Photoexcited Electron Transfer Research Articles

Spatially separated HOMO-LUMO sites in highly intra- and inter-plane crystalline g-C3N4 photocatalyst for exceptional H2 generation

Spatially separated HOMO-LUMO sites in the highly crystalline g-C3N4 can vastly facilitate the rapid transfer and separation of photogenerated charges to greatly improve its photocatalytic performance, which remains a great challenge to be achieved. In this study, the highly intra- and inter-plane crystalline g-C3N4 (c-CN) with the spatially separated HOMO-LUMO sites is explicitly produced through a moderate Na-modulated strategy to efficiently promote the directional transfer and separation of photoinduced charges. As a result, the optimized c-CN1.0 photocatalyst exhibits exceptional H2-evolution performance (313.5 μmol h−1, AQE = 13.38 %), which is ca. 14.3 times of the bulk g-C3N4. The excellent hydrogen-generation efficiency of c-CN photocatalyst is mainly ascribed to the synergism of high intra- and inter-layer crystallization of g-C3N4 and spatially separated HOMO-LUMO sites, which can vastly boost the directional transfer and effective separation of photoexcited electrons and holes. This research may open novel avenues to construct other photocatalysts with high efficiency.

Visible-Light-Driven Germyl Radical Generation via EDA-Catalyzed ET-HAT Process.

We have established a facile and efficient protocol for the generation of germyl radicals by employing photo-excited electron transfer (ET) in an electron donor-acceptor (EDA) complex to drive hydrogen-atom transfer (HAT) from germyl hydride (R3GeH). Using a catalytic amount of EDA complex of commercially available thiol and benzophenone derivatives, the ET-HAT cycle smoothly proceeds simply upon blue-light irradiation without any transition metal or photocatalyst. This protocol also affords silyl radical from silyl hydride.

Defective Cd0.3Zn0.7S / 1 T-2 H MoS2 Z-scheme heterojunctions: Rational design with efficient charge transfer for enhanced photocatalytic H2 generation

CdxZn1-xS photocatalysts have received increasing attention due to their better Photocatalytic hydrogen evolution. In this paper, Cd0.3Zn0.7S nanoparticles decorated by a small amount of 1 T-2 H mixed-phase MoS2 nanosheets ((X%) MoS2/Cd0.3Zn0.7S) were prepared by a secondary hydrothermal-hydrothermal precipitation method. The Z-scheme heterojunction between 2 H-MoS2 and Cd0.3Zn0.7S can effectively inhibit the recombination of photogenerated carriers in the photocatalysts, and 1 T-MoS2 with metallic properties in the mixed phase mainly acts as a bridge for the transfer of photoexcited electrons. Therefore, under UV–visible irradiation, when Na2S/Na2SO3 is used as the sacrificial agent, the photocatalytic hydrogen evolution reaction (HER) activity of 0.75% MoS2/Cd0.3Zn0.7S reaches 11172 umol.g−1.h−1, which is 1.8 fold higher than that of Cd0.3Zn0.7S. The apparent quantum yields of 0.75% MoS2/C3Z7S at 370 nm and 420 nm wavelength are 50.6% and 7.2%, respectively. There are no significant changes in the hydrogen production after three cycles, indicating that the 0.75% MoS2/C3Z7S sample has excellent stability. This study provides a facile and low-cost strategy for constructing composite photocatalysts with highly efficient steady hydrogen production activity.

Photoswitchable optoelectronic properties of 2D MoSe2/diarylethene hybrid structures

The ability to modulate optical and electrical properties of two-dimensional (2D) semiconductors has sparked considerable interest in transition metal dichalcogenides (TMDs). Herein, we introduce a facile strategy for modulating optoelectronic properties of monolayer MoSe2 with external light. Photochromic diarylethene (DAE) molecules formed a 2-nm-thick uniform layer on MoSe2, switching between its closed- and open-form isomers under UV and visible irradiation, respectively. We have discovered that the closed DAE conformation under UV has its lowest unoccupied molecular orbital energy level lower than the conduction band minimum of MoSe2, which facilitates photoinduced charge separation at the hybrid interface and quenches photoluminescence (PL) from monolayer flakes. In contrast, open isomers under visible light prevent photoexcited electron transfer from MoSe2 to DAE, thus retaining PL emission properties. Alternating UV and visible light repeatedly show a dynamic modulation of optoelectronic signatures of MoSe2. Conductive atomic force microscopy and Kelvin probe force microscopy also reveal an increase in conductivity and work function of MoSe2/DAE with photoswitched closed-form DAE. These results may open new opportunities for designing new phototransistors and other 2D optoelectronic devices.

