Rational Design of Stable and Highly Active Ni Single-Atom Catalysts for Efficient Photocatalytic Hydrogen Production

Rational Design of Stable and Highly Active Ni Single-Atom Catalysts for Efficient Photocatalytic Hydrogen Production | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Rational Design of Stable and Highly Active Ni Single-Atom Catalysts for Efficient Photocatalytic Hydrogen Production DongBo Wang, Jingwen Pan, Hehui Sun, Wen He, Donghai Wu, Heyin Chen, and 14 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6740158/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Single-atom catalysts (SACs) represent a new hotspot and frontier in the field of catalysis, owing to their high atomic utilization and unique electronic structure. However, metal particles at the single-atom level are affected by the Gibbs–Thomson effect, which leads to obvious atomic agglomeration phenomena, resulting in a decrease in photocatalytic hydrogen efficiency. Currently, how to enhance the metal–support interactions to improve the dispersion of metal single atoms is the key to the design of SACs. In addition, the understanding of co-catalyst metal–support interactions is still limited. This understanding is crucial for incorporating metal–support interactions into SACs and maximize their performance via innovative design. In this study, we leverage the modulation of the electronic structure of the catalyst. The optimal Ni SA–Zn 0.67 Cd 0.33 SSe 0.5 catalyst exhibited a photocatalytic hydrogen production performance up to 125.1 mmol g −1 h −1 at 10 °C, superior to many previously reported inorganic semiconductor photocatalysts. In particular, the hydrogen production could reach 168.1 mmol g −1 h −1 without cooling, due to the photothermal effect. Integrated experimental and theoretical studies reveal that incorporating electronegativity-modified dopants (Se/Te) into Ni SACs effectively tunes the electronic structures of active sites through Ni-S/Zn bond formation. This synergistic modification not only optimizes metal-support interactions via electronic configuration tailoring, but also regulates hydrogen adsorption energy (ΔGH*) and reaction barriers, thereby significantly enhancing the photocatalytic hydrogen evolution reaction (HER) activity. Our study demonstrates a rational design strategy for single-atom catalysts through electronic structure modulation, and investigates photothermal synergistic single-atom catalytic hydrogen production, which is expected to overcome efficiency limitations in solar fuel production. Physical sciences/Chemistry/Photochemistry/Photocatalysis Physical sciences/Materials science/Materials for energy and catalysis/Photocatalysis Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction With the depletion of fossil fuels and the increasingly severe atmospheric pollution, hydrogen, an environmentally friendly and clean energy source, has gradually become a hot topic of global research. 1, 2 Photocatalytic technologies meet the carbon neutrality target because they achieve energy conversion through a natural photocatalytic process, without additional carbon emissions. 3, 4 These technologies can provide effective support for the development of “net-zero emission” strategies. Based on environmental protection and high-efficiency solar energy-driven considerations, the photocatalytic water splitting for hydrogen production has witnessed remarkable advancements, with novel photocatalysts continuously emerging, fully highlighting the core advantages of hydrogen as a zero-carbon fuel with high energy density and clean combustion products. 4, 5 The design of efficient photocatalysts is the key to develop these technologies and achieve industrialized mass production. Current homogeneous catalysts have the disadvantages of being difficult to separate and recover for recycling, while heterogeneous catalysts have the problems of low activity and poor stability due to the uneven distribution of active sites. Interestingly, single-atom catalysts (SACs) are expected to bridge the gap between heterogeneous and homogeneous catalysis by combining the “isolated sites” of homogeneous catalysts with the structural stability and ease of separation of multiphase catalysts. 6-8 The concept of “single-atom catalysis” was introduced in 2011, and SACs have achieved remarkable results in different catalytic fields. 9 In recent years, SACs have become a new research hotspot, owing to their unique electronic structure, 100% atomic utilization, and homogeneous distribution of active sites. 10, 11 Many researchers are currently exploring the synthesis, active site incorporation, and catalytic mechanism of SACs via innovative approaches, focused on providing new ideas for the dynamic development and practical application of single-atom catalysis. 12, 13 However, the development of SACs faces three key challenges: non-scalable synthesis, instability under harsh conditions, and unresolved atomic-scale mechanistic details. From a structural optimization perspective, achieving high-density single-atom dispersion necessitates dual strategic approaches: strengthening metal-support electronic interactions through coordination engineering, and maximizing the density of accessible anchoring sites via hierarchical porous architectures. The efficacy of single-atom catalysts (SACs) is governed by two pivotal interfacial interactions: the electronic and structural coupling between the metal center and its hosting support, and the adsorption/activation dynamics between the metal active site and the target reactant species. 10, 14 Shi et al. reported that the activity of palladium (Pd 1 ) was linearly proportional to the position of the lowest unoccupied molecular orbital (LUMO) of the oxide supports, providing a new perspective on the correlation between the activity and the charge state of the metal atoms. This work further validated that SACs activity and stability are governed by metal–adsorbate binding energetics and metal–support interactions. 15 Therefore, cutting–edge research has concentrated on strengthening metal–support electronic interactions and refining the adsorption/desorption dynamics of active sites with reactants to maximize the catalytic efficiency of single-atom catalysts. Enhancing metal–support interactions by tuning the electron structure is a rapidly emerging research topic. Currently the understanding of the metal–support interactions is very limited, but crucial for maximizing the performance of SACs via innovative design. 16, 17 Advanced single-atom catalysts are engineered through precise electronic modulation of the metal center's coordination environment, enabling optimized metal-support electronic coupling and tailored adsorption/desorption energetics to govern reaction pathways. Typically, atomic doping can introduce additional electronic states, leading to a redistribution of the local electron density and creating a localization effect. 18, 19 The introduction of heteroatoms will tune the HOMO–LUMO gap to further refine the electronic structure, thus altering the energy band structure and photoelectric properties of the materials. Se and Te atoms not only have larger atomic sizes, lower electronegativity, and abundant d -electrons, but also exhibit unique photovoltaic and thermoelectric properties. 20, 21 Therefore, the introduction of Se or Te heteroatoms is expected to enable the modulation of the electronic structure, promote the formation of stronger metal–support interactions, as well as modulate the adsorption/activation kinetics with the target reactants, and thus greatly improve the photo- or thermal-catalytic activity. The non-precious metal nickel has attracted much attention owing to its unique electronic structure, surface catalytic properties, synergistic interactions with semiconductors, as well as low cost and good environmental compatibility. This metal exhibits excellent catalytic activity because of its suitable d -electron density, flexible oxidation state, moderate M–H bond strength, and high density of active sites, as well as electron transfer efficiency. 22, 23 These properties make nickel a rising star in the field of photocatalysis, in which it is expected to replace noble metals as an excellent co-catalyst. 24 When the size of the metal particles is reduced to the atomic level, a dispersed point-like distribution is formed by increasing the metal–support interaction to avoid atomic aggregation. 25, 26 Moreover, photothermal catalysis is an emerging field with great potential in sustainable chemical production processes. 27, 28 In general, atomically dispersed SAC systems have higher heat transfer efficiencies than clusters/nanoparticles, which expands their application in the photothermal catalysis. This is because individual atoms efficiently trap high-energy photogenerated carriers (e.g., hot electrons), thereby generating localized hot spots with elevated temperatures. The localized thermal gradients generated by these hot spots promote the kinetic activation of the adsorbed reactants and lower the activation energy barriers, thus significantly improving the catalytic efficiency under nonequilibrium conditions. Notably, the excellent structural and electronic state coordination of SACs can be dynamically optimized according to different reaction conditions during photothermal processes. 