Photocatalytic Hydrogen Evolution Performance Research Articles

Nitrogen-defective protonated porous C3N4 nanosheets for enhanced photocatalytic hydrogen production under visible light

Defect engineering with morphology control is strategy to tailoring photocatalytic performance of carbon nitride (C3N4) for producing clean hydrogen (H2). Herein, a kind of protonated C3N4 porous nanosheets with nitrogen-defects of N1-vacancy and cyano group (named C3N4-ND) was simple synthesized. In the process, the strong oxidizing nitric acid was used skillfully to introduce N1-vacancy and -CN group into C3N4 and achieves protonation. The nitrogen-defects engineering can shorten band gap, improve the separation of photogenerated carriers. And the defect site, can used as active center and effectively adsorb H+ for efficient photocatalytic hydrogen evolution performance. Simultaneously, the porous nanosheets greatly increase specific area enhanced contact with light and reaction fluids and more reactive sites than bulk C3N4 (BCN). Thus, the C3N4-ND can obtain brilliant photocatalytic hydrogen evolution performance. Typically, C3N4-ND1.7 exhibits excellent photocatalytic H2 evolution rate up to 1.12 mmol·g−1·h−1 for photocatalytic water splitting (PWS) and 39.18 mmol·g−1·h−1 for photocatalytic hydrogen evolution (PHE, 0.5 vol% TEOA as sacrificial agent) under visible light, which has 22.4 and 75.34 times increase over BCN, respectively. This work confirmed the positive effect of defect and morphology engineering on improving the photocatalytic hydrogen evolution performance of C3N4.

Modulating Electronic Structure of MoS2 Nanosheets by Sulfide Enrichment‐Induced Vacancies for Enhanced Photocatalytic Hydrogen Production

AbstractEnhancing photocatalytic activity by changing the electronic structure of the catalyst is an effective strategy. 2H‐MoS2 has semiconductor properties, and its unsaturated side S atom is the main active site for its photocatalytic activity. However, due to the weak S─H bond energy, its hydrogen adsorption capacity is weak. In this work, the electronic structure of MoS2 is adjusted by S‐rich treatment, resulting in the formation of Mo vacancy (MoS2‐VMo). The level of Mo vacancies was assessed using UV–vis diffuse reflectance spectroscopy (UV–vis DRS). As these vacancies can capture certain photogenerated electrons, thereby reducing the recombination of electron‐hole pairs. Through DFT calculation, it is found that the antibonding orbital electron filling of MoS2‐VMo is weakened, the bond energy of S─Mo bond is weakened, and the bond energy between S─H bond is enhanced, which is more conducive to proton adsorption. The photocatalytic activity for hydrogen evolution of MoS2‐3, which underwent the optimal S‐rich treatment, achieved a remarkable rate of 2404.6 µmol g−1 h−1 in dye eosin Y (EY) sensitization system, significantly surpassing that of MoS2 lacking the S‐enriched treatment. This study introduces a novel concept for enhancing the photocatalytic hydrogen evolution performance of metal sulfides via defect engineering.

Molecular Engineering of Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution from Water.

Covalent organic frameworks (COFs) have demonstrated significant potential as photocatalysts for efficiently generating hydrogen through photocatalytic water splitting. However, the design of COFs with distinct organic unit blocks at a molecular level profoundly influences their photocatalytic performance. In this study, we synthesized a series of β-ketoamine COFs through molecular engineering of nitrogen sites, including phenyl-structured TpBD, phenylpyridine-structured TpPpy, phenylpyrimidine-structured TpPpm, and bipyridine-structured TpBpy. Advanced characterization techniques reveal that TpPpm and TpBpy with more nitrogen sites exhibit superior efficiencies in electron transfer and charge separation compared to TpBD and TpPpy, thereby endowing them with enhanced photocatalytic performance for hydrogen evolution from water. As a result, the photocatalytic hydrogen production rates of TpPpm (33.80 mmol g-1 h-1) and TpBpy (29.18 mmol g-1 h-1) surpass those of TpBD (20.82 mmol g-1 h-1) and TpPpy (27.49 mmol g-1 h-1). Additionally, due to the different plane symmetries between Ppm and Bpy resulting from the various positions of nitrogen sites, TpPpm displays superior photochemical properties and better photocatalytic performance compared to TpBpy. Moreover, theoretical calculation results further confirm the exceptional intramolecular charge transfer ability of TpPpm among all COFs. This work underscores the significance of precisely controlling N sites in COFs for designing high-performance photocatalysts.

