Vanadium diboride as an efficient cocatalyst coupled with CdS for enhanced visible light photocatalytic H2 evolution

Exploiting active, stable, and cost-efficient cocatalysts is crucial to enhance the photocatalytic performance of semiconductor-based photocatalysts for H₂ evolution from water splitting. Herein, we report on using vanadium diboride (VB₂) as an efficient cocatalyst to enhance the photocatalytic H₂ evolution performance of CdS nanoparticles under visible light irradiation (λ ≥ 420 nm). The CdS/VB₂ composites prepared by a facile solution-mixing method exhibit much improved H₂ evolution activities in 10 vol% lactic acid (LA) solution relative to pristine CdS. The most efficient CdS/VB₂ composite with 20 wt% VB₂ (CB20) exhibits a H₂ evolution rate as high as 12.1 mmol h⁻¹ g⁻¹, which is about 11 times higher than that of CdS alone (1.1 mmol h⁻¹ g⁻¹). Moreover, the highest apparent quantum efficiency (AQE) of 4.4% is recorded on CB20 at 420 nm. The improved photocatalytic activity of CdS/VB₂ composite can be attributed to the excellent cocatalytic effect of VB₂, which can not only enhance the charge separation on CdS but also accelerate the H₂ evolution kinetics. This work demonstrates the great potential of using transition metal brodies (TMBs) as efficient cocatalysts for developing noble-metal-free and stable photocatalysts for solar photocatalytic H₂ evolution.     

A novel pathway toward efficient improvement of the photocatalytic activity and stability of CdS-based photocatalyst for light driven H2 evolution: The synergistic effect between CdS and SrWO4

It has been a research hot spot how to efficiently heighten the photocatalytic activity and stability of CdS-based photocatalysts for H₂ evolution. Here, SrWO₄/CdS nanoparticles which contained CdS/SrWO₄ heterojunctions were prepared. Meanwhile, their photocatalytic performance and stability were investigated in detail for H₂ evolution. At last, the photocatalytic mechanism of the SrWO₄/CdS nanoparticles was discussed roughly. The results show that the photocatalytic performance of CdS can be heightened significantly due to introduction of SrWO₄. The fastest evolution rate of H₂ over the SrWO₄/CdS nanoparticles is 392.5 μmol g⁻¹ h⁻¹, which is 5.8 times as high as that over the pure CdS nanomaterial. More interestingly, the SrWO₄/CdS nanoparticles possess excellent stability. The evolution rate of H₂ over the photocatalyst used 10 times can be up to 473 μmol g⁻¹ h⁻¹, which is the same as that over the once used sample, even is 37% higher than that over of the fresh one. In contrast, after used five times, the photocatalytic activity of the pure CdS nanomaterial is only 57% of that of the fresh sample. This study will supply a new idea for the design and development of highly stable and efficient CdS-based photocatalysts for H₂ evolution in the future.     

Noble-metal-free CdS@MoS2 core-shell nanoheterostructures for efficient and stabilized visible-light-driven H2 generation

Photocatalytic water splitting is considered to be a green H₂ generation approach and has potential to be applied in the future. As a photocatalytic active material for H₂ evolution, CdS is a good candidate. However, the pristine CdS still suffers from low efficiency and poor stability. To address those issues, we developed noble-metal-free CdS@MoS₂ core-shell nanoheterostructures which exhibit outstanding photocatalytic H₂ evolution performance thus far with rate of 62.55 mmol g⁻¹ h⁻¹, which exceeds that of pristine CdS by a factor of 148. Meanwhile, the photocatalytic stability can be well retained with no deterioration of activity in 24 h reaction. The excellent performance can be reasonably attributed to the low crystallinity of MoS₂ with numerous active sites provided, and the band alignment of CdS and MoS₂ as determined by valence band-XPS and Mott-Schottky plots analysis, which significantly promotes charge transportation and separation. The enhanced photocatalytic stability here should be ascribed to the intimate growth of MoS₂ shells which significantly passivate the surface trap states of CdS cores and thus the photocorrosion is remarkably retarded. This novel strategy will inspire the fabrication of other photocatalytic systems, and may high-efficient photocatalysts be obtained.     

