Exfoliated MoS2 with porous graphene nanosheets for enhanced electrochemical hydrogen evolution

Porous graphene (P-rGO) was synthesized from graphene oxide (GO) via a one-pot calcination method with CO₂ as an activation agent at 800 °C. Due to the special porous structure, the surface area of P-rGO can be increased to ～759 m²/g. The P-rGO was then used as a support to incorporate with chemical exfoliated molybdenum disulfide (MoS₂) for the fabrication of MoS₂/P-rGO composite. Compared to bulk MoS₂, the exfoliated MoS₂ is in the 1T phase with a metallic property and smaller charge transfer resistance, thus has a better activity in electrochemical hydrogen evolution reaction (HER). The HER activity of 1T MoS₂ could be further increased after the combination with P-rGO. The overpotential of 1T MoS₂/P-rGO was only ～130 mV vs. RHE, and the corresponding Tafel slope was ～75 mV Dec^?1. The special porous structure and good electric conductivity of P-rGO decrease the charge transfer resistance of the composite without sheltering too many active sites of MoS₂, thus leading to the enhanced HER activity. As an efficient noble metal free HER catalyst, the 1T MoS₂/P-rGO has great potential for large-scale hydrogen production.     

TiO2/CdS composite hollow spheres with controlled synthesis of platinum on the internal wall for the efficient hydrogen evolution

Solar driven semiconductor photocatalytic water splitting to produce hydrogen is an extremely charming process by storing photon energy in chemical bonds. In the present study, composite semiconductor TiO₂/CdS was structured into uniform and porous double-shelled hollow sphere with cocatalyst platinum selectively loaded onto the internal wall. The SEM, TEM, STEM, XRD, BET and EDS elemental distribution etc. were employed to evidence the formation of the targeted photocatalyst. It was demonstrated that the material has a high efficiency of visible-light-driven hydrogen evolution (296 μmol·h⁻¹/10 mg) with an apparent quantum efficiency (QE) of 14.5% at wavelength of 420 nm. Comparative experiment analysis and time-resolved infrared absorption study suggested that the high photocatalytic activity of the catalyst is attributed to the vectorial electron transfer (CdS → TiO₂ → Pt) and the spatial separation of reduction and oxidation active surfaces achieved by the special morphology.     

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.     

Highly efficient CuO incorporated TiO2 nanotube photocatalyst for hydrogen production from water

Highly dispersed CuO was introduced into TiO₂ nanotube (TNT) made by hydrothermal method via adsorption-calcination process or wet impregnation process, to fabricate CuO incorporated TNT photocatalysts (CuO-TNT) for hydrogen production. It was found that CuO-TNT possessed excellent hydrogen generation activity, which was constantly vigorous throughout 5 h reaction. Depending on the preparation method, hydrogen evolution rates over CuO-TNT were founded in the range of 64.2-71.6 mmol h⁻¹ g⁻¹_catalyst, which was much higher than the benchmark P25 based photocatalysts, and even superior to some Pt/Ni incorporated TNT. This high photocatalytic activity of CuO-TNT was mainly attributed to the unique 1-D tubular structure, large BET surface area and high dispersion of copper component. Compared to wet impregnation, adsorption-calcination process was superior to produce active photocatalyst, since it was prone to produce photocatalyst with more highly dispersed CuO.     

MoS2 supported on MOF-derived carbon with core-shell structure as efficient electrocatalysts for hydrogen evolution reaction

In this work, the porous carbon polyhedra were firstly obtained by carbonizing the zeolite imidazole framework (ZIF-8). Then the carbon polyhedra and precursors of MoS₂ were successfully combined by a hydrothermal reaction, forming the C-MoS₂ composites with different carbon contents. The well-tuned C-MoS₂ sample possesses a core-shell morphology, in which the carbon substrate is well decorated by vertically aligned MoS₂ ultrathin nanosheets. The resulting composites can be used as electrocatalysts of hydrogen evolution reaction (HER), displaying significantly superior activities to pure MoS₂ and carbon. It's found that the carbon content largely affects the architectures and HER behaviors of catalysts. In particular, the optimized catalyst yields the best catalytic activity with the lowest onset potential (35 mV), smallest Tafel slope (53 mv dec^?1), lowest overpotential (200 mV at 10 mA cm^?2), as well as extraordinary long-term stability in H₂SO₄. The enhanced HER activity can be attributed to the unique core-shell structure, where abundant active edge sites of MoS₂ are exposed and the underlying carbon substrate effectively improves the conductivity of the electrode.     

