one prominent peak from the Pt–Cl contribution
in K2PtCl6 is at about 1.9 Å and that the Pt–Pt bond is at
∼2.7 Å for Pt foil.77 The only prominent shell located at ap-
proximately 1.9 Å arises from the Pt–Cl contribution in
H2PtCl6 and the Pt–Pt contribution at about 2.7 Å for Pt foil
is absent, as shown in Fig. 4c.34 Fig. 4d demonstrates a main
peak at 1.95 Å that can be ascribed to Pt–Cl coordination in
H2PtCl6.78 Ref. 79 and 80 present a peak located at 2.75 Å
that was observed for the Pt–Pt bond in Pt foil.79,80 Thus, the
Pt–Cl contributions in H2PtCl6 and K2PtCl6 are at about 1.9 to
2.0 Å; the Pt–Pt bond in Pt foil is at about 2.61 to 2.75 Å
according to the FT-EXAFS results.
Fig. 5a shows that samples of 0.2%, 1.0%, 5.0%, and 7.5%
Pt/MoS2 SACs exhibited prominent peaks at 2.32 Å from the
Pt–S shell with a coordination number of 5.2. No other typi-
cal peaks for the Pt–Pt contribution at longer distances
(>2.50 Å) were observed, revealing the atomic dispersion of
the Pt atoms in these samples.79 Fig. 5b indicates that Pt/
HSC SAC shows a dominant peak at 2.29 Å, which can be
assigned to Pt–S coordination (CN = 3.8).80 Fig. 5c reveals
that only one sharp peak at 2.2 Å was detected from the Pt–S
contribution in Pt/NiS@Al2O3 SACs.81 Fig. 5d presents an ob-
vious peak located at about 2.2 Å, corresponding to the Pt–S
bond for Pt–MoS2 SACs.82 Therefore, the Pt–S contribution in
the SACs is in the range of 2.2 to 2.32 Å based on the FT-
EXAFS results.
Fig. 6a indicates that no Pt–Pt bonds were detected in
Pt0.1Cu14/Al2O3 or Pt0.2Cu12/Al2O3, which provides direct evi-
dence for isolated Pt atoms in the Pt/Cu bimetallic nano-
particles. The Pt–Cu first-shell interaction distance is 2.63 Å,

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Fig. 6 (a) EXAFS data collected at the Pt-LIII edge at room temperature from Pt foil and in H2 atmosphere at the Pt-LIII edge at room temperature
from pre-reduced Pt0.1Cu14/Al2O3, Pt0.2Cu12/Al2O3 and Pt2Cu6/Al2O3. Adapted with permission from ref. 83. Copyright 2015 Macmillan Publishers
Limited, part of Springer Nature. (b) The k 3-weighted χ(k)-functions of the EXAFS spectra. Adapted with permission from ref. 84. Copyright 2017
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) Fourier transforms of k 3-weighted Pt L3-edge EXAFS. Adapted with permission from ref. 85.
Copyright 2018 American Chemical Society. (d) Pt L3-edge EXAFS spectra in R space of Pt foil, Pt1/Ni, and Pt/C. Pt foil was used as a reference.
Adapted with permission from ref. 86. Copyright 2018 American Chemical Society.

which is between the bond lengths of Pt–Pt (2.77 Å) and Cu–
Cu (2.56 Å); this further supports single atom alloy forma-
tion.83 Fig. 6b shows a peak at 2.05 Å derived from the Pt–Cu
scattering pair and a peak centered at 2.56 Å that is related
to Pt–Pd coordination. Moreover, the atom distances of both
Pt–Cu and Pt–Pd are shorter than that of the Pt–Pt coordina-
tion observed in the spectrum of Pt foil (2.66 Å).84 Fig. 6c
demonstrates that the first shell peak in the FT spectrum of
FePt nanosheets at 1.7 Å is similar to the peak at 1.9 Å of
PtO2; this can be assigned to the Pt–O bond, in correspon-
dence with their oxidation state. The peak at 2.5 Å for the
FePt nanosheets arises from the Pt–Fe bond length, and the
peak at 3.1 Å represents the bond length of the second
nearest shell of Fe with Pt.85 Ref. 3 shows very weak peaks at
2.5 Å in the second shell that were fitted to the Pt–Fe coordi-
nation contribution from the interaction between Pt and the
FeOx support.3 For 0.2%Pt1/Ni, 0.5%Pt1/Ni, 1.0% Pt1/Ni, and
1.5%Pt1/Ni nanocrystals, only the Pt–Ni shell at 2.57 to 2.59 Å
with a coordination number of 5.6 to 6.1 was observed, with-
out any contribution from the Pt–Pt shell (Fig. 6d).86 In addi-
tion, ref. 87 shows a relatively weak peak at ∼2.9 Å from the
Pt–Ni contribution in the Pt1/NiIJOH)x catalyst.87 Thus, the FT-
EXAFS peak positions of Pt–Fe.Ni.Cu.Pd for Pt SACs are be-
tween 2.5 and 2.9 Å.
