Charge Transfer Kinetics Research Articles

Nitrogen-doped carbon coated Na3V2O2(PO4)2F as a cathode for high-performance sodium-ion batteries

Na3V2O2(PO4)2F (NVOPF), a cathode known for the advantages of high voltage, exceptional energy density, and thermal stability, is seen as a promising candidate for sodium-ion battery cathodes. However, the NVOPF exhibits poor performance in sodium storage. Here, we report a NVOPF composite cathode with a nitrogen-doped carbon produced from dopamine hydrochloride at an elevated temperature. Firstly, neutron power diffraction (NPD) is employed to determine the structure of pure NVOPF at different temperatures, including oxygen coordination and the mobility of Na+. The nitrogen-doped carbon layer facilitates electron conduction, prevents NVOPF nanoparticle agglomeration, and thus promotes efficient electron and ion transfer during sodium ion insertion/extraction processes, thereby improving the stability of the material structure. These results indicate that the N doped carbon@NVOPF cathode material exhibits outstanding electrochemical performance (111mAh/g at 0.1C and 85mAh/g at 1C), while maintaining 91.06 % capacity retention after 500 cycles. The enhanced electrochemical performance attributes to efficient charge transfer kinetics offer novel perspectives, and the methodology can be effectively adapted to other cathode materials.

Light harvesting S-scheme g-C3N4/TiO2/M photocatalysts for efficient removal of hazardous moxifloxacin

The development of advanced photocatalysts with enhanced efficiency for environmental remediation is critical for addressing persistent organic pollutants like Moxifloxacin. In this study, we present a novel S-scheme heterojunction g-C3N4/TiO2/M photocatalyst designed to optimize light harvesting and charge separation for the effective degradation of Moxifloxacin. The innovative S-scheme configuration enables superior charge transfer dynamics by retaining potent photogenerated electrons in the conduction band of TiO2 and holes in the valence band of g-C3N4, significantly improving photocatalytic performance compared to conventional Type-II systems. Heterogeneous photocatalysis, particularly using TiO2-based materials, offers a promising approach. Here, we synthesized TiO2 hybridized with metal-doped g-C3N4 (GCNTM) via a simple hydrothermal method. The fabricated nanocomposites were characterized using SEM, XRD, FTIR, and UV–Vis (DRS). These GCNTM nanocomposites were employed for the degradation of hazardous Moxifloxacin (MXF) under visible light. Detailed analysis of the photocatalytic mechanism reveals that the synergistic interaction between g-C3N4, TiO2, and the co-catalyst M not only broadens the light absorption spectrum but also enhances the separation and lifespan of charge carriers. Among the synthesized materials, GCNTLa demonstrated the highest degradation efficiency, achieving 96 % removal of MXF. This enhanced activity is attributed to the effective suppression of charge recombination, leading to the generation of reactive species responsible for MXF degradation. Additionally, GCNTM showed remarkable stability and reusability, with only a 6 % reduction in efficiency after five cycles, confirming its high reusability and mechanical stability. Our S-scheme photocatalyst demonstrates a marked increase in the degradation rate of Moxifloxacin under visible light irradiation, highlighting its potential for practical environmental applications.

Interfacial [S─Cu─C] Bonds Induced π-d Electron Coupling Toward Modulating Charge Transfer for Efficient Solar Water Oxidation.

Regulating the interfacial electric field to achieve rapid charge transfer is crucial for superior photoelectrochemical water splitting. Herein, the ultra-thin hydrogen-substituted graphdiyne (HsGDY) is precisely assembled on the surface of CdS nanorod array (Cu-CdS-HsGDY) by an in situ polymerization strategy. The strong π-d electron coupling is aroused by the delocalized π electrons of HsGDY and the delocalized d electrons of CdS through the interfacial [S─Cu─C] bonds. The strong interfacial electric field can effectively promote the charge localization distribution and reduce the charge transfer resistance. The optimized Cu-CdS-HsGDY photoanode obtain a photocurrent density as high as 4.83 mA cm-2 at 1.23 V versus reversible hydrogen electrode in neutral electrolyte solution under AM 1.5G illumination, which is 6.8 times that of the pristine CdS. Moreover, the photoanode maintains an initial photocurrent density of 84% within 4 h without any assistance of sacrificial agents, which is a rather competitive performance of similar sulfide photoanodes. The mechanism of strong π-d electron coupling on interfacial charge transfer and surface reaction kinetics is investigated by transient spectroscopy measurements, density functional theory calculation, and finite element simulation analysis. This work provides new insights into designing a reasonable interface structure to regulate charge transfer for achieve efficient PEC water splitting.