Defect-rich MoS2 nanosheets vertically grown on graphene-protected Ni foams for high efficient electrocatalytic hydrogen evolution

Defect-rich MoS₂ nanosheets are vertically grown on graphene-protected Ni foam by a facial hydrothermal route. The vertically aligned MoS₂ nanosheets with defects such as cracks, amorphousness and oxygen-incorporated disorders endow these as-synthesized catalysts with rich active sites, high conductivity and good stability. The graphene deposited on Ni foam increases its stability in acid. The optimized catalyst exhibits high activity for hydrogen evolution with a quite low overpotential of 140 mV at 10 mA cm^?2, a small Tafel slope of 42 mV decade^?1, and a large exchange current density of 63 μA/cm², as well as excellent stability. This performance is superior to most of its analogue MoS₂ and many transition metal sulfides. This work will broaden the vision to improve the activity of self-supported electrocatalysts by carefully designing the anchored catalysts.     

Cobalt sulfide quantum dots modified TiO2 nanoparticles for efficient photocatalytic hydrogen evolution

Cobalt sulfide quantum dots (CoSx QDs) modified TiO₂ nanoparticles are prepared with a precipitation-deposition method using TiO₂, cobalt acetate and sodium sulfide as the precursors. CoSx QD acts as an effective cocatalyst, which accelerates the transfer of the photo-generated electrons and serves as the active site for the reaction between electrons and H₂O, thus enhancing the separation of the e⁻/h⁺ pairs and the photocatalytic H₂ production activity of TiO₂. The amount of CoSx exhibits an optimum value at about 5% (mole ratio to TiO₂), at which the H₂ production rate achieves 838 μmol h⁻¹ g⁻¹ using ethanol as the sacrificial reagent. This exceeds that of the pure TiO₂ by more than 35 times.     

Low-temperature preparation of AgIn5S8/TiO2 heterojunction nanocomposite with efficient visible-light-driven hydrogen production

AgIn₅S₈ and AgIn₅S₈/TiO₂ heterojunction nanocomposite with efficient photoactivity for H₂ production were prepared by a low-temperature water bath deposition process. The resultant AgIn₅S₈ shows an absorption edge at ∼720 nm, corresponding to a bandgap of ∼1.72 eV, and its visible-light-driven photoactivity (100.1 μmol h⁻¹) for H₂ evolution is 9 times higher than that (11 μmol h⁻¹) of the product derived from a hydrothermal process, while the obtained AgIn₅S₈/TiO₂ heterojunction nanocomposites prepared by using commercially available TiO₂ nanoparticles (P25) as TiO₂ source exhibit remarkably improved photoactivity as compared to the pristine AgIn₅S₈, and the AgIn₅S₈/TiO₂ nanocomposite with molar ratio of 1:10 shows a maximum photocatalytic H₂ evolution rate (371.1 μmol h⁻¹), which is 4.3 times higher than that (85 μmol h⁻¹) of the corresponding AgIn₅S₈/TiO₂ nanocomposite derived from a hydrothermal method. This significant enhancement in the photocatativity of the present AgIn₅S₈/TiO₂ nanocomposite can be ascribed to the better dispersion of the AgIn₅S₈ formed on TiO₂ nanoparticle surfaces and the more intimate AgIn₅S₈/TiO₂ heterojunction structure during the water bath deposition process under continuously stirring as compared to the corresponding nanocomposite derived from a hydrothermal method. This configuration of nanocomposite results in fast diffusion of the photogenerated carriers in AgIn₅S₈ towards TiO₂, which is beneficial for separating spatially the photogenerated carriers and improving the photoactivity. The present findings shed light on the tuning strategy of spectral responsive region and photoactivity of photocatalysts for efficient light-to-energy conversion.     

