PtSe2/Pt Heterointerface with Reduced Coordination for Boosted Hydrogen Evolution Reaction

Article abstract of DOI:10.1002/anie.202110335

PtSe₂ is a typical noble metal dichalcogenide (NMD) that holds promising possibility for next-generation electronics and photonics. However, when applied in hydrogen evolution reaction (HER), it exhibits sluggish kinetics due to the insufficient capability of absorbing active species. Here, we construct PtSe₂/Pt heterointerface to boost the reaction dynamics of PtSe₂, enabled by an in situ electrochemical method. It is found that Se vacancies are induced around the heterointerface, reducing the coordination environment. Correspondingly, the exposed Pt atoms at the very vicinity of Se vacancies are activated, with enhanced overlap with H 1s orbital. The adsorption of H^. intermediate is thus strengthened, achieving near thermoneutral free energy change. Consequently, the as-prepared PtSe₂/Pt exhibits extraordinary HER activity even superior to Pt/C, with an overpotential of 42 mV at 10 mA cm^?2 and a Tafel slope of 53 mV dec^?1. This work raises attention on NMDs toward HER and provides insights for the rational construction of novel heterointerfaces.

Full text of DOI:10.1002/anie.202110335

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
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Accepted Article
Title: PtSe2/Pt heterointerface with reduced coordination for boosted
hydrogen evolution reaction
Authors: Zongpeng Wang, Beibei Xiao, Zhiping Lin, Yaping Xu, Yan
Lin, Fanqi Meng, Qinghua Zhang, Lin Gu, Baizeng Fang,
Shaojun Guo, and Wenwu Zhong
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202110335
Link to VoR: https://doi.org/10.1002/anie.202110335

10.1002/anie.202110335
Angewandte Chemie International Edition
PtSe2/Pt heterointerface with reduced coordination for boosted
hydrogen evolution reaction
Zongpeng Wang1,+, Beibei Xiao2,+, Zhiping Lin1, Yaping Xu1, Yan Lin1, Fanqi Meng3, Qinghua
Zhang3, Lin Gu3, Baizeng Fang4, Shaojun Guo5 and Wenwu Zhong1,*
1School of Advanced study, Taizhou University, Taizhou, China.
2School of Energy and Power Engineering, Jiangsu University of Science and Technology,
Zhenjiang, China.
3Institution of Physics, Chinese Academic of Science, Beijing, China.
4Department of Chemical & Biological Engineering, University of British Columbia, 2360 East
Mall, Vancouver, BC V6T 1Z3, Canada..
5School of Materials Science and Engineering, Peking University, Beijing, China.
*zhongww@tzc.edu.cn
+These authors contribute equally to this work.
Abstract
PtSe2 is a typical noble metal dichalcogenide (NMD) that holds promising possibility for next-
generation electronics and photonics. However, when applied in hydrogen evolution reaction
(HER), it exhibits sluggish kinetics due to the insufficient capability of absorbing active species.
Here, we construct PtSe2/Pt heterointerface to boost the reaction dynamics of PtSe2, enabled by an
in-situ electrochemical method. It is found that Se vacancies are induced around the heterointerface,
reducing the coordination environment. Correspondingly, the exposed Pt atoms at the very vicinity
of Se vacancies are activated, with enhanced overlap with H 1s orbital. The adsorption of H•
intermediate is thus strengthened, achieving near thermoneutral free energy change. Consequently,
the as-prepared PtSe2/Pt exhibits extraordinary HER activity even superior to Pt/C, with an
overpotential of 42 mV at 10 mA/cm2 and a Tafel slope of 53 mV/dec. This work raises attention
on NMDs toward HER and provides insights for the rational construction of novel heterointerfaces.
Keywords: Hydrogen evolution reaction, noble metal dichalcogenides, heterointerface
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10.1002/anie.202110335
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1. Introduction
Noble metal dichalcogenides (NMDs) are attracting wide attentions as a novel group in the 2D
material family, due to their high carrier mobility, tunable bandgap and excellent stability[1].
