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org/JACS Article

Spatially Confined PdHx Metallenes by Tensile Strained Atomic Ru

Layers for Efficient Hydrogen Evolution
Jinchang Fan,# Zhipeng Feng,# Yajing Mu, Xin Ge, Dewen Wang, Lei Zhang, Xiao Zhao, Wei Zhang,
David J. Singh, Jingyuan Ma, Lirong Zheng, Weitao Zheng,* and Xiaoqiang Cui*
Cite This: J. Am. Chem. Soc. 2023, 145, 5710−5717 Read Online

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ABSTRACT: Hydride metallenes show great potential for hydrogen-related catalytic

applications due to favorable electronic structures modulated by interstitial hydrogen atoms
and large active surface areas of metallenes. Metallene nanostructures generally have
compressive strain relative to bulk, which can affect both the stability and the catalytic
behavior of hydride metallenes but in general cannot be controlled. Here, we demonstrate
highly stable PdHx metallenes with a tensile strained Ru surface layer and reveal the spatial
confinement effect of the Ru skin by multiple spectroscopic characterizations and molecular
dynamics simulations. These PdHx@Ru metallenes with a 4.5% expanded Ru outer layer exhibit
outstanding alkaline hydrogen evolution reaction activity with a low overpotential of 30 mV at
10 mA cm−2 and robust stability with negligible activity decay after 10,000 cycles, which are
superior to commercial Pt/C and most reported Ru-based electrocatalysts. Control experiments
and first-principles calculations reveal that the tensile strained Ru outer layer lowers the energy barrier of H2O dissociation and
provides a moderate hydrogen adsorption energy.

■ INTRODUCTION
Metallenes, two-dimensional metals with atomically thin layers,
significantly enhance the stability of hydride metallenes by a
spatial confinement effect from an atomic Ru surface layer. We
are of great interest in energy and catalytic applications due to report the synthesis of highly stable PdHx@Ru metallenes with
the ultrahigh surface area and the resulting large fractions of a 4.5% tensile strained Ru skin. We note that Pd and Ru are
unsaturated metal atoms.1−4 Alloying metallenes with light immiscible and that Pd forms a hydride under normal
atoms, especially hydrogen, has been demonstrated as an conditions, but this hydride is destabilized above room
efficient strategy to further improve their atom utilization and temperature, while Ru does not form a hydride. We
demonstrate that the result is the formation of a PdHx
intrinsic activity.5−8 In particular, interstitial hydrogen can
metallene with a Ru surface layer. The expanded lattice of
optimize the structural and electronic properties of metal
PdHx relative to Pd leads to a tensile strain of Ru and results in
atoms or alter the reaction pathway.9,10 Thus, hydride
excellent catalytic activity. We find that the PdHx@Ru
metallenes have enormous potential in hydrogen-related
metallene system can withstand high temperatures in excess
catalysis processes, including for the hydrogen evolution
of 200 °C in air, which is a sharp contrast with PdHx
reaction (HER),11 the oxygen reduction reaction (ORR),12
metallenes that are only stable below 60 °C. Ab initio
and the nitrogen reduction reaction (NRR).13 However,
molecular dynamics (AIMD) simulations demonstrate that the
surface atoms in metallenes are unsaturated coordination
Ru skin can confine hydrogen atoms in the lattice. Importantly,
leading to strong attractive interactions and large intrinsic
the as-prepared PdHx@Ru metallenes exhibit outstanding
compressive strain.14 Such compressive strains generally
alkaline HER activity with a low overpotential of 30 mV at 10
destabilize these systems. This poor stability limits applications
mA cm−2. This surpasses most reported Ru-based electro-
of hydride metallenes. For instance, the excellent ORR activity
catalysts. In addition, we find the robust stability with
of PdHx metallenes displayed at room temperature cannot be
negligible activity decay after 10,000 cycles or at 50 mA
sustained at the working temperatures of practical membrane
cm−2 over 25 h. Combined with control experiments and first-
electrode assemblies due to low oxidative stability.12 Exploring
novel strategies to design and implement efficient and stable
metallenes with high catalytic activity is thus greatly needed Received: November 3, 2022
and remains an important challenge. Published: March 6, 2023
Recently, we showed that alloys based on immiscible
elements can stabilize interstitial hydrogen atoms based on
the Miedema rule and used this to obtain a series of stable
hydride bimetallenes.11,15 Here, we propose a new strategy to