29 Therefore, combining single-atom and photothermal catalysis to synergistically improve the catalytic performance would be a highly interesting task. Herein, Zn 0.67 Cd 0.33 S nanoflower structures doped with Se/Te atoms with high surface area and loaded with atomically isolated Ni sites on the surface were rationally synthesized via an effective strategy based on ethylenediamine-assisted coordination. The localization effect induced by the modulation of the electronic structure through the introduction of different atoms promoted the charge accumulation on Ni single atoms and S/Se/Te atoms. In addition, Ni single atoms and doped Se/Te heteroatoms with relatively low electronegativity synergistically optimized the H* adsorption kinetics, reduced the reaction barriers, and significantly improved the photocatalytic hydrogen production activity. The photocatalytic hydrogen production performance of Ni SA–Zn 0.67 Cd 0.33 SSe 0.5 and Ni SA–Zn 0.67 Cd 0.33 STe 0.2 exceeded that of previously reported Zn x Cd 1-x S-based semiconductor photocatalysts, as shown in Figure S1. In particular, the photothermal effect was confirmed by varying evolution temperatures. This work provides a feasible and effective synthesis strategy for the construction of single-atom photocatalysts for hydrogen production. Structures of single-atom catalysts The effect of doping on metal–support interactions modulated by single atoms was investigated by substituting the sulfur atoms in Zn0.67Cd0.33S (ZCS) nanoflowers with atoms of weakly electronegativities, specifically selenium (Se) and tellurium (Te). Aberration-corrected TEM images visually confirmed the presence of Ni single atoms. The spherical aberration electron microscopy images shown in Figures 1a and 1b reveal that the Ni atoms were uniformly distributed on the catalyst surface without obvious clustering or aggregation, indicating that the Ni single-atom catalyst was successfully prepared. The High-Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF–STEM) image reveals that the Ni SA-Zn 0.67 Cd 0.33 S-Se 0.5 (Ni SA–ZCSS) and Ni SA-Zn 0.67 Cd 0.33 S-Te 0.2 (Ni SA–ZCST) maintained the flower-like morphology of Zn 0.67 Cd 0.33 S-Se 0.5 (ZCSS) and Zn 0.67 Cd 0.33 S-Te 0.2 (ZCST), and the corresponding elemental distribution maps clearly show the uniform distribution of Ni, Zn, Cd, S, Se and Te, as shown in Figure 1c and Figure 1d , respectively. The actual Ni contents in Ni SA–ZCSS and Ni SA–ZCST, as obtained by ICP-MS, were 0.69 wt% and 0.52 wt%, respectively (Table S1). The actual Se content in Ni SA–ZCSS was 0.36 wt% and that of Te in Ni SA–ZCST was 0.23 wt%, indicating that the optimal doping content of Te was lower than that of Se atoms, due to the larger atomic radius of Te atom. In addition, the electronic and coordination structures of Ni in Ni SA–ZCSS and Ni SA–ZCST were confirmed by X-ray absorption fine structure spectroscopy (XAFS). A comparison of the Ni K-edge X-ray absorption near-edge structure (XANES) spectra of Ni SA–ZCSS and Ni SA–ZCST with those of Ni foil, Ni(OH) 2 , NiO, and NiS is shown in Figure 1e . The Ni K-edge absorption threshold of Ni SA–ZCSS was located between those of Ni foil and NiO, which suggests that the valence state of Ni in Ni SA–ZCSS was between 0 and +2. Moreover, the K-edge absorptions of Ni SA–ZCSS and Ni SA–ZCST were very close to each other, and the valence state of Ni (𝛿+) in Ni SA–ZCSS was slightly lower than that of Ni (𝛾+) in Ni SA–ZCST (0 < 𝛿 ~ 𝛾 < 2). The fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectra of the samples are shown in Figure 1f . No peaks corresponding to Ni–Ni bonds were found at 2–3 Å for either Ni SA–ZCSS or Ni SA–ZCST, in contrast with Ni foil, Ni(OH) 2 , and NiO. This suggests that the Ni species in Ni SA–ZCSS and Ni SA–ZCST existed as single atoms, validating the HAADF–STEM findings. Both Ni SA–ZCSS and Ni SA–ZCST displayed a main peak around ~1.98 Å, attributed to scattering interactions between Ni and other atoms. The coordination environments of Ni in Ni SA–ZCSS and Ni SA–ZCST were further analyzed by wavelet transform (WT) EXAFS, as shown in Figures 1g and S8 . The WT contour plots of Ni SA–ZCSS and Ni SA–ZCST showed only one main peak near 6.5 and 6.7 Å -1 , respectively, with a maximum intensity close to that of NiS, indicating that the nickel sites were atomically dispersed on both catalysts. Furthermore, the best-fit analysis of the EXAFS data (Figure S9 and Table S2) showed that the fitted Ni-S/Zn coordination structure was optimal. Notably, one Ni atom coordinated approximately three S, two Zn, and two O atoms on average. This feature is attributed to the presence of weakly electronegative atoms inducing hyperfine interactions between Ni and neighboring Zn/S atoms to form multiligand bonding interactions. The above results confirm that Ni single atoms in Ni SA–ZCSS and Ni SA–ZCST were firmly anchored to the surface, providing an atomic-level channel for charge transfer from the bulk phase to the surface. Performance analysis of single-atom catalysts In order to verify the effect of weakly electronegative atoms on metal–support interactions, the catalysts were further investigated by theoretical calculations and performance analysis. Based on the experimental observations and characterizations, the ZCS (101) surface with terminal S atoms (Figure S13a ) was employed as theoretical model to explore the hydrogen evolution reaction (HER) performance. The details of the calculations are described in the Supporting Information. As shown in Figures S13b and S13c , one of the surface S atoms was replaced by a Se/Te atom to simulate the Se/Te doped surfaces. Then, a Ni atom was placed on the hollow sites composed of two S and one Se or Te atoms (Figures S13d and S13e ) to build the Ni SAC model. After structural relaxation, all surfaces were found to remain flat, without obvious reconstruction. Different from the Se and Ni atoms remaining within the surface, the doped Te atoms slightly protruded from the surface, owing to their larger atomic radii. It is worth noting that the Ni atoms were held in the S/Se planes and did not protrude from the surface like the lattice Zn/Cd atoms, revealing their SAC feature. In order to identify the potential active sites for the HER, all possible positions were tested for H adsorption, and the most favorable (lowest-energy) configurations are displayed in Figure 2a–e . The adsorption energies of H atoms on various sites are listed in Table S3. Note that the top sites of S atoms always exhibited the highest H adsorption strength on all tested surfaces, followed by Se or Te, whereas the bridge Ni–Se/Te sites displayed the weakest adsorption of H atoms. The exceedingly strong H adsorption capacity of the S atoms was reduced as the Se/Te/Ni atoms were doped on the ZCS (101) surface. The Ni atoms led to the strongest reduction, followed by Te and then Se. Hence, the HER activity could be modulated by introducing the Se/Te/Ni heteroatoms. Interestingly, for the systems without Ni single atoms, regardless of the initial position of the H atom (e.g., bridge or hollow site), its optimized position would always be on top of S/Se/Te atoms (Figure 2a–c ). For the Ni SAC systems, although the S/Se/Te sites could also capture H atoms, an excessively strong adsorption would lead to H poisoning. 30 Thus, the bridge Ni-Se/Te sites were the optimal active centers for the HER (Figures 2d and 2e ). The visible light-catalyzed hydrogen production activity of the catalysts was evaluated as shown in Figures 2f , S14 , and S15 . According to Figure 2f , the hydrogen production performance of the ZCS nanoflower structure could reach 26.3 mmol g −1 h −1 , which was higher than that of the ZCS nanospheres (0.5 mmol g −1 h −1 ). Figure S14 shows that the performance of the ZCSS x (x = 0.2, 0.3, 0.4, 0.5, 0.6, and 0.7) photocatalysts doped with different amounts of Se atoms showed an increasing trend, followed by a decrease. The ZCSS 0.5 sample exhibits the optimal photocatalytic hydrogen evolution performance (45.2 mmol g −1 h −1 ), while further increasing Se incorporation leads to a marked decline in activity, likely due to excessive dopant concentrations inducing defect-mediated recombination centers. Moreover, upon adjusting the Ni single atom loading to 0.8 wt.%, the hydrogen production performance of the Ni SA–ZCSS catalyst was as high as 125.1 mmol g −1 h −1 (AQE 420 nm = 43.2%), which is the highest hydrogen production yield of ZCS-based catalysts reported in the literature to date. The activity decreased when the Ni loading exceeded 0.8 wt.%, which may be caused by increased Ni aggregation. The activity was evaluated for different Te atom doping contents as well as amounts of surface-loaded Ni single atoms, as shown in Figure S15 . ZCST 0.2 had the highest hydrogen production rate of 37.4 mmol g −1 h −1 . T Comparative analysis reveals a reduced optimal doping threshold for Te compared to Se, attributable to steric hindrance effects arising from the increased atomic size of Te relative to Se. Similarly, the Ni SA–ZCST catalyst with a surface-loaded Ni atom content of 0.8 wt.% could reach a hydrogen production of 95.2 mmol g −1 h −1 (AQE 420 nm = 39.1%). As shown in Figure S16 , Ni SA–ZCSS and Ni SA–ZCST maintained 95.1% and 87.6% of their original activities, respectively, during a 20 h cycling process, indicating their good stability. Figure 2g shows the calculated free energy diagram for the HER on the present systems. The pristine ZCS (101) surface had a very poor HER activity, with a η HER of 1.24 V due to the extremely strong H adsorption. Upon doping Se or Te anions, the HER activity was slightly enhanced, with η HER values of 0.81 and 0.31 V for Te- and Se-doped ZCS (101) surfaces, respectively. Correspondingly, the active sites changed from top S centers to Se or Te atoms. For the Ni SAC systems, benefiting from the introduction of Ni cations, the H adsorption strength at Ni single-atom active centers was greatly reduced, resulting in the highest HER activity, with η HER values of 0.20 and 0.24 V for Se- or Te-doped Ni SAC surfaces, respectively. For the H adsorbed systems, as shown in Figure 2h and Table S4, the adsorbed H atom on the pristine ZCS (101) surface lost 0.04 e and was thus positively charged, whereas its bonded S atom gained 0.43 e , carrying a negative charge. The attraction between the positive and negative charges led to a strong H adsorption. Upon substituting the S with a Se or Te atom, the Se atom also gained 0.24 e , while the Te atom lost 0.12 e . Intriguingly, the H atoms became negatively charged by gaining 0.03 and 0.16 e on Se- and Te-doped ZCS (101) surfaces, respectively. For the Se-doped Ni SAC system, the Ni atom lost 0.35 e , while the Se and H atoms gained 0.25 and 0.05 e , respectively. In contrast, except for the Ni atom that lost 0.26 e , the Te atom also lost 0.02 e and the H atom gained 0.10 e in the Te-doped Ni-SAC system. The electrostatic repulsive interactions between the negatively charged H atom and the surfaces could weaken the H adsorption. The charge density difference (CDD) plots of Ni SA–ZCSS and Ni SA–ZCST show that the H atoms gained electrons mainly from Ni atoms, and the apparent charge accumulation between H and Ni atoms stabilized the H adsorption. In fact, the CDD plots in Figure S17 show that, for the Se- or Te-doped ZCS (101) systems, the charge accumulation was mainly localized on Se or Te atoms; therefore, the top Se or Te site was the active center. In contrast, in Ni SA–ZCSS and Ni SA–ZCST the charge mainly accumulated between the Ni and S/Se/Te atoms, especially at the Ni–Se/Te bridge site, while minor charge accumulation was observed on the top Ni atom. Thus, the former was the active center for Se/Te-doped Ni SAC systems. Overall, the calculation results confirm the superiority of the Ni SAC configuration for the HER. In conclusion, the high-electronegativity