The interfacial Ni−O−V linkages drive built−in fields for high−efficiency alkaline hydrogen evolution

The interfacial Ni−O−V linkages drive built−in fields for high−efficiency alkaline hydrogen evolution | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 22 December 2025 V1 Latest version Share on The interfacial Ni−O−V linkages drive built−in fields for high−efficiency alkaline hydrogen evolution Authors : Shi Feng Zai 0000-0002-5231-4269 [email protected] , Zhi Yuan Li , Sen Mao Han , Xin Yu Liu , and Jun Yao Chen Authors Info & Affiliations https://doi.org/10.22541/au.176638890.07285423/v1 186 views 133 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Alkaline water electrolysis powered by renewables holds great promise for scalable green hydrogen production, yet the hydrogen evolution reaction (HER) is hindered by the high Volmer step barrier and intrinsic scaling relations among reaction intermediates. Herein, we report a density functional theory (DFT)-guided interfacial engineering strategy that integrates VO x into metallic Ni anchored on porous NiSe 2 to create Ni−O−V linkages that generate built-in electric fields and multitype active sites. DFT simulations show that these interfacial linkages promote charge redistribution, facilitate water activation and lower the water-dissociation barrier at Ni−O−V sites, while the downward shift of the Ni d -band center tunes H binding toward thermoneutrality. Guided by theory, we fabricated a self-supported NiVO x /NiSe 2 heterostructure electrode through a combination of electrochemical deposition and solvothermal selenization. As anticipated, such a heterostructure electrode delivers superior HER activities, requiring an overpotential of only 48 mV to achieve 10 mA cm −2 , a small Tafel slope of 44 mV dec −1 , a high Faradaic efficiency of 97%, and remarkable durability with negligible activity decay after 50 h continuous electrolysis, outperforming most of all reported Ni−based catalysts. Cite this paper: Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.70XXX The interfacial Ni−O−V linkages drive built−in fields for high−efficiency alkaline hydrogen evolution Shi Feng Zai,* ,‡ Zhi Yuan Li, ‡ Sen Mao Han, Xin Yu Liu and Jun Yao Chen Department of Materials Science and Engineering, Liaoning Technical University, Fuxin 123000, China Density functional theory simulations | Interfacial engineering | Ni−O−V linkages | Built−in fields | Hydrogen evolution reaction | Catalyst design | Heterostructure electrode | d -band center Comprehensive Summary Alkaline water electrolysis powered by renewables holds great promise for scalable green hydrogen production, yet the hydrogen evolution reaction (HER) is hindered by the high Volmer step barrier and intrinsic scaling relations among reaction intermediates. Herein, we report a density functional theory (DFT)-guided interfacial engineering strategy that integrates VO x into metallic Ni anchored on porous NiSe₂ to create Ni−O−V linkages that generate built-in electric fields and multitype active sites. DFT simulations show that these interfacial linkages promote charge redistribution, facilitate water activation and lower the water-dissociation barrier at Ni−O−V sites, while the downward shift of the Ni d -band center tunes H binding toward thermoneutrality. Guided by theory, we fabricated a self-supported NiVO x /NiSe 2 heterostructure electrode through a combination of electrochemical deposition and solvothermal selenization. As anticipated, such a heterostructure electrode delivers superior HER activities, requiring an overpotential of only 48 mV to achieve 10 mA cm −2 , a small Tafel slope of 44 mV dec −1 , a high Faradaic efficiency of 97%, and remarkable durability with negligible activity decay after 50 h continuous electrolysis, outperforming most of all reported Ni−based catalysts. Background and Originality Content Electrocatalytic water splitting, powered by renewable and sustainable energy sources, is emerging as a strategically important route for the large-scale production of green hydrogen to address climate change and the global energy crisis. [1-3] While water electrolysis can operate under either acidic or alkaline conditions, alkaline systems offer greater industrial application potential by mitigating catalyst corrosion and enabling the deployment of cost-effective, non−precious metal electrocatalysts, thereby collectively affording a more durable and economically attractive platform for large-scale hydrogen production. [4-6] Therefore, rationally designing high−efficiency alkaline HER electrocatalysts is essential to enable scalable green hydrogen production through renewable-powered