Mediation of Interfacial Mo2C Bridging Effect in MoS2@Carbon Colloid Dots Featuring Improved Photovoltaic Performances of Si‐Based Hybrid Solar Cells

AbstractAdvances in silicon‐based hybrid solar cells with high photovoltaic performance, low synthetic cost, and sound environmental resistance are emerged as potential candidate for solar conversion. Solution‐processed few‐layer MoS2 sheets are regarded as compelling constitutes that paves ways for tailoring the solar harvesting capability; yet the improvement on charge separation of photoexcited carriers remains demanded, and the lack of environmental stability due to intentionally grabbing electrons from adsorbed moistures constrains the scope of practical assessment. In this work, the employment of MoS2/Mo2C/carbon colloid dots (CCDs) heterostructures within PEDOT:PSS matrix is invoked, where the transfer of photoexcited electrons from MoS2 is mediated with Mo2C electron‐transport channels, which further couple out the creation of positive trions by combining with defect‐bound excitons at CCD surfaces. These features dynamically involve with slow recombination probability and further improve the photovoltaic gain. Thus, the noticeable improvement of conversion efficiency of 16.1% with 1.6 times of efficiency enhancement outperforming the bare conventional hybrid solar cells is accomplished, and further exhibits a sound long‐term stability, which opens new avenues for exploiting the photophysical bound‐carrier transition on advanced photovoltaic applications.

Simple Functionalization of a Donor Monomer to Enhance Charge Transfer in Porous Polymer Networks for Photocatalytic Hydrogen Evolution.

Porous polymer networks (PPNs) are promising candidates as photocatalysts for hydrogen production. Constructing a donor-acceptor structure is known to be an effective approach for improving photocatalytic activity. However, the process of how a functional group of a monomer can ensure photoexcited charges transfer and improve the hydrogen evolution rate (HER) has not yet been studied on the molecular level. Herein, we design and synthesize two kinds of triazatruxene (TAT)-based PPNs: TATR-PPN with a hexyl (R) group and TAT-PPN without the hexyl group, to understand the relationship between the presence of the functional group and charge transfer. The hexyl group on the TAT unit was found to ensure the transfer of photoexcited electrons from a donor unit to an acceptor unit and endowed the TATR-PPN with stable hydrogen production.

Investigation of g-C3N4/Ce2(WO4)3 Nanocomposites for the Removal of Basic Dyes.

Herein, we have synthesized pristine and g-C3N4-assisted Ce2(WO4)3 via a facile hydrothermal method. The structure was confirmed with the standard JCPDS card. g-C3N4 encapsulated the crystal and reduced the size. The Raman spectra revealed the presence of Ce-O, W-O stretching and bending vibrations. Electron hole transfer facilitation and controllable recombination were altered by g-C3N4 heterojunction with cerium tungstate. Ce2(WO4)3 possessed a larger band gap. As g-C3N4 was assisted, the band gap was reduced which facilitates Ce2(WO4)3 to utilize more visible light. The prepared photocatalysts were used to investigate the model pollutant removal with visible light. The pure Janus Green B sample showed lesser efficiency, as it does not show self-degradation under light. As Ce2(WO4)3 was added, it slightly improved the efficiency as it possesses lower electron hole transfer and high recombination. Thus, g-C3N4 was composited with Ce2(WO4)3 to make heterojunctions which will enhance the photo-excited electron and hole transfer and decrease e-/h+ recombination. The rate constant values of the photocatalysts were calculated, and the system follows the first-order pseudo-kinetic model. Ciprofloxacin, a well-known antibiotic, was also used to degrade under visible light. The pure sample showed lower efficiency, and the antibiotic was reduced well with the addition of prepared photocatalysts. The modification of Ce2(WO4)3 with the optimum-level g-C3N4 facilitated electron hole charge transfer, and numerous adsorbed dye molecules on the photocatalyst surface made 0.1 g g-C3N4-Ce2(WO4)3 a plausible photocatalyst for the water remediation process.