surface would firmly adsorb H atoms, making the H 2 desorption process extremely difficult, thereby resulting in low HER activity, that is, H poisoning. However, doping Se or Te heteroatoms with relatively low electronegativity, especially Ni cations forming Ni SACs, could make the surface less electronegative, while distorting the whole anion shells, resulting in charge redistribution and thus regulating the HER activity. Electronic structure modulation In order to explore in detail the mechanism for the HER activity enhancement discussed above, we further investigated the electronic properties of the catalysts. For the surface systems without adsorbed H, the S/Se/Te atoms always gain electrons, while the Zn/Cd/Ni metals donate electrons. As a result, the surfaces contain excess electrons and display electronegative shells, as evidenced by the electron localization function (ELF) plots in Figure 3a . Specifically, due to their lower electronegativity of Se and Te, the number of electrons gained by Se/Te atoms are less than those captured by S atoms, which could be verified quantitatively by analyzing the net charge in Table S5, as well as visually by examining the ELF in Figure 3a and the charge density plots in Figure S18 , where the electron density around S/Se/Te follows the order S > Se > Te. Hence, it can be inferred that the surface electronegativity is gradually reduced with the Se/Te doping, until the introduction of electron-donating Ni single atoms, when it reaches the minimum. In addition, the surface electronegativity of the Se-containing systems is slightly higher than that of Te-containing ones. In situ XPS analysis elucidated light-driven charge redistribution in Ni single-atom catalysts (Ni SA–ZCSS and Ni SA–ZCST), where binding energy shifts directly reflect electron density variations at atomic scales 6,31 . Under illumination, the Zn 2p and Cd 3d spectra of Ni SA–ZCSS shifted toward higher binding energies compared to dark conditions (Figure 3b ), indicative of electron depletion at Zn/Cd sites. Conversely, the Ni 2p spectra exhibited a distinct shift toward lower binding energies (Figure 3c ), signifying electron accumulation at Ni atoms through metal−support charge transfer. This directional redistribution was further corroborated by a concurrent shift of the Se 3d peak toward lower binding energies (Figures S19a ), confirming electron enrichment at Se sites. Collectively, the Zn/Cd electron depletion and Ni/Se electron enrichment reveal unidirectional charge transfer from the ZCSS matrix to Ni single atoms under photoexcitation. These observations demonstrate the critical role of metal−support interactions in governing electron delocalization and interfacial electric field formation, which synergistically enhance photogenerated charge separation. Building on this interfacial charge transfer framework, analogous in situ XPS analysis was performed for Ni SA–ZCST to probe its Zn 2p, Cd 3d, and Ni 2p spectral evolution under illumination (Figures 3d and 3e ). Under illumination, all three spectral peaks shifted significantly toward higher binding energies, reflecting electronic restructuring at the metal-support interface. This observation indicates that Ni atoms in Ni SA–ZCSS accumulate electrons under light irradiation, establishing them as active sites on the catalyst surface. In contrast, Te atoms in Ni SA–ZCST act as electron acceptors, facilitating electron transfer from Ni to Te (Figure S19b ), which reduces the overall electron utilization efficiency. The reversible charge accumulation observed on Ni single atoms during irradiation underscores their potential as both electron acceptors and donors in photothermal catalytic processes. These findings provide critical insights into the dynamic electron transfer mechanisms between single-atom catalysts and their supports under irradiation, highlighting the importance of tailored electronic interactions for optimizing photocatalytic performance. Analysis of energy band structures As shown in Figures 4a – c , the electronic energy band structures of ZCS, ZCSS, and ZCST were measured using UPS. The typical secondary electron cutoff energies of ZCS, ZCSS, and ZCST are 17.38, 17.83, and 17.31 eV, respectively. Based on the difference between the photon energy (21.22 eV) and the cutoff energy, the work function of ZCS, ZCSS and ZCST were determined to be 3.84, 3.39 and 3.91 eV, respectively. 32 UV–vis DRS analysis demonstrates pronounced doping-modulated light absorption in ZCS-based catalysts (Figure 4d ). 33 The pristine ZCS exhibits an intrinsic bandgap of 2.43 eV (absorption edge at 510 nm, Figure S20a ). Strategic Se doping triggers a redshift (bandgap narrowing to 2.38 eV, Figure S20b ), originating from quantum confinement effects and shallow donor levels formed via Se 4p–S 3p orbital hybridization. Conversely, Te doping induces an initial blue shift (bandgap widening to 2.47 eV, Figure S20c ) arising from Te-induced lattice distortion, followed by defect-mediated mid-gap transitions at elevated doping levels. As the doping amount of Se atoms increases, the absorption band edge of ZCS shifts to longer wavelengths (redshift) due to the introduction of shallow donor levels and quantum size effects. However, the visible light absorption first decreases and then increases, reflecting the competition between the formation of deep-level defects and the optimization of the band structure (Figure S21a ). Similarly, Te doping leads to a blue shift of the absorption band edge at low doping levels, followed by a redshift at higher doping levels, with visible light absorption also showing a decrease followed by an increase (Figure S21b ). These phenomena are attributed to the interplay of lattice distortion, defect formation, and band structure modulation caused by Se and Te doping. Notably, Ni single-atom loading on Se- or Te-doped ZnCdS enhances broad-spectrum absorption (500–700 nm) through synergistic interfacial polarization and gradient band engineering, suppressing carrier recombination while boosting light harvesting. This was confirmed by the PL spectra in Figure S22 , where the lowest fluorescence peak of Ni SA–ZCSS indicates that this catalyst had the strongest electron–hole separation ability. This conclusion is also supported by the photocurrent response and impedance results in Figure S23 . Further linear extrapolation along the tangent line to the initial part of the spectrum shows that the Fermi energy level maxima ( E VB-EF ) for ZCS, ZCSS, and ZCST were 1.76, 2.14 and 1.93 eV, respectively. Combined with the Tauc plots, energy band diagrams to determine energy band structure parameters of ZCS, ZCSS and ZCST could be derived as shown in Figure 4e . The conduction band (CB) and valence band (VB) potentials of ZCSS, with a band gap energy of 2.38 V, were located at −1.34 and 1.03 V vs. NHE, respectively. Moreover, the CB and VB potentials of ZCST were −1.13 and 1.34 V vs. NHE, respectively. To understand the surface properties of the catalysts, zeta potential and contact angle measurements were performed as shown in Figure 4f . At neutral pH (pH 7), both ZCSS and ZCST exhibit significantly reduced zeta potentials compared to ZCS, indicating lower surface charge density. This reduction in surface charge likely impairs colloidal stability through diminished electrostatic repulsion, thereby promoting nanoparticle agglomeration. In contrast, Ni SA–ZCSS and Ni SA–ZCST demonstrate substantially enhanced negative zeta potentials, which directly correlate with (i) improved colloidal stability and (ii) strengthened electrostatic attraction toward cationic species, consequently promoting proton adsorption. More importantly, the introduced nickel single-atom sites remarkably enhance surface hydrophilicity by inducing localized electric field redistribution and reconstructing the hydrogen-bonding network within the interfacial hydration layer, as unambiguously confirmed by the observed reduction in water contact angle. Photothermal effects The photothermal effect plays a pivotal role in modulating reaction kinetics by simultaneously facilitating charge carrier separation/transfer dynamics and adsorption-desorption equilibrium processes. 34,35 To quantitatively characterize the photothermal behavior of the as-synthesized catalysts, infrared thermographic measurements were systematically performed under simulated solar irradiation (300 W xenon lamp, AM 1.5G filter). As illustrated in Figure 4g , the initial surface temperatures of ZCSS and Ni SA-ZCSS reached 51 and 58 °C, respectively, significantly exceeding that of pristine ZCS (28 °C) in the dark. Upon light irradiation, both modified catalysts exhibited rapid temperature escalation during the initial 100 s, attaining 116 °C (ZCSS) and 139 °C (Ni SA-ZCSS), respectively. These elevated temperatures remained stable throughout the subsequent 30-minute illumination period. Similar photothermal behavior was observed for ZCST and Ni SA-ZCST, with their surface temperatures rapidly rising to 123 and 157 °C within 100 s before reaching thermal equilibrium. To investigate the photothermal effects, the photocatalytic activity of ZCSS, Ni SA–ZCSS, ZCST, and Ni SA–ZCST were measured under visible light irradiation at different temperatures. As shown in Figure 4h , the activities of both ZCSS and Ni SA–ZCSS gradually increased as the temperature increased from 10 to 15 and 25 °C. The activities of ZCSS and Ni SA–ZCSS also increased with increasing temperature. Remarkably, the hydrogen evolution rate of Ni SA–ZCSS was as high as 168.1 mmol g −1 h −1 without cooling, and increased by 34.4% due to the photothermal effect. These results unequivocally demonstrate the pivotal role of photothermal activation in boosting photocatalytic efficiency. Analogous photothermal coupling phenomena were observed for ZCST and Ni SA–ZCST. Among them, the hydrogen evolution rate of Ni SA-ZCST reached 136.56 mmol g −1 h −1 , which increased by 43.5%. This pronounced enhancement stems from the distinctive thermoelectric properties of Te atoms, which amplify the photothermal response through enhanced charge carrier mobilization and localized heat generation. These findings unequivocally establish that the photothermal effect serves as a dominant factor in enhancing photocatalytic performance. As evidenced by real-time infrared thermographic imaging (Figure S24), the catalyst demonstrated progressive temperature gradient evolution under continuous illumination, providing direct visual confirmation of photothermal coupling phenomena. Discussion and perspectives In summary, we have established a facile