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Figure 1. Morphology and structure characterizations of PdHx@Ru metallenes. (a) Scheme of the growth process of PdHx@Ru metallenes. (b)
TEM image, (c) HAADF-STEM image, (d) EDX mapping, and (e) EDX line scan profile of PdHx@Ru metallenes. Inset in (c) is the histogram of
the thickness distribution of PdHx metallenes and PdHx@Ru metallenes. (f) Atomic resolution HAADF-STEM image (top) of PdHx@Ru
metallenes and the corresponding measured intensity profiles along the rectangles (bottom). (g) EELS spectrum (bottom) and corresponding
HAADF-STEM image (top) of PdHx@Ru metallenes.

principles calculations, we show that the high HER activity of
PdHx@Ru metallenes is mainly derived from the tensile
strained Ru skin trigged by the PdHx substrate, which can
enhance the adsorption of H2O, lower the energy barrier of
H2O dissociation, and provide the moderate hydrogen
adsorption energy.
measured to be of 1/2.6 by the inductively coupled plasma
mass spectrometry. This Ru skin on PdHx@Ru metallenes was
further confirmed by the energy-dispersive X-ray spectroscopy
(EDX) mapping and line scan profile, where Pd is mainly in
the internal volume and Ru is mainly in the surface region
(Figure 1d,e). As shown in the atomic resolution HAADF-

■ RESULTS AND DISCUSSION

PdHx@Ru metallenes were synthesized using the seed-
mediated growth method by reducing RuCl3·xH2O in the
formaldehyde solution with Pd metallenes as the seed. During
the growth process, in situ generated hydrogen atoms from the
formaldehyde solution enter into the lattice of Pd to form
PdHx.16 Meanwhile, Ru ions were reduced into Ru atoms on
the PdHx surface to form PdHx@Ru (Figure 1a). The
morphology of PdHx@Ru metallenes was characterized by
transmission electron microscopy (TEM), high-angle annular
dark-field scanning transmission electron microscopy
(HAADF-STEM), and atomic force microscopy (AFM)
measurements. These show ultrathin sheet-like metallene
structures (Figures 1b,c and S1). The thickness of PdHx@Ru
metallenes was measured to be of 2.36 ± 0.37 nm by analyzing
samples standing vertically to the TEM copper grid (Figure
1c), which is thicker than that of PdHx metallenes (1.82 ± 0.22
nm, Figure S2). This difference in thickness indicates that the
Ru skin on the surface of PdHx metallenes consists of about
one to two atomic layers. The atomic ratio of Ru/Pd is
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STEM (Figure 1f), the spacing between the (111) planes of
PdHx@Ru metallenes is measured as 2.31 Å. This is larger than
in bulk Ru (2.21 Å, PDF no. 88-2333) and Pd metallenes (2.25
Å, Figure S3). Thus, the Ru skin has an extended lattice
spacing, specifically a 4.5% increase compared to bulk Ru.
Electron energy loss spectroscopy (EELS) was also performed
to detect the hydrogenation state of PdHx@Ru metallenes. As
shown in Figure 1g, the EELS peak occurs at an energy of 5.74
eV, which is lower than that in Pd metallenes (7.58 eV, Figure
S4). This matches well with the results in reported Pd−hydride
systems,17 confirming the hydride nature of PdHx@Ru
metallenes.
Multiple spectroscopic analyses were conducted to inves-
tigate the structural and electronic properties of PdHx@Ru
metallenes. The crystal phase of PdHx@Ru metallenes was
confirmed by X-ray diffraction (XRD) measurements. As
shown in Figure 2a, the diffraction peaks of PdHx@Ru
metallenes shift to the lower angle than those of Pd metallenes.
The peaks are thus assigned to the β-phase of Pd hydrides
(PDF no 87-0641). The H content was calculated to be of 0.3
based on the relationship between the lattice parameter and
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Figure 2. Structural and electronic properties of PdHx@Ru metallenes. (a) XRD patterns, (b) 1H ssNMR spectra, and (c) XPS valence band of Pd
metallenes and PdHx@Ru metallenes. (d) XANES spectra and (e) FT-EXAFS spectra of Pd K-edge for Pd foil, PdO, and PdHx@Ru metallenes. (f)
WT-EXAFS of Pd K-edge data for Pd foil and PdHx@Ru metallenes. (g) XANES spectra and (h) FT-EXAFS spectra of Ru K-edge for Ru foil,
RuO2, and PdHx@Ru metallenes. (i) WT-EXAFS of Ru K-edge EXAFS data for Ru foil and PdHx@Ru metallenes.