Adopting NMDs in electrocatalysis holds promising prospects[2]. For transition metals compounds,
the d-electrons define the phase structure, the coordination environment and the resulting
interaction strength with active species[3]. Notably, the d-bands are highly occupied in NMDs,
offering a unique platform for the research of regulative electrocatalytic activity. For example, Hu
et al. studied the layer dependent HER (hydrogen evolution reaction) performance of PtSe2
nanosheets, and found that the activity raised monotonically with increasing layer number[4]. Lin et
al. fabricated vertically stacked PtSe2 nanosheets through selenization of magnetron sputtering Pt
film to enlarge the edge density for optimized HER activity[5]. However, as demonstrated by these
works, the HER performance of PtSe2 is considerably low.
Constructing heterointerface is powerful strategy to design high-performance materials, where
exceptional phenomenon and physics can be observed, including band bending[6], charge
redistribution[7], phase transaction[8] and so on. In electrocatalytic HER, the density of active sites
and the intrinsic activity are two vital factors that define the efficiency of a catalyst[9]. Engineering
suitable heterointerfaces can not only regulate the morphology of materials, increasing active sites
loading, but also can modulate the electronic structure and optimize the adsorption behavior,
enhancing the intrinsic activity. For example, Zhu et al. used eutectic salt system to fabricate
Ru/RuS2 heterointerface, where the electronic state and charge distribution were regulated to
achieve optimized adsorption behavior with a resulting overpotential of 45 mV at 10 mA cm-2 in
acidic media[10]. Despite the numerous reports on various heterointerface forms, the effect of
innovative vacancies that induced by the construction of heterointerfaces is rarely explored.
In this work, to boost the HER activity of PtSe2 and demonstrate the versatile capability of
heterointerfaces, we constructed PtSe2/Pt interface through an electrochemical reduction method,
where tremendous Pt ultra-small particles are generated at the edges of PtSe2 nanosheets. It is
revealed that continuous Se vacancies are induced around the PtSe2/Pt boundary, resulting in
reduced coordination environment. Benefitting from this unique structure, the adsorption of H•
intermediate on this material is strengthened compared to the otherwise insufficient adsorption,
achieving optimal thermoneutral free energy change. Besides, the combination of Pt can effectively
improve the electrical conductivity of the material. Consequently, the as-prepared PtSe2/Pt exhibits
extraordinary HER activity even superior to Pt/C, with an overpotential of 42 mV at 10 mA/cm2
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10.1002/anie.202110335
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and a Tafel slope of 53 mV/dec.
2. Results and discussion
Figure 1. Morphology and crystal structure. a,b TEM images of PtSe2 and PtSe2/Pt, respectively.
c,d Magnified TEM and STEM image of PtSe2/Pt, respectively. e XRD pattern of PtSe2/Pt. Vertical
black lines are used to represent the information of the standard PDF card. f HAADF-STEM image
of the PtSe2 sheet in PtSe2/Pt sample, viewed from [001] direction Inset: overlap of corresponding
PtSe2 lattice with yellow dots representing Pt atoms and blue dots representing Se atoms. g
HAADF-STEM image of the boundary between PtSe2 sheet and Pt cluster in PtSe2/Pt. h The
intensity profile along the red-arrow line in g. i SEAD pattern of PtSe2/Pt. j Element mapping of
PtSe2/Pt.