Fabrication and Mechanism Insight of Multidimensional Coupled Metal-Free van der Waals Heterostructures for Enhanced Photocatalytic Hydrogen Evolution.

It is an arduous issue to significantly improve the charge separation efficiency of polymer photocatalysts due to their inherently high exciton binding energy. Herein, based on an interfacial coupling and atom diffusion strategy, a metal-free 3D/2D van der Waals (VdW) heterojunction is fabricated through the modification of rich-vacancy wrinkle-like S8 (Vs-S8) microspheres on the surface of S-doped polymeric carbon nitride (S-PCN) nanosheets. The insight into the mechanism reveals that the interfacial coupling effect induces a strong built-in electric field from S-PCN to Vs-S8, and the carrier transfer behavior abides by the type-II charge transfer pathway, thereby dramatically improving the separation efficiency and transport kinetics of photogenerated carriers. As a result, the as-prepared metal-free 3D/2D Vs-S8/S-PCN VdW heterojunction is endowed with more superior photocatalytic hydrogen evolution (PHE) performance than PCN. The highest average PHE rate is about 11.3 times higher than that of PCN, and the apparent quantum efficiency reaches 30.1% at 400 nm on the optimal 3%-Vs-S8/S-PCN sample. This work contributes a new design strategy for a metal-free VdW heterojunction and provides a feasible avenue for improving the carrier separation efficiency of polymer photocatalysts.

Preparation of high-efficient donor-π-acceptor system with crystalline g-C3N4 as charge transfer module for enhanced photocatalytic hydrogen evolution

Donor-π-acceptor (D-π-A) type photocatalysts with g-C3N4 as π-module have attracted much attention due to their optimized conjugate structure and enhanced electron directed driving. However, the inefficient charges migration of g-C3N4 due to its amorphous or semi-crystalline structure and limitation of available functional groups are present challenges. In this work, the D-π-A type high crystalline carbon nitride (HCCN) has been obtained by in-situ introducing amide and cyanide groups into the high-crystallinity melon framework. The synergistic effect of functional group modification and crystallinity regulation greatly enhances the electron induction driving and charge carrier density. Moreover, the density functional theory calculations demonstrate that the D-π-A structure could induce the local charge distribution of melon units to provide a unique and stable pathway for photoinduced charges migration. The as-prepared HCCN sample shows a superior visible-light photocatalytic performance for hydrogen evolution with an apparent quantum efficiency (AQE) of 12.2 ​% at 420 ​± ​15 ​nm, which is 23.7 times higher than that of original g-C3N4. Finally, the charge separation and transfer processes as well as the possible photocatalytic reaction mechanisms of HCCN sample are also investigated.

Charge transfer between layers of polymeric carbon nitride driven by surface grafting phosphotungstic polyanions toward efficient photocatalytic hydrogen evolution

It is a challenging issue to achieve efficient charge transfer between layers for the layered polymer photocatalysts, because the photogenerated carriers would prefer random migration within layers and thus have high reverse recombination rate due to their inherent anisotropy and high exciton binding energy. Herein, an innovative surface grafting strategy is developed to modify the layered polymeric carbon nitride (PCN) making use of phosphotungstic (PWO) polyanions. The surface coupling effect of PWO on PCN effectively improves reduction ability and utility rate of luminous energy through shifting the conduction band (CB) upward and broadening light absorption range to cover near infrared region up to 1000 nm, respectively. In especial, the strong electron-withdrawing effect of surface PWO moieties can reduce layer spacing to shorten electron transfer path and attract the photogenerated electrons transfer from PCN matrix to surface, thus conquering the charge transfer restriction between layers to improve the carrier separation efficiency. As a result, the photocatalytic hydrogen evolution (PHE) performance is dramatically enhanced. The optimal PWO-PCN-1% sample achieves an average PHE rate of 9.6 times that of PCN, stable operation for a total of 28 h on 7 cycles, and an AQY up to 22.3% at 400 nm. This contribution affords a viable modification avenue to overcome the limitation of charge transfer between layers for layered polymer photocatalysts.

