Enhanced hydrogen production from water splitting by Sn-doped ZnO/BiOCl photocatalysts and Eosin Y sensitization

The construction of semiconductor heterojunction for photocatalytic H₂ production from water splitting is an efficient and environment-friendly technology. In this work, ZnO/BiOCl (ZBC) and Sn-doped ZnO/BiOCl (ZBC-S) photocatalysts with Z-scheme heterojunction were successfully prepared by simple hydrothermal method. The photocatalytic H₂ evolution from water splitting by the as-prepared photocatalysts was investigated. The formation of ZnO/BiOCl heterojunction reduces the recombination probability of the photogenerated carriers. The impurity levels originated from Sn doping reduce the band gap width of ZnO and BiOCl to some extent, thereby enhancing the light absorption ability. The ZBC-S composite exhibits the best photocatalytic activity. In addition, the photocatalytic efficiency of H₂ production was improved by sensitization with Eosin Y (EY) dye. The H₂ production rate under simulated sunlight reaches 4146.77 μmol g^?1 h^?1, which is 27 times higher than that of pure ZnO. Finally, the Z-scheme electron transfer route in ZnO/BiOCl heterojunction was determined, and the photocatalytic H₂ production mechanism of EY sensitized ZBC-S was proposed.     

CuS-modified ZnO rod/reduced graphene oxide/CdS heterostructure for efficient visible-light photocatalytic hydrogen generation

Solar energy utilization is a promising strategy for the photocatalytic generation of H₂ from water. Herein, a CuS-modified ZnO rod/reduced graphene oxide (rGO)/CdS heterostructure was fabricated via Cu-induced electrochemical growth with Zn powder at room temperature. The resulting powder revealed good interfacial bonding and promoted photoexcited carrier transport. The CuS nanoparticles played a pivotal role in enhancing visible-light responses and demonstrated excellent catalytic performance. A high visible-light photocatalytic H₂ generation rate of 1073 μmol h⁻¹ g⁻¹ was obtained from the CuS–ZnO/rGO/CdS heterostructure containing 0.23% CuS and 1.62% CdS. Increased photoexcited electron lifetimes, improved carrier transport rates, and decreased fluorescence intensities confirmed the synergistic effects of each of the components of the heterostructure. This study provides an innovative strategy for constructing multi-component heterostructures to achieve efficient visible-light H₂ evolution.     

Nanoarchitectonics of CdS/ZnSnO3 heterostructures for Z-Scheme mediated directional transfer of photo-generated charges with enhanced photocatalytic performance

The construction of heterostructure is an effective strategy to synergetically couple wide-band-gap with the narrow-band-gap semiconductor with a mediate optical property and charge transfer capability. Herein, the Z-Scheme CdS/ZnSnO₃ (CdS/ZSO) heterostructures were constructed by anchoring CdS nanoparticles on the surface of double-shell hollow cubic ZnSnO₃ via the hydrothermal method. The direct recombination of excited electrons in the conduction band (CB) of ZSO and holes in the valence band (VB) of CdS via d-p conjugation at the interface greatly accelerated the internal electric field (IEF). The transfer mode follows the Z-Scheme mechanism, where CdS/ZSO synergistically facilitates the efficient charges transfer from CdS to ZnSnO₃ through the intimate interface. Here, ZnSnO₃ and CdS serve as an oxidation photocatalyst (OP) and reduction photocatalyst (RP), respectively. Thus, it can promote synergistically the oxidation half-reaction and reduction half-reaction of H₂ evolution. The density-functional theory (DFT) calculation further confirms the charges transfer from CdS to ZnSnO₃. The hydrogen evolution of 5% CdS/ZSO heterostructure reached 1167.3 μmol g^?1, which was about 8 and 3 folds high compared to pristine ZSO (141.9 μmol g^?1) and CdS (315.5 μmol g^?1), during 3 h of reaction respectively. Furthermore, the CdS/ZSO heterostructures could suppress the photo corrosion of CdS, resulting in its high stability. This work is expected to enlighten the rational design of heterostructure for OP and RP to promote the hybrid heterostructures photocatalytic H₂ evolution.     

