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Energy, Environmental, and Catalysis Applications

A Metal-Organic-Framework-Derived (Zn0.95Cu0.05)0.6Cd0.4S Solid
Solution as Efficient Photocatalysts for Hydrogen Evolution Reaction
Jing Liu, Jianrui Feng, Lele Lu, Boyuan Wu, Peng Ren, Wei Shi, and Peng Cheng
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b19257 • Publication Date (Web): 05 Feb 2020
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6 A Metal-Organic-Framework-Derived
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(Zn0.95Cu0.05)0.6Cd0.4S Solid Solution as
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Efficient Photocatalysts for Hydrogen
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14 Evolution Reaction
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17 Jing Liu,† Jianrui Feng,† Lele Lu,† Boyuan Wu,† Peng Ren,*,‡ Wei Shi*,† and Peng
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20 Cheng†
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23 †Key Laboratory of Advanced Energy Materials Chemistry (MOE), College of
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26 Chemistry, Nankai University, Tianjin 300071, China
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29 ‡School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen 518055,
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32 China
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35 KEYWORDS: Metal-Organic-Framework, Solid Solution, DFT calculation,
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38 Photocatalyst, hydrogen evolution reaction
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42 ABSTRACT: Photocatalytic water splitting taking the advantage of using solar energy
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directly is one of the most effective strategies for hydrogen evolution. The development
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47 of facile methods for synthesizing highly efficient and stable photocatalysts for
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50 hydrogen production still remains great challenges. Herein, a metal-organic framework
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52 (MOF)-templated strategy was designed for the synthesis of solid solutions of
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55 (Zn0.95Cu0.05)1-xCdxS that exhibit outstanding photocatalytic hydrogen production
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reaction activity. More importantly, efficient light capturing ability and photo-
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4 generated charges separation were accomplished via fine-tuned the composition of the
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7 photocatalysts by adjusting the concentrations of doping metals in the template MOFs.
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9 Under visible light (λ > 420 nm), an optimized nanocatalyst, (Zn0.95Cu0.05)0.6Cd0.4S,
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12 exhibited a higher durability and satisfied photocatalytic hydrogen evolution rate of
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4150.1 μmol g-1 h-1 of water splitting.
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19 INTRODUCTION
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21 Photocatalysts for water splitting have been paid wide attentions owing to their
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24 functions for the convertion of solar energy to the sustainable and green power resource
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26 of hydrogen to take the place of traditional fossil fuels in the future.1-6 ZnS, with the
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29 suitable conduction band (CB) potential which can provide sufficient reductive
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32 electrons is supposed as a common photocatalyst.7 But owing to the wide bandgap of
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34 3.5 eV, ZnS only absorbs UV light, which significantly hinders its application.
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37 Recently, scientists have made a lot of efforts to modify ZnS via constructing
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39 heterogeneous photocatalytic systems or incorporating Cu or Ni to form solid solutions
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42 to make ZnS use visible-light sufficiently.8-12 On the other hand, CdS, one of the most
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45 potential photocatalysts, has a broad range in visible-light absorption because of its
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47 narrow 2.4 eV band gap.13-16 However, pristine CdS showed poor photocatalytic
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50 performance because of the rapid recombination of photo-excited electron-hole pairs.17-
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52 21 It is desirable to form a solid solution by combining Cu-doped ZnS with CdS that can
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55 lead to the wider scope of solar light absorption and effective photo-excited electron-
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58 hole separation.22 The combination of ZnS in CdS can not only achieve fine-tuned
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4 chemical composition of the solid solution, but also reduce the photocorrosion effect of
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7 pure CdS to a certain extent,23 which can further improve the catalyst’s activity and
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9 stability of photocatalytic hydrogen production. However, a satisfactory synthetic
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12 strategy for such solid solution with high-performance, high-stability for photocatalytic
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water splitting is still highly challenging.
