Highly efficient photocatalytic hydrogen evolution by using Rh as co-catalyst in the Cu/TiO2 system

Cu/TiO₂ was modified by adding Rh as co-catalyst and used as a highly efficient photocatalyst for the hydrogen evolution reaction. A low amount of Rh was loaded onto Cu/TiO₂ by the deposition-precipitation with urea (DPU) method to observe the effect on the hydrogen production displayed by different samples. The Rh–Cu/TiO₂ oxide structure exhibited a remarkably high photocatalytic hydrogen evolution performance, which was about twofold higher than that of the Cu/TiO₂ monometallic photocatalyst. This outstanding performance was due to the efficient charge carrier transfer as well as to the delayed electron-hole recombination rate caused by the addition of Rh. The influence of the different parameters of the photocatalyst synthesis and reaction conditions on the photocatalytic activity was investigated in detail. Hydrogen evolution was studied using methanol, ethanol, 2-propanol and butanol as scavengers with an alcohol:water ratio of 20:80. The methanol-water system, which showed the highest hydrogen production, was studied under 254, 365 and 450 nm irradiation; Rh–Cu/TiO₂ showed high photocatalytic activity with H₂ production rates of 9260, 5500, and 1940 μmol h^?1 g^?1, respectively. The Cu–Rh/TiO₂ photocatalyst was active under visible light irritation due to its strong light absorption in the visible region, low band gap value and ability to reduce the electron (e^?) and hole (h⁺) recombination.     

A hydrothermal route for constructing reduced graphene oxide/TiO2 nanocomposites: Enhanced photocatalytic activity for hydrogen evolution

A series of reduced graphene oxide/TiO₂ (RGO/TiO₂) nanowire microsphere composites were synthesized with a facile one-step hydrothermal method using TiCl₃ and graphene oxide (GO) as the starting materials, during which the formation of TiO₂ and the reduction of GO occur simultaneously. The obtained nanocomposites were characterized with X-ray diffraction, field emission scanning electron microscope, transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and ultraviolet–visible (UV–vis) diffuse reflectance spectroscopy, respectively. UV–vis absorption spectra showed that the absorption edges of TiO₂ were extended into visible light region with the addition of RGO. The photocatalytic activities of the samples with and without Pt as cocatalysts were evaluated by hydrogen evolution from water photo-splitting under UV–vis light illumination. Enhanced photocatalytic properties were observed for the as-prepared RGO/TiO₂ nanocomposites. The amount of hydrogen evolution from the optimized photocatalyst reached to 43.8 μmol h⁻¹, which was about 1.6 times as high as that of bare TiO₂. The results shown here indicate a convenient and applicable approach to further exploitation of high activity materials for photocatalytic water splitting applications.     

Hydrogen production from sulphide wastewater using Ce3+–TiO2 photocatalysis

Cerium (Ce³⁺) doped TiO₂ powder was synthesized by a sol-gel method and characterized by Transmission Electron Microscope (TEM), X-ray Diffraction (XRD), UV–Vis Diffuse Reflectance Spectroscopy (UV-DRS), Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The Ce³⁺ doping strongly reduced the band gap of the TiO₂ from 3.2 eV (UV) to 2.7 eV (visible region). The photocatalytic activity of Ce³⁺ doped TiO₂ catalysts was evaluated by hydrogen production from sulphide wastewater under visible light illumination. The photocatalytic production of H₂ was studied in a batch recycle tubular photocatalytic reactor. The results show that 0.4% Ce³⁺–TiO₂ suspended in 500 mL of simulated sulphide wastewater irradiated at 150 W visible lamp produced maximum H₂ of 6789 μmol h^?1. It was noticed that the Ce³⁺ doped TiO₂ performs well than Nano TiO₂ and P25 TiO₂ photocatalysts.     