MoS2/Ti3C2 heterostructure for efficient visible-light photocatalytic hydrogen generation

The MoS₂/Ti₃C₂ catalyst with a unique sphere/sheet structure were prepared by hydrothermal method. The MoS₂/Ti₃C₂ heterostructure loading 30% Ti₃C₂ has a maximum hydrogen production rate of 6144.7  μmol g⁻¹ h⁻¹, which are 2.3 times higher than those of the pure MoS₂. The heterostructure maintains a high catalytic activity within 4 cycles. The heterostructure not only effectively reduce the recombination of photogenerated electrons and holes, but also provide more activation sites, which promotes the photocatalytic hydrogen evolution reaction (HER). These works can provide reference for the development of efficient catalysts in photocatalytic hydrogen evolution.     

Efficient and long-term photocatalytic H2 evolution stability enabled by Cs2AgBiBr6/MoS2 in aqueous HBr solution

Lead-free Cs₂AgBiBr₆ (CABB) double perovskite as a new-type photocatalytic material alternative to lead halide perovskites holds promise to implement the solar-H₂ conversion, but the interior recombination of photo-generated carriers and thus low photocatalytic hydrogen evolution reaction (HER) rate of CABB restrict its further industrial applications. Herein, we report the composite fabrication of MoS₂/CABB heterostructure for high-efficiency and durable photocatalytic HER by anchoring non-noble MoS₂ onto CABB via a facile dissolution-recrystallization method. The optimized MoS₂/CABB performs a visible-light HER rate of 87.5 μmol h^?1 g^?1 in aqueous HBr solution, ca. 20-fold compared to that of pure CABB (4.3 μmol h^?1 g^?1), and presents a discontinuous 500-h photocatalytic HER stability with no evident loss. The superb performance of MoS₂/CABB can be ascribed to the kinetics-facilitated heterostructure consisting of stable CABB and MoS₂. This work proposes a facile and versatile tactic to construct a low-cost Cs₂AgBiBr₆-based heterostructure for efficient and long-term photocatalytic HER.     

CdS-dots decorated WO3 nanorods photocatalyst with highly ordered interfacial structure for enhanced photocatalytic activities via Z-scheme mechanism

Constructing heterostructure is regarded as one of the most promising strategies for the enhancement of photocatalytic activities, because it can make charge carriers separated more efficiently at the interface. Herein, CdS-WO₃ heterostructure photocatalysts with highly ordered and intimate interfacial structure between the two constituent phases have been successfully prepared via a heterogeneous nucleation and growth of CdS nanoparticles on the surface of WO₃ nanorods, which were fulfilled through a controlled release of S^2? in the aqueous solution containing Cd²⁺ by the reaction of NH₃ with thioacetamide. The as-prepared photocatalysts were carefully studied in morphology and interfacial structure by FESEM and HRTEM, along with the other characterizations by XRD, XPS, and UV–visible absorption spectra. Under the irradiation of mercury lamp, the photocatalyst with 6 wt% CdS could afford a degradation rate of methyl orange (MO) of 94.6% in 70 min, 5.84 and 2.51 times as high as WO₃ and CdS, through a photocatalytic degradation process mainly controlled by·O₂^? as active species. In view of the distinctive alignment of energy bands of CdS-WO₃, the enhanced photocatalytic activities should be attributed to the more efficient Z-scheme mechanism that allows the photogenerated holes in WO₃ and electrons in CdS to function more efficiently thanks to the efficient interfacial recombination of the electrons in WO₃ and holes in CdS.     