Prolonging Charge Carrier lifetime via Intraband Defect Levels in S-scheme Heterojunctions for Artificial Photosynthesis.

S-scheme heterostructure photocatalysts, distinguished by unique charge-transfer pathways and exceptional catalytic redox capabilities, have found widespread applications in addressing challenging chemical processes, including the photocatalytic reduction of CO2 with a high reaction barrier. Nevertheless, the influence of intraband defect levels within S-scheme heterojunctions on charge separation, carrier lifetime, and surface catalytic reactions has, for the most part, been overlooked. Herein, we develop a tunable defect-level-assisted strategy to construct an electron reservoir, effectively prolonging the lifetime of charge carriers through the rapid capture and gradual release of photoelectrons within WO3-x/In2S3 S-scheme heterojunctions, as authenticated by femtosecond transient absorption spectroscopy and theoretical simulations. The surface photoredox mechanism, unraveled by Gibbs free energy calculations, demonstrates that oxygen-vacancy-induced defect states in WO3-x/In2S3 heterojunctions unlock the rate-determining H2O oxidation into free oxygen molecules by forming metastable oxygen intermediates, contributing to the facilitation of H2O photooxidation. This distinct role, combined with the extended carrier lifetime, results in boosted CO2 photoreduction with nearly 100% CO selectivity in the absence of any photosensitizer or scavenger. Our work sheds light on the role of controllable defect levels in governing charge transfer dynamics within S-scheme heterojunctions, thereby inspiring the development of more advanced photocatalysts for artificial photosynthesis.

Synergistic effect of molybdenum dioxide wrapped nitrogen doped carbon nanotubes in binder-free anodes for enhanced lithium storage properties

Molybdenum dioxide (MoO2) is regarded as a potential anode for lithium-ion batteries due to its highly theoretical specific capacity. However, its further application in lithium-ion battery is largely limited by insufficient practical discharge capacity and cyclic performance. Here, MoO2nanoparticles are in-situ grown on three-dimensional nitrogen doped carbon nanotubes (NCNTs) on nickel foam substrate homogeneously using a simple electro-deposition method. The unique structural features are favorable for lithium ions insertion and extraction and charge transfer dynamics at electrode/electrolyte interface. As a proof of concept, the as-synthesized nanocomposites have been employed as anode for lithium-ion battery, exhibiting a reversible and significantly improved discharge capacity of ∼517 mA h g-1at the current density of 150 mA g-1as well as superior cycle and rate performance. The first-principle calculations based on density functional theory and electrochemical impedance spectroscopy results demonstrate a reduced energy barrier of lithium ions diffusion, improved lithium storage behavior, reduced structure collapse, and significantly enhanced charge transfer kinetics in MoO2/NCNTs nanocomposites with respect to MoO2powder. The excellent performance makes as-prepared MoO2/NCNTs nanocomposites promising binder-free anode for high performance lithium-ion batteries. This work also provides important theoretical insights for other state-of-the-art batteries design.

Giant Charge Separation-Driving Force Together with Ultrafluent Charge Transfer in TiO2/ZnFe-LDH Photoelectrode via Ferroelectric Interface Engineering.

Hydrogen fuel production using photoelectrochemical (PEC) water-splitting technology is incredibly noteworthy as it provides a sustainable and clean method to alleviate the energy environmental crisis. A highly rapid electron shuttle at the semiconductor/WOC (water oxidation cocatalyst) interface is vital to improve the bulk charge transfer and surface reaction kinetics of the photoelectrode in the PEC water-splitting system. Yet, the inevitably inferior interface transition tends to plague the performance enhancement on account of the collision of hole-electron transport across the semi/cat interface. Herein, we address these critical challenges via inserting ferroelectric layer BTO (BaTiO3) into the semi/cat interface. The embedded polarization electric field induced by ferroelectric BTO remarkably pumped hole transfer at the semiconductor/WOC (TiO2/ZnFe-LDH) interface and selectively tailored the electronic structure of LDH surface-active sites, leading to overwhelmingly improved surface hole transfer kinetics at LDH/electrolyte interface, which minish the electron-hole recombination in bulk and on the surface of TiO2. The TiO2 nanorods encapsulated by ferroelectric-assisted ZnFe-LDH achieve 105% charge separation efficiency improvement and 53.8% charge injection efficiency enhancement compared with pure TiO2. This finding offers a strategic design for electrocatalytic-assisted photoelectrode systems by ferroelectric-pumped charge extraction and transfer at the semiconductor/WOC interface.