Fig. 7a indicates that a single Pt atom has only one domi-
nant peak at around 1.5 Å, attributed to Pt–N bonds; this ver-
ifies the sole presence of atomically dispersed Pt atoms.88
One prominent peak appears at ∼1.5 Å from the Pt–N contri-
bution, with the absence of significant Pt–Cl (∼1.9 Å) and Pt–
Pt (∼2.7 Å) bonds in Al-TCPP-0.1Pt (Fig. 4b); this confirms
that the single Pt atoms have been stabilized by nitrogen
atoms and that almost no (or very few) Pt particles or clusters
exist in Al-TCPP-0.1Pt.77 EXAFS of Pt–CN contains a domi-
nant peak centered at 1.5 Å, corresponding to the Pt–N/C

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Fig. 7 (a) Fourier transforms of k 3-weighted Pt L3-edge EXAFS experimental data for Pt-NPs and Pt-SAs. Adapted with permission from ref. 88.
Copyright 2018 Macmillan Publishers Limited, part of Springer Nature. (b) The k 2-weighted Fourier transform spectra of MeCpPtMe/graphene, Pt1/
graphene, and Pt2/graphene at the Pt L3-edge. The reference samples of Pt foil, PtO2, and MeCpPtMe3 are also shown for comparison. Adapted
with permission from ref. 89. Copyright 2017 Macmillan Publishers Limited, part of Springer Nature.
bond (Fig. 4a).76 The first shell peak in Pt1/graphene at 1.60
to 1.65 Å is assigned to Pt–O and/or Pt–C coordination
(Fig. 7b).89 Thus, the Pt–N and Pt–C contributions are about
1.5 Å and 1.6 to 1.65 Å, respectively, based on the FT-EXAFS
results for Pt SACs.
Fig. 8a shows a peak at ∼1.7 Å in the first shell of the
samples, which was fitted to the Pt–O contribution from the
interaction between Pt and the FeOx support.3 Fig. 8b indi-
cates the best fit for Pt–O at a distance of 1.7 Å of Pt single
atoms on Al2O3.90 Fig. 8c shows that the strong peak between
1 and 2 Å is due to a Pt–O shell for Pt single atoms on Al2O3.
No peak in the region of 2 to 3 Å, the characteristic peak of a
Pt–Pt shell, was observed.91 Fig. 8d revealed that the only
prominent shell, located at approximately 1.8 Å, arises from a
Pt–O contribution in Pt1/active carbon.92 Fig. 8e demon-
strates that Pt1δ+/TiO2 exhibits only one prominent peak at
about 1.6 Å, associated with the first shell of Pt–O scattering.
Moreover, no reflection from the Pt–Pt contribution is ob-
served compared with the FT curve of Pt foil.75 Fig. 8f shows
one prominent peak at ∼1.6 Å from the Pt–O contribution
but no peak at ∼2.6 Å from the Pt–Pt contribution,
confirming the sole presence of Pt single atoms in the Pt1/
NiIJOH)x catalyst.87 In addition, the only prominent shell peak
located at approximately 1.7 Å arises from the Pt–O contribu-
tion for 0.2Pt/m-Al2O3–O2 and 0.2Pt/m-Al2O3–H2 catalysts
(Fig. 4c).34 The first shell FT peak in the Pt1/graphene spec-
trum at 1.65 Å is assigned to Pt–O coordination.89 The Pt–O
contribution in Pt SACs is at about 1.6 to 1.8 Å from the FT-
EXAFS peaks. On the basis of the above literature, the sche-
matic in Fig. 9 summarizes the FT-EXAFS peak positions of
Pt–N, Pt–C, Pt–O, Pt–Cl, Pt–S, Pt–Pt, and Pt–Fe.Ni.Cu.Pd for
Pt single atoms on various supports. As can be seen, EXAFS
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can provide efficient characterization of the contribution of
the environment for the atomic dispersion of Pt catalysts.