LED light-induced enhanced photocatalytic hydrogen evolution on Au@TiO2 core–shell modified by nitrogen doping and reduced graphene oxide

This study focused on the large band gap of TiO₂ for its use as a photocatalyst under light emitting diode (LED) light irradiation. The photocatalytic activities of core–shell structured Au@TiO₂ nanoparticles (NPs), nitrogen doped Au@TiO₂ NPs, and Au@TiO₂/rGO nanocomposites (NCs) were investigated under various light intensities and sacrificial reagents. All the materials showed better photocatalytic activity under white LED light irradiation than under blue LED light. The N-doped core–shell structured Au@TiO₂ NPs (Au@N–TiO₂) and Au@TiO₂/rGO NCs showed enhanced photocatalytic activity with an average H₂ evolution rate of 9205 μmol h^?1g^?1 and 9815 μmol h^?1g^?1, respectively. All these materials showed an increasing rate of hydrogen evolution with increasing light intensity and catalyst loading. In addition, methanol was more suitable as a sacrificial reagent than lactic acid. The rate of hydrogen evolution increased with increasing methanol concentration up to 25% in DI water and decreased at higher concentrations. Overall, Au@TiO₂ core–shell-based nanocomposites can be used as an improved photocatalyst in photocatalytic hydrogen production.     

In-situ synthesis of novel plate-like Co(OH)2 co-catalyst decorated TiO2 nanosheets with efficient photocatalytic H2 evolution activity

Efficient separation of photo-generated electrons and holes is a crucial aspect for photocatalytic hydrogen evolution. Herein, novel plate-like Co(OH)₂ decorated TiO₂ nanosheets for photocatalytic water splitting were synthesized by a facile in-situ synthetic method. The results of X-ray diffractometry (XRD), transmission electron microscope (TEM), UV–Vis diffusion reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) indicate the successfully incorporation of Co(OH)₂ co-catalysts onto the surface of TiO₂ nanosheet photocatalysts. Further photocatalytic hydrogen evolution experiments illustrate that all Co(OH)₂ decorated TiO₂ samples show higher rate of hydrogen production performance than pure TiO₂ sample and the composite sample with Co(OH)₂ loading amount of 0.5mol% presents the highest photocatalytic hydrogen production activity of 746.93 μmol g^?1·h^?1. It is indicated that plate-like Co(OH)₂ particle act as an electron collector, which leads to photo-generated electrons transfer from TiO₂ to Co(OH)₂, and therefore enhance the photocatalytic activity. Based on above results, a possible mechanism is proposed and further verified by surface photovoltage spectra (SPV).     

A nanoreactor based on SrTiO3 coupled TiO2 nanotubes confined Au nanoparticles for photocatalytic hydrogen evolution

A TiO₂ nanotube-based nanoreactor was designed and fabricated by facile two steps synthesis: firstly, hydrothermal synthesized SrTiO₃ was deposited on TiO₂ nanotubes (TiO₂NTs). Secondly, the Au nanoparticles (NPs) were encapsulated inside the TiO₂NTs followed by vacuum-assisted impregnation. The as-synthesized composites were characterized using Transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Photoluminescence spectra (PL) and Ultraviolet–visible absorption spectroscopy (UV–vis). The photocatalytic performance was evaluated by the hydrogen evolution reaction. The results revealed that the SrTiO₃ modified TiO₂NTs confined Au NPs (STO-TiO₂NTs@Au) achieved an enhanced hydrogen evolution rate at 7200 μmol h⁻¹ g⁻¹, which was 2.2 times higher than that of bald TiO₂NTs@Au at 3300 μmol h⁻¹ g⁻¹. The improved photocatalytic activity could be attributed to the synergistic effect of the electron-donating of SrTiO₃ and TiO₂NTs confinement. The as-designed nanoreactor structure provides an example of efficient carriers' separation photocatalyst.     

