Efficient photocatalytic hydrogen evolution on amorphous MoSx-modified CdS/KTaO3 heterojunctions under visible light irradiation

Constructing heterostructures with efficient charge separation is a promising route to improve photocatalytic hydrogen production. In this paper, MoS_x/CdS/KTaO₃ ternary heterojunction photocatalysts were successfully prepared by a two-step method (hydrothermal method and photo deposition method), which improved the photocatalytic hydrogen evolution activity. The results show that the rate of hydrogen evolution for the optimized photocatalyst is 2.697 mmol g^?1·h^?1under visible light, which is 17 times and 2.6 times of the original CdS (0.159 mmol g^?1 h^?1) and the optimal CdS/KTaO₃(1.033 mmol g^?1 h^?1), respectively, and the ternary photocatalyst also shows good stability. The improvement on photocatalytic hydrogen evolution performance can be attributed to the formation of heterojunction between the prepared composite materials, which effectively promotes the separation and migration of photo-generated carriers. Amorphous MoS_x acts as an electron trap to capture photogenerated electrons, providing active sites for proton reduction. This provides beneficial enlightenment for hydrogen production by efficiently utilizing sunlight to decompose water.     

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.     

Fabrication of 1D/2D CdS/CoSx direct Z-scheme photocatalyst with enhanced photocatalytic hydrogen evolution performance

In this work, we fabricate a 1D/2D heterojunction photocatalyst composed of n-type CdS nanorods and p-type CoS_x nanoflake. This photocatalyst achieves a hydrogen evolution rate of 9.47 mmol g^?1 h^?1, which is 13.7 times higher than that of pure CdS nanorods. Scanning Kelvin Probe, Mott-Schottky plots, UV–Vis absorption spectra and surface photocarrier orienting reaction results indicate that the enhanced photocatalytic performance of CdS/CoS_x is owing to the fabrication of direct Z-Scheme heterojunction system which greatly improves the utilization, migration and separation rate of photo-generated carriers. To the best of our knowledge, this work is the first time to describe a CdS/CoS_x direct Z-scheme system with 1D/2D nanostructure, which can expedite the transfer process of photogenerated carriers with strong redox energy to participate in photocatalytic reactions.     

A ZIF-67-derived lamellar CoP@C cocatalyst for promoting photocatalytic hydrogen evolution from water

Photocatalytic hydrogen evolution from water is one of the top issues to achieve green hydrogen energy and utilize solar energy. Construction of cocatalyst is a major part for efficient photocatalysts. Lamellar flower-like CoP@C cocatalyst is synthesized via the phosphating of cobalt precursor derived from metal-organic framework ZIF-67. Different from usual phosphating of ZIF-67 directly, a typical solvothermal treatment of ZIF-67 contributes to tuning the formation of C nanodots on the lamellar CoP. CoP@C as cocatalyst exhibits a remarkable role of improving photocatalytic activity for hydrogen evolution. CoP@C/CdS composite shows a photocatalytic hydrogen evolution rate of 164.4 mmol g^?1 h^?1, which is much higher than those of pure CdS and other CoP/CdS photocatalysts. The heterojunction and interaction are verified between CoP@C and CdS. Light absorption and photoelectric properties of CoP@C/CdS are enhanced accompanying with strong reduction ability. A type-Ⅱ transfer path of photoelectrons is underway in CoP@C/CdS photocatalyst, accelerating the separation of electron-hole pairs and the transfer of carriers, and further resulting in the promoted photocatalytic performance. This work provides a suitable way to achieve carbon nanodots involved metal compound cocatalysts for efficient hydrogen production.     

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.     

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.     

The construction of 3D hierarchical CdS/NiAl-LDH photocatalyst for efficient hydrogen evolution

The development of excellent photocatalysts for hydrogen evolution is of great significance to solving the global energy crisis. In this work, a novel 3D hierarchical CdS/NiAl-LDH photocatalyst was fabricated by a facile electrostatic assembly strategy, which was composed of 1D CdS nanorods and 3D flower-like NiAl-LDH microspheres. Under the visible irradiation, the CNA-20 hierarchical photocatalyst presents the optimum hydrogen evolution rate achieved to 3.24 mmol g^?1 h^?1, which is improved 6.23-fold in comparison with the pure CdS. Through the analysis of energy band structures and first-principles calculation, the type-Ⅱ charge transfer mechanism was proposed. Driven by the built-in electric field, as well as the effect of intimate interface contact of CdS and NiAl-LDH, the photogenerated charge could be achieved rapidly separate and migrate, which effectively promotes the H₂ evolution. This well-designed synergistic 1D/3D interface interaction and provides an economic approach to rationally developing metal-free photocatalysts for hydrogen production.     