Li2MoO4 Tailored Anion‐enhanced Solvation Sheath Layer Promotes Solution‐phase Mediated Li‐O2 Batteries

AbstractThe high overpotential of Li‐O2 batteries (LOBs) is primarily triggered by sluggish charge transfer kinetics at the reaction interfaces. A typical LiBr redox mediator (RM) catalyst can effectively reduce the battery's overpotential. However, it is prone to shuttling and corroding the Li anode, leading to RM loss and reduced energy efficiency. To address these challenges, we introduced Li2MoO4 into the LiBr‐containing electrolyte to promote the solution‐phase mediated LOBs. This addition tailors the anion‐enhanced Li+ solvation sheath layer and forms a robust anion‐derived solid electrolyte interphases (SEI) on the Li anode. The robust SEI effectively mitigates the corrosion of soluble Br3−/Br2 and attacks by highly reactive oxygen species. Additionally, the dispersed and high‐density Li2MoO4 exhibits strong adsorption capabilities for O2/LiO2 and Br‐related species during the discharge/charge process, thereby promoting the growth and decomposition of Li2O2 in the solution phase and inhibiting the shuttle effect of Br‐related species in LOBs. Consequently, the LOBs demonstrate exceptional cycling stability (415 cycles) and high energy efficiency (86.2 %), paving the way for the sustainable development and practical application of these battery systems.

Li2MoO4 Tailored Anion-enhanced Solvation Sheath Layer Promotes Solution-phase Mediated Li-O2 Batteries.

The high overpotential of Li-O2 batteries (LOBs) is primarily triggered by sluggish charge transfer kinetics at the reaction interfaces. A typical LiBr redox mediator (RM) catalyst can effectively reduce the battery's overpotential. However, it is prone to shuttling and corroding the Li anode, leading to RM loss and reduced energy efficiency. To address these challenges, we introduced Li2MoO4 into the LiBr-containing electrolyte to promote the solution-phase mediated LOBs. This addition tailors the anion-enhanced Li+ solvation sheath layer and forms a robust anion-derived solid electrolyte interphases (SEI) on the Li anode. The robust SEI effectively mitigates the corrosion of soluble Br3 -/Br2 and attacks by highly reactive oxygen species. Additionally, the dispersed and high-density Li2MoO4 exhibits strong adsorption capabilities for O2/LiO2 and Br-related species during the discharge/charge process, thereby promoting the growth and decomposition of Li2O2 in the solution phase and inhibiting the shuttle effect of Br-related species in LOBs. Consequently, the LOBs demonstrate exceptional cycling stability (415 cycles) and high energy efficiency (86.2 %), paving the way for the sustainable development and practical application of these battery systems.

Enhanced PEC Activity of Hematite Photoanodes Driven by Improved Charge-Transfer Dynamics Investigated Using IMPS/IMVS

Enhanced PEC Activity of Hematite Photoanodes Driven by Improved Charge-Transfer Dynamics Investigated Using IMPS/IMVS

Reduced density matrix dynamics in multistate harmonic models via time-convolution and time-convolutionless quantum master equations with quantum-mechanical and semiclassical kernels.

In this work, we explore the electronic reduced density matrix (RDM) dynamics using time-convolution (TC) and time-convolutionless (TCL) quantum master equations (QMEs) that are based on perturbative electronic couplings within the framework of multistate harmonic (MSH) models. The MSH model Hamiltonian consistently incorporates the electronic-vibrational correlations between all pairs of states by satisfying the pairwise reorganization energies directly obtained from all-atom simulations, representing the globally heterogeneous environments that couple to the multiple states differently. We derive the exact quantum-mechanical and a hierarchy of semiclassical approximate expressions for the kernels in TC and TCL QMEs that project the full RDM for general shifted harmonic systems, including the MSH model. These QMEs are applied to simulate RDM dynamics of photoinduced charge transfer (PICT) in organic photovoltaic carotenoid-porphyrin-fullerene triad solvated in tetrahydrofuran solution and the excitation energy transfer (EET) dynamics in photosynthetic Fenna-Matthews-Olson complexes from C. tepidum and P. aestuarii. Our results show that while both TC and TCL QMEs capture similar phenomena in PICT and EET processes, TC QME generally provides more accurate results than TCL QME, particularly in the initial oscillation of EET population dynamics. This study highlights the effectiveness of the TC and TCL QMEs in modeling RDM dynamics of nonadiabatic processes, offering insights for realistic condensed phase systems.