Facile fabrication of CdSe/CuInS2 microflowers with efficient photocatalytic hydrogen production activity

Photocatalytic water splitting to produce hydrogen has attracted extensive attention and exhibited broad development prospects. In this work, CuInS₂ microflowers were fabricated through the solvothermal method, and decorated with CdSe quantum dots on the surface. As-prepared CdSe/CuInS₂ microflowers exhibited high photocatalytic hydrogen production activity (10610.37 μmol g^?1 h^?1) and high AQE of 48.97% at 420 nm. The enhanced photocatalytic hydrogen production activity owing to the construction of p-n heterostructure improved light absorption ability, increased electrons transfer efficiency and reduced recombination of photo-induced electrons and holes. Moreover, high stability and cyclic utilization of CdSe/CuInS₂ microflowers were beneficial to photocatalytic hydrogen production application.     

Efficient hydrogen evolution with ZnO/SrTiO3 S-scheme heterojunction photocatalyst sensitized by Eosin Y

Developing efficient, stable, and cheap photocatalysts for H₂ production has aroused great interest among researchers. Herein, noble-metal-free ZnO/SrTiO₃ composite photocatalysts have been successfully prepared by hydrothermal method. X-ray diffraction, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, ultraviolet–visible diffusion spectroscopy, and photoluminescence spectroscopy are used to characterize the obtained samples. The photocatalytic water splitting for H₂ production by ZnO/SrTiO₃ has been studied under simulated sunlight irradiation by using triethanolamine as a sacrificial agent and Eosin Y (EY) dye as a sensitizer. The orthogonal experiments are designed to optimize the photocatalytic reaction conditions for practical purposes. The influencing extents and trends of the factors have been investigated, including the catalyst composition and dosage, pH value of the solution, triethanolamine, and EY addition. Under the optimum conditions, the H₂ production rate with ZnO/SrTiO₃ is up to 16006.12 μmol g^?1 h^?1. The excellent performance of ZnO/SrTiO₃ is attributed to the formation of a step-scheme (S-scheme) heterojunction, which promotes the separation of photocarriers and reduces their recombination probability.     

In-situ constructing cobalt incorporated nitrogen-doped carbon/CdS heterojunction with efficient interfacial charge transfer for photocatalytic hydrogen evolution

Designing an efficient heterojunction interface is an effective way to promote the electrons' transfer and improve the photocatalytic H₂ evolution performance. In this work, a novel hollow hybrid system of Co@NC/CdS has been fabricated and constructed. CdS nanospheres are anchored on the hollow-structured cobalt incorporated nitrogen-doped carbon (Co@NC) through a one-pot in-situ chemical deposition approach, forming an intimate interface and establishing an excellent channel to improve the electrons transfer and charge carriers separation between CdS and Co@NC cocatalyst, which immensely promotes the photocatalytic activity. The rate of photocatalytic H₂ evolution over hollow structured Co@NC/CdS heterojunction can be achieved 8.2 mmol g^?1 h^?1, which is about 45 times of pristine CdS nanospheres. The photocatalytic H₂ evolution mechanism has been investigated by the techniques of photoluminescence (PL) spectra, photocurrent-time (i-t) curves, electrochemical impedance spectroscopy (EIS) etc. This work aims to provide a new way in developing of high-performance advanced 3D heterojunction for photocatalytic hydrogen evolution.     

Efficient interfacial charge transfer of 2D/2D CoP/CdS heterojunction for extremely boosted photocatalytic H2 evolution performance