2.2 Characterization techniques to provide indirect evidence
2.2.1 XANES. X-ray absorption near edge structure
(XANES), also known as near edge X-ray absorption fine
structure (NEXAFS), is a type of absorption spectroscopy that
indicates the features of the XAS of condensed matter due to
the photoabsorption cross section for electronic transitions
from the atomic core level to the final states in the energy re-
gion of 30 to 50 eV above the selected atomic core level ioni-
zation energy, where the wavelength of the photoelectron is
larger than the interatomic distance between the absorbing
atom and its first neighbour atoms. XANES is nondestructive,
element specific, and very sensitive to the electronic environ-
ment, oxidation state, and local symmetry of the element; it
can provide detailed information about the oxidation state
and coordination environment of the Pt species in Pt
SACs.67,93 Fig. 10a indicates that the oxidation state of the Pt
species increases with decreasing Pt loading, suggesting that
the Pt species becomes more positively charged with lower Pt
loading and increased electron transfer from Pt to the FeOx
support.94 Similarly, Chen et al. found that the absorption
edge position of Pt1/Ti3−xC2Ty was located between those of
the Pt foil and PtO2 from the XANES spectra of the Pt L3-
edge, suggesting that the single Pt atom carries a positive
charge and that its oxidation state is between 0 and +4.95
Fig. 10b shows that the white line intensity of Pt1/BP (without
N-doping) is between those of Pt foil and PtO2, showing the
oxidation of some Pt atoms in Pt1/BP. Meanwhile, the white-
line intensity of Pt1–N/BP is lower than that of Pt1/BP,
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Fig. 8 (a) The k 3-weighted Fourier transform spectra from EXAFS. The peaks at ∼1.7 Å in the first shells of samples A and B are fitted to the Pt–O
contribution from the interaction between Pt and the FeOx support, and the very weak peaks at 2.5 Å in the second shell are fitted to the Pt–Fe co-
ordination in sample A and the Pt–Pt coordination in sample B, respectively. Adapted with permission from ref. 3. Copyright 2011 Macmillan Pub-
lishers Limited, part of Springer Nature. (b) Non-phase-corrected, k 3-weighted Fourier transforms of Pt LIII-edge EXAFS for 0.18% Pt on θ-Al2O3.
Adapted with permission from ref. 90. Copyright 2013 American Chemical Society. (c) The k 3-weighted Fourier transforms of Pt LIII edge EXAFS for
Pt/NR-Al2O3-IP after use. Adapted with permission from ref. 91. Copyright 2017 American Chemical Society. (d) The k 3-weighted Fourier transform
spectra derived from EXAFS for AC-supported Pt catalysts and precatalyst, PtIJacac)2, and Pt foil. Adapted with permission from ref. 92. Copyright
2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (e). EXAFS FT spectra of Pt1δ+/TiO2 and Pt foil. Adapted with permission from ref. 75. Copy-
right 2018 American Chemical Society. (f) Fourier transform EXAFS spectrum of the Pt1/NiIJOH)x catalyst in comparison with PtO2 and Pt foil at the
Pt L3-edge. Adapted with permission from ref. 87. Copyright 2018 Macmillan Publishers Limited, part of Springer Nature.

indicating that the content of Pt oxide in Pt1–N/BP is lower
than that in Pt1/BP and confirming that doped N can prohibit
the oxidation of Pt single atoms.96
2.2.2 DRIFTS. Diffuse reflectance infrared Fourier trans-
form spectroscopy (DRIFTS) is an infrared spectroscopy tech-
nique in which diffuse reflection is produced by the reflec-
tion of light by a surface in all directions and is collected
using an ellipsoid or paraboloid mirror. The collected dif-
fusely reflected light carries information about both the ab-
sorption of the surface layer and the scattering properties of

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Fig. 9 Schematic of the FT-EXAFS peak positions for Pt–N, Pt–C, Pt–O,
Pt–Cl, Pt–S, Pt–Pt, and Pt–Fe.Ni.Cu.Pd.