the composition within the palladium−hydrogen system18
(Figure S5). The interaction between Pd and hydrogen atoms
was analyzed by 1H solid-state nuclear magnetic resonance
(ssNMR) and X-ray photoelectron spectroscopy (XPS)
valence band spectra. As shown in Figure 2b, a new peak at
26.5 ppm was observed in the 1H ssNMR spectrum of PdHx@
Ru metallenes compared to that of Pd metallenes. This is
attributed to the formation of the Pd−H bond following the
literature.19 The Pd−H interaction also results in a narrow
XPS valence band width of PdHx@Ru metallenes and two
perturbation peaks at the binding energy above 6 eV20 (Figure
2c). X-ray absorption spectroscopy was performed to further
characterize the electronic structures and coordination
environments in these PdHx@Ru metallenes. As shown in
the normalized Pd K-edge X-ray absorption near-edge
structures (XANES), the adsorption edge of PdHx@Ru
metallenes is close to that of Pd foil (Figure 2d). This shows
the predominantly metallic state of Pd atoms. The Fourier
transforms of extended X-ray absorption fine structure (FT-
EXAFS) and the wavelet transform (WT) of EXAFS spectra
indicate that Pd atoms in PdHx@Ru metallenes are mainly
coordinated with metal atoms with a Pd−Pd/Ru bond length
of 2.55 Å, which is 0.10 Å longer than that in Pd foil (Figure
2e,f). This expansion of the Pd−Pd/Ru bond length further
confirms the existence of interstitial hydrogen atoms. The Ru
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K-edge XANES spectra show that the adsorption edge of
PdHx@Ru metallenes occurs between the positions in Ru foil
and RuO2. This implies some increase in the oxidation state of
Ru (Figure 2g). The oxidation state and the low intensity of
Ru−Ru/Pd scattering shown in the FT-EXAFS and WT-
EXAFS spectra indicate that the Ru atoms are atomically
dispersed on the surface of PdHx@Ru metallenes. These atoms
would then be expected to be more readily oxidized under
ambient conditions21 (Figure 2h,i). Importantly, the Ru−Ru/
Pd bond length is 0.11 Å longer than that in Ru foil, indicating
an expansion of the Ru skin in PdHx@Ru metallenes,
consistent with the HAADF-STEM results.
We find that these PdHx@Ru metallenes have excellent
storage stability, and in particular, we can store PdHx@Ru
metallenes for at least 6 months under ambient conditions
without degrading the structure (Figure S6). In situ XRD
measurements were conducted at different temperatures to
investigate the thermal stability of PdHx@Ru metallenes. As
shown in Figure 3a,b, PdHx@Ru metallenes maintain their
original structure at 90 °C but are completely transformed into
metallic Pd at 210 °C. In contrast, PdHx metallenes are much
less stable. They maintain their structure at 30 °C but are then
completely transformed into metallic Pd at 60 °C (Figures 3c
and S7). Thus, the PdHx@Ru metallenes are much more
stable. This may be ascribed to the spatial confinement effect
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Figure 3. Stability of PdHx@Ru metallenes. (a) In situ XRD patterns of PdHx@Ru metallenes under different temperatures. (b) Corresponding
contour map of enlarged temperature-dependent XRD patterns. (c) Temperature-dependent lattice parameter of PdHx metallenes and PdHx@Ru
metallenes. Snapshots for optimized (d) PdH@Ru and (e) PdH configurations at different times in the AIMD simulations.

