Usage of natural leaf as a bio-template to inorganic leaf: Leaf structure black TiO2/CdS heterostructure for efficient photocatalytic hydrogen evolution

Herein, first time we report that highly efficient sheet like leaf structure black TiO₂ (LBT)/CdS hetero-structure (LBT/CdS). Photocatalytic hydrogen generation was tested for different material in the presence of visible light (λ ≥ 420 nm) irradiation. 10 wt% of LBT loaded CdS (10LBT/CdS) exhibit maximum photocatalytic H₂ generation rate about ~10 mmol h^?1 g^?1, which is higher than the H₂ production results of pristine CdS (6 mmol h^?1 g^?1) and leaf black-TiO₂ 5.1 mmol h^?1 g^?1) respectively. Detailed characterization revealed that higher photocatalytic activity was mainly attributed to enormous spatial transfer efficiency of photo-excited charge carriers at the hetero-junction between LBT and CdS in LBT/CdS. Additionally, introduction of 2D black leaf-TiO₂ to CdS act as a mat and enhances the mobility of charge carriers. In addition, presence of anatase-rutile surface-phase junction in leaf TiO₂ (synthesized at 750 °C) and more edges, steps and corners on the CdS synergistically increased the photocatalytic H₂ generation and photocurrent response of LBT/CdS.     

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.     

The ZnIn2S4/CdS hollow core-shell nanoheterostructure towards enhanced visible light photocatalytic H2 evolution via bimetallic synergism

The ZnIn₂S₄/CdS hollow core-shell nanoheterostructure with bimetallic synergism is synthesized via a hybrid chemical method. As revealed, the ZnIn₂S₄/CdS hollow core-shell nanoheterostructure (ZnIn₂S₄/CdS-3) exhibits remarkable visible light photocatalytic hydrogen evolution (～5209.43 μmol·g^?1·h^?1, AQE of ～20.26%) than that of single CdS (～40 folds) and single ZnIn₂S₄ (～12 folds), and achieves decent photocatalytic stability (average HER performance of ～5056.80 μmol·g^?1·h^?1), which is mainly ascribed to that, the formed ZnIn₂S₄/CdS heterostructure with appropriate potential gradient and Zn/In bimetallic synergism can improve carrier transportation, including increasing carrier transportation, prolonging lifetime and decreasing recombination, the hollow core-shell nanostructure can provide abundant active sites and increase solar efficiency, while can maintain a photocatalytic stability.     

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.     

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.     

Non-precious metal MoO2 co-catalysts efficiently enhance hydrogen production of ZnIn2S4 under visible light

Photogenerated electron-hole separation and transfer and band gap modulation are the main reasons for the performance of semiconductor catalysts. These problems can be effectively solved by the proper use of co-catalysts. However, the current co-catalysts are generally noble metal co-catalysts, which cannot be used industrially because of their high cost. Therefore, it is important to use non-noble metal co-catalyst to solve these problems. In this study, MoO₂ with localized surface plasmon resonance (LSPR) effect loaded onto ZnIn₂S₄ (ZIS) by primary hydrothermal method and structured to form type II heterojunctions. The formation of the heterojunctions not only tunes the band gap to improve the light absorption intensity, but also reduces the charge transfer resistance and promotes electron-hole directed movement to improve the electron-hole separation efficiency. The tuning of the band gap and the increase in the electron-hole separation rate lead to improved performance of all ZIS/MoO₂ heterojunctions under visible light (λ ≥ 420 nm). Among them, ZIS/MoO₂-4% has the best photocatalytic performance of 2.757 mmol g^?1 h^?1, which is 3.75 times higher than that of pure ZIS (0.736 mmol g^?1 h^?1). This study provides a new strategy for the preparation of high performance catalysts without precious metals.     

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.     

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.     