Robust photocatalytic hydrogen evolution performance of 0D/1D NiO/CdS S-scheme heterojunction

Constructing heterojunction, especially S-scheme heterojunction, is an effective strategy for achieving effective separation of photogenerated electron-hole pairs and obtaining high electrode potential. In this study, a unique 0D/1D NiO/CdS S-scheme heterojunction was constructed by solvent evaporation induced self-assembly method. The loading of NiO was found to greatly enhance the photogenerated carrier separation efficiency of CdS by photoluminescence (PL) spectroscopy, electrochemical impedance spectroscopy (EIS), Kelvin probe force microscopy (KPFM) and transient photocurrent tests. The best photogenerated carrier separation effect was observed at a NiO loading ratio of 15 wt% and the largest photocatalytic hydrogen evolution rate reached 7.89 mmol h-1g−1 under visible light, which was 24.66 times that of pristine CdS. In addition, the cycling experiments showed that the loading of NiO led to the alleviation of the photocorrosion phenomenon of CdS, and the performance remained at 94.2 % after five cycles. This is due to the fact that the formation of S-type heterojunction combines the photogenerated holes of CdS with the photogenerated electrons of NiO, which hinders the oxidation of S2- on the surface of CdS, thus alleviating the photocorrosion phenomenon of CdS and improving the stability of CdS. This work furnishes a new strategy for the development of stable and high-performance photocatalysts with inexpensive co-catalysts.

Excavating oxygen vacancies in BaZrO3 to boost photocatalysis via screening vantage crystal planes

Investigations into the design and advancement of oxygen vacancies (OVs) are at the forefront of high-efficiency catalyst research. However, the lack of experimental evidence and a comprehensive mechanistic understanding regarding the promotion of OVs poses challenges. Herein, we investigate the role of crystal planes in elucidating the mechanism of OVs formation and their impact on photocatalytic hydrogen evolution. Initially, the Vienna ab-initio simulation package was utilized to calculate the key characteristics and band parameters of BaZrO3, subsequently, the screening crystal planes of (110) was synthesized. Experimental findings indicated that the (110) crystal plane increased the OVs rate from 32 % to 56 %, consequently improving photocatalytic hydrogen evolution performance from 13.1 to 20.5 mmol·g−1·h−1. Furthermore, theoretical calculations were employed to delve into both OVs formation mechanisms and catalytic activity. This study presents an innovative approach for strategically modifying catalyst OVs for efficient and high-performance photocatalytic applications.

Enhancing photocatalytic hydrogen evolution performance for D-π-A conjugated polymers based on the perylene diimide

Efficient photocatalysts rely on constructing heterostructure with reasonable configuration. In this study, a novel conjugated polymer with a D-π-A structure was fabricated from polycondensation of perylene diimide and dibenzothiophene sulfone through the suzuki coupling reaction, during which the biphenyl was incorporated as a π-bridge. The photocatalytic hydrogen evolution performance of these copolymers were optimized by introducing different mass fractions of π-bridges via adjusting the additions of biphenyls The optimized PyBpDBSO-5 copolymer, with 17 wt.% perylene diimide and 5 wt% biphenyl, obtained photocatalytic hydrogen productivity of 48.54mmol/h g−1 under visible light without adding Pt as cocatalyst, which is 146.1 % improvement compared to the poly(dibenzothiophene-S,S-dioxide) (PDBTSO, 19.72mmol/h g−1). Based on the analysis of physical and chemical properties, electrochemical testing, the significant advantages of D-π-A configuration in promoting light absorption, photogenerated carriers transfer and separation was confirmed, which was further rationalized by the larger co-planarity of the polymer based on DFT calculations. This study provides inspiration about construction of conjugated organic polymer catalyst towards efficient photocatalysts.

Boosting hydrogen evolution performance of nanofiber membrane-based composite photocatalysts with multifunctional carbon dots

Recent progress in the co-spinning of nanofibers and semiconductor particles offers a promising strategy for the development of photocatalytic devices, solving aggregation and catalyst recovery challenges. However, composite photocatalysts based on nanofiber membranes often suffer from poor conductivity, low hydrophilicity, and easy recombination of photogenerated electron-hole pairs in the semiconductor components. Here, to tackle the aforementioned issues of ZnIn2S4/polyacrylonitrile (ZIS/PAN) nanofiber-based catalysts, we prepared a composite carbon dots/ZnIn2S4/polyacrylonitrile (CZP) nanofiber membrane by blending carbon dots (CDs) with ZIS/PAN using the electrospinning process. The hydrogen evolution performance of the CZP photocatalyst was significantly improved by CDs, which enhanced the hydrophilicity, increased the light absorption, facilitated the transfer of photogenerated electrons, and reduced the recombination of photogenerated electron-hole pairs. Notably, the optimal CZP photocatalyst achieved a hydrogen evolution rate of 2250 μmol g-1h−1, which is about 23 % higher than that of the nanofiber membrane without CDs and 4.55 times higher than that of ZIS particles. The present work successfully improved the CZP nanofiber membrane of photocatalytic hydrogen evolution performance, and the membrane may benefit further device development by eliminating the need for stirring and simplifying the recovery process.