Adenine-functionalized conjugated polymer as an efficient photocatalyst for hydrogen evolution from water

Conjugated polymers have emerged as a promising class of organic photocatalysts for photocatalytic hydrogen evolution from water splitting due to their adjustable chemical structures and electronic properties. However, developing highly efficient organic polymer photocatalysts with high photocatalytic activity for hydrogen evolution remains a significant challenge. Herein, we present an efficient approach to enhance the photocatalytic performance of linear conjugated polymers by modifying the surface chemistry via introducing a hydrophilic adenine group into the side chain. The adenine unit with five nitrogen atoms could enhance the interaction between the surface of polymer photocatalyst and water molecules through the formation of hydrogen bonding, which improves the hydrophilicity and dispersity of the resulting polymer photocatalyst in the photocatalytic reaction solution. In addition, the strong electron-donating ability of adenine group with plentiful nitrogen atoms could promote the separation of light-induced electrons and holes. As a result, the adenine-functionalized conjugated polymer PF6A-DBTO2 shows a high photocatalytic activity with a hydrogen evolution rate (HER) of 25.21 mmol g^?1 h^?1 under UV-Vis light irradiation, which is much higher than that of its counterpart polymer PF6-DBTO2 without the adenine group (6.53 mmol g^?1 h^?1). More importantly, PF6A-DBTO2 without addition of a Pt co-catalyst also exhibits an impressive HER of 21.93 mmol g^?1 h^?1 under visible light (λ > 420 nm). This work highlights that it is an efficient strategy to improve the photocatalytic activity of conjugated polymer photocatalysts by the modification of surface chemistry.     

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.     

Hydrogen generation by photocatalytic reforming of glucose with heterostructured CdS/MoS2 composites under visible light irradiation

A binary heterostructured CdS/MoS₂ flowerlike composite photocatalysts was synthesized via a simple one-pot hydrothermal method. This photocatalyst demonstrated higher photocatalytic hydrogen production activity than pure MoS₂. The heterojunction formed between MoS₂ and CdS seems to promote interfacial charge transfer (IFCT), suppress the recombination of photogenerated electron–hole pairs, and enhance the hydrogen generation. Based on the good match between the conduction band (CB) edge of CdS and that of MoS₂, electrons in the CB of CdS can be transferred to MoS₂ easily through the heterojunction between them, which prevents the accumulation of electrons in the CB of CdS, inhibiting photocorrosion itself and greatly enhancing stability of catalyst. Hydrogen evolution reaction (HER) using Na₂S/Na₂SO₃ or glucose as sacrificial agents in aqueous solution was investigated. The ratio between CdS and MoS₂ plays an important role in the photocatalytic hydrogen generation. When the ratio between CdS and MoS₂ reaches 40 wt%, the photocatalyst showed a superior H₂ evolution rate of 55.0 mmol g⁻¹ h⁻¹ with glucose as sacrificial agent under visible light, which is 1.2 times higher than using Na₂S/Na₂SO₃ as sacrificial agent. Our experimental results demonstrate that MoS₂-based binary heterostructured composites are promising for photocorrosion inhibition and highly efficient H₂ generation.     

Rationally designed ternary CdSe/WS2/g-C3N4 hybrid photocatalysts with significantly enhanced hydrogen evolution activity and mechanism insight

Excellent light harvest, efficient charge separation and sufficiently exposed surface active sites are crucial for a given photocatalyst to obtain excellent photocatalytic performances. The construction of two-dimensional/two-dimensional (2D/2D) or zero-dimensional/2D (0D/2D) binary heterojunctions is one of the effective ways to address these crucial issues. Herein, a ternary CdSe/WS₂/g-C₃N₄ composite photocatalyst through decorating WS₂/g-C₃N₄ 2D/2D nanosheets (NSs) with CdSe quantum dots (QDs) was developed to further increase the light harvest and accelerate the separation and migration of photogenerated electron-hole pairs and thus enhance the solar to hydrogen conversion efficiency. As expected, a remarkably enhanced photocatalytic hydrogen evolution rate of 1.29 mmol g⁻¹ h⁻¹ was obtained for such a specially designed CdSe/WS₂/g-C₃N₄ composite photocatalyst, which was about 3.0, 1.7 and 1.3 times greater than those of the pristine g-C₃N₄ NSs (0.43 mmol g⁻¹ h⁻¹), WS₂/g-C₃N₄ 2D/2D NSs (0.74 mmol g⁻¹ h⁻¹) and CdSe/g-C₃N₄ 0D/2D composites (0.96 mmol g⁻¹ h⁻¹), respectively. The superior photocatalytic performance of the prepared ternary CdSe/WS₂/g-C₃N₄ composite could be mainly attributed to the effective charge separation and migration as well as the suppressed photogenerated charge recombination induced by the constructed type-II/type-II heterojunction at the interfaces between g-C₃N₄ NSs, CdSe QDs and WS₂ NSs. Thus, the developed 0D/2D/2D ternary type-II/type-II heterojunction in this work opens up a new insight in designing novel heterogeneous photocatalysts for highly efficient photocatalytic hydrogen evolution.     