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17 Metal-organic frameworks (MOFs),24-26 as a type of porous compounds consisting
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20 of metal nodes and organic linkers, were studied as precursors for nanomaterials
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22 because of their large surface areas, various composition and structures, as well as long-
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25 range ordered structures at molecular level.27-29 Taking advantages of the accurate
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molecular organization, inerratic morphology features, well-defined channels and
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30 structural varieties, post-synthesis calcination of MOFs has been demonstrated as a
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33 powerful approach in energy-related materials.30-33 In comparison to other well-known
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35 methods for synthesizing solid solutions,22 the MOF-templated strategy can result in
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38 the nanomaterials with high porosity, crystallinity and uniformity and hence is
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beneficial for efficient transportation and separation of the photo-excited electron-hole
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43 pairs. In addition, enhanced light capturing ability could be accomplished by fine-tuned
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46 of the bandgap via well-controlled molar ratio of the components of the MOF
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48 precursors. Nevertheless, a well-designed preparation strategy for excellently active
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51 and stable solid solution catalysts derived from MOFs for photocatalytic hydrogen
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evolution reaction (HER) has not been documented.
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4 In this work, we demonstrated the preparation of (Zn0.95Cu0.05)1-xCdxS solid solutions
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7 as HER catalyst without any cocatalysts based on a rationally designed MOF-templated
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9 method for the first time. The above-mentioned solid solutions with well-proportioned
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12 composition distribution were obtained through solvothermal method followed by high
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temperature calcination for a Zn, Cu doped Cd-MOF. On the basis of definite molar
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17 ratio of Zn and Cu, the composition of (Zn0.95Cu0.05)1-xCdxS can be well-controlled via
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20 altering the Cd ratio in (Zn0.95Cu0.05)1-xCdx-MOF. The fine-tuned conduction band edge
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22 can influence the hydrogen production rate of the catalyst for photocatalytic water
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25 splitting. Among these as-prepared solid solutions, (Zn0.95Cu0.05)0.6Cd0.4S exhibits the
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highest photocatalytic hydrogen generation performance by visible-light (λ > 420 nm)
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30 irradiation with excellent stability and superior sustainability, due to the wider scope of
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33 solar light absorption capacity and effective separation of photo-excited electron-hole
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35 pairs.
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38 EXPERIMENTAL SECTION
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40 Chemicals and Materials. Zn(NO3)2·6H2O, Cd(NO3)2·4H2O, Ni(NO3)2·6H2O,
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42 polyvinylpyrrolidone (PVP, M r = 8000) and 1,4-benzenedicarboxylate (H2bdc) were
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45 purchased from Alfa Aesar. N, N-dimethylformamide (DMF), methanol, and absolute
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47 ethanol were from Tianjin Guangfu Fine Chemical Research Institute. Thioacetamide
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49 (TAA) was from Sigma-Aldrich. Sodium sulfide nonahydrate (Na2S·9H2O) and sodium
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52 sulfite (Na2SO3) were from Sinopharm Chemical Reagent Co., Ltd. High-purity water
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54 was used for the photocatalytic HER. All chemicals were used as received.
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4 Preparation of (Zn0.95Cu0.05)1-xCdxS. A two-step synthetic method was used for
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7 (Zn0.95Cu0.05)1-xCdxS nanocatalysts. The (Zn0.95Cu0.05)1-xCdx-MOF or Zn1-xCdx-MOF
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9 (Supporting Information) (70 mg), TAA (250 mg) and 16 mL of absolute ethanol were
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12 sealed in a 23 mL Teflon-lined stainless-steel autoclave. After reaction at 120 °C for 4
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h and cooled to room temperature, the mixture was centrifugated and washed by ethanol
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17 of three times, and then dried at 50 ºC overnight. The obtained product was annealed at
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20 200 °C for 4 h with a heating speed of 2 ºC min-1 in a tube furnace under Ar atmosphere.
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22 A series of products were collected and named (Zn0.95Cu0.05)1-xCdxS ((Zn0.95Cu0.05)S,
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25 (Zn0.95Cu0.05)0.8Cd0.2S, (Zn0.95Cu0.05)0.6Cd0.4S, (Zn0.95Cu0.05)0.4Cd0.6S,
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(Zn0.95Cu0.05)0.2Cd0.8S and CdS) and Zn1-xCdxS (ZnS, Zn0.8Cd0.2S, Zn0.6Cd0.4S,
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30 Zn0.4Cd0.6S and Zn0.2Cd0.8S), accordingly.