Lanthanum modified Ni2P/CdS ohmic contact for significantly enhanced photocatalytic hydrogen production performance

Photocatalytic selective organic transformations (SOTs) with H₂ production in one reaction system represent a route with great promise for green and sustainable organic synthesis and clean fuel generation. In this work, a new La-ion engineering strategy was employed to elaborately fabricate Ni₂P/CdLaS (NP/CLS) composite photocatalysts, which significantly improved the visible light-initiated alcohol oxidation-hydrogen production performance. The optimized 1.5% NP/CLS sample showed a maximum production rate of H₂ (15.35 mmol·h⁻¹·g⁻¹) and aromatic aldehyde (15.83 mmol·h⁻¹·g⁻¹) under visible light illumination (λ ≥ 420 nm), which are 3.4 times higher than that of Ni₂P/CdS (NP/CS) and 20 times higher than that of CLS. The apparent quantum efficiency over 1.5% NP/CLS sample could reach up to 11.22% at 450 nm. The superior performance of the photocatalytic H₂ production results over 1.5% NP/CLS sample could be mainly ascribed to the following synergistic effects. Firstly, the formed intimate Ohmic contact between NP and CLS can increase the separation speed of photo-generated charge carriers, meantime, reducing the overpotential for H₂ evolution. Secondly, the introduced La ions in NP/CLS effectively strengthen photogenerated electron transfer. The detailed physical and chemical characterization results, in-situ XPS analysis, and density functional theory (DFT) calculations provide effective support for the proposed photocatalytic reaction mechanism. This work shows a strategy with great promise to design noble-metal-free photocatalysts for high H₂ production performance.     

Efficient photocatalytic hydrogen evolution with high-crystallinity and noble metal-free red phosphorus-CdS nanorods

The photocatalytic production of H₂ by low-cost semiconductors is a promising approach to store solar energy. Photocatalysts with heterojunctions convert visible light into H₂ faster because of more efficient charge separation. The morphology, the structure, and the crystallinity are additional factors to consider when developing a photocatalyst. Here, highly-crystalline CdS nanorod (NR) were synthesized by a facile one-pot process. Under visible light, pure CdS NR produced H₂ 2.1 times faster than conventional CdS nanoparticles (NP). CdS NR were then combined with the semiconductor red phosphorus (RPh). A CdS NR-based heterojunction photocatalyst with RPh_5% had an excellent photocatalytic H₂ evolution rate of 11.72 mmol g⁻¹ h⁻¹, which was 3.6 times higher than pure CdS NR. The apparent quantum efficiency of RPh_5%/CdS NR was 19.57%. Furthermore, RPh_5%/CdS NR exhibited a superior photogenerated charge separation efficiency and was stable with little photocorrosion compared to CdS NP showing the high potential of this heterojunction photocatalyst.     

Facile in-situ synthesis of α-NiS/CdS p-n junction with enhanced photocatalytic H2 production activity

Constructing active sites on photocatalysts is one of the most effective approaches for promoting photocatalytic H₂ production activity. In this paper, a p-type semiconductor α-NiS is in-situ grown on an n-type semiconductor CdS by a simple solid state method, which results in a strong interfacial contact between α-NiS and CdS. Benefitting from the built-in electric field caused by a p-n junction, the photoinduced electrons of CdS and holes of α-NiS migrate to their interface and recombine rapidly, which results in the formation of a Z system. The more negative CB potential of α-NiS/CdS possesses stronger ability to reduce H⁺ to H₂, thereby exhibiting higher photocatalytic H₂ evolution activity. Furthermore, the strong interface contact is beneficial to the charge migration and promotes the charge separation efficiency. The H₂ evolution rate of 1.0% α-NiS/CdS reaches 9.8 mmol h^?1 g^?1, corresponding to an AQY of 65.7% at λ = 420 nm.     

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.     

Well-designed NiS/CdS nanoparticles heterojunction for efficient visible-light photocatalytic H2 evolution

Heterojunction photocatalysts based on semiconducting nanoparticles show excellent performance in many photocatalytic reactions. In this study, 0D/0D heterojunction photocatalysts containing CdS and NiS nanoparticles (NPs) were successfully synthesized by a chemical precipitation method. The NiS NPs were grown in situ on CdS NPs, ensuring intimate contact between the semiconductors and improving the separation efficiency of hole-electron pairs. The obtained NiS/CdS composite delivered a photocatalytic H₂ evolution rate (7.49 mmol h^?1 g^?1), which was 39.42 times as high as that of pure CdS (0.19 mmol h^?1 g^?1). This study demonstrates the advantages of 0D/0D heterojunction photocatalysts for visible light-driven photocatalytic hydrogen production.     