Ecologically sustainable removal of pharmaceuticals: A mechanistic study of bismuth sulfide-graphene oxide/silver nanocomposite

Bismuth sulfide nanoparticles (BiS NPs) were synthesized via the hydrothermal method, and reduced graphene oxide(rGO) and silver nanoparticles (Ag), which acted as substrates, have prepared using the chemical reduction method. The synthesized nanoparticles have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible spectroscopy, and photoluminescence spectroscopy. Commercially available paracetamol-500 mg (PAM) and aspirin-300 mg (ASP) were selected for photodegradation under visible light using the as-prepared composites in an aqueous solution. Photoluminescence spectroscopy was used to detect PAM and ASP using the photo-excited electron transfer (PET) process, and the limit of detection (LOD) has obtained for PAM(8.70 ppm) and ASP(4.43 ppm) with a sensitivity of 0.9954 and 0.8002, respectively. Fourier transform infrared spectroscopy (FTIR) was used to analyze the before and after degradation products and to confirm the disintegrated products such as –COOH and –CH– both before and after disintegration.. The experimental data were found to fit well with the Freundlich isotherm, suggesting that the as-prepared nanocomposites exhibited a heterogeneous nature for PAM (5119 mg/L), and the pseudo-first-order kinetic model suggests ASP (1030 mg/L) with R2 values of 0.9119 and 0.7075. The risk assessment analysis of PAM was 9.823 μg/L(RQ > 1) and that of ASP was 0.2106 μg/L(RQ < 1), indicating that PAM has a higher potential risk than ASP. The demographic data of the participants indicated that PAM was the most stockpiled medicine at home; this work also encompasses the action of a single PAM and ASP tablet toward the environment, if it is accidently disposed of improperly could create massive water/soil pollution; hence, the care/duty of each person should follow the proper disposal of medical waste because we cannot replace this environment.

Three-Dimensional Tetrathiafulvalene-Based covalent organic frameworks for efficient photocatalytic nitrogen fixation

Preparing photocatalytic nitrogen-fixing catalysts that can effectively produce ammonia under mild conditions is an urgent problem to be solved. Herein, we for the first time present two three-dimensional tetrathiafulvalene-based covalent organic frameworks with high crystallinity and permanent pores, termed 3D-TTF-COFs, specifically designed for photocatalytic nitrogen fixation. The incorporation of TTF-based building blocks not only enhances light absorption capabilities but also facilitates the rapid transfer of photoexcited electrons, ensuring efficient charge carrier separation. It is worth noting that the resultant COFs exhibit remarkable NH3 generation rates of 313.8 ± 5.6 and 106.8 ± 4.2 μmol g−1h−1 under visible light irradiation, surpassing the performance of most photocatalyst materials reported so far. Furthermore, these COFs maintain structural integrity and excellent performance during cyclic testing. Additionally, we carried out density functional theory calculations to elucidate the reaction mechanism between N2 and NH3. This work provides a feasible strategy for constructing 3D COFs to achieve efficient photocatalytic nitrogen fixation.

In situ pump-flow-probe XAFS study of photoexcited electron transfer over single atom-Pt/CoOOH photocatalysts

Abstract We applied pump-flow-probe X-ray absorption fine structure (PFP-XAFS) spectroscopy to photoexcited electron transfer from semiconductor to cocatalyst in a single atom(SA)-Pt/CoOOH photocatalyst to trace the process with microsecond (μs) time resolution. Upon photoirradiation, photoexcited electrons in the CoOOH semiconductor are found to transfer into Pt 5d orbitals, reaching a maximum population at 10 μs delay time. The accumulation of photoelectrons in the Pt 5d and the following decay process are reasonably explained by sequential first-order kinetics with rate constants of k1 = 0.11 ± 0.03 μs−1 and k2 = 0.06 ± 0.01 μs−1.

A photocatalyst with an enhanced Schottky effect and an efficient electron-transfer channel fabricated by assembling Ni–WC heterojunction nanoparticles on g-C3N4 for highly efficient removal of chlorophenols

An enhanced Schottky effect and efficient electron-transfer channel in Ni–WC/CN enable the efficient separation and transfer of photoexcited electrons, which boosts efficient photocatalytic degradation of toxic 4-chlorophenol.

1,1'-Bis-(diphenylphosphino)ferrocene appended d8- and d10-configuration based thiosquarates: the molecular and electronic configurational insights into their sensitization and co-sensitization properties for dye sensitized solar cells.