Stimuli-Triggered Diffusion Dynamics in Single-Junction Electrode for Enhanced Supercapacitor Performance: Insights into the Carrier Relaxation and Charge Transfer Kinetics.

Study of external triggers add new chemistry to energy storage research by virtue of controlling diffusion and charge transfer dynamics. Herein, we have chosen a model system, Ag2S-BiVO4 (Ag2S-BVO), for examining the diffusion dynamics upon light illumination using electrochemical and carrier relaxation studies. Favorable band alignments in the single-junction electrode lead to optimized carrier movement across the interfaces, developing a partial positive charge on the electrode, thereby enhancing the mass-transport of electrolyte ions toward the active electrode for efficient charge storage. Synergistic coupling across the heterojunction provides a high areal capacity of 338 mF cm-2 at 0.5 mA cm-2 under light illumination by facilitating the dominant diffusion characteristics within system. In addition, the Ag2S-BVO-based asymmetric supercapacitor exhibits an areal energy density of 32 mWh cm-2 @ 700 mW cm-2 under illumination. This study provides a strategy to tune the capacitive and diffusion contributions for high-performance light-sensitive supercapacitor devices.

High-entropy perovskite (Pr1/6Nd1/6Sm1/6Ba1/6Sr1/6)6/7(Mn1/6Co)6/7O3-δ as a highly active and CO2 durable cathode for solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are environmentally friendly energy conversion devices that convert the chemical energy in fuels directly into electrical power. The development of high-catalytic activity and durability cathode materials is crucial for the commercialization of SOFCs. Herein, a novel A-site deficient high-entropy perovskite oxide (Pr1/6Nd1/6Sm1/6Ba1/6Sr1/6)6/7(Mn1/6Co)6/7O3-δ (PNSBSMC) was designed. The strong disorder effect associated with entropy increase in high-entropy perovskite oxide is anticipated to accelerate oxygen reduction reaction (ORR) kinetics. PNSBSMC demonstrates excellent catalytic activity for oxygen reduction, primarily due to the entropy-driven enhancement that promotes oxygen adsorption, dissociation, and charge transfer dynamics. The increase in entropy not only significantly mitigates the thermal expansion of PNSBSMC but also provides additional pathways for ionic/electronic transport. At 800 °C, the PNSBSMC-based single cell achieved a remarkable peak power density of 1.41 W cm−2, representing an 88.0 % improvement over the single-phase PBC. Additionally, PNSBSMC demonstrates superior performance stability and CO2 tolerance. These findings suggest that high-entropy PNSBSMC perovskite holds significant potential as an effective cathode for SOFCs. This study offers new insights for the future development of high-stability, high-activity SOFC cathode materials.

Electrochemical behavior and L-tyrosine sensing properties of nanostructured Cr, Sn and La-doped α-Fe2O3 interfaces

L-tyrosine (Tyr) is a promising biomarker for the diagnosis and monitoring of metabolic disorders and neurodegenerative diseases. This study reports on the electrochemical properties of α-Fe2O3 nanostructures doped with Cr, Sn and La, referred to as CrFeOx, SnFeOx and LaFeOx, respectively, and their application in the enzyme-free electrochemical Tyr sensors. These disposable sensors offer accurate Tyr concentration analysis at room temperature, addressing the limitations of current point-of-care diagnostic methods. The CrFeOx, SnFeOx, and LaFeOx nanostructures serve as selective agents for binding and recognizing Tyr, deposited onto disposable graphite pencil electrodes to form the electrochemical interface. The interfacial resistance, charge-transfer kinetics, mechanism, and reversibility are studied via extensive electrochemical measurements employing electro¬chemical impedance spectroscopy and cyclic voltammetry. Furthermore, differen¬tial pulse voltammetry demonstrates excellent Tyr sensing performance in the concen¬tration range of 0 to 80 μM with 2.65 µA µM-1 cm-2 sensitivity and 360 nM thres¬hold detection limit for the best-performing CrFeOx sensors. Hence, these α-Fe2O3-based sensor systems are practical and efficient for selective Tyr detection, offering potential advancements in personalized healthcare and early disease diagnosis.