MoS2 grown in situ on CdS nanosheets for boosted photocatalytic hydrogen evolution under visible light

A novel nano-heterojunction photocatalysts of CdS/MoS₂ with appropriate interfacial contact was successfully obtained by the facile two-step hydrothermal synthesis. The MoS₂ ultrathin layer was well combined with CdS nanosheets and formed the interaction, which facilitated the transfer and separation of charges. The CdS/MoS₂ 15 wt% possessed much higher H₂ evolution photocatalytic performance (35.24 mmol h^?1 g^?1), exhibiting an 85.95 times enhancement as compared to that of pure CdS (0.41 mmol h^?1 g^?1). Moreover, the photochemical stability of CdS/MoS₂ heterojunctions was excellent, which showed no significant decrease in activity after four cycles of experiments. The finding provides a novel method to integrate the structure of MoS₂ with CdS, which exhibits great potential in solar energy conversion.     

Metal (oxide) modified (M= Pd,Ag, Au and Cu) H2SrTa2O7 for photocatalytic CO2 reduction with H2O: The effect of cocatalysts on promoting activity toward CO and H2 evolution

Ag, Pd, Au, Cu₂O as cocatalysts were loaded on the layered H₂SrTa₂O₇ (HST) for photocatalytic CO₂ reduction with H₂O. The characterization revealed that cocatalysts loaded on the surface of HST can effectively promote the separation of photogenerated electrons and holes due to the formation of Schottky barrier or p-n junction, thus enhancing photocatalytic activity. Of note, Ag, Pd, Au, Cu₂O loading exhibited obviously different performance on promoting photocatalytic activity of HST toward CO evolution and H₂ evolution because of the different overpotentials of CO evolution and H₂ evolution on loaded photocatalysts. Cocatalysts with low overpotentials of CO or H₂ evolution act as active sites for CO or H₂ evolution, thus controlling the selectivity toward CO or H₂. The Au/HST exhibited high activity for only H₂ evolution (17.5 μmol g⁻¹ h⁻¹) due to relative low overpotential for H₂ evolution (0.67 V) while the Cu₂O/HST exhibited high activity only for CO evolution (0.23 μmol g⁻¹ h⁻¹) due to relative low overpotential for CO evolution (0.40 V). The Pd/HST sample exhibits high photocatalytic activity for both CO and H₂ evolution rates due to the low overpotential for CO and H₂ evolution, reaching 4.0 and 4.7 times of bare HST, respectively. This work here gives an in-depth understanding of the effect of cocatalysts on promoting photocatalytic activity and selectivity and can also give guidance to design photocatalysts with high activity and selectivity for photocatalytic CO₂ reduction with H₂O.     

Noble metal free efficient photocatalytic hydrogen generation by TaON/CdS semiconductor nanocomposites under natural sunlight

Tantalum oxynitride have narrow band gap and its band potentials are suitable for visible light induced hydrogen generation. However, due to fast electron-hole recombination, the efficiency of photocatalytic hydrogen evolution reaction is very low. Herein, we have synthesized semiconductor heterojunction photocatalyst, i.e., TaON/CdS with suitable band positions by a simple precipitation method. Ratio between two semiconductors is optimized to obtain maximum hydrogen evolution. XRD, XPS and TEM analysis demonstrate the formation of heterojunction between these semiconductors. Among the synthesized catalysts, 3% TaON/CdS heterostructure exhibits the highest hydrogen evolution activity with H₂ production rate of 7.5 mmol h⁻¹ under natural solar light, whereas the rate is 11 mmol h⁻¹ under the visible light generated by xenon (Xe) lamp without the addition of any noble metal as the co-catalyst. The CdS and 3% TaON/CdS nanomaterials show an AQE of 5.1% and 12.2%, respectively. Combination of Mott-Schottky, UPS and DR UV–visible spectroscopy studies revealed the formation of S scheme semiconductor heterojunction between these nanomaterials with valence, conduction band positions, i.e., 1.46, −0.78 eV for CdS and 2.19, −0.66 eV for TaON, respectively. These band positions help in efficient e-h pair separation to produce hydrogen from water.     

MoS2/CdS rod-like nanocomposites as high-performance visible light photocatalyst for water splitting photocatalytic hydrogen production

This study demonstrates a high-performance visible-light-driven photocatalyst for water splitting H₂ production. CdS nanorods (30 nm in diameters) with shorter radial transfer paths and fewer defects were prepared by a solvothermal method. To mitigate the recombination of electrons and holes, MoS₂ nanosheets with rich active sites were modified on the surface of CdS nanorods by a room-temperature sonication treatment. The photocatalytic water splitting tests show that the MoS₂/CdS nanocomposites exhibit excellent H₂ evolution rates. The highest H₂ evolution rates (63.71 and 71.24 mmol g^?1h^?1 in visible light and simulated solar light irradiation) was found at the 6% MoS₂/CdS nanocomposites, which was 14.61 times and 13.39 times higher than those of the corresponding pristine CdS nanorods in visible light and simulate solar light irradiation, respectively. The apparent quantum efficiency (AQE) of the 6% MoS₂/CdS nanocomposites at 420 nm was calculated to be 33.62%. The electrochemistry tests reveal that the enhanced photocatalytic activity is a result of extra photogenerated charge carries, greatly enhanced charge separation and transfer ability of the MoS₂/CdS composites. This study may give new insights for the rational design and facile synthesis of high-performance and cost-effective bimetallic sulfide photocatalysts for solar-hydrogen energy conversion.     