Constructing 2D/2D heterojunction photocatalysts has attracted great attentions due to their inherent advantages such as larger interfacial contact areas, short transfer distance of charges and abundant reaction active sites. Herein, 2D/2D CoP/CdS heterojunctions were successfully fabricated and employed in photocatalytic H₂ evolution using lactic acid as sacrificial reagents. The multiple characteristic techniques were adopted to investigate the crystalline phases, morphologies, optical properties and textual structures of heterojunctions. It was found that integrating 2D CoP nanosheets as cocatalysts with 2D CdS nanosheets by Co–S chemical bonds would significantly boost the photocatalytic H₂ evolution performances, and the 7 wt% 2D/2D CoP/CdS heterojunction possessed the maximal H₂ evolution rate of 92.54 mmol g^?1 h^?1, approximately 31 times higher than that of bare 2D CdS nanosheets. Photoelectrochemical, steady photoluminescence (PL) and time-resolved photoluminescence (TRPL) measurements indicated that there existed an effective charge separation and migration over 2D/2D CoP/CdS heterojunction, which then markedly lengthened the photoinduced electrons average lifetimes, retarded the recombination of charge carriers, and caused the dramatically boosted photocatalytic H₂ evolution activity. Moreover, the density functional theory (DFT) calculation further corroborated that the efficient charge transfer occurred at the interfaces of CoP/CdS heterojunction. This present research puts forward a promising strategy to engineer the 2D/2D heterojunction photocatalysts endowed with an appealing photocatalytic H₂ evolution performance.     

Boosting photocatalytic hydrogen evolution of g-C3N4 via enhancing its interfacial redox activity and charge separation with Mo-doped CoSx

To achieve low-cost photocatalytic hydrogen (H₂) production, it is necessary to develop low-priced transition metal co-catalysts to replace the roles of noble metals for photocatalytic H₂ evolution. Herein, a co-catalyst of Mo-doped CoS_x (Mo-CoS_x) was synthesized by using the hydrothermal procedure, then attached to g-C₃N₄ to construct a composite photocatalyst. As a co-catalyst, Mo-CoS_x can work as an electron acceptor, it is utilized to receive electrons generated by g-C₃N₄ photocatalyst on the surface of the catalyst, and inhibit the recombination of those electrons, thus showing enhanced charge transfer ability as well as reduction ability. The optimized Mo-CoS_x/g-C₃N₄ delivered a prominent photocatalytic H₂ evolution rate of 2062.4 μmol h^?1 g^?1, which was ～193 times higher than g-C₃N₄. Its AQE at 400 nm and 420 nm were 11.05% and 6.83%, respectively. This work provides a novel non-precious metal co-catalyst/g-C₃N₄ photocatalyst that is expected to be an acceptable cost route to solar energy conversion.     

Direct Z-Scheme NiWO4/CdS nanosheets-on-nanorods nanoheterostructure for efficient visible-light-driven H2 generation

Exploiting efficient catalysts is of interest for solar-driven water splitting. Herein, a novel NiWO₄/CdS nanosheets-on-nanorods direct Z-Scheme heterostructure was developed by using a facile in-situ approach. The optimized NiWO₄/CdS heterostructure shows a H₂ evolution rate of 26.43 mmol g^?1 h^?1 exceeding that of bare CdS by more than 75 folds. Systematic investigations reveal the nanostructures with numerous active sites, intimate contact interface, and enhanced charge separation rate synergistically account for the outstanding performance of the NiWO₄/CdS. Moreover, the band structures were detailedly analyzed and the tentative photocatalytic mechanism was proposed, which could contribute to deeply understanding the catalytic process and guide the synthesis of the efficient heterostructure. These findings and strategies may have great significance in promoting the development of highly efficient and low-cost photocatalysts.     

Rational design of ZnO–CuO–Au S-scheme heterojunctions for photocatalytic hydrogen production under visible light

An integration of S-scheme heterojunction catalyst with surface plasmon resonance effect is the prime focus of current research activites in the field of visible light driven photocatalytic hydrogen (H₂) evolution. Herein, a sol-gel route is used to design a heterojunction of ZnO–CuO–Au. The effect of process parameters, including irradiation time, catalyst dose, and sacrificial reagents on the hydrogen evolution is studied. The S-scheme ZnO–CuO–Au heterojunction catalyst demonstrated high surface area, better optical absorption response in the visible part of light spectrum, and improved separation and transportion of charge carriers as verified by DRS, PL, and photoelectrochemical studies. The maximum H₂ evolution rateof ZnO–CuO–Au reaches 4655 μmolh⁻¹g⁻¹, which is 5 and 3.2 times higher than ZnO–CuO and Au–ZnO catalysts, respectively. A possible reason of this increase in H₂ evolution rate is inhibited recombination of charge carriers because of the S-scheme design to increase electrons with strong reduction potential and prolong lifetime, Au serves as an SPR source and conductive channel to swift the transfer of electrons and high density of active sites. This work offers innovative insight into designing plasmonic metals-modified S-scheme systems for solar fuel production.     