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.     

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.     

NiSe2/Cd0.5Zn0.5S as a type-II heterojunction photocatalyst for enhanced photocatalytic hydrogen evolution

A designed type-II heterojunction photocatalyst, NiSe₂/Cd_0.5Zn_0.5S (NiSe₂/CZS), was successfully synthesized and it exhibits outstanding photocatalytic hydrogen evolution performance. The optimal loading amount of NiSe₂ on Cd_0.5Zn_0.5S is 13 wt %, and the corresponding hydrogen production rate is approximately 121.01 mmol g^?1 h^?1 under visible light. The heterojunction structure between Cd_0.5Zn_0.5S and NiSe₂ promoted the separation of photogenerated electron-hole pairs, effectively suppressed the photogenerated carrier recombination and endowed the material with excellent interfacial charge transfer properties, thus improving the photocatalytic performance.     

ZIF-L-derived porous C-doped ZnO/CdS graded nanorods with Z-scheme heterojunctions for enhanced photocatalytic hydrogen evolution

This study presents a novel approach for synthesizing C–ZnO/CdS graded nanorods derived from metal–organic frameworks (MOFs) that can be applied as a catalyst for photocatalytic hydrogen evolution from pure water. Porous C-doped ZnO was prepared by a self-template method using imidazole-like metal–organic backbone (ZIF-L) as a precursor through a two-step calcination method. CdS nanoparticles were deposited on ZIF-L surface by chemical deposition. The two-step calcination method introduced elemental C, and the unique architecture of ZIF-L played an essential role in forming the hierarchical structure of the porous ZnO nanorods. Compared with other ZnO/CdS catalysts, the C-doped ZnO/CdS graded nanorods exhibited remarkable photocatalytic activity for hydrogen production. The highest hydrogen production rate of 20.25 mmol g^?1 h^?1 with an apparent quantum yield (AQY) of 24.7% at 365 nm obtained over C–ZnO/CdS with Pt as co-catalyst, which was 24.4 and 65.3 times higher than that over CdS (0.83 mmol g^?1 h^?1) and ZnO (0.31 mmol g^?1 h^?1), respectively. This outcome was attributed to (i) the formation of Z-scheme heterojunction that significantly promoted the separation and migration of photogenerated electron–hole pairs; (ii) C doping that reduced the bandgap of ZnO and broadened its spectral response range; and (iii) the ordered arrangement of porous nanorods that effectively reduced the recombination rate of the electron–hole pairs.     

Promoted charge separation on 3D interconnected Ti3C2/MoS2/CdS composite for enhanced photocatalytic H2 production

The construction of heterojunction has been regarded as an effective way to promote photocatalytic H₂ evolution activity, in which an intimately interfacial contact between the materials forming heterojunction is a positive effect on enhancing activity. Herein, a ternary 3D interconnected nanocomposite Ti₃C₂/MoS₂/CdS was synthesized by a hydrothermal method. MoS₂ nanosheet with a vertically aligned structure grew on the surface of multi-layered Ti₃C₂ to form 3D Ti₃C₂/MoS₂ with tightly interfacial contact, which works as a cocatalyst for enhancing photocatalytic H₂ evolution. CdS as a photocatalyst covered the surface of Ti₃C₂/MoS₂ to absorb light energy. Benefitting to the synergistic effect between Ti₃C₂ and MoS₂, the Ti₃C₂/MoS₂ further accelerates electron transfer and inhibits the recombination of carriers. The H₂ evolution rate of Ti₃C₂/MoS₂/CdS reaches 15.2 mmol h^?1 g^?1 and the apparent quantum yield is 42.1% at λ = 420 nm. The result provides a useful insight for developing cocatalysts with new nanostructures via controlled interfacial engineering.     