Novel 2D Zn-porphyrin metal organic frameworks revived CdS for photocatalysis of hydrogen production

The main challenge of photocatalysis is how to improve the coefficient of utilization and conversion rate for solar energy. Herein, we report a composite photocatalyst related to a novel porphyrin metal organic frameworks (MOFs), in which cadmium sulfide nanoparticles (CdS NPs) are grown in situ on the surface of two-dimensional (2D) zinc porphyrin nanosheets (Zn-TCPP NSs) by hydrothermal method. Interestingly, Zn-TCPP NSs and CdS NPs form a Type II heterojunction structure, which reduces the photogenerated electron-hole recombination rate of CdS. Moreover, in the near-infrared region, the photo-excited electrons generated by Zn-TCPP NSs are transmitted to CdS NPs, so that cadmium sulfide can realize both visible light and near-infrared light for photocatalytic hydrogen production. The Zn-TCPP NSs not only has excellent light absorption capacity, but also has a unique frame design that effectively reduces the recombination rate of photoinduced electron hole pairs, thus improving the conversion rate of solar energy. As expected, the photocatalytic performance of the porphyrin MOFs modified materials is significantly enhanced compared to CdS NPs. The hydrogen production rate of the Pt@CdS NPs/Zn-TCPP NSs(C-Z-T) composite material in the visible light region is about 15.3 mmol g^?1 h^?1, which is 11 times for Pt@CdS NPs. Furthermore, the Pt@CdS NPs/Zn-TCPP NSs(C-Z-T) also has a considerable hydrogen production rate in the near-infrared region, such as 200 μmol g^?1 h^?1 at 600 nm, 90 μmol g^?1 h^?1 at 765 nm and 20 μmol g^?1 h^?1 at > 800 nm.     

High-temperature sulfurized synthesis of MnxCd1-xS composites for enhancing solar-light driven H2 evolution

In recent years, tremendous efforts have been devoted to develop new photocatalyst with wide spectrum response for H₂ generation from water or aqueous solution. In this paper, Mn_xCd_1-xS composites were in-situ fabricated via the high-temperature sulfurization to enhance the solar-light photocatalytic capacity of H₂ evolution. Benefiting from the S defects and junction interface between MnS and CdS, Mn_xCd_1-xS composites exhibited the better H₂ evolution rate than pure MnS. The H₂ evolution rate of optimal Mn_0.5Cd_0.5S with a Mn(II) content of 22.52% and a Mn/Cd mole ratio of 0.95:1 was 9.27 mmol g^?1 h^?1, which was 35.65 and 2.38 times higher than pure MnS (0.26 mmol g^?1 h^?1) and CdS (3.89 mmol g^?1 h^?1), respectively. In addition, H₂ evolution capacity of Mn_0.5Cd_0.5S decreased from 44.83 to 41.66 mmol g^?1 after three cycles. Mn_0.5Cd_0.5S prepared via the high-temperature sulfurization was thus a potential material for solar-light induced H₂ generation.     

Ni-doped CdS porous cubes prepared from prussian blue nanoarchitectonics with enhanced photocatalytic hydrogen evolution performance

In this paper, Ni_xCd_yS composite photocatalysts were synthesized by using Ni-doped Cd–Co PBA as the precursor, which retains the advantages of PBA such as porous structure, large specific surface and highly dispersed metal active sites. The photocatalytic hydrogen production performance over Ni_xCd_yS is three times higher than that of pure CdS with H₂ yield of 8.45 mmol g^?1 h^?1. The catalyst was analyzed by the UV/Vis absorption spectra, photoluminescence spectra, time-resolved photoluminescence spectra, transient photocurrent responses, electrochemical impedance spectra, Mott-Schottky test, etc. A series of characterization results prove that the electron-hole recombination rate, electrochemical resistance and band gap of nickel-doped CdS composites are obviously smaller than CdS, which are important factors to improve the photocatalytic hydrogen production performance. This work may provide some reference value for the fabrication of other functional materials using PBA as precursors.     

In2Se3/CdS nanocomposites as high efficiency photocatalysts for hydrogen production under visible light irradiation

Hydrogen energy is an important clean energy. Using visible light to produce hydrogen by semiconductor photocatalysts is one of the current research hotspots. In this work, In₂Se₃/CdS nanocomposite photocatalysts with different mass content of CdS are prepared. The In₂Se₃/CdS photocatalyst with 85.25% CdS mass content exhibits the optimal photocatalytic hydrogen evolution activity (1.632 mmol g^?1 h^?1), which is much higher than that of CdS (0.715 mmol g^?1 h^?1) and In₂Se₃ (trace). Moreover, the In₂Se₃/CdS photocatalyst still maintains a high hydrogen evolution rate after five cycles. The high photocatalytic activity and stability of the In₂Se₃/CdS nanocomposite is due to the formation of heterojunction between In₂Se₃ and CdS. The existence of heterojunction is confirmed by high resolution transmission electron microscopy image and X-ray photoelectron spectra. Theoretical calculations and experimental results indicate that the electron transfer route at the heterojunction is step-scheme. The step-scheme helps the separation of photogenerated electrons and holes, and maximize the hydrogen evolution activity. This work provides a high efficiency step-scheme photocatalyst for hydrogen production.     