Figure 4. Alkaline HER performances of PdHx@Ru metallenes. (a) HER polarization curves of PdHx@Ru metallenes, Pd@Ru metallenes, and
commercial Ru/C and commercial Pt/C catalysts. (b) Corresponding Tafel slopes of different electrocatalysts. (c) Comparison of the HER
performance metrics between Pd@Ru metallenes and PdHx@Ru metallenes. (d) Comparison of the overpotential at 10 mA cm−2 and the Tafel
slope for reported Ru-based catalysts in the recent literature. (e) HER polarization curves of PdHx@Ru metallenes recorded before and after
different potential cycles. (f) Chronopotentiometry tests of PdHx@Ru metallenes at current densities of 10, 20, and 50 mA cm−2.

of the tensile strained Ru skin. This is further supported by
AIMD simulations (Figure S8). These were done starting with
the structural characterization, as above, of the PdHx@Ru
metallenes. A simulation model with two atomic layers of
tensile strained Ru atoms on the surface of PdH was adopted
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with hydrogen atoms initially located at the octahedral
interstitial sites of the Pd lattice as is the case in bulk PdH.
As shown in Figure 3d, interstitial hydrogen atoms in the
PdH@Ru model remain confined in the lattice after 10 ps
simulations at 350 K. As a contrast, all interstitial hydrogen
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Figure 5. Theoretical studies of HER performances. (a) ΔGH* values under different hydrogen coverages on the Ru, Pd@Ru, and PdH@Ru
surfaces. Insets show the corresponding adsorption configurations of the PdH@Ru surface. (b) Reaction free energy pathways of H2O dissociation
for the Ru, Pd@Ru, and PdH@Ru surfaces. Insets show the atomic structures of reaction intermediates for PdH@Ru. (c) Schematic illustration of
the strain variation in the Ru, Pd@Ru, and PdH@Ru surfaces (top) and the ΔGH* value at 1 ML, the ΔGH2O* value, and the energy barrier of H2O
dissociation as a function of the tensile strain of Ru atoms (bottom).
atoms in the PdH model migrate out to the surface in a similar
simulation without the Ru skin (Figure 3e). This result
demonstrates that the tensile strained Ru surface layer impedes
hydrogen release. In any case, the high observed stability
means that these PdHx@Ru metallenes can be regarded as
potential catalysts for aqueous electrocatalysis, including HER,
ORR, NRR, and beyond. We now turn to the catalytic
performance.
The HER performance of PdHx@Ru metallenes was
evaluated in an Ar-saturated 1 M KOH electrolyte.
Commercial Pt/C, commercial Ru/C, PdHx metallenes
(Figure S9), and Pd@Ru metallenes (Figure S10) were used
as references. As shown in Figures 4a and S11, PdHx@Ru
metallenes show the best alkaline HER performance among
these catalysts. PdHx@Ru metallenes have the lowest over-
potential (30 ± 1 mV) under a current density of 10 mA cm−2
(η10). In fact, this is much lower than that of commercial Pt/C
(46 ± 3 mV), commercial Ru/C (71 ± 4 mV), and Pd@Ru
metallenes (53 ± 2 mV). Tafel plots were obtained based on
HER polarization curves in order to evaluate the HER catalytic
kinetics. As shown in Figure 4b, PdHx@Ru metallenes exhibit
the lowest Tafel slopes of 30 mV dec−1, indicating the fastest
HER kinetics and the Volmer−Tafel mechanism with H2
desorption as the rate-determining step. The outstanding
HER performances of PdHx@Ru metallenes underscore the
importance of interstitial hydrogen atoms. To clearly
demonstrate this, we systemically compared the HER perform-
ance metrics of Pd@Ru metallenes and PdHx@Ru metallenes,
including η10, Tafel slope, exchange current density (j0),
turnover frequency, and mass activity at an overpotential of 50
mV. As shown in Figure 4c, all these metrics of PdHx@Ru
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d
metallenes are superior in comparison to the Pd@Ru
metallenes. This shows the key role of interstitial hydrogen
atoms in boosting HER performance, endowing PdHx@Ru
metallenes as one of the best reported Ru-based alkaline HER