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The morphology and structure of the prepared samples were characterized, shown in Figure 1 and
Figure S1. The TEM images of PtSe2 and PtSe2/Pt are shown in Figure 1 a and b, respectively. PtSe2
nanosheets exhibit layered crystal structure, which can be reflected by the fringes at the edges of
the sample in Figure 1a. In the TEM image of PtSe2/Pt, one can see clearly that tremendous ultra-
small Pt particles were loaded on PtSe2 nanosheets. To examine the distribution of ultra-small Pt
particles more distinctly, the enlarged TEM and STEM (scanning TEM) image of PtSe2/Pt were
captured in Figure 1 c and d, respectively. As one can see, the ultra-small Pt particles were
distributed along the edges of PtSe2 nanosheets. This unique distribution of ultra-small Pt particles
not only increases the electrical conductivity of PtSe2/Pt sample, but also modulates the local
structure of PtSe2/Pt, forming highly active sites for HER. Figure 1e presents the XRD (X-ray
diffraction) pattern of the sample, which matches well with the standard peaks of PtSe2 (PDF card
No. 65-3374, Table S1). The first six peaks located at 17°, 28°, 33°, 45°, 49° and 52° correspond
to the (001), (010), (011), (012), (110) and (111) facets of PtSe2, respectively. The strongest peak is
different from the standard PDF card, which is due to the layered structure of PtSe2. The dominate
(001) peak is also observed in many 2D materials. Note that the XRD patterns of Pt are invisible
due to the extremely low mass ratio of ultra-small Pt particles. The presence of Pt is evidenced by
more surface-sensitive characterizations in the following. To further explore the structure of the
prepared PtSe2/Pt sample, Figure 1 f and g display the HAADF-STEM (high angle annular dark
filed STEM) images of PtSe2/Pt sample at the basal plane and the boundary, respectively. The
brighter and bigger spots represent the heavier Pt atoms, while the darker and smaller spots are Se
atoms. Figure 1f matches exactly with the [001] facets of PtSe2 crystal, indicating the successful
preparation of the desired sample. Figure 1g depicts a typical boundary area between PtSe2
nanosheet and Pt cluster. It is worthy to note that Se vacancies appear at the very close neighbor
along the boundary. The intensity distribution of Se signal along the red arrow is shown in Figure
1h. One can see the Se signal decreases obviously at the vacancy positions. The SAED (selected
area electron diffraction) pattern of the prepared PtSe2/Pt sample is shown in Figure 1i, which can
be indexed to diffraction along [001] direction. Corresponding facets in the diffraction
parallelogram are marked. Figure 1j presents the element mapping of the PtSe2/Pt sample. One can
see the Pt signal is much brighter with the appearance of the ultra-small Pt particles, indicating the
chemical nature of the observed particles.
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Figure 2. Oxidation state of PtSe2/Pt. a,b High-resolution XPS spectra of Pt 4f orbitals of PtSe2 and
PtSe2/Pt, respectively. c,d High-resolution XPS spectra of Se 3d orbitals of PtSe2 and PtSe2/Pt,
respectively. e XANES of corresponding samples. f EXAFS of corresponding samples.
The valence state and chemical coordination environment of the prepared samples were
characterized by XPS (X-ray photoelectron spectroscopy) and XAS (X-ray absorption
spectroscopy). The XPS spectra were calibrated using the C1s peak (Figure S2). Figure 2a and
Figure 2b compare the high-resolution XPS spectra of Pt 4f orbitals of PtSe2 and PtSe2/Pt,
respectively. The deconvoluted peaks located at around 76 and 72.6 eV correspond to the 4f5/2 and
4f7/2 orbitals of Pt2+, respectively, which is in consistent with references[11]. It is observed that
another pair of peaks emerges for the PtSe2/Pt sample, located at 74.4 and 71.1 eV. These peaks
correspond to the 4f5/2 and 4f7/2 orbitals of Pt0, respectively, reflecting the presence of ultra-small
Pt particles. We noticed the formula of PtSe2 indicates a +4 valence of Pt. However, based on the
comparison of the binding energy of Pt in different oxides[12], the peaks around 76 and 72.6 eV
belong to the doublets of Pt2+ state. Therefore, we believe Pt in PtSe2 should exhibit a +2 valence.
The high-resolution XPS spectra of Se 3d orbitals of PtSe2 and PtSe2/Pt are displayed in Figure 2c
and Figure 2d, respectively. The peaks located at 55 and 54.1 eV correspond to Se 3d3/2 and 3d5/2
orbitals, respectively[13]. Figure 2e presents the XANES (X-ray absorption near edge structure) of
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samples with various valence states of Pt. The absorption edges originate from the Pt L3 electron
transaction. One can see the absorption edge of PtSe2/Pt locates between Pt foil and PtSe2 samples,
indicating the valence state of Pt in PtSe2/Pt is between 0 and +2. This is because the generation of
Pt cluster at the edges of PtSe2 nanosheets. Figure 2f and Figure S3 show the EXAFS (extended X-
ray absorption fine structure) of corresponding samples. The characteristic peak at 2.6 Å stands for
Pt-Pt coordination, while the peak at 2.2 Å stands for Pt-Se coordination. The presence of ultra-
small Pt particles could also be reflected by the reduced Pt-Se coordination in PtSe2/Pt, compared
to PtSe2.