water electrolysis. The alkaline HER proceeds through an initial Volmer step (H 2 O + e − → H* + OH − ), followed by H 2 formation via either the Tafel (2H* → H 2 ) or Heyrovsky (H 2 O + H* + e − → H 2 + OH − ) pathway. [7,8] However, alkaline HER kinetics are 2~3 orders of magnitude slower than in acidic conditions. This is mainly owing to the high energy barrier for water dissociation in the Volmer step and the strong adsorption of H* and OH⁻ that—despite facilitating initial bond cleavage−impedes H* desorption and blocks active sites. [9,10] According to the Sabatier principle, this inherent trade-off renders single-component catalysts incapable of simultaneously optimizing water dissociation and the adsorption/desorption of H. To circumvent this trade-off, multicomponent heterogeneous hybrids with multi-site functionality are typically constructed to simultaneously facilitate Volmer step and subsequent Heyrovsky/Tafel processes. [3,11,12] In such hybrids, water dissociation is primarily promoted at sites provided by various transition metal oxides, such as Fe−, Co−, Ni−, and V−based oxides. [13-15] Among these, vanadium oxides (VO x ), [16,17] as an early transition metal oxide, exhibit multiple valence states, strong oxygen affinity, earth-abundant reserves with low cost, and excellent chemical stability in alkaline media. [18-20] Thus, VO x serves as a highly effective active center within the hybrid for water dissociation, while synergistically modulating electronic structure and enhancing charge transfer efficiency to boost overall HER activity in alkaline media. Concurrently, hydrogen adsorption and desorption are optimized at complementary sites furnished by components with favorable hydrogen binding energetics, such as precious metals or transition metal phosphides. For example, Tao et al. [27] reported a Ru/VO x hybrid featuring a crystalline/amorphous heterostructure based on solvothermal method and heat treatment. After integrating amorphous VO x and crystalline Ru regions, interfacial charge redistribution induces an electron-deficient state on the Ru surface, optimizing the adsorption energetics of HER intermediates and effectively lowering the thermodynamic energy barriers. Consequently, the Ru/VO x hybrid exhibits excellent HER performance under alkaline conditions. Although these strategies have yielded impressive HER performance, the reliance on precious metals such as Ru remains a critical bottleneck due to their scarcity and prohibitive cost, which impede scalable deployment in industrial water electrolysis. Considering that Ni exhibits high stability, abundant reserves, superior stability in alkaline environments, and moderate adsorption capability toward H, Ni is selected to construct heterojunctions with VO x . A high specific surface area and hierarchical porous architecture are pivotal for HER catalysts, as they expose a plethora of active sites, promote electrolyte infiltration and rapid desorption of H₂ bubbles, and facilitate efficient mass/charge transport, thereby markedly boosting catalytic performance and durability. Based on prior reports and our present study, [21,22] NiSe 2 with a 3D porous architecture serves as an ideal support, primarily owing to its metal-like conductivity and robust chemical stability across a wide pH range. Therefore, the integration of VO x onto metallic Ni, anchored within porous, highly conductive, and high-surface-area NiSe₂, is expected to optimize interfacial charge redistribution, accelerate electron transfer, and lower the energy barrier for water dissociation, thereby significantly improving the kinetics of alkaline HER. Inspired by the above−mentioned report, we design and fabricate VOx integrated into Ni supported on NiSe 2 (NiVO x /NiSe 2 ), aided by density functional theory (DFT) simulations. DFT calculations reveal that interfacial Ni−O−V linkages substantially enhance alkaline HER activity by establishing a built-in electric field that promotes charge redistribution, facilitates water activation, and lowers the water dissociation barrier at Ni−O−V sites, while upshifting the Ni d−band center to optimize hydrogen adsorption. We successfully fabricated the NiVO x /NiSe 2 heterostructure electrode using a combined electrochemical deposition and solvothermal selenization method. As expected, the resultant heterostructure electrode exhibits superior HER performance with an overpotential of only 48 mV to achieve 10 mA cm−2, a small Tafel slope of 44 mV dec−1, a high Faradaic efficiency of 97%, and remarkable durability with negligible activity decay after 50−h continuous electrolysis, surpassing most of all reported Ni−based