electrocatalysts (Figure 4d and Table S1). Operando XANES
spectra revealed that surface Ru atoms are gradually reduced
from a slight oxidation state to a metallic state under the HER-
relevant potentials (Figure S12). This result confirms that
metallic Ru atoms with tensile strain are active centers of
PdHx@Ru metallenes for HER.
Besides outstanding HER activity, PdHx@Ru metallenes
also exhibit high HER cycling and long-term stability. As
shown in Figure 4e, only 4 mV positive shift of η10 is observed
on PdHx@Ru metallenes after 10,000 sweeping cycles.
Furthermore, there is negligible loss of the current density
and no obvious change in the hydride structure and sheet-like
morphology of PdHx@Ru metallenes after the continuous
chronopotentiometric testing at current densities of 10, 20, and
50 mA cm−2 for 25 h (Figures 4f and S13).
Density functional theory (DFT) calculations of the active
site and the reaction mechanism were performed in order to
understand the outstanding HER activity of PdHx@Ru
metallenes. We first investigated the hydrogen adsorption
Gibbs free energy (ΔGH*) with different coverages on the
PdH@Ru, Pd@Ru, and Ru surfaces.22,23 It is noted that Ru
atoms in PdHx@Ru metallenes and simulated PdH@Ru
surface are in the face-centered cubic (fcc) structure.24,25
Therefore, an fcc-Ru surface was adopted for comparison
(Figure S14). As shown in Figure 5a, the PdH@Ru surface
shows the over-binding of hydrogen atoms under the coverage
of 1/9 monolayer (ML) while exhibits a similar ΔGH* value
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compared to the Ru surface with a hydrogen coverage of 1 ML.
This result shows that the ΔGH* of PdH@Ru is slightly
improved, indicating that it may be not suitable to merely use
ΔGH* to understand the enhanced HER activity. We then
focused on the elementary steps involved in the H2O
dissociation process (Volmer step, H2O* → OH* + H*)
since sluggish kinetics of this step is generally recognized as the
main factor restricting alkaline HER efficiency.26,27 As shown
in Figure 5b, the adsorption free energy of H2O (ΔGH2O*) is
−0.32 eV on the PdH@Ru surface, which is lower than the
value of −0.14 eV on the Ru surface. The strong adsorption of
d
H2O on the PdH@Ru surface will increase the H2O capture
rate to offer a sufficient proton source. Furthermore, the energy
barrier of the H2O dissociation is 0.35 eV on the PdH@Ru
surface. This is lower than that on the Ru surface (0.51 eV).
The lower energy barrier of the PdH@Ru surface indicates the
more favorable kinetics for the H2O dissociation, leading to an
improved proton supply. To gain further insight into the
observed enhanced HER activity, we investigated how the
strain influences the main descriptors involved in the HER
process, including the ΔGH* value at 1 ML, the ΔGH2O* value,
d
and the energy barrier of H2O dissociation. The calculated
average Ru−Ru bond distance in the PdH@Ru surface is 2.92
Å, exhibiting a 7.7% tensile strain compared to that in the Ru
surface (2.71 Å, Figure S15). This is a consequence of the
interaction with the PdH substrate. This calculated tensile
strain in our DFT calculations is higher than the value of 4.5%
measured by HAADF-STEM and EXAFS. This is reasonable
since the saturated stoichiometric hydrogen content is used in
the simulated PdH@Ru surface, which is almost certainly
higher than that in experimentally realized PdHx@Ru metal-
lenes. As shown in Figure 5c, there is a linear relationship
between the ΔGH* value at 1 ML, the ΔGH2O* value, the energy
d
barrier of H2O dissociation, and the tensile strain of Ru atoms.
Specifically, with increase of the tensile strain, the ΔGH* value
at 1 ML increases slightly, while the ΔGH2O* value and the
d
energy barrier of H2O dissociation decrease significantly. All
these modifications are beneficial for boosting H2O dissocia-
tion and hydrogen production. Therefore, the outstanding
HER activity of PdHx@Ru metallenes is attributed to the
tensile strain of the Ru skin, which is a consequence of the