ethylenediamine-mediated coordination strategy to construct Se/Te co-doped Zn 0.67 Cd 0.33 S nanoflower architectures with precisely controlled Ni single-atom sites through atomic-level engineering. The synergistic modulation of both electronic configuration and local coordination geometry in surface-anchored Ni single-atom sites, induced by heteroatoms with tailored electronegativities, was systematically investigated to elucidate their cooperative effects on hydrogen adsorption/desorption kinetics. The photocatalytic hydrogen production performances of Ni SA–Zn 0.67 Cd 0.33 SSe x and Ni SA–Zn 0.67 Cd 0.33 STe y were as high as 125.1 and 95.2 mmol g −1 h −1 , respectively. The exceptional catalytic performance originates from the formation of Ni–S/Zn bonds, which generate new hybrid orbitals and increase the Ni d-electron density. This electronic configuration facilitates the capture of photogenerated electrons while promoting their directional transfer to active sites. The synergistic interaction between isolated Ni atoms and low-electronegativity Se/Te atoms in the Ni SACs, mediated by Ni-S/Zn bond formation, precisely regulates H* adsorption kinetics and consequently enhances hydrogen evolution reaction activity. These findings provide fundamental insights into metal-support interactions for single-atom catalyst design, while demonstrating a rationally engineered approach for developing high-performance SACs systems. Declarations Acknowledgements This work was supported by the National Key Research and Development Program of China, grant number 2019YFA0705201, the National Natural Science Foundation of China under the Grant No. U2032129 and 51502061, the Olle Engkvist foundation (grant no. SOEB-2015/167), and the Swedish Energy Agency (grant no. 46641-1). E.W. thanks the Swedish Research Council Formas (2023-01008), and The Knut and Alice Wallenberg Foundation (2022.0192) and the Wallenberg Initiative Materials Science for Sustainability (WISE) for financial support. Author contributions D.W. supervised the project. J.P. designed and conducted the experiments, performed the testing and analysis of the experimental data, and wrote the manuscript. D.W. carried out the first-principles calculations and related analyses. W.H. contributed to the theoretical calculations. H.C. supervised and analyzed the XPS data. B.Z., C.Z., D.L., and S.L. performed the XRD characterization and related analyses. G.L., S.J., Y.Z., and Z.X. contributed to the development of the paper's ideas. X.F., X.C., J.W., and H.S. enhanced the electrochemical analyses. J.Z., L.Z., and E.W. guided and revised the paper. All authors discussed the results and commented on the manuscript. Competing interests The authors declare no competing interests. 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Commun. 15 , 7599 (2024). Additional Declarations There is NO Competing Interest. Supplementary Files 1.ZCS.mp4 Figure S24. Infrared thermal video of ZCS after 30 min (Video acceleration 100x). 2.ZCSS.mp4 Figure S24. Infrared thermal video of ZCSS after 30 min (Video acceleration 100x). 3.NiSAZCSS.mp4 Figure S24. Infrared thermal video of Ni SA-ZCSS after 30 min (Video acceleration 100x). 4.ZCST.mp4 Figure S24. Infrared thermal video of ZCST after 30 min (Video acceleration 100x). 5.NiSAZCST.mp4 Figure S24. Infrared thermal video of Ni SA-ZCST after 30 min (Video acceleration 100x). SupportingInformation.doc Supporting Information Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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\u003cstrong\u003ee\u003c/strong\u003e) The normalized X-ray absorption near-edge spectra at the Ni K-edge. \u003cstrong\u003ef\u003c/strong\u003e) The k\u003csup\u003e3\u003c/sup\u003e-weighted Fourier transform extended X-ray absorption fine structure spectra (EXAFS) in r-space. \u003cstrong\u003eg\u003c/strong\u003e) Wavelet Transformation for the k\u003csup\u003e2\u003c/sup\u003e-weighted EXAFS signal of Ni SA-ZCSS and Ni SA-ZCST.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/ff4fd1af167f3beeabe72608.png"},{"id":84182973,"identity":"cdecc9a7-37ff-4378-aa91-381d3914a422","added_by":"auto","created_at":"2025-06-09 04:35:38","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":255693,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePerformance analysis of single-atom catalysts.\u003c/strong\u003e Top and side views of the H adsorption configurations with the highest HER activity for a) ZCS (101), b) ZCSS (101), c) ZCST (101), d) Ni SA-ZCSS (101), e) Ni SA-ZCST (101) surfaces. The yellow, green, orange, rose red, gray, blue, and pink balls represent the S, Se, Te, Cd, Zn, Ni, and H atoms, respectively. f) Photocatalytic H\u003csub\u003e2\u003c/sub\u003e evolution rates of different catalysts. g) Free energy diagram for HER on the studied systems, and h) Top and side views of the charge density difference plots for H adsorption on ZCS (101), ZCSS (101), ZCST (101), Ni SA-ZCSS (101) and Ni SA-ZCST (101) surfaces. The yellow and cyan regions denote electron accumulation and depletion, respectively with an isosurface of 0.002 e/bohr\u003csup\u003e3\u003c/sup\u003e. The yellow, green, orange, rose red, gray, blue, and pink balls represent the S, Se, Te, Cd, Zn, Ni, and H atoms, respectively.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/cc7ecc610999ffe02574b3e2.png"},{"id":84182984,"identity":"f55c8a6b-94a6-4747-9dc1-2e3906f2c483","added_by":"auto","created_at":"2025-06-09 04:35:39","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":324604,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAnalysis of electronic structure modulations.\u003c/strong\u003e a) Electron localization function plots for ZCS (101), ZCSS (101), ZCST (101), Ni SA-ZCSS (101) and Ni SA-ZCST (101) surfaces. \u003cem\u003eIn situ\u003c/em\u003e XPS spectra of b) Zn \u003cem\u003e2p\u003c/em\u003e and Cd \u003cem\u003e3d\u003c/em\u003e, c) Ni \u003cem\u003e2p\u003c/em\u003e of Ni SA-ZCSS, and d) Zn\u003cem\u003e 2p\u003c/em\u003e and Cd \u003cem\u003e3d\u003c/em\u003e, e) Ni \u003cem\u003e2p\u003c/em\u003e of Ni SA-ZCST.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/8e4d7d1bb5ad97118563d15f.png"},{"id":84182975,"identity":"8b12bd52-d940-4227-86ff-20f2ec988d1e","added_by":"auto","created_at":"2025-06-09 04:35:38","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":206764,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAnalysis of energy bands and photothermal effects on catalysts. \u003c/strong\u003ea-c) UPS spectra and e) Schematic energy level diagrams of ZCS, ZCSS and ZCST. d) UV-vis DRS, f) Zeta-potential (The inset shows the contact angle with water) and g) Average temperatures as a function of time during light irradiation of ZCS, ZCSS, Ni SA-ZCSS and ZCST, Ni SA-ZCST. H\u003csub\u003e2\u003c/sub\u003e evolution rates of ZCSS, Ni SA-ZCSS and i) ZCST, Ni SA-ZCST at different external condensation temperatures.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/0b9398a3094030d8fa94c152.png"},{"id":85952838,"identity":"abd24ae5-ecc5-4766-bc5f-4acee62faaf1","added_by":"auto","created_at":"2025-07-03 14:15:11","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1957426,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/0f089daa-09ef-4cdf-afe2-d75623d7d670.pdf"},{"id":84182976,"identity":"0e40f56b-f8b1-4849-898a-ff834724b49c","added_by":"auto","created_at":"2025-06-09 04:35:38","extension":"mp4","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":948558,"visible":true,"origin":"","legend":"\u003cp\u003eFigure S24. Infrared thermal video of ZCS after 30 min (Video acceleration 100x).\u003c/p\u003e","description":"","filename":"1.ZCS.mp4","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/0d21ad8b3f0a50da62fc7a0e.mp4"},{"id":84182982,"identity":"728e4a76-a468-49ab-8365-6e0cc65d2201","added_by":"auto","created_at":"2025-06-09 04:35:38","extension":"mp4","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":2264776,"visible":true,"origin":"","legend":"\u003cp\u003eFigure S24. Infrared thermal video of ZCSS after 30 min (Video acceleration 100x).\u003c/p\u003e","description":"","filename":"2.ZCSS.mp4","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/514e84ae8e2d08c76ed088cd.mp4"},{"id":84182995,"identity":"5798fca0-e1cd-4960-83a1-8fe84841d587","added_by":"auto","created_at":"2025-06-09 04:35:39","extension":"mp4","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":3692622,"visible":true,"origin":"","legend":"\u003cp\u003eFigure S24. Infrared thermal video of Ni SA-ZCSS after 30 min (Video acceleration 100x).\u003c/p\u003e","description":"","filename":"3.NiSAZCSS.mp4","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/8856707c6d151e9e11371fb8.mp4"},{"id":84182978,"identity":"db97c20d-6863-4d9f-981a-902d1da24047","added_by":"auto","created_at":"2025-06-09 04:35:38","extension":"mp4","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":1311118,"visible":true,"origin":"","legend":"\u003cp\u003eFigure S24. Infrared thermal video of ZCST after 30 min (Video acceleration 100x).\u003c/p\u003e","description":"","filename":"4.ZCST.mp4","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/d020f59368dfe2a01ed5f90d.mp4"},{"id":84182996,"identity":"7c11ff9e-7c8e-4178-b29e-d6b7b0f587d8","added_by":"auto","created_at":"2025-06-09 04:35:39","extension":"mp4","order_by":5,"title":"","display":"","copyAsset":false,"role":"supplement","size":2931802,"visible":true,"origin":"","legend":"\u003cp\u003eFigure S24. Infrared thermal video of Ni SA-ZCST after 30 min (Video acceleration 100x).\u003c/p\u003e","description":"","filename":"5.NiSAZCST.mp4","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/8bd7a8db0b18912379e5dab9.mp4"},{"id":84182988,"identity":"cada6fcb-8e1d-4201-b878-90934451c0e2","added_by":"auto","created_at":"2025-06-09 04:35:39","extension":"doc","order_by":6,"title":"","display":"","copyAsset":false,"role":"supplement","size":17171968,"visible":true,"origin":"","legend":"\u003cp\u003eSupporting Information\u003c/p\u003e","description":"","filename":"SupportingInformation.doc","url":"https://assets-eu.researchsquare.com/files/rs-6740158/v1/4f9ce345e9c31fc7e199108c.doc"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Rational Design of Stable and Highly Active Ni Single-Atom Catalysts for Efficient Photocatalytic Hydrogen Production","fulltext":[{"header":"Introduction","content":"\u003cp\u003eWith the depletion of fossil fuels and the increasingly severe atmospheric pollution, hydrogen, an environmentally friendly and clean energy source, has gradually become a hot topic of global research.