catalysts. Results and Discussion Catalyst design aided by DFT simulations To theoretically validate the feasibility of the NiSe 2 /NiVO x heterostructure and elucidate the origin of its enhanced alkaline HER performance, density functional theory (DFT) calculations were performed. The computational model was constructed by integrating VO x clusters onto the Ni-terminated NiSe 2 (111) surface, as schematically depicted in Figure S1a. For comparison, the Ni (111) surfaces supported on NiSe 2 (111) facets are used to simulate the Ni/NiSe 2 (Figure S1b). As revealed by the charge density difference distributions of Ni/NiSe 2 and NiVO x /NiSe 2 in Figures1a and 1b, incorporating VO x into Ni/NiSe 2 induces obvious interfacial charge transfer, evidenced by a pronounced reduction in charge density at the VO x −NiSe 2 interface. This is further confirmed by a marked depletion of charge density (−0.30 e) at the VO x /Ni interface. To elucidate the driving mechanism behind this interfacial electron transfer and the resulting charge redistribution, work function (WF) calculations were carried out. As illustrated in Figure 1c, the calculated WF of the NiVO x /NiSe 2 heterostructure is 5.93 eV, which is 0.79 eV higher than that of the Ni/NiSe 2 (5.14 eV). Such a substantial increase in WF induces a built-in electric field that drives electrons from Ni/NiSe 2 toward VO x , thereby significantly strengthening interfacial coupling. This directional interfacial charge transfer is expected to facilitate water dissociation and optimize hydrogen adsorption, [23,24] thereby significantly enhancing the alkaline HER activity of the NiVO x /NiSe 2 heterostructure. For the typical HER process in alkaline media, H 2 O undergoes initial adsorption and subsequent dissociation to yield H 2 via the formation of adsorbed hydrogen intermediates. Accordingly, the adsorption−free energies of the H 2 O molecule (ΔG H2O ) were systematically calculated on different potential sites in the optimized Ni/NiSe 2 and NiVO x /NiSe 2 models. As shown in Figure S2, the most favorable ΔG H2O on the Ni/NiSe 2 is 0.016 eV at the Ni top sites. Upon formation of the NiVO x /NiSe 2 heterostructure through VO x cluster incorporation, this value shifts markedly to −0.34 eV at the interfacial Ni sites adjacent to VO x (Figure S3). The corresponding adsorption configurations (Figure S4) further identify significantly shortened Ni−O distances at these interfacial sites, confirming the substantially strengthened H 2 O binding that facilitates the water activation. This strengthened interaction is further evidenced by crystal orbital Hamilton population (COHP) analysis (Figures 1d and 1e), which exhibits a more negative integrated COHP (ICOHP) value of −0.96 for NiVO x /NiSe 2 compared to −0.75 for the Ni/NiSe 2 , reflecting reinforced bonding strength and enhanced orbital overlap. [25,26] This electronic perturbation is expected to facilitate the activation of adsorbed water molecules. To verify this point, we carried out transition−state calculations for water dissociation at the most stable H 2 O adsorption sites on both model surfaces. As exhibited in Figures 1f and S5, the calculated free−energy barriers indicate that the NiVO x /NiSe 2 heterostructure exhibits a markedly lower water dissociation barrier of 0.13 eV compared to the Ni/NiSe 2 (0.82 eV). This substantial difference suggests that the Ni−O−V linkages at the NiVO x /NiSe 2 interface act as highly active centers, efficiently facilitating O−H bond cleavage. The hydrogen adsorption−free energy (ΔG H ) serves as a well-established descriptor for evaluating the deprotonation kinetics, with values near zero indicating optimal adsorption strength. As shown in Figures S6,S7 and 1g, the ΔG H on the Ni sites of the Ni/NiSe 2 is relatively negative (−0.42 to −0.44 eV), implying the strong hydrogen binding which hinders H desorption. [27,28] In contrast, interfacial Ni sites in NiVO x /NiSe 2 heterostructure exhibit a more moderate ΔG H of only −0.22 eV, suggesting that VO x incorporation effectively optimizes the H adsorption strength and facilitates hydrogen desorption kinetics. The optimized hydrogen adsorption is further supported by a downshifted d−band center (ε), as revealed by projected density of states (PDOS) calculations (Figure 1h). Specifically, the ε value of the Ni atoms in N iVO x /NiSe 2 heterostructure is negatively shifted toward the Fermi energy level (−3.65 eV for spin up and −1.71 eV for spin down) compared to that in the Ni/NiSe 2 (−2.94 eV and −1.26 eV). According to d−band theory, this downshifted d−band center weakens the interaction between the Ni sites and hydrogen