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.     

Construction of porous Ni2P cocatalyst and its promotion effect on photocatalytic H2 production reaction and CO2 reduction

Due to superior light absorption abilities, porous materials are suitable to be served in photocatalytic reactions. In this study, porous Ni₂P is target-constructed from porous Ni(OH)₂ nanoflower. Promotion effect of the porous Ni₂P as cocatalyst is confirmed on photocatalytic performance of Ni₂P/CdS composite. The constructed porous Ni₂P/CdS photocatalyst shows much higher photocatalytic H₂ evolution rate (111.3 mmol h⁻¹ g⁻¹) from water and much higher CO (178.0 μmol h⁻¹ g⁻¹) and CH₄ (61.2 μmol h⁻¹ g⁻¹) evolution rates from CO₂ reduction than non-porous Ni₂P/CdS photocatalyst. Characterizations including UV-Vis diffuse reflectance, photoluminescence, transient photocurrent response, electrochemical impedance and electron paramagnetic resonance are conducted to verify the role of porous Ni₂P cocatalyst. The slow photon effect derived from porous structure Ni₂P is found to improve light path and increase the absorption utilization of light. The enhanced photocurrent intensity and the lowered resistance of porous Ni₂P/CdS due to the formed heterojunctions indicate much rapid isolation of photogenerated electron-hole pairs and rapid charge transfer of electrons. The higher signal of ⋅O₂- radicals is detected in porous Ni₂P/CdS than non-porous Ni₂P/CdS, which result in the remarkable photocatalyst activities of porous Ni₂P/CdS. Reaction mechanisms over Ni₂P/CdS photocatalyst are illustrated with a Z-scheme charge transfer path.     

CdS/CuCo2S4 dots-on-rods boosting charge separation and hydrogen evolution

Herein, we report a new class of CdS/CuCo₂S₄ dots-on-rods nanostructures that exhibit efficient visible-light-induced H₂ evolution from water. The material CuCo₂S₄ nanodots over CdS nanorods are fabricated through controlled loading in a facile hydrothermal process and formed a heterojunction, maximizing the energy conversion, that shows advanced performance in photochemical H₂ evolution (rate: 33.32 mmol g^?1h^?1 and AQY: 13.2% at λ = 420 ± 15 nm) from water. The experimental and theoretical results on physical and chemical properties revealed that the photocatalytic system is positively correlated with the H₂ production rate and suggest that CuCo₂S₄ nanodots in CdS nanorods plays a critical role in relative efficiency of the H₂ generation. The surprisingly high activity was attributed to enhanced charge carriers’ separation and transfer efficiency, confirmed by the kinetic measurements (TAS) and further reinforced from the Kelvin probe force microscopy (KPFM) analysis and theoretical understanding.     

Bamboo-charcoal-loaded graphitic carbon nitride for photocatalytic hydrogen evolution

Crystalline graphitic carbon nitride is an excellent photocatalyst for hydrogen production due to its non-toxicity, stability, elemental abundance, and visible-light response. Herein, we present a new type of composite photocatalysts, eco-friendly bamboo-charcoal-loaded graphitic carbon nitrides to accelerate the separation of electron-hole pairs. The suitable loading of bamboo charcoal on graphitic carbon nitrides shows an increased specific surface area from 85 to 120 m² g^?1, and excellent visible-light photocatalytic hydrogen production activity of 4.1 mmol g^?1 h^?1, which is 2.3 times higher than that of pristine carbon nitride (1.8 mmol g^?1 h^?1). Under irradiation, the photogenerated electrons fast migrate from graphitic carbon nitride to bamboo charcoal through an ohmic contact between them, reducing the recombination of electron-hole pairs. This study highlights the effect of carbonaceous material loading on photocatalytic activity of carbon nitrides and opens an avenue to design efficient loaded photocatalysts with natural abundant materials.     