\u003csup\u003e1, 2\u003c/sup\u003e Photocatalytic technologies meet the carbon neutrality target because they achieve energy conversion through a natural photocatalytic process, without additional carbon emissions.\u003csup\u003e3, 4\u003c/sup\u003e These technologies can provide effective support for the development of \u0026ldquo;net-zero emission\u0026rdquo; strategies. Based on environmental protection and high-efficiency solar energy-driven considerations, the photocatalytic water splitting for hydrogen production has witnessed remarkable advancements, with novel photocatalysts continuously emerging, fully highlighting the core advantages of hydrogen as a zero-carbon fuel with high energy density and clean combustion products.\u003csup\u003e\u0026nbsp;4, 5\u003c/sup\u003e The design of efficient photocatalysts is the key to develop these technologies and achieve industrialized mass production. Current homogeneous catalysts have the disadvantages of being difficult to separate and recover for recycling, while heterogeneous catalysts have the problems of low activity and poor stability due to the uneven distribution of active sites. Interestingly, single-atom catalysts (SACs) are expected to bridge the gap between heterogeneous and homogeneous catalysis by combining the \u0026ldquo;isolated sites\u0026rdquo; of homogeneous catalysts with the structural stability and ease of separation of multiphase catalysts.\u003csup\u003e6-8\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eThe concept of \u0026ldquo;single-atom catalysis\u0026rdquo; was introduced in 2011, and SACs have achieved remarkable results in different catalytic fields.\u003csup\u003e9\u003c/sup\u003e In recent years, SACs have become a new research hotspot, owing to their unique electronic structure, 100% atomic utilization, and homogeneous distribution of active sites.\u003csup\u003e10, 11\u003c/sup\u003e Many researchers are currently exploring the synthesis, active site incorporation, and catalytic mechanism of SACs via innovative approaches, focused on providing new ideas for the dynamic development and practical application of single-atom catalysis.\u003csup\u003e12, 13\u003c/sup\u003e However,\u0026nbsp;the development of SACs faces three key challenges: non-scalable synthesis, instability under harsh conditions, and unresolved atomic-scale mechanistic details.\u0026nbsp;From a structural optimization perspective, achieving high-density single-atom dispersion necessitates dual strategic approaches: strengthening metal-support electronic interactions through coordination engineering, and maximizing the density of accessible anchoring sites via hierarchical porous architectures. The efficacy of single-atom catalysts (SACs) is governed by two pivotal interfacial interactions: the electronic and structural coupling between the metal center and its hosting\u0026nbsp;support, and the adsorption/activation dynamics between the metal active site and the target reactant species.\u003csup\u003e\u0026nbsp;10, 14\u0026nbsp;\u003c/sup\u003eShi et al. reported that the activity of palladium (Pd\u003csub\u003e1\u003c/sub\u003e) was linearly proportional to the position of the lowest unoccupied molecular orbital (LUMO) of the oxide supports, providing a new perspective on the correlation between the activity and the charge state of the metal atoms.\u0026nbsp;This work further validated that SACs activity and stability are governed by metal\u0026ndash;adsorbate binding energetics and metal\u0026ndash;support interactions.\u003csup\u003e15\u003c/sup\u003e Therefore,\u0026nbsp;cutting\u0026ndash;edge research has\u0026nbsp;concentrated on strengthening metal\u0026ndash;support electronic interactions and refining the adsorption/desorption dynamics of active sites with reactants to maximize the catalytic efficiency of single-atom catalysts.\u003c/p\u003e\n\u003cp\u003eEnhancing metal\u0026ndash;support interactions by tuning the electron structure is a rapidly emerging research topic. Currently the understanding of the metal\u0026ndash;support interactions is very limited, but crucial for maximizing the performance of SACs \u003cem\u003evia\u0026nbsp;\u003c/em\u003einnovative design.\u003csup\u003e16, 17\u003c/sup\u003e Advanced single-atom catalysts are engineered through precise electronic modulation of the metal center\u0026apos;s coordination environment, enabling optimized metal-support electronic coupling and tailored adsorption/desorption energetics to govern reaction pathways. Typically, atomic doping can introduce additional electronic states, leading to a redistribution of the local electron density and creating a localization effect.\u003csup\u003e18, 19\u003c/sup\u003e The introduction of heteroatoms will tune the HOMO\u0026ndash;LUMO gap to further refine the electronic structure, thus altering the energy band structure and photoelectric properties of the materials. Se and Te atoms not only have larger atomic sizes, lower electronegativity, and abundant \u003cem\u003ed\u003c/em\u003e-electrons, but also exhibit unique photovoltaic and thermoelectric properties.\u003csup\u003e20, 21\u003c/sup\u003e Therefore, the introduction of Se or Te heteroatoms is expected to enable the modulation of the electronic structure, promote the formation of stronger metal\u0026ndash;support interactions, as well as modulate the adsorption/activation kinetics with the target reactants, and thus greatly improve the photo- or thermal-catalytic activity. The non-precious metal nickel has attracted much attention owing to its unique electronic structure, surface catalytic properties, synergistic interactions with semiconductors, as well as low cost and good environmental compatibility. This metal exhibits excellent catalytic activity because of its suitable \u003cem\u003ed\u003c/em\u003e-electron density, flexible oxidation state, moderate M\u0026ndash;H bond strength, and high density of active sites, as well as electron transfer efficiency.\u003csup\u003e22, 23\u003c/sup\u003e These properties make nickel a rising star in the field of photocatalysis, in which it is expected to replace noble metals as an excellent co-catalyst.\u003csup\u003e24\u003c/sup\u003e When the size of the metal particles is reduced to the atomic level, a dispersed point-like distribution is formed by increasing the metal\u0026ndash;support interaction to avoid atomic aggregation.\u003csup\u003e25, 26\u003c/sup\u003e Moreover, photothermal catalysis is an emerging field with great potential in sustainable chemical production processes.\u003csup\u003e27, 28\u003c/sup\u003e In general, atomically dispersed SAC systems have higher heat transfer efficiencies than clusters/nanoparticles, which expands their application in the photothermal catalysis. This is because individual atoms efficiently trap high-energy photogenerated carriers (e.g., hot electrons), thereby generating localized hot spots with elevated temperatures. The localized thermal gradients generated by these hot spots promote the kinetic activation of the adsorbed reactants and lower the activation energy barriers, thus significantly improving the catalytic efficiency under nonequilibrium conditions. Notably, the excellent structural and electronic state coordination of SACs can be dynamically optimized according to different reaction conditions during photothermal processes.\u003csup\u003e29\u003c/sup\u003e Therefore, combining single-atom and photothermal catalysis to synergistically improve the catalytic performance would be a highly interesting task.\u003c/p\u003e\n\u003cp\u003eHerein,\u0026nbsp;Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eS nanoflower structures doped with Se/Te atoms with high surface area and loaded with atomically isolated Ni sites on the surface were rationally synthesized \u003cem\u003evia\u003c/em\u003e an effective strategy based on ethylenediamine-assisted coordination. The localization effect induced by the modulation of the electronic structure through the introduction of different atoms promoted the charge accumulation on Ni single atoms and S/Se/Te atoms. In addition, Ni single atoms and doped Se/Te heteroatoms with relatively low electronegativity synergistically optimized the H* adsorption kinetics, reduced the reaction barriers, and significantly improved the photocatalytic hydrogen production activity. The photocatalytic hydrogen production performance of Ni SA\u0026ndash;Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eSSe\u003csub\u003e0.5\u003c/sub\u003e and Ni SA\u0026ndash;Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eSTe\u003csub\u003e0.2\u003c/sub\u003e exceeded that of previously reported Zn\u003csub\u003ex\u003c/sub\u003eCd\u003csub\u003e1-x\u003c/sub\u003eS-based semiconductor photocatalysts, as shown in Figure S1. In particular, the photothermal effect was confirmed by varying evolution temperatures. This work provides a feasible and effective synthesis strategy for the construction of single-atom photocatalysts for hydrogen production.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eStructures of single-atom catalysts\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe effect of doping on metal\u0026ndash;support interactions modulated by single atoms\u0026nbsp;was investigated by substituting the sulfur atoms in Zn0.67Cd0.33S (ZCS) nanoflowers with atoms of weakly electronegativities, specifically selenium (Se) and tellurium (Te). Aberration-corrected TEM images visually confirmed the presence of Ni single atoms. The spherical aberration electron microscopy images shown in Figures \u003cstrong\u003e1a\u003c/strong\u003e and \u003cstrong\u003e1b\u003c/strong\u003e reveal that the Ni atoms were uniformly distributed on the catalyst surface without obvious clustering or aggregation, indicating that the Ni single-atom catalyst was successfully prepared. The High-Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF\u0026ndash;STEM) image reveals that the Ni SA-Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eS-Se\u003csub\u003e0.5\u003c/sub\u003e (Ni SA\u0026ndash;ZCSS) and Ni SA-Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eS-Te\u003csub\u003e0.2\u003c/sub\u003e (Ni SA\u0026ndash;ZCST) maintained the flower-like morphology of Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eS-Se\u003csub\u003e0.5\u0026nbsp;\u003c/sub\u003e(ZCSS) and Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eS-Te\u003csub\u003e0.2\u0026nbsp;\u003c/sub\u003e(ZCST), and the corresponding elemental distribution maps clearly show the uniform distribution of Ni, Zn, Cd, S, Se and Te, as shown in Figure \u003cstrong\u003e1c\u0026nbsp;\u003c/strong\u003eand\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eFigure \u003cstrong\u003e1d\u003c/strong\u003e, respectively. The actual Ni contents in Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST, as obtained by ICP-MS, were 0.69 wt% and 0.52 wt%, respectively (Table S1). The actual Se content in Ni SA\u0026ndash;ZCSS was 0.36 wt% and that of Te in Ni SA\u0026ndash;ZCST was 0.23 wt%, indicating that the optimal doping content of Te was lower than that of Se atoms, due to the larger atomic radius of Te atom.