intermediates, [29,30] thereby reducing the adsorbate binding strength and enhancing HER kinetics. Taken together, these DFT results reveal that interfacial Ni−O−V linkages substantially enhance alkaline HER activity by establishing a built-in electric field that promotes charge redistribution, facilitates water activation, and lowers the water dissociation barrier at Ni−O−V linkages . Meanwhile, the downshifted d−band center weakens overly strong hydrogen adsorption toward a more thermoneutral binding strength, thereby synergistically accelerating the overall HER kinetics. Figure 1 (a) Charge density difference of NiVO x /NiSe 2 (Isosurface value: 0.005 e Å −3 ) and (b) corresponding plane−averaged charge density difference (∆ρ) along the Z−axis. Yellow represents electron accumulation, while blue indicates electron depletion. (c) The calculated work function of Ni/NiSe 2 and NiVO x /NiSe 2 . Projected crystal orbital Hamilton population (COHP) for Ni−O interactions for (d) Ni/NiSe 2 and (e) NiVO x /NiSe 2 . (f) Free energy diagrams of H 2 O dissociation on pristine NiSe 2 and NiVO x /NiSe 2 . (g) Free energy profiles for hydrogen adsorption on pristine NiSe 2 and NiVO x /NiSe 2 . (h) The projected density of states of Ni active sites in Ni/NiSe 2 and NiVO x /NiSe 2 . Morphological and Structural Characterization Inspired by the aforementioned DFT predictions, a self−supporting NiVO x /NiSe 2 heterostructure electrode was fabricated, and its electrocatalytic performance toward the alkaline HER was investigated. As schematically illustrated in Figure 2, the NiVO x /NiSe 2 electrode was constructed via a combination of electrochemical deposition and solvothermal selenization. Specifically, Ni(OH) 2 nanosheets were first grown on nickel foam (NF) by potentiostatic electrodeposition. These nanosheets were subsequently converted into NiSe 2 nanoparticles through solvothermal selenization. Finally, NiVO x was electrodeposited onto the NiSe₂ surface using a similar potentiostatic deposition approach, yielding the NiVO x /NiSe 2 hybrid electrode. The actual vanadium content in NiVO x was determined to be 2.1 at% by inductively coupled plasma-optical emission spectroscopy (ICP-OES). For comparison, the pristine NiSe 2 was also prepared by performing only the first two steps of the NiVO x /NiSe 2 synthesis procedure, while the individual Ni/NiSe₂ was obtained by conducting the third-step electrodeposition without adding NH 4 VO 3 . The synthesis procedures for electrodes described herein are provided in the Experimental Section . To investigate the phase composition and structural characteristics of the as−fabricated electrodes, X-ray diffraction (XRD) analysis was conducted. The XRD patterns (Figure 3a) reveal that both the Ni/NiSe 2 and NiVO x /NiSe 2 electrodes exhibit characteristic diffraction peaks corresponding to both metallic Ni (JCPDS no. 70-0989) and NiSe 2 (JCPDS no. 88-1711) phases. Figure 2 Schematic diagrams for the synthesis process of NiVO x /NiSe 2 heterostructure electrode. Specifically, the peaks located at approximately 44.6°, 52.0° and 76.6° were assigned to the (111), (200) and (220) facets of cubic metallic Ni phase, respectively, whereas those peaks at 29.9°, 33.6°, 36.9°, 55.5°, 57.8°, 62.2°, 72.6° and 74.6° corresponded to the (200), (210), (211), (023), (321), (400), (421) and (332) planes of cubic NiSe 2 phase, respectively. It is noteworthy that no characteristic diffraction peaks corresponding to the VO x phase were observed, likely due to the formation of an amorphous structure, which is consistent with reports in the previous literature. [19,20] The specific surface area and pore structure of the catalyst are crucial for catalytic activity. To evaluate these properties, Brunauer–Emmett–Teller (BET) analysis was performed. The N 2 adsorption/desorption isotherms presented in Figure 3b reveal a specific surface area of 19 m 2 g −1 for the heterostructure electrode. Moreover, the Barrett–Joyner–Halenda (BJH) pore-size distribution curve (Figure 3c) displays a narrow peak centered at 3.7 nm, indicating the presence of well-defined mesopores in the NiVO x /NiSe 2 heterostructure electrode. The microstructure and morphology of the as-synthesized electrode materials were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). NiSe 2 exhibits a typical nanopolyhedral morphology with edge lengths ranging from ~130–220 nm, featuring a rough surface which contributes to a large specific surface area and provides abundant anchoring sites for catalytically active sites, as noted in our previous study. [31] After anchoring NiVO x nanoparticles on the surface of NiSe 2 support, the resulting