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33 Materials characterization. The solid solutions were characterized by powder X-ray
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35 diffraction (PXRD), thermogravimetric analyses (TGA), X-ray photoelectron
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38 spectroscopy (XPS), UV-vis spectroscopy, photoluminescence spectroscopy (PL),
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elemental analyses (EA), inductively coupled plasma optical emission spectrometry
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43 (ICP-OES), scanning electron microscopy (SEM), transmission electron microscopy
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46 (TEM), and nitrogen adsorption isotherm measurement. The photoelectrochemical
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48 experiments were performed using a CHI660D electrochemical workstation. The
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51 photocatalytic water splitting tests were performed using a photocatalytic testing
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system as we used previoulsy.28,29 Calculation method and other details are available in
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4 RESULTS AND DISCUSSION
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7 Characterizations. A facile and economic method instead of conventional
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9 solvothermal method was applied to synthesize a Cd-MOF ([Cd(bdc)(DMF)]n) as the
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12 precursor with micro-sized particles (Figure S1). According to the photocatalytic
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performance optimization test, ZnS doped by Cu with a mole ratio of Zn to Cu of 0.95
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17 : 0.05 showed the optimum photocatalytic activity and hence the ratio of Zn to Cu in
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20 (Zn1-xCux)-MOF was determined (Figures S2-S4). The (Zn0.95Cu0.05)1-xCdx-MOF
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22 (Figures S5 and S6, x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) were successfully prepared by
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25 replacing Cd2+ sites with Cu2+ and Zn2+ ions. During the hydrothermal process of
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ethanol solution containing TAA and (Zn0.95Cu0.05)1-xCdx-MOF, H2S was produced.34
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30 The generated H2S spread into the pores and reacted with (Zn0.95Cu0.05)1-xCdx-MOF
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33 followed by calcination to produce (Zn0.95Cu0.05)1-xCdxS nanocomposites (x = 0, 0.2,
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35 0.4, 0.6, 0.8 and 1.0) (Scheme 1).
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38 Scheme 1. The synthesis route of the (Zn0.95Cu0.05)1-xCdxS solid solutions.
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51 The PXRD patterns of (Zn0.95Cu0.05)1-xCdxS showed that the phase structures
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54 transform from hexagonal CdS (JCPDS 1-780) to cubic ZnS (JCPDS 1-792) with
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decreased amount of Cd (Figure 1a). The difference between the diffraction peaks of
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4 (Zn0.95Cu0.05)1-xCdxS and Zn1-xCdxS (Figure S7) is not obvious owing to the similar
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7 radius of Cu2+ and Zn2+ and the low amount of Cu2+ in the composition. The elemental
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9 mapping images and electron dispersive spectroscopy (EDS), as shown in Figures S8-
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12 S13 and Figure S14, respectively, showed that Cd-MOFs doped with various ratios of
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Zn and Cu were successfully obtained and Zn/Cu/Cd distributed homogeneously. After
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17 the calcination at 200 °C for 4 h, the products were measured by SEM (Figure S15) to
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20 study the morphologies and microstructures. Furthermore, high-resolution transmission
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22 electron microscopy (HRTEM) and electron diffraction (ED) images of
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25 (Zn0.95Cu0.05)0.6Cd0.4S were measured. The size of the nanoparticles of
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(Zn0.95Cu0.05)0.6Cd0.4S are ~ 9 nm (Figure 1b). The distinct three diffraction rings can
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30 be assigned to (111), (220) and (311) planes of cubic ZnS phase (Figure 1b, inset).35 As
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33 shown in Figure 1c, the lattice fringes of a spacing 0.310 nm is closed to the (111) plane
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35 of cubic ZnS. Additionally, elemental mapping images of (Zn0.95Cu0.05)0.6Cd0.4S (Figure
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38 1d) confirmed that overall elements (Cu, Zn, Cd and S) were uniformly dispersed
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throughout the solid solution.