\u003c/p\u003e\n\u003cp\u003eIn addition, the electronic and coordination structures of Ni in Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST were confirmed by X-ray absorption fine structure spectroscopy (XAFS). A comparison of the Ni K-edge X-ray absorption near-edge structure (XANES) spectra of Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST with those of Ni foil, Ni(OH)\u003csub\u003e2\u003c/sub\u003e, NiO, and NiS is shown in Figure \u003cstrong\u003e1e\u003c/strong\u003e. The Ni K-edge absorption threshold of Ni SA\u0026ndash;ZCSS was located between those of Ni foil and NiO, which suggests that the valence state of Ni in Ni SA\u0026ndash;ZCSS was between 0 and +2. Moreover, the K-edge absorptions of Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST were very close to each other, and the valence state of Ni (𝛿+) in Ni SA\u0026ndash;ZCSS was slightly lower than that of Ni (𝛾+) in Ni SA\u0026ndash;ZCST (0 \u0026lt; 𝛿 ~ 𝛾 \u0026lt; 2). The fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectra of the samples are shown in Figure\u003cstrong\u003e\u0026nbsp;1f\u003c/strong\u003e. No peaks corresponding to Ni\u0026ndash;Ni bonds were found at 2\u0026ndash;3 \u0026Aring; for either Ni SA\u0026ndash;ZCSS or Ni SA\u0026ndash;ZCST, in contrast with Ni foil, Ni(OH)\u003csub\u003e2\u003c/sub\u003e, and NiO. This suggests that the Ni species in Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST existed as single atoms, validating the HAADF\u0026ndash;STEM findings. Both Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST displayed a main peak around ~1.98 \u0026Aring;, attributed to scattering interactions between Ni and other atoms. The coordination environments of Ni in Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST were further analyzed by wavelet transform (WT) EXAFS, as shown in Figures \u003cstrong\u003e1g\u003c/strong\u003e and \u003cstrong\u003eS8\u003c/strong\u003e. The WT contour plots of Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST showed only one main peak near 6.5 and 6.7 \u0026Aring;\u003csup\u003e-1\u003c/sup\u003e, respectively, with a maximum intensity close to that of NiS, indicating that the nickel sites were atomically dispersed on both catalysts. Furthermore, the best-fit analysis of the EXAFS data (Figure \u003cstrong\u003eS9\u003c/strong\u003e and Table S2) showed that the fitted Ni-S/Zn coordination structure was optimal. Notably, one Ni atom coordinated approximately three S, two Zn, and two O atoms on average. This feature is attributed to the presence of weakly electronegative atoms inducing hyperfine interactions between Ni and neighboring Zn/S atoms to form multiligand bonding interactions. The above results confirm that Ni single atoms in Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST were firmly anchored to the surface, providing an atomic-level channel for charge transfer from the bulk phase to the surface.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePerformance analysis of single-atom catalysts\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn order to verify the effect of weakly electronegative atoms on metal\u0026ndash;support interactions, the catalysts were further investigated by theoretical calculations and performance analysis.\u0026nbsp;Based on the experimental observations and characterizations, the ZCS (101) surface with terminal S atoms (Figure \u003cstrong\u003eS13a\u003c/strong\u003e) was employed as theoretical model to explore the hydrogen evolution reaction (HER) performance. The details of the calculations are described in the Supporting Information. As shown in Figures\u003cstrong\u003e\u0026nbsp;S13b\u003c/strong\u003e and \u003cstrong\u003eS13c\u003c/strong\u003e, one of the surface S atoms was replaced by a Se/Te atom to simulate the Se/Te doped surfaces. Then, a Ni atom was placed on the hollow sites composed of two S and one Se or Te atoms (Figures \u003cstrong\u003eS13d\u003c/strong\u003e and \u003cstrong\u003eS13e\u003c/strong\u003e) to build the Ni SAC model. After structural relaxation, all surfaces were found to remain flat, without obvious reconstruction. Different from the Se and Ni atoms remaining within the surface, the doped Te atoms slightly protruded from the surface, owing to their larger atomic radii. It is worth noting that the Ni atoms were held in the S/Se planes and did not protrude from the surface like the lattice Zn/Cd atoms, revealing their SAC feature. In order to identify the potential active sites for the HER, all possible positions were tested for H adsorption, and the most favorable (lowest-energy) configurations are displayed in Figure \u003cstrong\u003e2a\u0026ndash;e\u003c/strong\u003e. The adsorption energies of H atoms on various sites are listed in Table S3. Note that the top sites of S atoms always exhibited the highest H adsorption strength on all tested surfaces, followed by Se or Te, whereas the bridge Ni\u0026ndash;Se/Te sites displayed the weakest adsorption of H atoms. The exceedingly strong H adsorption capacity of the S atoms was reduced as the Se/Te/Ni atoms were doped on the ZCS (101) surface. The Ni atoms led to the strongest reduction, followed by Te and then Se. Hence, the HER activity could be modulated by introducing the Se/Te/Ni heteroatoms. Interestingly, for the systems without Ni single atoms, regardless of the initial position of the H atom (e.g., bridge or hollow site), its optimized position would always be on top of S/Se/Te atoms (Figure \u003cstrong\u003e2a\u0026ndash;c\u003c/strong\u003e). For the Ni SAC systems, although the S/Se/Te sites could also capture H atoms, an excessively strong adsorption would lead to H poisoning.\u003csup\u003e30\u003c/sup\u003e Thus, the bridge Ni-Se/Te sites were the optimal active centers for the HER (Figures \u003cstrong\u003e2d\u003c/strong\u003e and \u003cstrong\u003e2e\u003c/strong\u003e).\u003c/p\u003e\n\u003cp\u003eThe visible light-catalyzed hydrogen production activity of the catalysts was evaluated as shown in Figures \u003cstrong\u003e2f\u003c/strong\u003e, \u003cstrong\u003eS14\u003c/strong\u003e, and \u003cstrong\u003eS15\u003c/strong\u003e. According to Figure \u003cstrong\u003e2f\u003c/strong\u003e, the hydrogen production performance of the ZCS nanoflower structure could reach 26.3 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e,\u0026nbsp;which was higher than that of the ZCS nanospheres (0.5 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e). Figure \u003cstrong\u003eS14\u003c/strong\u003e shows that the performance of the ZCSS\u003csub\u003ex\u003c/sub\u003e (x = 0.2, 0.3, 0.4, 0.5, 0.6, and 0.7) photocatalysts doped with different amounts of Se atoms showed an increasing trend, followed by a decrease. The ZCSS\u003csub\u003e0.5\u003c/sub\u003e sample exhibits the optimal photocatalytic hydrogen evolution performance (45.2 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e), while further increasing Se incorporation leads to a marked decline in activity, likely due to excessive dopant concentrations inducing defect-mediated recombination centers. Moreover, upon adjusting the Ni single atom loading to 0.8 wt.%, the hydrogen production performance of the Ni SA\u0026ndash;ZCSS catalyst was as high as 125.1 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e (AQE\u003csub\u003e420 nm\u003c/sub\u003e = 43.2%), which is the highest hydrogen production yield of ZCS-based catalysts reported in the literature to date. The activity decreased when the Ni loading exceeded 0.8 wt.%, which may be caused by increased Ni aggregation. The activity was evaluated for different Te atom doping contents as well as amounts of surface-loaded Ni single atoms, as shown in Figure \u003cstrong\u003eS15\u003c/strong\u003e. ZCST\u003csub\u003e0.2\u003c/sub\u003e had the highest hydrogen production rate of 37.4 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e. T Comparative analysis reveals a reduced optimal doping threshold for Te compared to Se, attributable to steric hindrance effects arising from the increased atomic size of Te relative to Se. Similarly, the Ni SA\u0026ndash;ZCST catalyst with a surface-loaded Ni atom content of 0.8 wt.% could reach a hydrogen production of 95.2 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e (AQE\u003csub\u003e420 nm\u003c/sub\u003e = 39.1%). As shown in Figure \u003cstrong\u003eS16\u003c/strong\u003e, Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST maintained 95.1% and 87.6% of their original activities, respectively, during a 20 h cycling process, indicating their good stability.\u0026nbsp;Figure \u003cstrong\u003e2g\u003c/strong\u003e shows the calculated free energy diagram for the HER on the present systems. The pristine ZCS (101) surface had a very poor HER activity, with a \u003cem\u003e\u0026eta;\u003c/em\u003e\u003csub\u003eHER\u003c/sub\u003e of 1.24 V due to the extremely strong H adsorption. Upon doping Se or Te anions, the HER activity was slightly enhanced, with \u003cem\u003e\u0026eta;\u003c/em\u003e\u003csub\u003eHER\u003c/sub\u003e values of 0.81 and 0.31 V for Te- and Se-doped ZCS (101) surfaces, respectively. Correspondingly, the active sites changed from top S centers to Se or Te atoms. For the Ni SAC systems, benefiting from the introduction of Ni cations, the H adsorption strength at Ni single-atom active centers was greatly reduced, resulting in the highest HER activity, with \u003cem\u003e\u0026eta;\u003c/em\u003e\u003csub\u003eHER\u003c/sub\u003e values of 0.20 and 0.24 V for Se- or Te-doped Ni SAC surfaces, respectively.