NiVO x /NiSe 2 heterostructure presents irregular nanoparticle-like morphology with particle sizes ranging from 219 to 246 nm, as observed by SEM and TEM images in Figure S8 and Figure 1d,e. High-resolution TEM image (Figure 1f) reveals lattice fringes with spacings of 0.20 nm and 0.34 nm, which can be indexed to the (111) plane of cubic metallic Ni and the (111) plane of cubic NiSe 2 , respectively, while VO x displays typical amorphous features without discernible lattice fringes. This is consistent with the XRD and X-ray photoelectron spectroscopy (XPS) observations, where only oxidized V is detected (see below). The scanning TEM and the corresponding energy-dispersive X-ray (EDX) elemental mapping images (Figure 3g−k) indicate that Ni and Se are predominantly distributed throughout the interior of the nanopolyhedra, while V and O are mainly enriched on the surface. Figure 3 Structure and morphology characterizations. (a) XRD patterns of pristine NiSe 2 , Ni/NiSe 2 and NiVO x /NiSe 2 electrodes. (b) N 2 adsorption/desorption isotherms and (c) pore size distribution curve of NiVO x /NiSe 2 electrode. (d) SEM, (e) TEM and (f) high−resolution TEM images of the NiVO x /NiSe 2 . (g-k) TEM image and the corresponding elemental mappings of the NiVO x /NiSe 2 . Surface-sensitive XPS was performed to investigate the electronic structure information of the NiVO x /NiSe 2 heterostructure electrode. The XPS survey spectrum (Figure 4a) reveals prominent signals for C, Ni, Se, and O, whereas the V signal is notably weak, further supporting the low V content previously identified by ICP-OES. The C 1s peak (Figure 4b), originating from carbon-containing adventitious species introduced during synthesis and air exposure, is calibrated to 284.8 eV and serves as the binding-energy reference for all other elements. The high-resolution Ni 2p spectrum (Figure 4c) presents two spin-orbit doublets at 852.8 and 869.9 eV that are characteristic of Ni–Se bonding. [32] In addition, two broader peaks located at 855.4 eV for 2p 3/2 and 873.1 eV for 2p 1/2 , together with their satellite features, reveal the presence of Ni 2+ species. The Se 3d spectrum (Figure 4d) shows a distinct spin−orbit doublet at 55.1 eV (3d 5/2 ) and 55.9 eV (3d 3/2 ), characteristic of Ni–Se coordination in NiSe 2 . [33,34] A weaker peak at 59.5 eV is assigned to surface oxidized Se species, [35] probably arising from Se–O formation during unavoidable ambient exposure. The high-resolution V 2p 3/2 spectrum (Figure 4e) displays two distinct peaks at 516.9 eV and 516.0 eV, corresponding to V 5+ and V 4+ species, respectively, indicating the presence of VO x with reduced vanadium oxidation states. [19] For the high-resolution O 1s XPS spectrum (Figure 4f), the peaks observed at 531.1 and 532.0 eV are attributed to O−M and O−Se bonds, respectively. Figure 4 XPS analysis of NiVO x /NiSe 2 . (a) Survey spectrum. High−resolution spectra of (b) C 1s, (c) Ni 2p, (d) Se 3d, (e) V 2p and (f) O 1s. Electrocatalytic activities for HER The HER performance was evaluated in N 2 −saturated 1.0 M KOH electrolyte at room temperature using a typical three−electrode electrochemical setup. To explore the influence of the VO x species and NiSe 2 support, the pristine NiSe 2 and Ni/NiSe 2 heterostructure electrode were also examined under identical conditions. As seen from the polarization curves in Figure 5a, the pristine NiSe 2 requires a large overpotential of 136 mV to reach a current density of 10 mA cm −2 , consistent with our prior work and literature reports on the sluggish Volmer step limiting alkaline HER on NiSe 2 . Deposition of metallic Ni onto the NiSe 2 surface yields the Ni/NiSe 2 composite with a reduced overpotential of 80 mV, which can probably be attributed to the improved conductivity and active site exposure from conductive Ni phase integration. Upon integration of VO x to form NiVO x /NiSe 2 heterointerfaces featuring Ni−O−V linkages, the overpotential reaches a minimum of 48 mV at 10 mA cm −2 , experimentally validating the synergistic VO x −Ni/NiSe 2 interaction and corroborating DFT predictions that Ni−O−V active sites enhance reaction kinetics by lowering the water dissociation barrier and optimizing H adsorption. To further elucidate the reaction kinetics, Tafel slopes were derived from the polarization curves. As presented in Figure 5b, the NiVO x /NiSe 2 electrode exhibits a Tafel slope of 44 mV dec −1 , which is remarkably lower than those of the pristine NiSe 2 (85 mV dec −1 ) and Ni/NiSe 2 (72 mV dec −1 ), revealing the superior reaction kinetics of NiVO x /NiSe 2 electrode. To further probe the intrinsic roles of NiVO x and NiSe 2 in the NiVO