Cobaltous selenide/g-C3N4 heterojunction photocatalyst based on double-electron migration mechanism promotes hydrogen production and tetracycline hydrochloride degradation

Regulating photogenerated charge carrier transfer kinetics in multi-component heterostructure by surface-interface design is of great significance for accelerating efficiently photocatalytic hydrogen evolution reaction. Herein, a novel binary CoSe₂/CN_NS composite is successfully fabricated by a successive high-temperature calcination method of g-C₃N₄ followed by in-situ hot injection process of CoSe₂ for the first time. The optimal 7.5% CoSe₂/CN_NS heterostructure reaches moderate hydrogen production rate of 1386.8 μmol·g^?1·h^?1 and exhibits good mineralization efficiency for tetracycline hydrochloride (40.6%) within 120 min under light irradiation, respectively. The photogenerated charge migration behaviors, the generation process and function of various radical species (H₂O₂, ·OH and ·O₂^?) are detailedly analyzed. Moreover, photocatalytic hydrogen evolution reaction process and the intermediates and active species for tetracycline hydrochloride degradation can also be discussed. Such significantly enhanced photocatalytic activity can be resulting from good light trapping ability, rapid photocarriers transfer efficiency and accelerated H₂O₂ decomposition ability via a continuous two-electron/two-step reduction route. This work provides an effective strategy to control and understand the charge migration kinetics as well as to suppress H₂O₂ production during photocatalytic hydrogen evolution process.     

Construction of 1D/0D/2D Zn0.5Cd0.5S/PdAg/g-C3N4 ternary heterojunction composites for efficient photocatalytic hydrogen evolution

A high-efficiency and easy-available approach was developed to obtain a ternary heterojunction composites with advanced hydrogen evolution reaction (HER) performance under visible light by water split. PdAg bimetallic nanoparticles make a close contact interface between g-C₃N₄(CN) and Zn_0.5Cd_0.5S(ZCS). Under visible light irradiation, CN and ZCS are both excited to generate electron-hole pairs, PdAg bimetallic nanoparticles act as a bridge between CN and ZCS. Not only can the photogenerated electrons from CN be captured, but they can also be quickly transferred to the surface of ZCS and participate in the photocatalytic reaction to release H₂, and the recombination of charge carriers between the contact interface of ZCS and CN can be significantly inhibited. In addition, the thin CN layer reduces the photocorrosion of the ZCS and enhances the specific surface area of the composite material. After testing, the composite material with 30 wt% ZCS and 4 wt% PdAg demonstrates hydrogen evolution performance, up to 6250.7 μmol g^?1h^?1, which is 753 times the hydrogen evolution rate of single-component CN and 12.6 times of ZCS/CN. Compared with single-component and two-component photocatalysts, the ternary ZCS/PdAg/CN photocatalyst achieves significantly enhanced photocatalytic activity.     