Figure 3. Electrochemical measurements of the prepared samples for HER. a iR-corrected linear
sweep polarization curves in 1 M KOH. b Corresponding Tafel slopes. c Derived double layer
capacitance Cdl. d Electrochemical impedance diagrams of PtSe2 and PtSe2/Pt samples,
respectively. e Stability test at 10 mA cm-2. f Comparison of the Tafel slope and overpotential for
various Pt-based or typical HER catalysts in alkaline electrolyte, with data extracted from
references[14]
.
The HER activity of PtSe2/Pt is evaluated in 1 M KOH, with results shown in Figure 3. The iR-
corrected linear sweep voltammetry of the prepared samples is shown in Figure 3a. As one can see
in Figure 3a and Figure 3b, the PtSe2 nanosheet exhibits an overpotential of 294 mV at 10 mA/cm2
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and a Tafel slope of 147 mV/dec, while those of PtSe2/Pt sample are 42 mV and 53 mV/dec,
respectively. The HER activity of PtSe2/Pt is far superior to that of PtSe2. More importantly,
PtSe2/Pt performs even better than Pt/C electrode (with an overpotential of 65 mV at 10 mA/cm2
and a Tafel slope of 58 mV/dec), especially at large current density. Also, the mass activity of
PtSe2/Pt and Pt/C are compared in Figure S5. This observation reveals that the outstanding activity
of PtSe2/Pt does not originate totally from Pt, indicating new highly active sites other than Pt are
generated. To further explore the nature of the observed high activity of PtSe2/Pt, we measured the
electrical double layer capacitances (Cdl) in Figure 3c. The value of Cdl is obtained by data
processing of cyclic voltammetry at different scanning speeds, as shown in Figure S4. It is found
that the electrochemical active area of PtSe2/Pt and PtSe2 is similar to each other with 5.8 mF cm-2
for PtSe2/Pt and 4.9 mF cm-2 for PtSe2, respectively, suggesting similar active sites loading.
Therefore, the large improvement of the HER activity of PtSe2/Pt must be deduced from the
upgrading of the activity of single site. The electrochemical impedance diagrams of PtSe2 and
PtSe2/Pt are shown in the up and down panels in Figure 3d, which can be fitted by the equivalent
circuits. The electrochemical data is summarized in Table S2. As one can see, the electrical
impedance of PtSe2/Pt is much smaller than PtSe2, which implies the improved conductivity
facilitates the superior activity of PtSe2/Pt. The long-term stability test of PtSe2/Pt is shown in
Figure 3e, which confirms the as-prepared PtSe2/Pt maintains its high low overpotential and shows
good stability. The polarization curve after 1000 CV circles is illustrated in Figure S8, showing the
same results. The Faraday efficiency of our sample was evaluated using a gas chromatography and
a gas proof H-shaped electrolytic tank (Figure S6), with results listed in Figure S7. The XRD, TEM
and XPS characterizations after stability test are shown in Figure S9, Figure S10 and Figure S11,
respectively. It can be deduced that the PtSe2/Pt keeps its structure, morphology, crystal and
oxidation state after the harsh stability test. The stability of PtSe2/Pt sample can be further
confirmed by these characterizations. To emphasis the high performance of PtSe2/Pt, a brief
summarization of the Tafel slope and overpotential for various Pt-based or typical HER catalysts
in alkaline electrolyte is shown in Figure 3f.
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Figure 4. DFT calculations. a The structure model in the DFT calculation: PtSe2 nanosheet
decorated with Pt13 cluster. Colored circles mark the active centers. Vn means that n Se vacancies
are included. b The formation energy relative to V0 model. c Electron deformation density of the
V2 model. d Partial density of states of the V2 model. e The H adsorption free energy of the active
sites marked in a. f Absolute value of the H adsorption free energy. g The partial density of states
between H and active sites of the V2 model.