x /NiSe 2 heterostructure electrode, electrochemical impedance spectroscopy (EIS) measurements were conducted. The Nyquist plots were fitted with an equivalent circuit comprising series resistance ( R s ), constant phase element (CPE), and charge-transfer resistance ( R ct ). As illustrated in Figure S9, the NiVO x /NiSe 2 heterostructure electrode exhibits a R s of 0.6 Ω, comparable to those of the pristine NiSe 2 (0.9 Ω) and Ni/NiSe 2 (0.8 Ω) electrodes. In contrast, the R ct of NiVO x /NiSe 2 electrode (26.1 Ω) is significantly smaller than that of both the pristine NiSe 2 (131.5 Ω) and Ni/NiSe 2 (54.3 Ω). This reduction in R ct indicates an enhanced interfacial charge transfer between the components, [36,37] suggesting that the synergy between NiVO x and NiSe 2 plays a key role in accelerating electrocatalytic kinetics. To clarify the origin of the enhanced electrocatalytic activity of the NiVO x /NiSe 2 heterostructure electrode, the electrochemical surface areas (ECSAs) of the pristine NiSe 2 , Ni/NiSe 2 and NiVO x /NiSe 2 were derived from the double-layer capacitances ( C dl ), which were extracted from cyclic voltammograms recorded at various scan rates. [38,39] As displayed in Figure S10−S12, the C dl are 19.3, 20.4 and 28.0 mF cm −2 for pristine NiSe 2 , Ni/NiSe 2 and NiVO x /NiSe 2 electrode, respectively. Note the fact that a high C dl value means a larger ECSA and thus greater accessibility to active sites, the large C dl of the NiVO x /NiSe 2 provides abundant active sites, thereby contributing to the enhanced HER activity. To elucidate the intrinsic activity by mitigating geometric influences, the polarization curves were subsequently normalized with respect to the ECSA. Based on the ECSA−normalized analysis in Figure S13 and Figure 5c, the NiVO x /NiSe 2 electrode exhibits a specific activity of 0.13 mA\(\text{cm}_{\text{ECSA}}^{-2}\) at an overpotential of 0.1 V, which is as high as 25.3 times that of the pristine NiSe 2 and 3.3 times that of the Ni/NiSe 2 . This remarkable enhancement in intrinsic activity underscores that coupling NiVO x with NiSe₂ likely generates highly efficient active sites, markedly accelerating alkaline HER kinetics in agreement with DFT calculations. Furthermore, the selectivity of the NiVO x /NiSe 2 electrode for HER was further determined by the Faradaic efficiency. As shown in Figure 5d, the measured H 2 production basically matched the theoretical value, yielding a high Faradaic efficiency of 97% in 1 M KOH. Figure 5 Electrocatalytic HER performance in 1.0 M KOH. (a) Polarization curves of pristine NiSe 2 , Ni/NiSe 2 and NiVO x /NiSe 2 electrodes . (b) The corresponding Tafel curves. (c) Specific activity normalized to ECSA at the overpotential of 0.1 V. (d) Faradaic efficiency of the NiVO x /NiSe 2 electrode for H 2 production. (e) Multi−step chronopotentiometric response of the NiVO x /NiSe 2 electrode at various current densities (without iR compensation). (f) Long−term chronopotentiometry measurement of the NiVO x /NiSe 2 electrode . Comparisons of (g) overpotentials at 10 mA cm −2 and (h) Tafel slopes among this work and most of typical Ni-based electrocatalysts for alkaline HER (see Table S1 for more details) Mass transport and durability In order to evaluate the response of the carrier migration, chronopotentiometric experiments with multiple current steps were conducted in 1 M KOH. As depicted in Figure 5e, the current was increased from 50 to 800 mA cm −2 in eight steps, and the corresponding changes of potential were recorded. At the beginning of 50 mA cm −2 , the potential rapidly remained constant for the following 500 s. This stable behavior was consistently investigated across all current density steps. Such chronopotentiometric characteristics reflect the excellent mass transport properties (OH − and H 2 bubbles) of the NiVO x /NiSe 2 heterostructure electrode during the HER. To assess the durability of the NiVO x /NiSe 2 electrode, the chronopotentiometric measurements were performed at a constant potential of 48 mV in 1.0 M KOH solution. Figure 5f illustrates that the NiVO x /NiSe 2 hybrid electrode undergoes no substantial current density degradation during 50−h continuous HER testing, suggesting remarkable durability in alkaline environments. As illustrated by XRD patterns (Figure S14) after the durability test, the phase structure could remain. Moreover, XPS analysis (Figures S15−S18) shows that the surface largely retains its initial chemical state, reflecting the superior durability of the NiVO x /NiSe 2 electrode. Taking these together, the catalytic activities of the NiVO x /NiSe 2 electrode outperforms most of all reported