Three new d8- and d10-configuration based 1,1'-bis-(diphenylphosphino)ferrocene (dppf) appended thiosquarates complexes with general composition [M(mtsq)2dppf] (M = Ni2+ (NiL2); Zn2+ (ZnL2) and Cd2+ (CdL2)) (mtsq = 3-ethoxycyclobutenedione-4-thiolate) have been synthesized and characterized spectroscopically as well as in case of NiL2 by single crystal X-ray diffraction technique. The single crystal X-ray analysis reveals square planar geometry around Ni(II) in NiL2, where Ni(II) coordinates with two sulfur centres of two mtsq ligands in monodentate fashion and two phosphorus of a dppf ligand in chelating mode. The supramolecular architecture of NiL2 is sustained by intermolecular C-H⋯O interactions to form one-dimensional chain. Further, the application of these newly synthesized complexes as sensitizers and co-sensitizers/co-absorbents with ruthenium based N719 sensitizer in dye-sensitized solar cells (DSSCs) have been explored. The DSSC set-up based on NiL2 offers best photovoltaic performance with photovoltaic efficiency (η) 5.12%, short-circuit current (Jsc) 11.60 mA cm-2, open circuit potential (Voc) 0.690 V and incident photon to current conversion efficiency (IPCE) 63%. In co-sensitized DSSC set-up, ZnL2 along with state-of-the-art N719 dye displays best photovoltaic performance with η 6.65%, Jsc 14.47 mA cm-2, Voc 0.729 V and IPCE 69%, thereby showing an improvement by 15.25% in photovoltaic efficiency in comparison to the photovoltaic efficiency of N719 sensitized DSSC set-up. Variation in co-sensitization behaviour have been ascribed to the differences in the excited state energy level of co-sensitizers. The ZnL2 and CdL2 have a higher energy level position than N719 dye, allowing efficient electron transfer to N719 during light irradiation, while excited state of NiL2 is lower than N719 dye, preventing photoexcited electron transfer to N719, resulting in its lowest overall efficiency among the three co-sensitized DSSC setups.

Photoexcited electron transfer in hydrophobic fluorescent FAPbBr3 perovskite nanocrystals and graphene heterostructures

Photoexcited electron transfer in hydrophobic fluorescent FAPbBr3 perovskite nanocrystals and graphene heterostructures

Photosynthetic System Based on a Polyoxometalate-Based Dehydrated Metal-Organic Framework for Nitrogen Fixation.

In nature, biological nitrogen fixation is accomplished through the π-back-bonding mechanism of nitrogenase, which poses significant challenges for mimic artificial systems, thanks to the activation barrier associated with the N≡N bond. Consequently, this motivates us to develop efficient and reusable photocatalysts for artificial nitrogen fixation under mild conditions. We employ a charge-assisted self-assembly process toward encapsulating one polyoxometalate (POM) within a dehydrated Zr-based metal-organic framework (d-UiO-66) exhibiting nitrogen photofixation activities, thereby constructing an enzyme-mimicking photocatalyst. The dehydration of d-UiO-66 is favorable for facilitating nitrogen chemisorption and activation via the unpaired d-orbital electron at the [Zr6O6] cluster. The incorporation of POM guests enhanced the charge separation in the composites, thereby facilitating the transfer of photoexcited electrons into the π* antibonding orbital of chemisorbed N2 for efficient nitrogen fixation. Simultaneously, the catalytic efficiency of SiW9Fe3@d-UiO-66 is enhanced by 9.0 times compared to that of d-UiO-66. Moreover, SiW9Fe3@d-UiO-66 exhibits an apparent quantum efficiency (AQE) of 0.254% at 550 nm. The tactics of "working-in-tandem" achieved by POMs and d-UiO-66 are extremely vital for enhancing artificial ammonia synthesis. This study presents a paradigm for the development of an efficient artificial catalyst for nitrogen photofixation, aiming to mimic the process of biological nitrogen fixation.