Decoration of nicale phosphide nanoparticles on CdS nanorods for enhanced photocatalytic hydrogen evolution

Manipulation of the co-catalyst plays an important role in charge separation and reactant activation to enhance the activity of CdS based photocatalysts. Transition-metal phosphides have aroused widespread interest in catalysis owing to their special structure and catalytic behavior. Herein, Ni₂P as a cocatalyst coupled with CdS for efficient photocatalytic hydrogen evolution with a rate of 483.25 mmol g^?1.h^?1, which was nearly 525 and 1.92 times higher than that of CdS (0.92 mmol g^?1.h^?1) and 1 wt% noble metal Pt modified CdS (251.29 mmol g^?1.h^?1), respectively. Its apparent quantum yield reaches 70% at 420 nm. Based on data analysis, Schottky heterostructure was constructed by combining Ni₂P with CdS. The Schottky junction provides a convenient way for photoinduced electrons to transfer and promotes the effective separation of photoinduced carriers.     

Oxygen vacancies mediated in-situ growth of noble-metal (Ag,Au, Pt) nanoparticles on 3D TiO2 hierarchical spheres for efficient photocatalytic hydrogen evolution from water splitting

Defect engineering is effective to extend the light absorption range of TiO₂. However, the oxygen vacancy defects in TiO₂ may serve as recombination centers, hampering the separation and transfer of photo-generated charges. Here, we present a strategy of in-situ depositing noble-metal (M = Ag, Au or Pt) nanoparticles (NPs) on defective 3D TiO₂ hierarchical spheres (THS) with large surface area through the redox reaction between metal ions in solution and the electrons trapped at oxygen vacancies in THS. The oxygen vacancies at the THS surface are consumed, resulting in direct contact between TiO₂ and noble-metal NPs, while the other oxygen vacancies in the bulk are retained to promote visible light absorption. The noble-metal NPs with well-controlled size and distribution throughout the porous hierarchical structure not only facilitate the generation of electron-hole pairs in THS due to the effect of surface plasmon-induced resonance energy transfer (SPRET) from noble-metal NPs to TiO₂, but also expediate the electron transfer from TiO₂ to noble-metal NPs due to the Schottky junction at the TiO₂/M interface. Therefore, THS-M shows improved photocatalytic performance in water splitting compared to THS. The optimum performance is achieved on THS-Pt (13.16 mmol h⁻¹g⁻¹) under full-spectrum (UV–Vis) irradiation but on THS-Au (1.49 mmol h⁻¹g⁻¹) under visible-light irradiation. The underlying mechanisms are proposed from the surface plasmon resonance of noble-metal NPs as well as the Schottky junction at the TiO₂/M interface.     

In-situ construction of Mo3S4/Cd0.5Zn0.5S heterojunction: An efficient and stable photocatalyst for H2 evolution

In this work, Mo₃S₄/Cd_0.5Zn_0.5S heterojunction with abundant porosity was in-situ synthesized by one-step hydrothermal method. Characterization results clearly indicate that the composite material are composed of nanoparticles with an average particle diameter about 65 nm and abundant inter-particle pores are present in between. The XPS analysis found that when Mo₃S₄ was introduced, the XPS peak positions of Cd²⁺ and Zn²⁺ were shifted from the XPS peak positions of Cd²⁺ and Zn²⁺ in pristine Cd_0.5Zn_0.5S, which indicates that there is an interaction between Mo₃S₄ and Cd_0.5Zn_0.5S at the interface. Subsequently, the Mo₃S₄/Cd_0.5Zn_0.5S (72.1 mmol h⁻¹ g⁻¹) heterojunction can achieve much higher photocatalytic hydrogen production rate than the pristine Cd_0.5Zn_0.5S (7.54 mmol h⁻¹ g⁻¹), and even higher than Cd_0.5Zn_0.5S (56.44 mmol h⁻¹ g⁻¹) loaded with the noble metal Pt (2.0%), indicating that heterojunction can effectively enhance photocatalytic activity. In addition, the improvement in photocatalytic activity of Mo₃S₄/Cd_0.5Zn_0.5S is highly related with enhanced absorption and utilization of light due to the presence of the inter-particle pores which inhibit recombination of electron-hole pairs, promote charge separation and accelerate the migration of photogenerated carriers.     

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.