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.     

Separation of hot electrons and holes in Au/LaFeO3 to boost the photocatalytic activities both for water reduction and oxidation

Construction of plasmon-based nanostructures is an effective way to enhance the photocatalytic activities of semiconductor photocatalysts for water-splitting. However, the synergistic effect of plasmon-related hot electrons and holes for water splitting in the plasmon-hybrid photocatalyst is rarely considered. Herein, we construct a plasmon-based Au/LaFeO₃ composite photocatalyst to investigate the complex roles of hot electrons and holes for solar water splitting. Benefiting from the formation of Schottky junction and surface plasmon resonance effect of the Au nanoparticles, the synthesized photocatalyst exhibits an excellent photocatalytic activity for each half-reaction of water splitting, and the rates for H₂ and O₂ generation are obtained as high as 202 μmol g⁻¹ h⁻¹ and 23 μmol g⁻¹ h⁻¹, respectively. Moreover, an in-depth investigation reveals that the improved hydrogen evolution is caused by the hot electron injection from Au to LaFeO₃, and the hot holes in Au induced by the separation of hot charges can initiate the water oxidation directly on the surface of gold. Thus, this work provides a new insight into the synergistic effect of plasmon-related hot electrons and holes for boosting the photocatalytic reactions.     

Sonochemistry synthesis of Bi2S3/CdS heterostructure with enhanced performance for photocatalytic hydrogen evolution

Photocatalytic hydrogen evolution from water splitting is an efficient, eco-friendly method for the conversion of solar energy to chemical energy. A great number of photocatalysts have been reported but only a few of them can respond to visible-light. Metal sulfides, a class of visible-light response semiconductor photocatalysts for hydrogen evolution and organic pollutant degradation, receive a lot of attention due to their narrow band gaps. Herein, we report the sonochemical synthesis of Bi₂S₃/CdS nanocrystal composites with microsphere structure at mild temperature. The phases of Bi₂S₃ and CdS can be observed obviously in HRTEM image. The heterostructure consisting of the two species of nanocrystals plays a key role in separating photo-generated charge carriers. Photocatalytic activities for water splitting are investigated under visible-light irradiation (λ > 400 nm) and an enhanced photocatalytic activity is achieved. The initial rate of H₂ evolution is up to 5.5 mmol h⁻¹ g⁻¹ without resorting to any cocatalysts.     

Interfacing CdS particles on Ni foam as a three-dimensional monolithic photocatalyst for efficient visible-light-driven H2 evolution

Solar photocatalytic water splitting using particulate semiconductors has been valued as a potentially scalable way for the production of clean H₂ energy, yet the performances of the powder-suspension systems are constrained by insufficient utilization of light energy and tedious recycling of photocatalyst particles. Here, we present a high-performance photocatalytic H₂ evolution using a visible-light-driven CdS-based monolithic photocatalyst with three-dimensional (3D) heterostructure. The monolithic photocatalyst is fabricated by firmly growing CdS microspheres on a Ni(OH)₂ nanosheet-modified Ni foam (NF) (denoted as CdS-NiS_x/NF) via a simple hydrothermal process. The structure and component synergy endows the monolithic CdS-NiS_x/NF photocatalyst advantageous features including high-density CdS microspheres for visible light harvesting, multiple heterojunction interfaces for efficient electron-hole separation, and abundant interfacial NiS_x active sites for efficient H₂ evolution reaction (HER). Upon visible light irradiation, the monolithic CdS-NiS_x/NF photocatalyst exhibits an outstanding photocatalytic H₂ evolution activity with an enhanced rate of 6.2 mmol·h⁻¹ g⁻¹_CdS, which is 6 times higher than that of the suspended CdS powder. In addition, the structural integrity of the CdS-NiS_x/NF enables a good stability for H₂ evolution over a 30 h reaction. This monolithic photocatalyst is scalable in preparation and compatible for device fabrication, which offers great potentials for applications in solar cells, photoelectrocatalysis, and electrocatalysis.     