Synergistic enhancement of photocatalytic H2 production by Ni decorated 2D bubble-like carbon nitride

In this paper, a novel 2D bubble-like g-C₃N₄ (B–CN) with a highly porous and crosslinked structure is successfully synthesized via a cost-effective bottom-up process. The as-prepared B–CN photocatalyst delivers a considerably expanded specific surface area and increased active sites. Moreover, the 2D bubble-like structure can afford shortened diffusion paths for both photogenerated charge carriers and reactants. As a result, the photocatalytic H₂ evolution rate of B–CN reached 268.9 μmol g^?1 h^?1, over 5 times more than that of bulk C₃N₄. The Ni ions were further deposited on B–CN as a cocatalyst to enhance the photocatalytic activity. Benefit from the synergy of 2D bubble-like structure and Ni species cocatalyst, recombination of photoinduced charges was greatly inhibited and the hydrogen evolution reaction (HER) was significantly accelerated. The resulted catalyst achieved a dramatically high H₂ evolution rate of 1291 μmol g^?1 h^?1. This work provides an alternative way to synthesize novel porous carbon nitride together with non-noble metal cocatalysts toward enhanced photocatalytic activity for H₂ production.     

Rational regulation of vacancy species to manage migration paths of carriers in MoS2/TiO2 heterojunctions for efficient photocatalytic H2 generation

Photocatalytic water splitting to produce hydrogen (H₂), as one means to solve environmental pollution and energy shortage, is limited by the serious recombination of photogenerated electrons and holes, resulting in low solar energy conversion efficiency. Thus, steering the behaviors of charge carriers by rationally designing their transport pathway is essential, which can effectively suppress the recombination of electrons and holes. Herein, we designed a MoS₂/TiO₂ heterojunction with different vacancy species to manage the migration paths of photogenerated charge carriers. As demonstrated by experimental characterizations and density functional theory (DFT) calculations, oxygen and sulfur vacancies can induce defect energy levels in heterostructures, which can capture photogenerated holes and electrons, respectively, resulting in substantially promoted charge separation efficiency and longer lifetime of electrons. As expected, the optimized photocatalyst shows a stable H₂ production rate of 1.41 mmol g^?1 h^?1, which is significantly better than that of the bare MoS₂/TiO₂ heterojunction. This finding informs the significance in rational design of the nanostructures for promoting the photocatalytic performance.     

Fabrication of the SnS2/ZnIn2S4 heterojunction for highly efficient visible light photocatalytic H2 evolution

A series of SnS₂/ZnIn₂S₄ (x-SS/ZIS) photocatalysts with different mass ratios of SnS₂ were prepared by a hydrothermal method. The resulted composites were used for photocatalytic hydrogen evolution under visible light excitation. All the SS/ZIS composites exhibited significantly enhanced photocatalytic activity for H₂ evolution. Obviously, the highest H₂ evolution rate of 769 μmol g^?1 h^?1 was observed over 2.5-SS/ZIS, which was approximately 10.5 times that of the ZnIn₂S₄ (73 μmol g^?1 h^?1). The enhanced photocatalytic performance was attributed to the successful construction of SnS₂/ZnIn₂S₄ heterojunctions, leading to rapid charge separation and fast transfer of the photo-generated electrons and holes under light irradiation. On the basis of PL, electrochemical impedance spectroscopy (EIS), photocurrent measurements and the H₂ evolution tests, a plausible photocatalytic mechanism was proposed.     

Bandgap control of p-n heterojunction of Cu–Cu2O @ ZnO with modified reduced graphene oxide nanocomposites for photocatalytic hydrogen evolution

Here, we describe the in-situ synthesis of multicomponent ZnO-based photocatalysts for hydrogen production. We fabricated ZnO coupled with Cu–Cu₂O nanoparticles and modified reduced graphene oxide (mRGO) to ameliorate hydrogen production. The simultaneous introduction of mRGO and Cu–Cu₂O enhanced the generation rate of photocatalytic hydrogen to 3085.02 μmol g^?1 h^?1 due to significant alteration of the electronic structure. The bandgap energy of the prepared catalysts decreased from 3.2 eV for pristine ZnO to 2.64 eV for a composite containing 15% Cu–Cu₂O. The optimal designed heterostructure efficiently separates photo charge carriers and prevents charge carriers’ recombination by accelerating charge transfer with the help of mRGO and metallic Cu and as a result leading to efficient hydrogen yields.