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43 According to the XPS spectra, characteristic peaks were in good agreement with the
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46 Cu 2p, Zn 2p, Cd 3d and S 2p spectra of CuS,36 ZnS37 and CdS,38,39 respectively,
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48 indicating the existence of Cu, Zn, Cd, and S in (Zn0.95Cu0.05)0.6Cd0.4S (Figure S16).
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51 Low-intensity diffraction peaks detected from the spectrum of Cu 2p and C 1s are
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attributed to its small amount in the nanocomposite and adventitious hydrocarbon.40
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56 Meanwhile, owing to the relatively low calcination temperature, there was partially
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4 amorphous carbon, which is conductive and has no direct influence to the photocatalytic
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7 performance but it can increase the conduction rate of photo-generated electrons and
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9 enhance the light capturing ability. The amounts of metal elements in the (Zn0.95Cu0.05)1-
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12 xCdxS nanocomposites play a key important in photocatalytic activity; furthermore, the
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amounts of Cu, Zn and Cd in the target products are not in accordance with those of
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17 added in the synthetic process of MOFs owing to the different binding capability of
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20 metal ions and the ligands, as attested via ICP-OES and EA (Table S1).
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51 Figure 1. (a) PXRD patterns of (Zn0.95Cu0.05)1-xCdxS solid solutions. (b) TEM image,
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ED image (Figure 1b, inset), (c) HRTEM image and (d) elemental mapping images of
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4 To study the influence of specific surface areas of the photocatalysts on the
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7 photocatalytic performance,41 the isotherms of nitrogen adsorption/desorption of CdS
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9 and (Zn0.95Cu0.05)0.6Cd0.4S was measured to obtain the Brunauer-Emmett-Teller (BET)
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12 surface areas (Figure S17) and the pore size distributions (Figure S18).42 The surface
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area of (Zn0.95Cu0.05)0.6Cd0.4S (86.67 m2 g-1) is higher than that of CdS (54.89 m2 g-1),
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17 possibly due to an decrease of the material density and complicated surface of the solid
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20 solution.43
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48 Figure 2. (a) UV-Vis spectra, (b) PL spectra, (c) EIS plots and (d) Photocurrent-time
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51 dependence of (Zn0.95Cu0.05)1-xCdxS.
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54 To study the electronic band structures of (Zn0.95Cu0.05)1-xCdxS, we measured UV-
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57 Vis spectra and PL spectra. In contrast to pure CdS, the absorption band edges of
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4 (Zn0.95Cu0.05)1-xCdxS became narrow (Figure 2a), indicating the efficient utilization of
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7 the visible light of (Zn0.95Cu0.05)1-xCdxS nanocomposites could be fine-tuned via
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9 altering the amount of CdS. In addition, the estimated bandgap energy (Eg) of
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12 (Zn0.95Cu0.05)1-xCdxS were decreased from 3.14 to 2.38 eV with the x value increased
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from 0 to 1 on the basis of the Kubelka-Munk calculation (Figure S19).44 Based on
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17 Mott-Schottky plots, the CB/VB levels and redox potentials of different samples were
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20 also provided (Figure S20 and Table S2). This result means that the increased amount
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22 of doped Cu and Zn ions in CdS led to the wided bandgap and narrowed absorption
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25 range of CdS to an extensive long tail in the visible range. For the PL spectra, as shown
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in Figure 2b, (Zn0.95Cu0.05)0.6Cd0.4S showed the weakest PL intensity among
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30 (Zn0.95Cu0.05)1-xCdxS. The PL quenching indicates the efficient restraint for the
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33 recombination of the photo-excited charges.45 Higher recombination velocity could
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35 weaken the photocatalytic performance. The lifetimes of (Zn0.95Cu0.05)1-xCdxS solid
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38 solutions and CdS obtained from the time-resolved PL decay curves were 0.3855,
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0.4406, 0.4563, 0.4482, 0.4478, 0.4315 µs, respectively (Figure S21). Furthermore, in
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43 the electrochemical impedance spectra (EIS) plot of Figure 2c, the Nyquist arc radius