Enhanced photocatalytic hydrogen evolution over semi-crystalline tungsten phosphide

Increasing the separation efficiency and transfer rate of photogenerated charges is the dominant factor for improving photocatalytic activity. Herein, we successfully prepared semi-crystalline WP (SC-WP) with good optical properties and as a cocatalyst to modify CdS nanorods (CdS NRs) to construct SC-WP/CdS (PD) composite catalyst by simple electrostatic self-assembly method for photocatalytic hydrogen evolution. Two high-efficiency and stable photocatalytic hydrogen evolution systems were constructed with 1.0 M ammonium sulfite solution and 10 vol% lactic acid solution as sacrificial agents, respectively. Surprisingly, the maximum photocatalytic H₂ production rate of 15446.21 μmol h⁻¹ g⁻¹ is obtained over 10PD composite, which is 10.58 times greater than that of pure CdS. The improved photocatalytic activity can be attributed to the fact that the SC-WP nanoparticles provides a large number of exposed active sites on the surface of CdS for hydrogen evolution reaction, which can efficiently capture photogenerated electrons from CdS nanorods and promotes the transport and separation of light-induced charges. And the introduction of SC-WP nanoparticles with excellent optical properties can efficiently improve the visible light absorption range and the utilization rate of the absorbed light of the PD composite. In addition, the SC-WP nanoparticles show semi-crystalline state, which is also conducive to enhancing the photocatalytic activity.     

Fabrication of CdS/Zn2GeO4 heterojunction with enhanced visible-light photocatalytic H2 evolution activity

CdS/Zn₂GeO₄ (CG) composites were synthesized through the simple hydrothermal process. The crystal structure, morphology and light absorption property of the products were studied in detail. The CG composites showed excellent photocatalytic hydrogen production performance upon visible light illumination. Especially, the CG-3 composite displayed the highest H₂ evolution rate of 1719.8 μmol h⁻¹ g⁻¹, which was about 3.80 and 4.28 times higher than the pure CdS and Zn₂GeO₄. Besides, the cyclic stability of the CG-3 composite was also excellent. The PL, photocurrent response and EIS spectra results testified that the efficient separation and transfer of photoinduced charge carriers achieved between CdS and Zn₂GeO₄, which could result in the promotion of photocatalytic performance. Moreover, a possible mechanism of H₂ generation over CdS/Zn₂GeO₄ heterojunction was discussed. The practicable way to construct heterojunction composites would be helpful for the design of other systems with excellent photocatalytic property.     

Self-assembled CdS@BN core-shell photocatalysts for efficient visible-light-driven photocatalytic hydrogen evolution

CdS@BN NRs core-shell photocatalysts for hydrogen evolution were synthesized by a solvothermal and chemical adsorption method. CdS NRs coated by 5 wt% boron nitride (BN) shell exhibited remarkably visible-light photocatalytic hydrogen evolution activity of up to 30.68 mmol g⁻¹ h⁻¹, nearly 6.79 times higher than that of pure CdS NRs, and the apparent quantum efficiency at 420 nm was 7.5%. Transmission electron microscopy showed the CdS NRs were coated with a thin (~5 nm) BN layer, which together with the hydrogen evolution results proved the photocatalytic ability of CdS NRs was significantly improved. The hydrogen evolution rate of CdS NRs coated by 5 wt% BN remained at 91.4% after four cycles, indicating the photocorrosion of CdS NRs was effectively alleviated. Moreover, the large and close coaxial interfacial contact between the CdS core and the BN shell was beneficial to the separation and transfer of photogenerated electron-hole pairs.     

The one-step hydrothermal synthesis of CdS nanorods modified with carbonized leaves from Japanese raisin trees for photocatalytic hydrogen evolution

The photocatalytic performance of the semiconductor CdS can be improved with carbon materials capable of limiting photocorrosion and the fast recombination of photogenerated charges. For this purpose, carbon derived from biomass exhibit several advantages including low cost, high abundance, and renewability. Here, photocatalytic CdS nanorods modified with carbon derived from the leaves of Japanese raisin trees were synthesized via a single hydrothermal step. Composite CdS nanorods with 5% biomass-derived carbon photocatalyzed H₂ evolution 1.8 times faster than unmodified CdS at a rate of 5.71 mmol g^?1 h^?1. The apparent quantum efficiency of 5%C/CdS nanorods was 14.96%. Furthermore, the addition of biomass-derived carbon to CdS nanorods augmented the stability of the semiconductor under visible light. The characterization of the composite PC indicated that a larger specific surface area, as well as upgraded charge separation caused by biomass-derived carbon, were involved in the acceleration of photocatalytic hydrogen production.