Development of engineered Zn-MOF/g-C3N4 based photoelectrochemical system for real-time sensors and removal of naproxen in wastewater

Naproxen-contaminated water may lead to the accumulation of the drug in aquatic organisms and can pose high risks to an aquatic environment and human beings. Therefore, this work aimed to develop photoelectrochemical sensing and degradation of naproxen (NPX) using zinc-metal organic framework /graphitic carbon nitride thin film-based fluorine-doped tin oxide (Zn-MOF/g-C3N4/FTO) as anode material for the sensing and degradation of naproxen (NPX). The surface morphology, structure, surface property, surface area, optical property, photocurrent, and charge transfer kinetics abilities were studied using different techniques. The nanocomposites showed a superior photocurrent response (0.815 mA cm-2) compared to the original g-C3N4 (0.328 mA cm-2). The photo-anode made of Zn-MOF@g-C3N4/FTO displayed the highest photocurrent value, indicating that the alignment of the two semiconductor bands prevented the quick recombination of electron-hole pairs. Owing to these attractive features, the Zn-MOF/g-C3N4/FTO electrode was applied for photoelectrochemical detection of NPX using chronoamperometry. Interestingly, the nanocomposites-based FTO ascribed a lower detection limit (2.3 ng l-1) with a wide linear range concentration of NPX (0.5 to 200 µg l-1). Additionally, the analytical assessment of repeatability and reproducibility demonstrated robust performance, with commendable relative standard deviations (RSD%) of 2.54 % and 2.40 %, respectively. On the other hand, a remarkable degradation efficiency of 97.52 % was attained when employing a bias potential of 0.1 V during a 2 h photoelectrocatalytic oxidation of NPX. The degradation process was primarily driven by the active participation of holes and hydroxyl radicals in ring opening and subsequent cleavage of by-products. The notable effectiveness of this degradation can be attributed to the combined and synergistic effects of both electrochemical and photocatalytic degradation techniques. The current state demonstrates its effectiveness in the photoelectrochemical sensing and removal of NPX using MOF/g-C3N4 nanocomposites-based electrode materials in wastewater.

Regulation of electron delocalization on porous carbon/manganese-iron oxide for enhancing nonradical processes of sulfamethoxazole: Oxidation pathway and mechanism

Transition metal oxide defect engineering can regulate the electronic properties of materials, thereby realizing nonradical reactions during catalytic processes. In this study, porous carbon/manganese-iron oxide (PC@MFO) composites with different Mn/Fe ratios were prepared via in-situ encapsulation strategy. PC@MFO exhibited superior catalytic degradation and stable recycling performance during peroxymonosulfate (PMS) activation to degrade sulfamethoxazole (SMX). After 10 min of reaction, >92 % of SMX was rapidly degraded, with high selectivity, through oxidative SMX removal from a complex aqueous solution. The kinetics of SMX degradation over different as-prepared samples were also investigated. A recycling study and regeneration treatment revealed no clear deactivation between the 1st and 6th cycles, suggesting that PC@MFO is a reusable heterogeneous catalyst for utilization in efficient oxidative SMX removal. Multiple characterization techniques and density functional theory calculations were used to study the mechanism of SMX degradation process. Nonradical oxidation was found to be the dominant reaction in the catalytic reaction, leading to SMX degradation. This was possibly due to the highly conjugated electron delocalization induced by Mn-Fe in the O-octahedra close to the oxygen vacancies, promoting rapid charge transfer and interfacial reaction kinetics. This study expands the understanding for the activation mechanism driven by Mn-Fe spinel oxides in deep-water treatment.

Effect of Presodiation Additive on Structural and Interfacial Stability of Hard Carbon | P2‐Na0.66Mn0.75Ni0.2Mg0.05O2 Full Cell

AbstractThe compatibility between a corncob‐derived hard carbon anode and a layered oxide cathode (Na0.66Mn0.75Ni0.2Mg0.05O2), as well as the effect of presodiation via cathode additive (Na2C4O4), are investigated in a sodium‐ion full cell. Extensive physicochemical and electrochemical characterizations are performed to deeply investigate the structural and interfacial evolution of the materials in the presodiated cell, either within the single cycle or upon long‐term cycling. The use of sacrificial cathode additives is generally regarded as a method to improve full cell performance, especially when using sodium‐deficient materials. However, undesired effects upon decomposition of the sacrificial salt may arise due to the complexity of the system. In this study, it is evidenced that the presodiation changes the properties of the electrodes causing a worsening of the electrochemical performance of the cell during long‐term cycling. The surface morphology of the cathode is negatively affected by the formation of holes/cracks, while redox processes associated with structural transformations are suppressed in the voltage window of interest, with partial structural deformations occurring during activation cycles. The SEI and CEI are also affected by the formation of insulating organic species, which lead to an increased thickness and interphase resistance hampering the charge transfer kinetics of the cell.