Fragmentation engineering on the edge of hydroxy-functional COFs for the enhanced photocatalytic production of H2O2 and direct photo-oxidation of benzene to phenol in aqueous systems

Structural design is important and challenging for the fabrication of covalent organic frameworks (COFs) in the photocatalytic applications. Hydroxyl groups have been found to be the active sites for O2 adsorption and promote the electron-donating conjugation effects, which favorable for the oxygen reduction reaction (ORR) in photocatalytic hydrogen peroxide (H2O2) evolution. This study reports the preparation of “fragmentized” COFs (TxHy-COFs) photocatalysts and their application in H2O2 synthesis, as well as the direct hydroxylation of benzene to phenol. The results demonstrate that the functional design of surface hydroxyl (–OH) modification on fragmentized TxHy-COFs was achieved by varying the feed ratio of TAPT and THTA monomers, which greatly enhances surface hydrophilicity and effectively improves the separation and transfer of photoexcited electrons and holes. Under visible light irradiation without sacrificial agents, the fragmentized T1H1.8-COF exhibits a boosting H2O2 yield of 2567 μmol g−1h−1, which is 4.2 times higher than the original T1H1-COF. Furthermore, the introduction of metal ions (Fe3+ etc.) into the COF framework through the impregnation method enables the in situ activation of H2O2, allowing the direct hydroxylation of benzene to phenol in aqueous systems, with yield of 9.4 % and selectivity of 99 %. The results of this work demonstrate that the prepared photocatalyst exhibits high stability and photocatalytic activity by structural design optimization, showing great potential for industrial applications in H2O2 production and direct photo-oxidation.

Graphitic C3N4 and Ti3C2 nanocomposites for the enhanced photocatalytic degradation of organic compounds and the evolution of hydrogen under visible irradiation

Graphitic carbon nitride (g-C3N4) and Ti3C2 nanocomposites were formed in aqueous dispersions under ultrasound, by the calcination of the mixtures of solid dicyandiamide (DCDA) and Ti3C2, and of dissolved DCDA and Ti3C2 in an aqueous phase. A heterojunction between g-C3N4 and Ti3C2, based on mutual chemical bonds, was created in all the synthetized materials as observed by X-ray photoelectron spectroscopy and also indicated by the decrease of band bap energies from 2.71 eV to 2.59 eV. The transfer of photoexcited electrons from g–C3N4 to Ti3C2 was documented by photoluminescence spectroscopy.Molecular modelling confirmed an observation provided by scanning electron microscopy that Ti3C2 was not equally dispersed in g-C3N4 but formed separated agglomerates.It was calculated that the interactions of g-C3N4/g-C3N4 and Ti3C2/Ti3C2 layers were stronger than those of g-C3N4/Ti3C2, and the interactions of Ti3C2 functionalized with oxygen were stronger than those of Ti3C2 functionalized with fluorine.The g-C3N4/Ti3C2 nanocomposites were further tested for photocatalytic oxidation reactions, such as the degradation of phenol and ofloxacin, and for reduction reactions, such as the evolution of hydrogen. Ofloxacin was degraded more efficiently (max. 79.4 %) than phenol (max. 20.1 %) during 120 min. The highest hydrogen yield was 76.9 μmol after 4 h of irradiation. All the photocatalytic experiments were performed under visible irradiation and confirmed the electron transfer from g-C3N4 to Ti3C2 enhancing the photocatalytic activity of g-C3N4.

In-plane electric field induced by cyano groups and graphitic carbon structure for enhancing photocatalytic hydrogen production of carbon nitride

Inducing an intrinsic driving force into a two-dimensional semiconductor plane to boost the separation and transfer of photoexcited electrons and holes near the photoexcited sites is an effective way of suppressing the recombination of photogenerated carriers. In this work, a photocatalyst (CN-g-C3N4-C) with in-plane continuous π-conjugated bonds was developed by introducing cyano groups (abbreviated as CN) and graphitic carbon (abbreviated as C) in the in-plane structure of carbon nitride (g-C3N4). Different from traditional interface modulation approaches based on the van der Waals forces or hydrogen bonds, chemical bonds are formed between the cyano groups and graphitic carbon component in the CN-g-C3N4-C atomic junction, which facilitate the efficient migration of photogenerated carriers. The ultra-thin porous lamellar structure of CN-g-C3N4-C not only shortens the carrier transfer distance, but also effectively increases the specific surface area. In the CN-g-C3N4-C plane, the strong in-plane electric field can drive the orderly transfer of photoexcited electrons and holes to the graphitic carbon end and the cyano group end, respectively, resulting in enhanced separation and transfer of the electrons and holes near the photoexcited sites. Due to its high charge carrier separation efficiency, CN-g-C3N4-C possesses excellent photocatalytic activity, and its hydrogen production rate is 14.8 times higher than that of pristine g-C3N4. This work provides an atomic-level strategy for designing efficient and economical photocatalysts.