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFor the H adsorbed systems, as shown in Figure \u003cstrong\u003e2h\u003c/strong\u003e and Table S4, the adsorbed H atom on the pristine ZCS (101) surface lost 0.04 \u003cem\u003ee\u003c/em\u003e and was thus positively charged, whereas its bonded S atom gained 0.43 \u003cem\u003ee\u003c/em\u003e, carrying a negative charge. The attraction between the positive and negative charges led to a strong H adsorption. Upon substituting the S with a Se or Te atom, the Se atom also gained 0.24 \u003cem\u003ee\u003c/em\u003e, while the Te atom lost 0.12 \u003cem\u003ee\u003c/em\u003e. Intriguingly, the H atoms became negatively charged by gaining 0.03 and 0.16 \u003cem\u003ee\u003c/em\u003e on Se- and Te-doped ZCS (101) surfaces, respectively. For the Se-doped Ni SAC system, the Ni atom lost 0.35 \u003cem\u003ee\u003c/em\u003e, while the Se and H atoms gained 0.25 and 0.05 \u003cem\u003ee\u003c/em\u003e, respectively. In contrast, except for the Ni atom that lost 0.26 \u003cem\u003ee\u003c/em\u003e, the Te atom also lost 0.02 \u003cem\u003ee\u003c/em\u003e and the H atom gained 0.10 \u003cem\u003ee\u003c/em\u003e in the Te-doped Ni-SAC system. The electrostatic repulsive interactions between the negatively charged H atom and the surfaces could weaken the H adsorption. The charge density difference (CDD) plots of Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST show that the H atoms gained electrons mainly from Ni atoms, and the apparent charge accumulation between H and Ni atoms stabilized the H adsorption. In fact, the CDD plots in Figure \u003cstrong\u003eS17\u003c/strong\u003e show that, for the Se- or Te-doped ZCS (101) systems, the charge accumulation was mainly localized on Se or Te atoms; therefore, the top Se or Te site was the active center. \u0026nbsp;In contrast, in Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST the charge mainly accumulated between the Ni and S/Se/Te atoms, especially at the Ni\u0026ndash;Se/Te bridge site, while minor charge accumulation was observed on the top Ni atom. Thus, the former was the active center for Se/Te-doped Ni SAC systems. Overall, the calculation results confirm the superiority of the Ni SAC configuration for the HER. In conclusion, the high-electronegativity surface would firmly adsorb H atoms, making the H\u003csub\u003e2\u003c/sub\u003e desorption process extremely difficult, thereby resulting in low HER activity, that is, H poisoning. However, doping Se or Te heteroatoms with relatively low electronegativity, especially Ni cations forming Ni SACs, could make the surface less electronegative, while distorting the\u0026nbsp;whole anion shells, resulting in charge redistribution and thus regulating the HER activity.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eElectronic structure modulation\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn order to explore in detail the mechanism for the HER activity enhancement discussed above, we further investigated the electronic properties of the catalysts.\u0026nbsp;For the surface systems without adsorbed H, the S/Se/Te atoms always gain electrons, while the Zn/Cd/Ni metals donate electrons.\u0026nbsp;As a result, the surfaces contain excess electrons and display electronegative shells, as evidenced by the electron localization function (ELF) plots in Figure \u003cstrong\u003e3a\u003c/strong\u003e. Specifically, due to their lower electronegativity of Se and Te, the number of electrons gained by Se/Te atoms are less than those captured by S atoms, which could be verified quantitatively by analyzing the net charge in Table S5, as well as visually by examining the ELF in Figure \u003cstrong\u003e3a\u003c/strong\u003e and the charge density plots in Figure \u003cstrong\u003eS18\u003c/strong\u003e, where the electron density around S/Se/Te follows the order S \u0026gt; Se \u0026gt; Te. Hence, it can be inferred that the surface electronegativity is gradually reduced with the Se/Te doping, until the introduction of electron-donating Ni single atoms, when it reaches the minimum.\u0026nbsp;In addition, the surface electronegativity of the Se-containing systems is slightly higher than that of Te-containing ones.\u003c/p\u003e\n\u003cp\u003e\u003cem\u003eIn situ\u003c/em\u003e XPS analysis elucidated light-driven charge redistribution in Ni single-atom catalysts (Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST), where binding energy shifts directly reflect electron density variations at atomic scales\u003csup\u003e6,31\u003c/sup\u003e. Under illumination, the Zn 2p and Cd 3d spectra of Ni SA\u0026ndash;ZCSS shifted toward higher binding energies compared to dark conditions (Figure \u003cstrong\u003e3b\u003c/strong\u003e), indicative of electron depletion at Zn/Cd sites. Conversely, the Ni 2p spectra exhibited a distinct shift toward lower binding energies (Figure \u003cstrong\u003e3c\u003c/strong\u003e), signifying electron accumulation at Ni atoms through metal\u0026minus;support charge transfer. This directional redistribution was further corroborated by a concurrent shift of the Se 3d peak toward lower binding energies (Figures \u003cstrong\u003eS19a\u003c/strong\u003e), confirming electron enrichment at Se sites. Collectively, the Zn/Cd electron depletion and Ni/Se electron enrichment reveal unidirectional charge transfer from the ZCSS matrix to Ni single atoms under photoexcitation. These observations demonstrate the critical role of metal\u0026minus;support interactions in governing electron delocalization and interfacial electric field formation, which synergistically enhance photogenerated charge separation. Building on this interfacial charge transfer framework, analogous in situ XPS analysis was performed for Ni SA\u0026ndash;ZCST to probe its Zn 2p, Cd 3d, and Ni 2p spectral evolution under illumination (Figures \u003cstrong\u003e3d\u003c/strong\u003e and \u003cstrong\u003e3e\u003c/strong\u003e). Under illumination, all three spectral peaks shifted significantly toward higher binding energies, reflecting electronic restructuring at the metal-support interface. This observation indicates that Ni atoms in Ni SA\u0026ndash;ZCSS accumulate electrons under light irradiation, establishing them as active sites on the catalyst surface. In contrast, Te atoms in Ni SA\u0026ndash;ZCST act as electron acceptors, facilitating electron transfer from Ni to Te (Figure \u003cstrong\u003eS19b\u003c/strong\u003e), which reduces the overall electron utilization efficiency. The reversible charge accumulation observed on Ni single atoms during irradiation underscores their potential as both electron acceptors and donors in photothermal catalytic processes. These findings provide critical insights into the dynamic electron transfer mechanisms between single-atom catalysts and their supports under irradiation, highlighting the importance of tailored electronic interactions for optimizing photocatalytic performance.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAnalysis of energy band structures\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAs shown in Figures \u003cstrong\u003e4a\u003c/strong\u003e\u0026ndash;\u003cstrong\u003ec\u003c/strong\u003e, the electronic energy band structures of ZCS, ZCSS, and ZCST were measured using UPS. The typical secondary electron cutoff energies of ZCS, ZCSS, and ZCST are 17.38, 17.83, and 17.31 eV, respectively. Based on the difference between the photon energy (21.22 eV) and the cutoff energy, the work function of ZCS, ZCSS and ZCST were determined to be 3.84, 3.39 and 3.91 eV, respectively.\u003csup\u003e32\u003c/sup\u003e UV\u0026ndash;vis DRS analysis demonstrates pronounced doping-modulated light absorption in ZCS-based catalysts (Figure \u003cstrong\u003e4d\u003c/strong\u003e).\u003csup\u003e33\u003c/sup\u003e The pristine ZCS exhibits an intrinsic bandgap of 2.43 eV (absorption edge at 510 nm, Figure \u003cstrong\u003eS20a\u003c/strong\u003e). Strategic Se doping triggers a redshift (bandgap narrowing to 2.38 eV, Figure \u003cstrong\u003eS20b\u003c/strong\u003e), originating from quantum confinement effects and shallow donor levels formed via Se 4p\u0026ndash;S 3p orbital hybridization. Conversely, Te doping induces an initial blue shift (bandgap widening to 2.47 eV, Figure \u003cstrong\u003eS20c\u003c/strong\u003e) arising from Te-induced lattice distortion, followed by defect-mediated mid-gap transitions at elevated doping levels. As the doping amount of Se atoms increases, the absorption band edge of ZCS shifts to longer wavelengths (redshift) due to the introduction of shallow donor levels and quantum size effects. However, the visible light absorption first decreases and then increases, reflecting the competition between the formation of deep-level defects and the optimization of the band structure (Figure \u003cstrong\u003eS21a\u003c/strong\u003e). Similarly, Te doping leads to a blue shift of the absorption band edge at low doping levels, followed by a redshift at higher doping levels, with visible light absorption also showing a decrease followed by an increase (Figure \u003cstrong\u003eS21b\u003c/strong\u003e). These phenomena are attributed to the interplay of lattice distortion, defect formation, and band structure modulation caused by Se and Te doping. Notably, Ni single-atom loading on Se- or Te-doped ZnCdS enhances broad-spectrum absorption (500\u0026ndash;700 nm) through synergistic interfacial polarization and gradient band engineering, suppressing carrier recombination while boosting light harvesting. This was confirmed by the PL spectra in Figure \u003cstrong\u003eS22\u003c/strong\u003e, where the lowest fluorescence peak of Ni SA\u0026ndash;ZCSS indicates that this catalyst had the strongest electron\u0026ndash;hole separation ability. This conclusion is also supported by the photocurrent response and impedance results in Figure \u003cstrong\u003eS23\u003c/strong\u003e. Further linear extrapolation along the tangent line to the initial part of the spectrum shows that the Fermi energy level maxima (\u003cem\u003eE\u003c/em\u003e\u003csub\u003eVB-EF\u003c/sub\u003e) for ZCS, ZCSS, and ZCST were 1.76, 2.14 and 1.93 eV, respectively. Combined with the Tauc plots, energy band diagrams to determine energy band structure parameters of ZCS, ZCSS and ZCST could be derived as shown in Figure \u003cstrong\u003e4e\u003c/strong\u003e. The conduction band (CB) and valence band (VB) potentials of ZCSS, with a band gap energy of 2.38 V, were located at \u0026minus;1.34 and 1.03 V \u003cem\u003evs.\u003c/em\u003e NHE, respectively. Moreover, the CB and VB potentials of ZCST were \u0026minus;1.13 and 1.34 V\u003cem\u003e\u0026nbsp;vs.\u003c/em\u003e NHE, respectively.\u003c/p\u003e\n\u003cp\u003eTo understand the surface properties of the catalysts, zeta potential and contact angle measurements were performed as shown in Figure \u003cstrong\u003e4f\u003c/strong\u003e. At neutral pH (pH 7), both ZCSS and ZCST exhibit significantly reduced zeta potentials compared to ZCS, indicating lower surface charge density. This reduction in surface charge likely impairs colloidal stability through diminished electrostatic repulsion, thereby promoting nanoparticle agglomeration. In contrast, Ni SA\u0026ndash;ZCSS and Ni SA\u0026ndash;ZCST demonstrate substantially enhanced negative zeta potentials, which directly correlate with (i) improved colloidal stability and (ii) strengthened electrostatic attraction toward cationic species, consequently promoting proton adsorption. More importantly, the introduced nickel single-atom sites remarkably enhance surface hydrophilicity by inducing localized electric field redistribution and reconstructing the hydrogen-bonding network within the interfacial hydration layer, as unambiguously confirmed by the observed reduction in water contact angle.