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46 of (Zn0.95Cu0.05)1-xCdxS decreased dramatically compared to that of pristine
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48 (Zn0.95Cu0.05)S, while (Zn0.95Cu0.05)0.6Cd0.4S exhibited the smallest diameter. It is
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51 suggested a more efficient interfacial charge transfer of (Zn0.95Cu0.05)0.6Cd0.4S, which
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probably attributes to the fact that the solid-solution has stronger electron attraction and
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4 (Zn0.95Cu0.05)0.6Cd0.4S exhibited the highest photocurrent on account of the high-
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7 efficiency separation of the photo-induced charge carriers (Figure 2d).48,49
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9 Photocatalytic HER Tests. The photocatalytic HER of (Zn0.95Cu0.05)1-xCdxS was
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12 investigated under visible light irradiation (λ > 420 nm), with Na2S·9H2O and Na2SO3
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as the hole sacrificial reagent in the absence of any cocatalysts. The HER rate of the
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17 best material, (Zn0.95Cu0.05)0.6Cd0.4S, reached 4150.1 μmol g-1 h-1, ~26 times greater
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20 than that of CdS (161.1 μmol g-1 h-1) (Figure 3a), which is eight times higher than
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22 (Zn0.95Cu0.05)0.67Cd0.33S synthesized by stirring method at room temperature,22 due to
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25 more homogeneous distribution of Cu/Zn/Cd/S elements and well crystallinity
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throughout the solid solution obtained by this Cd-MOF-template. A comparison of the
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30 HER rates of CdS-based solid solution for water splitting was listed in Tables S3 and
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33 S4, suggesting that the photocatalytic performance of this solid solution is better than
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35 most of the ZnxCd1-x semiconductors with or without CuS as cocatalyst. Additionally,
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38 the increase of the CdS amount in (Zn0.95Cu0.05)1-xCdxS led to improved photocatalytic
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activity from (Zn0.95Cu0.05)S to (Zn0.95Cu0.05)0.6Cd0.4S and decreased from
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43 (Zn0.95Cu0.05)0.6Cd0.4S to CdS (Figure 3b). It is noted that the light capturing capability
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46 and conduction band potential of the photocatalyst have an important influence for
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48 photocatalytic activity. Considering that (Zn0.95Cu0.05)S and CdS exhibited low
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51 photocatalytic HER performance owing to the large bandgap and lower conduction
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band position, respectively, (Zn0.95Cu0.05)0.6Cd0.4S achieved optimized light absorption
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4 (Zn0.95Cu0.05)S and CdS in solid solutions. We further investigated the photocatalytic
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7 performance of Zn1-xCdxS for hydrogen evolution reaction to emphasize the importance
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9 of Cu in the material (Figures S22-S25). (Zn0.95Cu0.05)1-xCdxS showed remarkable
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12 photocatalytic hydrogen-production activities than that of Zn1-xCdxS nanocomposites,
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suggesting that doping Cu in Zn1-xCdxS to form (Zn0.95Cu0.05)1-xCdxS can enhance the
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17 photocatalytic performance. The apparent quantum efficiency (AQE) for
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20 (Zn0.95Cu0.05)0.6Cd0.4S reached the maximum value of 7.91% at 420 nm, which
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22 decreased prominently for longer wavelengths, achieving 7.55%, 6.01%, 4.51%, and
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25 2% at 435, 450, 500, and 520 nm, respectively (Figure 3c). In comparison, Zn0.6Cd0.4S
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had a relatively low AQE of 6.11% at 420 nm. The AQE was calculated based on the
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30 following equation with the data acquired with a cutoff filter (cut on 420, 435, 450, 500,
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33 and 520 nm, respectively) under a uniform reaction condition.
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number of reacted electrons
35 AQE (%) = × 100%
36 number of incident photons
37 2 × number of evolved H2 molecules
38 = number of incident photons × 100%
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31 Figure 3. (a) Photocatalytic hydrogen evolution over (Zn0.95Cu0.05)1-xCdxS. (b)
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34 Comparison of photocatalytic HER rates of (Zn0.95Cu0.05)1-xCdxS solid solutions and
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37 CdS. (c) Wavelength dependence of external quantum efficiency for
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39 (Zn0.95Cu0.05)0.6Cd0.4S. (d) HER cycle testing for (Zn0.95Cu0.05)0.6Cd0.4S. All experiments
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42 were carried out under visible light (λ > 420 nm, 300 W Xe lamp).