Photothermal-assisted magnetic recoverable Cd0.9Zn0.1S/NiCoB heterojunction with extraordinary photocatalytic hydrogen evolution

Easily recyclable photocatalysts hold great potential in the field of photocatalysis. Guided by rational theoretical predictions, this study designs a novel tetrapod-like Cd0.9Zn0.1S/NiCoB (CZS/NCB) Schottky heterojunction with magnetic and photothermal properties, and demonstrates its excellent photocatalytic hydrogen evolution performance. Under the combined effects of the photothermal properties and the Schottky heterojunction, the photocatalytic hydrogen evolution rate extraordinarily reaches 108.39 mmol g−1 h−1 after 3 h of visible light irradiation, which is 4.69 times that of pure CZS. Additionally, photocatalytic hydrogen evolution tests conducted using infrared thermography and alternating visible and visible plus infrared light irradiation have confirmed the material’s outstanding photothermal properties. In-depth density functional theory (DFT) calculations reveal potential charge transfer pathways and confirm the formation of the Schottky heterojunction. This work provides guidance for the rational construction of magnetic recoverable photocatalysts with practical application.

Interfacial chemical bonds and sulfur vacancies synergistically modulated charge transfer in ZnIn2S4/MoO2-C Ohmic-junction photocatalyst for efficient hydrogen evolution

The construction of an Ohmic contact with a strong built-in electric field is crucial for the photocatalytic hydrogen evolution performance. However, consciously modulating Ohmic contacts to facilitate charge transfer remains very difficult. Herein, a sulfur vacancies-rich ZnIn2S4/MoO2-C Ohmic contact structure was synthesized by solvothermal method. Experimental results and DFT calculations indicated that the structure of MoO2-C changes under high temperature and pressure conditions, leading to the formation of interfacial Mo-S bonds with sulfur-vacancy-rich ZnIn2S4 in close contact. Importantly, the electronic structure of the Ohmic junction was synergistically modulated by interfacial chemical bonds and sulfur vacancies, creating a strong built-in electric field that effectively facilitated charge transfer and exciton dissociation at the interface. The optimized ZnIn2S4/MoO2-C composite exhibited a photocatalytic hydrogen evolution rate of 59.9 µmol h−1, which was 12 times and 4.7 times higher than that of ZnIn2S4 without sulfur vacancies and with sulfur vacancies, respectively. This work presented a novel method of synergistically modulating charge transfer in Ohmic junctions, promising improved photocatalytic performance.

Scalable fabrication of high surface area g-C3N4 nanotubes for efficient photocatalytic hydrogen production

In this research, we present a novel facile, scalable, and template-free technique of synthesizing graphitic carbon nitride (g-C3N4) nanotubes for generating hydrogen through photocatalysis. The hybrid technique involves a two-fold mixing of the precursor materials melamine (M) and cyanuric acid (CA), involving ball milling followed by solution mixing. By varying the M:CA molar ratios, different compositions of g-C3N4 nanotubes were fabricated. The study focused on examining the surface characteristics and the photocatalytic hydrogen evolution performance of these nanotubes. Nanotubes with high specific surface area of 206 m2 g−1 for M:CA molar ratio of 1:3 and 178 m2 g−1 for M:CA molar ratio of 1:5 were produced, with H2 evolution rates of 543 μmol h−1 g−1 and 740 μmol h−1 g−1 respectively, which were an increase of 4 and 5-fold, respectively, in comparison to the pristine sample. The enhanced efficiency of hydrogen production through photocatalysis by nanotubes, when contrasted with pristine material, can be ascribed to their high crystallinity, superior specific surface areas, decreased recombination rates of electron-hole pairs generated during light exposure, and improved dynamics of charge carriers. This hybrid technique provides a new pathway for cost-effective fabrication of g-C3N4 nanotubes with substantial surface areas and high yield photocatalysts on an industrial scale, without the use of templates and hydrothermal processes for efficient hydrogen generation.