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePhotothermal effects\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe photothermal effect plays a pivotal role in modulating reaction kinetics by simultaneously facilitating charge carrier separation/transfer dynamics and adsorption-desorption equilibrium processes.\u003csup\u003e34,35\u003c/sup\u003e To quantitatively characterize the photothermal behavior of the as-synthesized catalysts, infrared thermographic measurements were systematically performed under simulated solar irradiation (300 W xenon lamp, AM 1.5G filter). As illustrated in Figure \u003cstrong\u003e4g\u003c/strong\u003e, the initial surface temperatures of ZCSS and Ni SA-ZCSS reached 51 and 58 \u0026deg;C, respectively, significantly exceeding that of pristine ZCS (28 \u0026deg;C) in the dark. Upon light irradiation, both modified catalysts exhibited rapid temperature escalation during the initial 100 s, attaining 116 \u0026deg;C (ZCSS) and 139 \u0026deg;C (Ni SA-ZCSS), respectively. These elevated temperatures remained stable throughout the subsequent 30-minute illumination period. Similar photothermal behavior was observed for ZCST and Ni SA-ZCST, with their surface temperatures rapidly rising to 123 and 157 \u0026deg;C within 100 s before reaching thermal equilibrium. To investigate the photothermal effects, the photocatalytic activity of ZCSS, Ni SA\u0026ndash;ZCSS, ZCST, and Ni SA\u0026ndash;ZCST were measured under visible light irradiation at different temperatures. As shown in Figure\u0026nbsp;\u003cstrong\u003e4h\u003c/strong\u003e, the activities of both ZCSS and Ni SA\u0026ndash;ZCSS gradually increased as the temperature increased from 10 to 15 and 25 \u0026deg;C. The activities of ZCSS and Ni SA\u0026ndash;ZCSS also increased with increasing temperature. Remarkably,\u0026nbsp;the hydrogen evolution rate of Ni SA\u0026ndash;ZCSS was as high as 168.1 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e without cooling, and increased by 34.4% due to the photothermal effect.\u0026nbsp;These results unequivocally demonstrate the pivotal role of photothermal activation in boosting photocatalytic efficiency.\u0026nbsp;Analogous photothermal coupling phenomena were observed for ZCST and Ni SA\u0026ndash;ZCST. Among them, the hydrogen evolution rate of Ni SA-ZCST reached 136.56 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e, which increased by 43.5%. This pronounced enhancement stems from the distinctive thermoelectric properties of Te atoms, which amplify the photothermal response through enhanced charge carrier mobilization and localized heat generation. These findings unequivocally establish that the photothermal effect serves as a dominant factor in enhancing photocatalytic performance. As evidenced by real-time infrared thermographic imaging (Figure S24), the catalyst demonstrated progressive temperature gradient evolution under continuous illumination, providing direct visual confirmation of photothermal coupling phenomena.\u003c/p\u003e"},{"header":"Discussion and perspectives","content":"\u003cp\u003eIn summary, we have established a facile ethylenediamine-mediated coordination strategy to construct Se/Te co-doped Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eS nanoflower architectures with precisely controlled Ni single-atom sites through atomic-level engineering. The synergistic modulation of both electronic configuration and local coordination geometry in surface-anchored Ni single-atom sites, induced by heteroatoms with tailored electronegativities, was systematically investigated to elucidate their cooperative effects on hydrogen adsorption/desorption kinetics. The photocatalytic hydrogen production performances of Ni SA\u0026ndash;Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eSSe\u003csub\u003ex\u003c/sub\u003e and Ni SA\u0026ndash;Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eSTe\u003csub\u003ey\u003c/sub\u003e were as high as 125.1 and 95.2 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;1\u003c/sup\u003e, respectively. The exceptional catalytic performance originates from the formation of Ni\u0026ndash;S/Zn bonds, which generate new hybrid orbitals and increase the Ni d-electron density. This electronic configuration facilitates the capture of photogenerated electrons while promoting their directional transfer to active sites. The synergistic interaction between isolated Ni atoms and low-electronegativity Se/Te atoms in the Ni SACs, mediated by Ni-S/Zn bond formation, precisely regulates H* adsorption kinetics and consequently enhances hydrogen evolution reaction activity. These findings provide fundamental insights into metal-support interactions for single-atom catalyst design, while demonstrating a rationally engineered approach for developing high-performance SACs systems.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the National Key Research and Development Program of China, grant number 2019YFA0705201, the National Natural Science Foundation of China under the Grant No. U2032129 and 51502061, the Olle Engkvist foundation (grant no. SOEB-2015/167), and the Swedish Energy Agency (grant no. 46641-1). E.W. thanks the Swedish Research Council Formas (2023-01008), and The Knut and Alice Wallenberg Foundation (2022.0192) and the Wallenberg Initiative Materials Science for Sustainability (WISE) for financial support.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eD.W. supervised the project. J.P. designed and conducted the experiments, performed the testing and analysis of the experimental data, and wrote the manuscript. D.W. carried out the first-principles calculations and related analyses. W.H. contributed to the theoretical calculations. H.C. supervised and analyzed the XPS data. B.Z., C.Z., D.L., and S.L. performed the XRD characterization and related analyses. G.L., S.J., Y.Z., and Z.X. contributed to the development of the paper's ideas. X.F., X.C., J.W., and H.S. enhanced the electrochemical analyses. J.Z., L.Z., and E.W. guided and revised the paper. All authors discussed the results and commented on the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eHussain, J., Khan, A., Zhou, K. The impact of natural resource depletion on energy use and CO\u003csub\u003e2\u003c/sub\u003e emission in Belt \u0026amp; Road Initiative countries: A cross-country analysis. \u003cem\u003eEnergy\u003c/em\u003e\u003cstrong\u003e199\u003c/strong\u003e (2020).\u003c/li\u003e\n \u003cli\u003eRan, J., Zhang, J., Yu, J., Jaroniec, M., Qiao, S.Z. Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting. \u003cem\u003eChem. Soc. Rev.\u003c/em\u003e\u003cstrong\u003e43\u003c/strong\u003e, 7787-7812 (2014).\u003c/li\u003e\n \u003cli\u003eZhou, P., Navid, I. 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Commun.\u003c/em\u003e\u003cstrong\u003e15\u003c/strong\u003e, 7599 (2024).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-6740158/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6740158/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eSingle-atom catalysts (SACs) represent a new hotspot and frontier in the field of catalysis, owing to their high atomic utilization and unique electronic structure. However, metal particles at the single-atom level are affected by the Gibbs–Thomson effect, which leads to obvious atomic agglomeration phenomena, resulting in a decrease in photocatalytic hydrogen efficiency. Currently, how to enhance the metal–support interactions to improve the dispersion of metal single atoms is the key to the design of SACs. In addition, the understanding of co-catalyst metal–support interactions is still limited. This understanding is crucial for incorporating metal–support interactions into SACs and maximize their performance via innovative design. In this study, we leverage the modulation of the electronic structure of the catalyst. The optimal Ni SA–Zn\u003csub\u003e0.67\u003c/sub\u003eCd\u003csub\u003e0.33\u003c/sub\u003eSSe\u003csub\u003e0.5\u003c/sub\u003e catalyst exhibited a photocatalytic hydrogen production performance up to 125.1 mmol g\u003csup\u003e−1\u003c/sup\u003e h\u003csup\u003e−1\u003c/sup\u003e at 10 °C, superior to many previously reported inorganic semiconductor photocatalysts. In particular, the hydrogen production could reach 168.1 mmol g\u003csup\u003e−1\u003c/sup\u003e h\u003csup\u003e−1\u003c/sup\u003e without cooling, due to the photothermal effect. Integrated experimental and theoretical studies reveal that incorporating electronegativity-modified dopants (Se/Te) into Ni SACs effectively tunes the electronic structures of active sites through Ni-S/Zn bond formation. This synergistic modification not only optimizes metal-support interactions via electronic configuration tailoring, but also regulates hydrogen adsorption energy (ΔGH*) and reaction barriers, thereby significantly enhancing the photocatalytic hydrogen evolution reaction (HER) activity. Our study demonstrates a rational design strategy for single-atom catalysts through electronic structure modulation, and investigates photothermal synergistic single-atom catalytic hydrogen production, which is expected to overcome efficiency limitations in solar fuel production.\u003c/p\u003e","manuscriptTitle":"Rational Design of Stable and Highly Active Ni Single-Atom Catalysts for Efficient Photocatalytic Hydrogen Production","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-09 04:35:33","doi":"10.21203/rs.3.rs-6740158/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"560a8039-bb66-4f62-bd8e-e97bddeebb35","owner":[],"postedDate":"June 9th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":49609407,"name":"Physical sciences/Chemistry/Photochemistry/Photocatalysis"},{"id":49609408,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Photocatalysis"}],"tags":[],"updatedAt":"2025-07-03T14:07:04+00:00","versionOfRecord":[],"versionCreatedAt":"2025-06-09 04:35:33","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6740158","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6740158","identity":"rs-6740158","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}