Photoactive TiO2/MoS2 electrode with prolonged stability

TiO₂/MoS₂ composites are synthesized by means of a novel and environmentally friendly electrodeposition technique. MoS₂ is prepared via the hydrothermal process from Na₂MoO₄ and CH₄N₂S with the use of different surfactants such as Pluronic, SDBS, CTAB, and PEG-1000. TiO₂ in the form of nanotubes grows on Ti foil via anodization. The physicochemical properties of the obtained materials are studied by means of XRD, Raman spectroscopy, and SEM. MoS₂ forms a layered structure, while TiO₂ features well-defined and highly crystallized nanotubes. The deposition of MoS₂ on the surface of TiO₂ via the electrochemical method is conducted in a three-electrode cell with the use of a water-based suspension of MoS₂ at a pH close to neutral. The morphology and photoelectrochemical properties of the MoS₂-modified TiO₂ photoanodes are studied. The stability of TiO₂/MoS₂ composites is successfully investigated by repeating photocurrent-time characteristics in the period of 8 months. A shift in flat-band potential accompanied by increased photocurrent and hydrogen production indicate a type II heterostructure.     

Highly stable CdS-modified short TiO2 nanotube array electrode for efficient visible-light hydrogen generation

A highly stable photoelectrocatalytic electrode made of CdS-modified short, robust, and highly-ordered TiO₂ nanotube array for efficient visible-light hydrogen generation was prepared via sonoelectrochemical anodization and sonoelectrochemical deposition method. The short nanotube electrode possesses excellent charge separation and transfer properties, while the sonoelectrochemical deposition method improves the combination between CdS and TiO₂ nanotubes, as well as the dispersion of CdS nanoparticles. Different characterization techniques were used to study the nanocomposite electrode. UV-vis absorption and photoelectrochemical measurements proved that the CdS coating extends the visible spectrum absorption and the solar spectrum-induced photocurrent response. Comparing the photoactivity of the CdS/TiO₂ electrode obtained using sonoelectrochemical deposition method with others that synthesized using plain electrochemical deposition, the current density of the former electrode is ∼1.2 times higher that of the latter when biased at 0.5 V. A ∼7-fold enhancement in photocurrent response is obtained using the sonoelectrochemically fabricated CdS/TiO₂ electrode in comparison with the pure TiO₂ nanotube electrode. Under AM1.5 illumination the composite photoelectrode generate hydrogen at a rate of 30.3 μmol h⁻¹ cm⁻², nearly 13 times higher than that of pure titania nanotube electrode. Recycle experiments demonstrated the excellent stability and reliability of CdS/TiO₂ electrode prepared by sonoelectrochemical deposition. This composite electrode, with its strong mechanical stability and excellent combination of CdS and TiO₂ nanotubes, offers promising applications in visible-light-driven renewable energy generation.     

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.     

NiS2 Co-catalyst decoration on CdLa2S4 nanocrystals for efficient photocatalytic hydrogen generation under visible light irradiation

NiS₂ nanoparticles as noble metal-free co-catalysts were deposited onto the CdLa₂S₄ nanocrystals through a hydrothermal process. The loading of NiS₂ co-catalyst resulted in remarkable enhancement for H₂ production over the CdLa₂S₄ photocatalyst under visible light irradiation. The optimal hybrid photocatalyst with 2 wt% NiS₂ loading exhibited a H₂ production rate of 2.5 mmol h⁻¹ g⁻¹, which was more than 3 times higher than that of the pristine CdLa₂S₄ photocatalyst. The promoted photocatalytic H₂ production by NiS₂-loading is attributed to the enhanced separation of photogenerated electrons and holes as well as the activation effect of NiS₂ for H₂ evolution.     