To investigate the underlying mechanism that triggers the activity enhancement, the density
function theory (DFT) calculations are performed within an electrochemical framework to ascertain
the HER activity of the functional PtSe2/Pt material. Since Pt nanoparticle with a size of ~ 2 nm is
nearly impossible for DFT calculations, the Pt13 cluster is adopted as the alternative in our present
work. In the optimized structure, several Se atoms tend to transfer to the Pt13 cluster, leaving Se
vacancies in the basal PtSe2 nanosheet. This trend is in accord with the STEM observation. The
stimulation models are descripted in Figure 4a and Figure S12, where Vn stands for the number of
Se vacancies that are induced due to the Pt decoration. As illustrated in Figure 4b, the formation
energy of Vn is clearly negative compared to the V0 model (Table S3 for details), which
thermodynamically accounts for the generation of Se vacancies. Moreover, strong Pt-Pt bonding
between the cluster and the PtSe2 substrate is formed to anchor the Pt cluster, which indicates high
stability of this material. Additionally, Figure 4 c and Figure 4d character the electron deformation
density and partial band structure of the reprehensive V2 model, respectively. One can see the large
overlap between the Pt 5d and Se 4p orbitals, as well as the dense electron cloud between the Pt
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cluster and PtSe2 basal plane, which verifies again the generation of Se vacancies. Overall, these
results indicate that the thermodynamic preference of Se vacancies stems from the strong covalent
bonding of Pt-Se bonds.
According to the Sabatier principle, the ideal HER electrocatalyst should possess the subtle balance
between H adsorption and the H protonation, which means that the universal descriptor, H
adsorption free energy G, features with the thermo-neutrality to represent the superior HER
activity[15]. In the regard, Figure 4e provides the free energy profiles of the active centers and the
absolute value of G is summarized in Figure 4f. The G of 1.02 eV clearly uncovers the
insufficient proton adsorption on the Se site of the pristine PtSe2, suggesting poor activity of pristine
PtSe2 nanosheet. By decorating Pt nanoparticles, the affinity of active H• species can be largely
improved on the exposed Pt sites at the very vicinity of Se vacancies and the Pt/Se sites on the Pt
cluster, delivering high HER activity. Taking V2 model as an illustration, the corresponding G are
-0.04, 0.30 and -0.06 eV, respectively, some of which even outperforms the art-of-state Pt (G =
-
0.09 eV). The similar tendencies are preserved for V1 and V3 models. The free energy values of
various sites in the considered calculation models are summarized in Table S4. Figure 4g provides
the density of states of the active centers to shed lights on the enhanced H adsorption. The Se-H
bond originates from the sp hybridization while the Pt-H stems from the sd couplings, in line with
the previous reports. What’s more, to better mimic the ultra-small Pt particle, the Pt38 cluster models
were also calculated with results shown in Figure S13, Table S3 and Table S4, which show the same
trend with the Pt13 model. The theoretical data confirms the good HER activity of the advanced
PtSe2/Pt material.
3. Conclusions
In summary, we report large performance improvement on the HER activity of PtSe2 nanosheet, a
typical NMD compound. Ultra-small Pt nanoparticles are in situ generated on the edge of PtSe2
nanosheet to form the PtSe2/Pt heterointerface, with induced Se vacancies distributed along the
boundary. The Se vacancies reduce the coordination environment, exposing highly active Pt centers.
DFT calculations reveals that the free energy change can be optimized benefitting from this unique
interface structure. The excellent HER activity is examined in alkaline electrolyte, with an
overpotential of 42 mV at 10 mA/cm2 and a Tafel slope of 53 mV/dec.
Acknowledgements
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10.1002/anie.202110335
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This study was supported by Key Research and Development of Ministry of Science and
Technology of China (No. 2018YFE0202601), National Natural Science Foundation of China
(51902220, 52072255) and Natural Science Foundation of Zhejiang Province (No. LY21E020001,
LTY20E020001).
Conflict of Interest
The authors declare no conflict of interests regarding the publication of this article.
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