Cyclometalated Iridium(III) Complex with Substituted Benzimidazole: pH Directed Organelle-Specific Localization Within Lysosome.

We report the synthesis and pH dependent emission spectral behaviour of four emissive iridium(III) complexes (Ir1-Ir4) with two isomeric pairs of bis-trifluoromethyl appended benzimidazole ligands. The imidazolyl hydrogen(N-H) has been replaced by phenyl groups (N-Ph) in two ligands to understand the impact of hydrogen bonding on the photophysical properties of the complexes and it indeed plays interesting role in the charge-transfer dynamics. The pH dependent electronic spectral change is observed for two of the complexes. The enhancement of emission intensity is observed at different wavelength for pH<7 and pH>7 for Ir1 and Ir3. The emission sensing of biogenic amines with pka values ranging from 5.80-9.74 is reported along with cellular imaging. The complex Ir1 specifically localizes within lysosome (pH=4.5-5) and thus image this organelle with great precision. The detail electronic spectra and electrochemical behaviour were reported here along with TDDFT results.

Cover Feature: Electrochemical Charge Transfer Kinetics of Ferrocene in the Light of Different Working Electrodes (Chem. Asian J. 21/2024)

Cover Feature: Electrochemical Charge Transfer Kinetics of Ferrocene in the Light of Different Working Electrodes (Chem. Asian J. 21/2024)

Aluminium-doped vanadium nitride as cathode material for high-performance aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) are increasingly favored for their environmentally friendly and impressive energy storage performance. Vanadium nitride (VN) is receiving much attention as a cathode material for AZIBs due to its high electrical conductivity and controllable structure. However, the direct use of VN in AZIBs presents challenges such as sluggish kinetics, insufficient specific capacity and limited stability. Herein, a heteroatom doping strategy is utilized to improve the electrochemical energy storage performance of the VN by incorporating aluminium (Al) via a hydrothermal process and a subsequent calcination treatment. Electrochemical characterizations indicate that the as-synthesized aluminium-doped VN (Al-doped VN) exhibits an outstanding specific capacity of 544 mAh·g−1 at 1 A g−1 and retains a high rate capacity of 275.6 mAh·g−1 at 10 A g−1. Further studies show that the Al incorporation effectively modulates the electronic configuration of the VN, which accelerates the charge transfer kinetics and thus enhances the electrochemical storage performance of VN. The phase transformation mechanism of the Al-doped VN is also investigated and the results show that the VN undergoes partial conversion into Zn3(OH)2V2O7·2H2O during the charge/discharge process.

Enhanced charge transfer kinetics across the graphdiyne-metal sulfide ohmic interface for boosting photocatalytic hydrogen evolution

The design and construction of photocatalysts are the crucial step for solar-driven hydrogen evolution. Herein, a new type of graphdiyne (CnH2n-2)-based photocatalyst, which was prepared by one pot method, was used to promote hydrogen evolution reaction by constructing GDY/VS2 ohmic junction with S sites anchoring on the surface. Actually, the unique two-dimensional conjugated carbon network of GDY can maintain the structural stability. The uneven surface facilitates the flow of electrons, which makes GDY a good electron donor. In addition, the expanded interlayer spacing of VS2 exposes more hydrogen evolution active sites. The increase in surface electronegativity of composite catalysts enhances their redox ability and charge transfer kinetics. The band edge of the graphdiyne-metal sulfide Ohmic contact interface is bent, allowing electrons to flow into the co catalyst without resistance. These synergistic effects lead to the robust hydrogen production of GDY/VS2, which was increased by nearly 10.3 times compared with that of pure GDY. Finally, charge migration at the interface of graphdiyne-metal sulfide heterojunction was proposed and further verified combining in situ XPS and theory calculation. This research marks a significant stride for enhance the efficiency of photocatalytic hydrogen evolution by designing and constructing composite heterojunction materials.