In situ growth of a-few-layered MoS2 on CdS nanorod for high efficient photocatalytic H2 production

An ultrathin MoS₂ was grown on CdS nanorod by a solid state method using sulfur powder as sulfur source for photocatalytic H₂ production. The characterization result reveals that the ultrathin MoS₂ nanosheets loaded on CdS has a good contact state. The photoelectrochemical result shows that MoS₂ not only are beneficial for charge separation, but also works as active sites, thus enhancing photocatalytic activity. Compared with pure CdS, the photocatalytic activity of MoS₂ loaded CdS was significantly improved. The hydrogen evolution rate on m(MoS₂): m(CdS) = 1: 50 (m is mass) reaches 542 μmol/h, which is 6 times of that on pure CdS (92 μmol/h). This work provides a new design for photocatalysts with high photocatalytic activities and provides a deeper understanding of the effect of MoS₂ on enhancing photocatalytic activity.     

Facile synthesis of MoS2/N-doped macro-mesoporous carbon hybrid as efficient electrocatalyst for hydrogen evolution reaction

A novel three-dimensional (3D) hybrid consisting of molybdenum disulfide nanosheets (MoS₂) uniformly bound at N-doped macro-mesoporous carbon (N-MMC) surface was fabricated by the solvothermal method. The resulting MoS₂/N-MMC hybrid possesses few-layer MoS₂ nanosheets structure with abundant edges of MoS₂ exposed as active sites for hydrogen evolution reaction (HER), in sharp contrast to large aggregated MoS₂ nanoflowers without N-MMC. The high electric conductivity of N-MMC and an abundance of exposed edges on the MoS₂ nanosheets make the hybrid excellent electrocatalytic performance with a low onset potential of 98 mV, a small Tafel slope of 52 mV/decade, and a current density of 10 mA cm^?2 at the overpotential of 150 mV. Moreover, the MoS₂/N-MMC hybrid exhibits outstanding electrochemical stability and structural integrity owing to the strong bonding between MoS₂ nanosheets and N-MMC.     

Highly efficient TiO2 nanotube photocatalyst for simultaneous hydrogen production and copper removal from water

1-D mesoporous TiO₂ nanotube (TNT) with large BET surface area was successfully synthesized by a hydrothermal-calcination process, and employed for simultaneous photocatalytic H₂ production and Cu²⁺ removal from water. Cu²⁺, across a wide concentration range of 8-800 ppm, was removed rapidly from water under irradiation. The removed Cu²⁺ then combined with TNT to produce efficient Cu incorporated TNT (Cu-TNT) photocatalyst for H₂ production. Average H₂ generation rate recorded across a 4 h reaction was between 15.7 and 40.2 mmol h⁻¹ g⁻¹_catalyst, depending on initial Cu²⁺/Ti ratio in solution, which was optimized at 10 atom%. In addition, reduction process of Cu²⁺ was also a critical factor in governing H₂ evolution. In comparison with P25, its large surface area and 1-D tubular structure endowed TNT with higher photocatalytic activity in both Cu²⁺ removal and H₂ production.     

Visible-light-driven HSr2Nb3O10/CdS heterojunctions for high hydrogen evolution activity

In this study, layered perovskite HSr₂Nb₃O₁₀ ultrathin nanosheets (HSNO-ns) was successfully exfoliated within 2 h by a facile microwave-assisted method. Then, HSNO-ns/CdS heterojunction was fabricated through a facile hydrothermal route for deposition of CdS nanoparticles on HSNO-ns. The photocatalytic performances of composites were systematically investigated and discussed by varying the CdS content. The results illustrated that the photocatalytic hydrogen production rate of HSNO-ns were significantly increased by coupled CdS nanoparticles on the HSNO-ns. The optimized HSNO-ns/CdS3 composites without noble metal showed highest photocatalytic activity, which was about 8.38 times and 330 times higher than that of pristine CdS and HSNO-ns, respectively, under the visible light irradiation (≥420 nm) using triethanolamine as sacrificial agent. The enhanced photocatalytic H₂ production activity was predominantly attributed to the strong optical absorption capacity, high specific surface area and improved charge carrier separation efficiency. Our present work provides a new pathway into the design of two-dimension nanosheets-based photocatalysts and promotes their practical application in various environmental and energy issues.     