PdHx substrate.
■ CONCLUSIONS
We report the synthesis of highly stable PdHx@Ru metallenes
with the formation of a tensile strained Ru skin. The as-
prepared PdHx@Ru metallenes exhibit outstanding HER
performances, including both high activity and robust stability.
The observed performance is much better than that of
commercial Pt/C and most previously reported Ru-based
catalysts. Multiple spectroscopic analyses and DFT calculations
reveal that the high HER activity of PdHx@Ru metallenes is
due to the tensile strained Ru skin, which is a consequence of
interaction with the PdHx substrate. In particular, this situation
enhances the H2O dissociation and at the same time provides
moderate hydrogen adsorption energy. This work presents a
new approach for producing stable catalytically active metal-
lenes and offers a powerful strategy for developing efficient and
robust electrocatalysts via tensile strain modulation.
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■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.2c11692.
AFM images, TEM images, XRD patterns, EDX
mapping, operando XANES spectra, XPS results, and
comparison HER performances (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Weitao Zheng − School of Materials Science and Engineering,
Key Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China; Email: wtzheng@jlu.edu.cn
Xiaoqiang Cui − School of Materials Science and Engineering,
Key Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China; orcid.org/0000-0002-5858-6257; Email: xqcui@
jlu.edu.cn
Authors
Jinchang Fan − School of Materials Science and Engineering,
Key Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China; orcid.org/0000-0001-9560-6790
Zhipeng Feng − School of Materials Science and Engineering,
Key Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China
Yajing Mu − School of Materials Science and Engineering, Key
Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China
Xin Ge − School of Materials Science and Engineering, Key
Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China
Dewen Wang − School of Materials Science and Engineering,
Key Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China
Lei Zhang − College of Chemistry, Jilin University, Changchun
130012, China
Xiao Zhao − School of Materials Science and Engineering, Key
Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China; orcid.org/0000-0002-8183-8205
Wei Zhang − School of Materials Science and Engineering, Key
Laboratory of Automobile Materials of MOE, State Key
Laboratory of Automotive Simulation and Control, Electron
Microscopy Center, Jilin University, Changchun 130012,
China; orcid.org/0000-0002-6414-7015
David J. Singh − Department of Physics and Astronomy and
Department of Chemistry, University of Missouri, Columbia,
https://doi.org/10.1021/jacs.2c11692
J. Am. Chem. Soc. 2023, 145, 5710−5717
Journal of the American Chemical Society
Missouri 65211, United States; orcid.org/0000-0001-
7750-1485
Jingyuan Ma − Shanghai Synchrotron Radiation Facility,
Shanghai Institute of Applied Physics, Chinese Academy of
Sciences, Shanghai 201204, China
Lirong Zheng − Beijing Synchrotron Radiation Facility,
Institute of High Energy Physics, Chinese Academy of
Sciences, Beijing 100049, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.2c11692
Author Contributions
# 8106−8114.
J.F. and Z.F. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (nos. 12034002, 51872116,
22279044, and 22202080), the project for Self-innovation
Capability Construction of Jilin Province Development and
Reform Commission (2021C026), and the Jilin Province
Science and Technology Development Program
(20210301009GX). We also thank the XAFS station
(BL14W1) of the Shanghai Synchrotron Radiation Facility
(SSRF) and the XAFS station (1W1B) of the Beijing
Synchrotron Radiation Facility (BSRF). This work was
performed at the LvLiang Cloud Computing Center of
China, and the calculations were carried out on TianHe-2.
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