In-situ construction of CdS@ZIS Z-scheme heterojunction with core-shell structure: Defect engineering,enhance photocatalytic hydrogen evolution and inhibit photo-corrosion

Designing the core-shell structure and controlling defect engineering are desirable for improving the performance and stability of semiconductor photocatalysts. Herein, CdS nanorods covered with ultra-thin ZnIn₂S₄ nanosheets, named as CdS@ZnIn₂S₄-S_V (CdS@ZIS-S_V), was synthesized through the strategy of constructing core-shell structure and regulating vacancies. The core-shell structure can confine Cd²⁺ and S^2? locally around CdS instead of rapidly diffusing into the solution, thereby inhibiting photo-corrosion. The abundant S vacancies can capture photogenerated electrons and promote the separation of electron-hole pairs, thereby preventing the oxidation of S^2? by the holes. In addition, Z-Scheme heterojunction structure helps the effective separation of electron-hole pairs. Notably, the hydrogen production rate of CdS@ZIS-S_V reached 18.06 mmol g^?1 h^?1, which was 16.9 and 19.6 times than pristine CdS (1.16 mmol g^?1 h^?1) and ZIS (0.92 mmol g^?1 h^?1), respectively. Photoelectric Characterization (PEC), Scanning Kelvin Probe (SKP), UV–vis diffuse reflectance spectra (UV–Vis DRS), Finite-Difference Time-Domain (FDTD) explain the electron transfer mechanism and the reason for the enhanced photocatalytic activity. This work has guiding significance for the preparation of photo-catalysts with high activity and inhibiting photo-corrosion by adjusting S vacancies.     

MoS2/CdS nanosheet-on-nanorod: An efficient photocatalyst for H2 generation from lactic acid decomposition

The CdS shows high selectivity on H₂ for photocatalytic lactic acid decomposition. However, the low efficiency caused by ultrafast charge recombination was not well addressed. Herein, MoS₂/CdS nanoheterostructure with intimate contact interface was synthesized in-situ and used as an efficient photocatalyst for H₂ generation. The optimum H₂ generation rate of MoS₂/CdS is 45.20 mmol g^?1 h^?1 which significantly boosts the activity of CdS (0.27 mmol g^?1 h^?1) by more than 167 folds. Band alignment of MoS₂ and CdS promoting charge transfer and separation contributes to the enhanced catalytic activity, which was well verified by multiple characterization approaches.     

Photocatalytic performance and mechanism of hydrogen evolution from water over ZnCdS/Co@CoO in sacrificial agent-free system

Photocatalytic efficient hydrogen evolution from pure water with non-noble metal system has more practical application value. In this study, the ZnCdS/Co@CoO composite photocatalyst was prepared by a simple hydrothermal reduction method. The hydrogen evolution rate from water can reach to 793 μmol·g^?1·h^?1 in sacrificial agent-free system, and 5445 μmol·g^?1·h^?1 with Na₂S and Na₂SO₃ as sacrificial agent. The S-scheme heterojunction formed between ZnCdS and Co@CoO, as well as the abundant S vacancy were proved to be the key factors to effectively improve the photocatalytic performance. The study on the high hydrogen production efficiency and catalytic mechanism of ZnCdS/Co@CoO in sacrificial agent-free can provide ideas for the design and preparation of more efficient non-noble metal photocatalysts.     

Designing of a novel Mn0.2Cd0.8S@ZnO heterostructure with Type-II charge transfer path for efficient photocatalytic hydrogen evolution reaction

The development of photocatalysts with efficient hydrogen evolution activity has been the goal for sustainable hydrogen production. In this work, heterojunction composite photocatalyst is formed by hydrothermal coupling of ZnO and Mn_0.2Cd_0.8S. Compared with pure ZnO and Mn_0.2Cd_0.8S, the composite photocatalyst has the ability to provide more abundant active sites and better photogenerated carriers separation efficiency. The optimized composite photocatalyst shows a 9.36-fold increase in hydrogen evolution activity (4297.99 μmol g^?1 h^?1) compared to Mn_0.2Cd_0.8S (459.31 μmol g^?1 h^?1) and exhibits excellent cycling stability. Density functional theory calculations identifies Type-II charge transfer path in the composite photocatalyst, achieving effective separation in space of photogenerated electrons from holes and suppressing recombination within the semiconductor. The results show that the construction of Type-II heterojunction in this work achieves a significant enhancement of the hydrogen evolution activity of the photocatalyst by constructing carrier transport channels at the contact interface of the heterojunction.