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.     

CuCr2O4/TiO2 heterojunction for photocatalytic H2 evolution under simulated sunlight irradiation

CuCr₂O₄/TiO₂ heterojunction has been successfully synthesized via a facile citric acid (CA)-assisted sol-gel method. Techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectrum (UV-vis DRS) have been employed to characterize the as-synthesized nanocomposites. Furthermore, photocatalytic activities of the as-obtained nanocomposites have been evaluated based on the H₂ evolution from oxalic acid solution under simulated sunlight irradiation. Factors such as CuCr₂O₄ to TiO₂ molar ratio in the composites, calcination temperature, photocatalyst mass concentration, and initial oxalic acid concentration affecting the photocatalytic hydrogen producing have been studied in detail. The results showed that the nanocomposite of CuCr₂O₄/TiO₂ is more efficient than their single part of CuCr₂O₄ or TiO₂ in producing hydrogen. The optimized composition of the nanocomposites has been found to be CuCr₂O₄·0.7TiO₂. And the optimized calcination temperature and photocatalyst mass concentration are 500 °C and 0.8 g l⁻¹, respectively. The influence of initial oxalic acid concentration is consistent with the Langmuir model.     

Enhanced photocatalytic hydrogen evolution using a novel in situ heterojunction yttrium-doped Bi4NbO8Cl@Nb2O5

The novel in situ Z-scheme heterostructure materials Y-doped Bi₄NbO₈Cl@Nb₂O₅ (Bi_4-xY_xNbO₈Cl, x = 0, 1, 1.33, 2, 2.67, 3) have been synthesized successfully via a solid-state method. The as-prepared samples were characterized by XRD, Raman spectrum, SEM, EDS, element mapping, HRTEM, XPS and UV–vis spectrum to explore the structures, morphologies and optical properties. Photocatalytic activities were evaluated for hydrogen generation using the Pt as the co-catalysts. HRTEM results indicated the Pt particles were deposited on the surface of the Bi₄NbO₈Cl. Photocatalytic activities were evaluated by hydrogen generation. While photocatalytic results showed that BiY₃NbO₈Cl composites exhibited the best performance of hydrogen production under the full-range irradiation (λ > 300 nm) while the Y-doped Bi₄NbO₈Cl@Nb₂O₅ with Y:Bi molar ratio 1:1 obtained the highest efficiency with ultraviolet light eliminated. The H₂ production was 1.35 mmol and 0.9 mmol in 8 h, respectively. Furthermore, a direct Z-scheme mechanism with enhanced hydrogen evolution competent for accelerating the separation of photogenerated carries has been presented and proved by electrochemical impedance spectroscopy (EIS). Finally, considering the conclusions of the electron spin-resonance spectroscopy (EPR), ·OH radicals served as an active species played an important role in the hydrogen production. Mechanisms about the action of the ·OH radicals were also proposed.     

Formation of multilayer-Eosin Y-sensitized TiO2 via Fe coupling for efficient visible-light photocatalytic hydrogen evolution

An efficient visible-light active photocatalyst of multilayer-Eosin Y-sensitized TiO₂ is prepared through linkage of Fe³⁺ between not only TiO₂ and Eosin Y but also different Eosin Y molecules to form three-dimensional polymeric dye structure. The multilayer-dye-sensitized photocatalyst is found to have high light harvesting efficiency and photocatalytic activity for hydrogen evolution under visible light irradiation (λ > 420 nm). On the optimum conditions (1:1 initial molar ratio of Eosin Y to Fe(NO₃)₃, initial 10 × 10⁻³ M Eosin Y, and 1.0 wt% Pt deposited by in situ photoreduction), its maximal apparent quantum yield for hydrogen evolution is 19.1% from aqueous triethanolamine solution (TEOA aq). The present study highlights linking between dye molecules via metal ions as a general way to develop efficient visible-light photocatalyst.