Ni−based catalysts (Figure 5g,h and Table S1). Conclusions In conclusion, guided by DFT insights, we developed a VO x −integrated Ni/NiSe 2 heterostructure (NiVO x /NiSe 2 ) featuring interfacial Ni–O–V linkages that induce a built-in electric field to enhance water activation, lower the dissociation barrier, and optimize hydrogen adsorption. Such a heterostructure electrode delivers superior alkaline HER performance, requiring an overpotential of only 48 mV to drive 10 mA cm −2 , a small Tafel slope of 44 mV dec −1 , a high Faradaic efficiency of 97%, and remarkable durability with negligible activity decay after 50 h continuous electrolysis, outperforming most of all reported Ni−based catalysts. This work proposes an interfacial electronic strategy that creates built-in fields through Ni−O−V linkages, enabling simultaneous optimization of water activation and hydrogen adsorption, thereby offering a robust pathway for designing highly efficient and low-cost alkaline HER electrocatalysts. Experimental Computational method All calculations were performed with the Vienna Ab initio Simulation Package (VASP) using a spin−polarized density functional theory. In the calculations, the projector−augmented wave (PAW) method was applied to describe ionic cores, whereas the exchange-correlation interactions were evaluated using the Perdew−Burke−Ernzerhof (PBE) functional within the generalized gradient approximation. To better describe the 3 d electrons, the effective Hubbard term ( U eff ) was set to 5.5 and 3.4 eV for Ni and V, respectively. A plane wave kinetic energy cut-off of 520 eV was employed for the full cell geometry optimization, and 400 eV for slab calculations with fixed cell parameters. The force and energy convergence thresholds were set at 0.03 eV Å⁻¹ and 10⁻⁵ eV, respectively. Based on our earlier work, [40] the NiSe 2 (111) plane was represented by an eight-layer (√3×√3)R30° periodic slab serving as the substrate, with the lower four layers constrained to the bulk lattice constant and the remaining atoms fully relaxed. The Ni/NiSe 2 heterostructure was built using the previously obtained NiSe 2 (111) layers as the substrate, supporting a two-layer (√3×√3)R30° periodic Ni (111) slab. The NiVO x /NiSe 2 model was modelled by adding VO 4 cluster on the surface of Ni (111) in Ni/NiSe 2 . To prevent the interactions between the slab and its neighboring periodic images, a vacuum spacing of 15 Å along the z−axis was added. Geometry optimization and self-consistent field (SCF) calculations were performed using a 1×2×1 Monkhorst-Pack k-point mesh, while non-self-consistent field (NSCF) calculations utilized a denser 2×3×1 k-point grid. The van der Waals density functional approach was used to describe the van der Waals interaction. In addition, the DFT−D3 method was used to describe van der Waals interactions. [41] The transition state for water dissociation was identified by employing the climbing image nudged elastic band (CI-NEB) method coupled with the improved dimer method. [42] The Gibbs free energies (Δ G ) were calculated by considering zero-point energy correction and entropy contribution terms. [43,44] Crystal orbital Hamilton population (COHP) analysis was conducted with LOBSTER software, [45,46] and geometrical configurations along with charge density difference maps were visualized using VESTA. [47] Preparation of Ni(OH) 2 nanosheet electrode The Ni(OH) 2 nanosheet electrode was synthesized following a modified procedure from our previous report. 39 Briefly, Ni(OH) 2 nanosheets were electrodeposited onto pre-cleaned nickel foam (NF) using a potentiostatic method in a typical three-electrode system, where NF served as the working electrode, a graphite rod as the counter electrode, and Ag/AgCl (saturated KCl) as the reference electrode. The deposition was performed at −0.95 V vs. Ag/AgCl in a 40 mM Ni(NO 3 ) 2 solution for 1000 s. After deposition, the Ni(OH) 2 electrode was thoroughly rinsed with deionized water and ethanol and dried under vacuum. Synthesis of NiSe 2 nanoparticle electrode NiSe 2 nanoparticle electrode was synthesized by solvothermal selenization of the resultant Ni(OH) 2 nanosheet electrode. Typically, a mixed solution was prepared by dissolving 4 mmol Se powder into a mixed solvent consisting of 25 mL N,N-dimethylformamide (DMF), 0.5 mL n-butylamine, and 0.15 mL hydrazine under vigorous stirring. The resulting solution, together with the Ni(OH) 2 nanosheet electrode, was then transferred into a 50 mL Teflon-lined autoclave and heated at 180 °C for 1 h. After naturally cooling to room temperature, the NiSe 2 nanoparticle electrode was retrieved. Fabrication of NiVO x /NiSe 