Pt nanoclusters as co-catalysts for efficient photocatalytic hydrogen evolution

Photocatalytic water splitting for hydrogen production is an ideal strategy to relieve the energy crisis. In this work, Pt nanoclusters are employed as a co-catalyst to modify g-C3N4 for optimizing the photocatalytic hydrogen evolution performance. Compared with the pristine g-C3N4, the Pt nanoclusterss/g-C3N4 nanocomposites exhibit dramatic enhancement toward H2 production, where the H2 evolution rate of CN-Pt-C2 is nearly 425.1 times higher than pristine g-C3N4. The phase structure, morphology, optical properties, and surface chemical states of the fabricated samples are fully investigated. Based on the systematical characterizations, the reason for the enhanced H2 generation performance is disclosed. It is expected this work can provide a valuable reference for the fabrication of a co-catalyst-based photocatalytic system.

0D/2D Ti3+-TiO2/P-doped g-C3N4 S-scheme heterojunctions for efficient photocatalytic H2 evolution

The integration of heterogeneous photocatalysts has emerged as a promising approach to boost the effectiveness of photocatalytic reactions for hydrogen evolution. In this study, we explore the synergistic effects of Ti3+-TiO2/P-doped g-C3N4 heterojunctions on the enhancement of visible light-induced hydrogen generation efficiency. The photocatalytic hydrogen evolution performance of the as-prepared TPCN100 (280.38 μmol g−1 h−1) surpasses that of pristine P-doped g-C3N4 (34.89 μmol g−1 h−1) and Ti3+-TiO2 (39.71 μmol g−1 h−1) by factors of 8.0 and 7.1 respectively. Through a comprehensive investigation of the structural, electronic, and photocatalytic properties, the underlying mechanisms accountable for the observed enhancement in efficiency within the heterojunction system were elucidated. Based on the in-situ X-ray photoelectron spectrometer (XPS) examination, measurement of band edge, and electron paramagnetic resonance (EPR) analysis, the S-scheme photocatalytic mechanism was proposed. The integration of Ti3+-TiO2 and P-doped g-C3N4 offers new insights into the design of advanced photocatalytic materials for sustainable energy applications.

Strong electron coupling effect of non-precious metal Schottky junctions enhanced square meter level photocatalytic hydrogen evolution

Photocatalytic hydrogen production technology utilizes solar energy to decompose water into hydrogen, helping to alleviate the pressure of energy depletion. Engineering of non-precious metal nanomaterials as cocatalysts can play a significant role in low-cost, sustainable, and large-scale photocatalytic hydrogen production. Herein, MnCdS-Vs/NiCo2S4 (MCSN) Schottky junction nanomaterials with strong electron coupling effect were prepared by a two-step hydrothermal method and successfully applied to a square meter hydrogen evolution device. The optimized MCSN material demonstrated high hydrogen evolution activity of 34.28 mmol g−1 h−1, which is 9.34 and 685.60 times higher than that of pure MnCdS-Vs and NiCo2S4, respectively. More importantly, in a square meter (1 m2) flat-plate reactor, MCSN produced H2 evolution approximately 201 mmol in 5 h, showcasing its potential for large-scale applications. In-situ XPS and DFT calculations demonstrated that MnCdS-Vs interacts with NiCo2S4 to produce a strong electron coupling effect and form a Schottky junction. It promotes the facilitated the directional migration of photogenerated electrons from MnCdS-Vs to NiCo2S4, but also effectively suppressed electron backflow through the Schottky barrier. Furthermore, the abundance of sulfur vacancies enhanced visible light absorption capability, further improving photocatalytic hydrogen evolution performance. This work delves into the role of defect engineering and Schottky junction design in enhancing photocatalytic performance, providing new insights into transitioning photocatalytic hydrogen production technologies from small-scale laboratory experiments to large-scale practical applications.

Ultrasonic-Induced Surface Disordering Promotes Photocatalytic Hydrogen Evolution of TiO2.

Surface disordering has been considered an effective strategy for tailoring the charge separation and surface chemistry of semiconductor photocatalysts. A simple but reliable method to create surface disordering is, therefore, urgently needed for the development of high-performance semiconductor photocatalysts and their practical applications. Herein, we report that the ultrasonic processing, which is commonly employed in the dispersion of photocatalysts, can induce the surface disordering of TiO2 and significantly promote its performance for photocatalytic hydrogen evolution. A 40 min ultrasonic treatment of TiO2 (Degussa P25) enhances the photocatalytic hydrogen production by 42.7 times, achieving a hydrogen evolution rate of 1425.4 μmol g-1 h-1 without any cocatalyst. Comprehensive structural, spectral, and electrochemical analyses reveal that the ultrasonic treatment induces the surface disordering of TiO2, and consequently reduces the density of deep electron traps, extends the separation of photogenerated charges, and facilitates the hydrogen evolution reaction relative to oxygen reduction. The ultrasonic treatment manifests a more pronounced effect on disordering the surface of anatase than rutile, agreeing well with the enhanced photocatalysis of anatase rather than rutile. This study demonstrates that ultrasonic-induced surface disordering could be an effective strategy for the activation of photocatalysts and might hold significant implications for the applications in photocatalytic hydrogen evolution, small molecule activation, and biomass conversion.