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45 To evaluate the stability and reusability of the photocatalyst, a 40-hour experiment
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48 was carried out over the best-performing (Zn0.95Cu0.05)0.6Cd0.4S. Compared with the
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patterns (Figure S26), TEM image and elemental mapping images (Figure S27),
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Figure 4. (a) Projected band structure of the model, where blue indicates more
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43 contribution of Cu and red indicates less contribution of Cu, (b) Projected density of
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46 states of (Zn0.95Cu0.05)1-xCdxS model, implying that Cu and S occupy the valence band
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48 maximum while there is almost no contribution from Cu in conduction band.
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To further study the importance of Cu in the increased photocatalytic performance
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54 of (Zn0.95Cu0.05)1-xCdxS, density functional theory (DFT) calculations were performed
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57 using the Vienna ab initio simulation package (VASP) to optimize the structures and
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4 calculate the projected band structure and density of states (PDOS). The solid solution
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7 model employed for this calculation is shown in Figure S28. Compared with the
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9 experimental value, the calculated band gap of 1.0 eV for (Zn0.95Cu0.05)0.6Cd0.4S is lower
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12 than the experimental value owing to the proverbial limitation of DFT calculation
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(Figure 4a).50,51 Additionally, the band structure of (Zn0.95Cu0.05)0.6Cd0.4S suggested that
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17 Cu (the bule color) has certain contribution to the valence band and almost no
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20 contribution to the conduction band, which is in accordance with the projected density
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22 of states. As shown in Figure 4b, Cu and S occupy the valence band maximum,
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25 confirming that the certain contribution from Cu in the valence band, while there is no
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obvious contribution from Cu in the conduction band.
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30 CONCLUSIONS
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33 In summary, as efficient photocatalysts, well-designed solid solutions of
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35 (Zn0.95Cu0.05)1-xCdxS were synthesized by a metal-organic framework-templated
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38 approach of solvothermal sulfidation followed by calcination for photocatalytic water
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splitting. Wider range of solar light absorption and effective photo-excited charges
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43 separation were accomplished via well-designed control of the homogeneous chemical
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46 composition of polymetallic sulfide at a molecular level. Under visible light, the
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48 optimized (Zn0.95Cu0.05)0.6Cd0.4S showed significant enhanced photocatalytic
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51 hydrogen-production rate of 4150.1 μmol g-1 h-1 and stability over 40 h arising from its
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suitable bandgap and ideal position of the conduction band edge. The study presents
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4 photocatalyst but also the incorporation of nanomaterials science and metal-organic
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7 framework chemistry for solar energy conversion.
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9 ASSOCIATED CONTENT
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Supporting Information
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16 The Supporting Information is available free of charge on the ACS Publications website
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18 at DOI: 10.1021/acsami.xxxxxxx
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20
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22 Details of experimental/method section; Calculation Method and Models; PXRD
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24 patterns, EDS, Elemental mapping images and TG curves of (Zn0.95Cu0.05)1-xCdx-
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27 MOF; SEM images, the bandgaps, and EA of (Zn0.95Cu0.05)1-xCdxS; XPS spectra,
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nitrogen adsorption isotherm of (Zn0.95Cu0.05)0.6Cd0.4S; additional figures and
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32 tables. (PDF)
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35 AUTHOR INFORMATION
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Corresponding Author
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42 * E-mail: shiwei@nankai.edu.cn (W.S.).
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45 * E-mail: renpeng@hit.edu.cn (P.R.)
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48 ORCID
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Wei Shi: 0000-0001-6130-1227
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55 Notes
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4 The authors declare no competing financial interest.
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7 ACKNOWLEDGEMENTS
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12 This work was supported by the National Natural Science Foundation of China
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14 (21622105, 21421001 and 21702038), the Natural Science Foundation of Tianjin
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17 (18JCJQJC47200) and the Ministry of Education of China (B12015) and Shenzhen
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19 Fundamental Research Project (JCYJ20170811161344569). W.S. acknowledges the
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22 receipt of a Newton Advanced Fellowship from Royal Society.
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24
25
26 REFERENCES
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