2 heterostructure electrode: The NiVO x /NiSe 2 heterostructure electrode was obtained by potentiostatic electrodeposition, similar to the synthesis of the Ni(OH) 2 nanosheets electrode, except that the as−prepared NiSe 2 was employed as the support instead of NF as the substrate. Specifically, the deposition was carried out at −1.95 V ( vs. Ag/AgCl) for 600 s in an electrolyte bath containing 38 mM NiSO 4 ∙6H 2 O 2 mM NH 4 VO 3 and 50 mM H 3 BO 3 , yielding the NiVO x /NiSe 2 heterostructure electrode. Material characterization The phase compositions of the as−prepared electrodes were analyzed by XRD using a Rigaku D/max-2600 X-ray diffractometer equipped with Cu Kα radiation. The morphology and elemental distribution of the samples were characterized using SEM (JSM−7500F) and TEM (JEOL JEM−2100F). The specific surface area and pore size distribution were determined from N 2 adsorption/desorption isotherms recorded on a Micromeritics ASAP 2460 analyzer. The surface compositions and elemental valence states of the electrodes analyzed by XPS using the Thermo Scientific K-Alpha X-ray photoelectron spectrometer with Al Kα radiation. Inductively coupled plasma-optical emission spectroscopy (ICP-OES, Agilent 725ES) was employed to measure the atomic percentages of elements in the electrode materials. Electrochemical measurements Electrochemical measurements were performed in a typical three-electrode configuration using a DH7003 electrochemical workstation. The as−prepared electrode as the working electrode, an Ag/AgCl as the reference electrode, and a graphite rod as the counter electrode. All potentials recorded herein (unless otherwise stated) are referenced to the reversible hydrogen electrode (RHE) scale using the equation of E ( vs. RHE) = E ( vs. Ag/AgCl) + 0.197 + 0.059 × pH. Ohmic drop correction was applied using solution resistance obtained from electrochemical impedance spectroscopy (EIS) measurements. EIS was carried out at an initial potential of −0.1 V vs. RHE with a 5 mV AC perturbation in the frequency range of 100 kHz to 10 mHz. . Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.70XXX. Acknowledgement This project is financially supported by Liaoning Province Joint Fund Project (No. 20240316), Educational Department of Liaoning Province (No. JYTQN2023200), and the PhD Startup Fund of Liaoning Technical University (CN) (No. 636250018). 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[46] Maintz, S.; Deringer, V.L.; Tchougréeff, A.L.; Dronskowski, R. Lobster: A tool to extract chemical bonding from plane-wave based dft. 2016 , 37, 1030-1035. [47] Momma, K.; Izumi, F. Vesta 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 2011 , 44, 1272-1276. Manuscript received: XXXX, 2024 Manuscript revised: XXXX, 2024 Manuscript accepted: XXXX, 2024 Version of record online: XXXX, 2024 Left to Right: Shi Feng Zai, Zhi Yuan Li, Sen Mao Han, Xin Yu Liu and Jun Yao Chen Entry for the Table of Contents The interfacial Ni−O−V linkages drive built−in fields for high−efficiency alkaline hydrogen evolution Shi Feng Zai,*,‡ Zhi Yuan Li‡, Sen Mao Han, Xin Yu Liu and Jun Yao Chen Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.70XXX A NiVO x /NiSe 2 heterostructure electrode through a combined electrochemical deposition and solvothermal selenization was developed. DFT simulations reveal that interfacial linkages promote charge redistribution, facilitate water activation and lower the water-dissociation barrier at Ni−O−V sites, while a downward shift of the Ni d -band center tunes H binding toward thermoneutrality. Such an electrode delivers superior alkaline HER performance. Information & Authors Information Version history V1 Version 1 22 December 2025 Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords built−in fields density functional theory simulations hydrogen evolution reaction interfacial engineering ni−o−v linkages Authors Affiliations Shi Feng Zai 0000-0002-5231-4269 [email protected] Liaoning Technical University View all articles by this author Zhi Yuan Li Liaoning Technical University View all articles by this author Sen Mao Han Liaoning Technical University View all articles by this author Xin Yu Liu Liaoning Technical University View all articles by this author Jun Yao Chen Liaoning Technical University View all articles by this author Metrics & Citations Metrics Article Usage 186 views 133 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Shi Feng Zai, Zhi Yuan Li, Sen Mao Han, et al. The interfacial Ni−O−V linkages drive built−in fields for high−efficiency alkaline hydrogen evolution. Authorea . 22 December 2025. 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