the surface, which can provide insight into the local geome-
try, stability, reactivity, and homogeneity of the active species
and thus reveal the surface quality.45,97,98 Both in situ (or
operando) and ex situ DRIFTS techniques have been used in
the literature;45,97–99 the former is a convincing characteriza-
tion technique that can be applied to discriminate and quan-
tify the concentration of isolated platinum group metal spe-
cies in a catalyst. Because CO possesses several advantages in
the characterization of supported Pt species,100 the CO ad-
sorption behaviors of samples were examined using the in
situ DRIFTS technique for Pt SACs.101–104 The stair group in-
dicates that the DRIFTS peaks of adsorbed CO on Pt/HZSM-5
samples with Pt single atoms are centered at 2115 cm−1 and
those of the Pt nanoparticles are centered at 2070 to 2090
cm−1 (Fig. 11a).105 Wang et al. found that the CO adsorption
on the ionic Pt atom at a band of 2098 cm−1 was very strong
at 180 °C in Pt/CeO2 catalysts (Fig. 11b).63 Yan et al. demon-
strated a band for CO adsorption in the range of 2084 to
Fig. 10 (a) Normalized XANES spectra at the Pt LIII-edge of different Pt/FeOx samples. The increased white-line intensity with decreasing Pt load-
ing indicates that the single-atom and pseudo-single-atom structures of Pt are more positively charged than other structures. Adapted with per-
mission from ref. 94. Copyright 2014 Macmillan Publishers Limited, part of Springer Nature. (b) Pt L3-edge XANES for Pt foil, PtO2, Pt1/BP, and Pt1–
N/BP. Adapted with permission from ref. 96. Copyright 2017 Macmillan Publishers Limited, part of Springer Nature.
4830 | Catal. Sci. Technol., 2019, 9, 4821–4834
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Catalysis Science & Technology
2087 cm−1 in a 0.2Pt/m-Al2O3–O2 SAC and a band at 2058
cm−1 belonging to linearly bonded CO on Pt nanoparticles.34
In addition, for CO adsorption on Pt1/Fe2O3, only a weak
band appeared at 2080 cm−1; this can be ascribed to CO
adsorbed on single Pt atoms, and the band at 2030 cm−1 was
caused by linearly adsorbed CO on Pt nanoparticles.3 The
possible reasons for the difference in the CO adsorption peak
values on Pt single atoms and nanoparticles reported by dif-
ferent groups can be attributed to support effects. Different
supports can change the coordination conditions of the Pt
centers in Pt SACs, resulting in shifting of the CO adsorption
peaks. Additionally, the location of Pt single atoms over sup-
ports (e.g. on the surface or in the interior) can affect the
DRIFTS peaks of adsorbed CO.
2.2.3 XPS. X-ray photoelectron spectroscopy (XPS) is a
widely used characterization technique to probe the chemical
and compositional properties of solid surfaces and to deter-
mine their surface electronic structures.106,107 XPS is a
surface-sensitive quantitative spectroscopic technique that
measures the elemental composition in the parts per thou-
sand range; its quantitative accuracy and precision can meet
the requirements for analysis of SACs. The chemical state
and electronic state of Pt within a SAC material can be deter-
mined by this technique, which is very helpful to analyze its
electronic environment and coordination information.108,109
Lou et al. showed two peaks with binding energies of 71.28
and 74.53 eV in the Pt 4f XPS spectrum of Pt@PCM for Pt sin-
gle atoms, in contrast to the peaks for Pt0 at 70.89 and 74.23
eV in Pt nanoparticles (Fig. 12a).74 Li and co-workers demon-
strated two peaks in the Pt 4f spectrum at binding energies
of 75.8 and 72.4 eV, corresponding to 4f5/2 and 4f7/2 levels be-
tween those of Pt2+ and Pt0 (Fig. 12b).75 In addition, Pt single
atoms in Pt/CeO2 catalysts were in the Pt2+ ionic form,
according to the XPS spectrum.63 Thus, Pt single atoms carry
partial positive charges through electron transfer between the
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Fig. 11 (a) IR spectra of CO adsorbed on different Pt/HZSM-5 samples after desorption processes. Adapted with permission from ref. 105.