Engineering cotton fibers with zirconium metal-organic frameworks as a recyclable material for sensing and removing aflatoxins in water

The presence of aflatoxins in natural water bodies has been discovered in more and more countries and regions. The simultaneous removal and detection of aflatoxins are urgently needed to prevent and control their contamination. In this research, water-stable and luminescent zirconium metal-organic frameworks (Zr-LMOFs) were in-situ grown on natural cotton fibers. Then, the as-prepared Zr-LMOFs@Cotton was utilized as a recyclable dual-functional material for removal and detection of aflatoxins in aqueous solutions. The removal efficiency towards different AFB1 concentrations (25–100 µg/L) in irrigation water and rice vinegar reached 92 % and 97 %, respectively. The possible mechanism for efficient removal was investigated and attributed to the synergistic effect of π-π interactions and hydrophobic effect. The Zr-LMOFs@Cotton maintained more than 95 % of its removal efficiency even after 10 cycles. Further, utilizing the Zr-LMOFs@Cotton for visual and semi-automatic removal of the most concerned AFB1 in water samples was verified. Also, the fluorescent Zr-LMOFs@Cotton has been combined with a microplate reader to explore a high throughput method for rapidly detecting aflatoxins. A low detection limit of 0.1 μg/L (0.32 nM) and a wide linear range from 0.05 to 20 mg/L was realized. The efficient quenching of Zr-LMOFs@Cotton by AFB1 resulted from both the inner filter effect and photoexcited electron transfer. The Zr-LMOFs@Cotton could accomplish the simultaneous removal and detection of aflatoxins in 5 min with simple and convenient operations. The excellent absorptivity, stable fluorescence, and easy renewability of the developed Zr-LMOFs@Cotton provides a cost-effective and environment-friendly material and strategy for simultaneously removing and monitoring aflatoxins in liquid samples.

Construction of ZnO@CDs@Co3O4 sandwich heterostructure with multi-interfacial electron-transfer toward enhanced photocatalytic CO2 reduction

Photocatalytic conversion of CO2 into small-molecule chemical feedstocks can meet the growing demand for energy and alleviate the global warming. Herein, a p-n ZnO@CDs@Co3O4 heterojunction with sandwich structure was constructed by calcination method of self-assembled ZIF-8@CDs@ZIF-67. The ZnO@CDs@Co3O4 with well-defined interfacial structure exhibited the significantly enhanced photocatalytic CO2 reduction activity, and the optimal catalyst indicated the (CO + CH4) evolution rate of 214.53 µmol g−1 h−1 under simulated solar light, which was superior to ZnO, Co3O4 and binary ZnO@Co3O4. The internal cavity, exposed active sites, multiple interfaces and constructed p-n heterojunction can facilitate the light harvesting and photoexcited electron transfer. Besides, after introduction of CDs placed in the middle layer between ZnO and Co3O4, CDs with excellent photoelectric property further promoted charge separation and migration. This work represents an appealing strategy to construct well-defined photocatalysts for boosting CO2 photoreduction.

Position-selected cocatalyst modification on a Z-scheme Cd0.5Zn0.5S/NiTiO3 photocatalyst for boosted H2 evolution

Photocatalytic water splitting by semiconductors is a promising technology to produce clean H2 fuel, but the efficiency is restrained seriously by the high overpotential of the H2-evolution reaction together with the high recombination rate of photoinduced charges. To enhance H2 production, it is highly desirable yet challenging to explore an efficient reductive cocatalyst and place it precisely on the right sites of the photocatalyst surface to work the proton reduction reaction exclusively. Herein, the metalloid NixP cocatalyst is exactly positioned on the Z-scheme Cd0.5Zn0.5S/NiTiO3 (CZS/NTO) heterostructure through a facile photodeposition strategy, which renders the cocatalyst form solely at the electron-collecting locations. It is revealed that the directional transfer of photoexcited electrons from Cd0.5Zn0.5S to NixP suppresses the quenching of charge carriers. Under visible light, the CZS/NTO hybrid loaded with the NixP cocatalyst exhibits an optimal H2 yield rate of 1103 μmol h−1 (i.e., 27.57 mmol h−1 g−1), which is about twofold of pristine CZS/NTO and comparable to the counterpart deposited with the Pt cocatalyst. Besides, the high apparent quantum yield (AQY) of 56% is reached at 400 nm. Further, the mechanisms of the cocatalyst formation and the H2 generation reaction are discussed in detail.