Energy band engineering over NiFe-PBA-S/graphdiyne of S-scheme heterojunction for enhance photocatalytic hydrogen production

Photocatalytic hydrogen evolution technology faces great challenges in designing efficient and stable photocatalysis. Adjusting the energy band structure of photocatalyst is one of the means to design efficient and stable photocatalyst. In this work, the bimetallic Prussian blue analog (PBA) was sulfurized. It is worth noting that the process of vulcanizing NiFe-PBA (NF) into NiFe-PBA-S (NFS) has an adjustment effect on the energy band structure. NFS and graphdiyne (GDY) are combined to form NFS/GDY composite catalyst with S-scheme heterojunction, NFS/GDY has the best photocatalytic hydrogen evolution activity of 2847.86 μmol h-1 g-1. The analysis of XPS test, in-situ XPS test and Mott-Schottky test further shows that the regulation of energy band structure accelerate the electron transport and provide sufficient active sites of surface. This work offers a useful approach for developing photocatalyst of energy band engineering to enhance the performance of photocatalytic hydrogen evolution.

Surface nitrogen defect modified crystalline carbon nitride spheres with boosted carrier dynamics for efficient solar hydrogen production

Engineering of the defective structure and crystallinity of semiconductor photocatalysts to promote carrier dynamics has attracted considerable attention. This study presents the design of surface nitrogen defect modified crystalline carbon nitride spheres (QCN) with synergistically boosted surface and bulk carrier separation through a rapid thermal treatment coupled with a flux assisted strategy. Using supramolecular self-assembled polymer as the precursor, spherical crystalline CN heterojunctions are firstly prepared by a molten salt method to improve the separation of bulk carriers. Abundant nitrogen defects are then introduced onto the surface of crystalline CN through the following quick thermal treatment in air, which can generate a higher exciton density and drive rapid migration of surface carriers by acting as effective electron sinks. Furthermore, the defect level also improves the visible light utilization and provides more active centers for reactant adsorption and activation. As a result, QCN samples exhibit excellent performance in photocatalytic hydrogen evolution, with an optimal hydrogen production rate 4.3 times higher than that of pristine bulk CN under visible light irradiation. Moreover, the photocatalytic activities of QCN are dependent on the concentration of nitrogen defects, which can be flexibly adjusted via thermal treatment temperature. Such a two-step regulation strategy combining the distinctive advantages of surface defect structure and high crystallinity is beneficial for synergistic enhancement of photocatalytic performance, and provides new insights for sustainable energy production in the future.

Optimizing photocatalytic hydrogen evolution performance by rationally constructing S-scheme heterojunction to modulate the D-band center

The research in the field of photocatalysis has progressed, with the development of heterojunctions being recognized as an effective method to improve carrier separation efficiency in light-induced processes. In this particular study, CuCo2S4 particles were attached to a new cubic CdS surface to create an S-scheme heterojunction, thus successfully addressing this issue. Specifically, owing to the higher conduction band and Fermi level of CuCo2S4 compared to CdS, they serve as the foundation and driving force for the formation of an S-scheme heterojunction. Through in-situ X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis, the direction of charge transfer in the composite photocatalyst under light exposure was determined, confirming the charge transfer mechanism of the S-scheme heterojunction. By effectively constructing the S-scheme heterojunction, the d-band center of the composite photocatalyst was adjusted, reducing the energy needed for electron filling in the anti-bonding energy band, promoting the transfer of photogenerated carriers, and ultimately enhancing the photocatalytic hydrogen production. performance. After optimization, the hydrogen evolution activity of the composite photocatalyst CdS-C/CuCo2S4-3 reached 5818.9 μmol g−1h−1, which is 2.6 times higher than that of cubic CdS (2272.3 μmol g−1h−1) and 327.4 times higher than that of CuCo2S4 (17.8 μmol g−1h−1), showcasing exceptional photocatalytic activity. Electron paramagnetic resonance and in situ X-ray photoelectron spectroscopy have established a theoretical basis for designing and constructing S-scheme heterojunctions, offering a viable method for adjusting the D-band center to enhance the performance of photocatalytic hydrogen evolution.