Copyright 2015 The American Association for the Advancement of Science. (b) CO adsorption DRIFTS for Pt/CeO2. After 30 min of CO oxidation
(black lines), the CO flow was discontinued, and recording of the spectra continued for 15 min with continuing O2 flow (magenta lines).
Temperature, 180 °C; a.u., arbitrary units. Adapted with permission from ref. 63. Copyright 2017 The American Association for the Advancement of
Science.

Fig. 12 (a) Pt 4f XPS spectra of Pt@PCM and Pt/C-20%. Adapted with permission from ref. 74. Copyright 2018 The American Association for the
Advancement of Science. (b) XPS spectra for Pt 4f of Pt1δ+/TiO2. Adapted with permission from ref. 75. Copyright 2018 American Chemical Society.

metal and the support. However, it is difficult to obtain the
characteristic valence states of Pt single atoms in the XPS
spectra of Pt 4f in SACs at low Pt loading.
2.2.4 Other characterization techniques. In addition to the
above characterization techniques, H2-TPR or CO-TPR and H2–
O2 titration are usually used to analyze the reducibility and H2/
O2 adsorption capacity of single-atom Pt catalysts because
atomically dispersed Pt and Pt nanoparticles exhibit different
performance.110,111 Sykes used CH3I to add methyl groups to
Pt/Cu single-atom alloys, and TPR studies of the subsequent
methane evolution was used to examine the C–H activation en-
ergetics.57 Zhang et al. used H2–O2 titration to probe the
surface-available Pt atoms. During H2–O2 titration, the single-
atom 0.2Pt/m-Al2O3–O2 and 0.2Pt/m-Al2O3–H2 consumed 2.7
equivalents of H2 per mole of Pt, which was much higher than
the samples with 0.5 and 2.0 wt% Pt loading (0.8 to 1.3 equiva-
lents of H2 per mole of Pt), demonstrating the excellent disper-
sion and reactivity of Pt atoms towards O2 and H2 at 0.2 wt%
Pt loading.34 In addition, ICP is a powerful testing instrument
to accurately measure the Pt contents of single-atom Pt cata-
lysts.112 Moreover, conventional characterization techniques
such as XRD, SEM, and N2 absorption can provide the funda-
mental physical and chemical properties of SACs, which is
helpful to comprehensively understand these catalysts.113–116
3. Conclusions
With the rapid development of characterization techniques
in recent years, Pt single-atom catalysts can be analyzed accu-
rately and conveniently via different characterization tech-
niques. High-resolution STM and HAADF-STEM can provide
crucial and intuitive evidence for the successful formation of
Pt single-atom catalysts. EXAFS provides radial distance reso-
lution and the resolution in the K space of atomic disper-
sions of Pt species on supports. The white-line intensity of
XANES reflects the oxidation state and coordination

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Mini review
environment of the Pt species. DRIFTS can reveal the surface
information of Pt single-atom catalysts, especially for CO ab-
sorption in the CO oxidation reaction, which shows different
peaks with changes of the adsorption position and the parti-
cle size of metallic Pt. By employing XPS, the valence state
and the surface electronic structure of Pt species in a single-
atom catalyst can be confirmed. In addition, we summarize
the FT-EXAFS peaks positions of Pt–N, Pt–C, Pt–O, Pt–Cl, Pt–
S, Pt–Pt, and Pt–Fe.Ni.Cu.Pd to be at about 1.5, 1.6 to 1.65,
1.9 to 1.8, 1.9 to 2.0, 2.2 to 2.32, 2.61 to 2.75, and 2.5 to 2.9
Å, respectively, over the Pt single-atom catalysts. In addition
to the above techniques, TPR, H2–O2 titration and ICP are im-
Published on 15 July 2019. Downloaded by Virginia Tech on 3/24/2021 3:53:34 PM.
portant for the characterization of Pt single-atom catalysts.
However, the current characterization techniques are almost
all ex situ techniques; in situ characterization techniques will
be needed for further research of the formation processes,
thermal stability and catalytic mechanisms of Pt single-atom
catalysts in the future.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors gratefully acknowledge support from the Na-
tional Natural Science Foundation of China (No. 21606146
and 51402299), Scientific Research Foundation of Shandong
University of Science and Technology for Recruited Talents
(No. 2016RCJJ005), and Foundation of State Key Laboratory of
High-efficiency Utilization of Coal and Green Chemical Engi-
neering (No. 2018-K29).
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