Photocatalytic H2 production from water splitting under visible light irradiation using Eosin Y-sensitized mesoporous-assembled Pt/TiO2 nanocrystal photocatalyst

Sensitized photocatalytic production of hydrogen from water splitting is investigated under visible light irradiation over mesoporous-assembled titanium dioxide (TiO₂) nanocrystal photocatalysts, without and with Pt loading. The photocatalysts are synthesized by a sol–gel process with the aid of a structure-directing surfactant and are characterized by N₂ adsorption–desorption analysis, X-ray diffraction, UV–vis spectroscopy, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray analysis. The dependence of hydrogen production on the type of TiO₂ photocatalyst (synthesized mesoporous-assembled and commercial non-mesoporous-assembled TiO₂ without and with Pt loading), the calcination temperature of the synthesized photocatalyst, the sensitizer (Eosin Y) concentration, the electron donor (diethanolamine) concentration, the photocatalyst dosage and the initial solution pH is systematically studied. The results show that in the presence of the Eosin Y sensitizer, the Pt-loaded mesoporous-assembled TiO₂ synthesized by a single-step sol–gel process and calcined at 500 °C exhibits the highest photocatalytic activity for hydrogen production from a 30 vol.% diethanolamine aqueous solution with dissolved 2 mM Eosin Y. Moreover, the optimum photocatalyst dosage and initial solution pH for the maximum photocatalytic activity for hydrogen production are 3.33 g dm⁻³ and 11.5, respectively.     

TiO2 nanosheets loaded with Cu: A low-cost efficient photocatalytic system for hydrogen evolution from water

Rutile TiO₂ nanosheets were prepared by a simple solvothermal process, and Cu was loaded on the surface of TiO₂ nanosheets using the in situ photo-deposition method. Meanwhile, photocatalytic H₂ evolution from water over the as-prepared TiO₂ nanosheets loaded with Cu was explored using methanol as a sacrificial reagent. The results indicate that the TiO₂ nanosheets loaded with Cu is an efficient photocatalyst under UV irradiation. During the first 5 h, a rate of H₂ evolution of approximately 22.1 mmol g⁻¹ h⁻¹ was achieved under optimal conditions. Furthermore, for practical purposes, the photocatalytic hydrogen evolution was studied as a function of content of Cu, pH of solution, concentration of methanol and dosage of photocatalyst, respectively. At last, the photocatalytic mechanism was preliminarily discussed.     

Vertically-heterostructured TiO2-Ag-rGO ternary nanocomposite constructed with {001} facetted TiO2 nanosheets for enhanced Pt-free hydrogen production

TiO₂ nanosheets with high ratio of {001} facets were coupled with reduced graphene oxide (rGO) nanosheets through the link of silver (Ag) nanoparticles, forming a novel ternary nanocomposite photocatalyst with a vertical heterostructure, TiO₂-Ag-rGO. The vertical anchoring of TiO₂-Ag nanosheets between rGO sheets was confirmed by transmission electron microscopy (TEM), Raman spectroscopy, energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Due to excellent separation of electron-hole pairs in the TiO₂ nanosheets, enhanced electron transfer to rGO via Ag nanoparticles, the TiO₂-Ag-rGO nanocomposite exhibited an outstanding performance in photocatalytic hydrogen production, with a hydrogen production rate of 593.56 μmol g^?1 h^?1. This study provides new insights to the development of Pt-free photocatalysts for hydrogen production.     

Enhanced photocatalytic hydrogen evolution from reduced graphene oxide-defect rich TiO2-x nanocomposites

Solar-driven photocatalytic hydrogen generation by splitting water molecules requires an efficient visible light active photocatalyst. This work reports an improved hydrogen evolution activity of visible light active TiO_2-x photocatalyst by introducing reduced graphene oxide via an eco-friendly and cost-effective hydrothermal method. This process facilitates graphene oxide reduction and incorporates intrinsic defects in TiO₂ lattice at a one-pot reaction process. The characteristic studies reveal that RGO/TiO_2-x nanocomposites were sufficiently durable and efficient for photocatalytic hydrogen generation under the visible light spectrum. The altered band gap of TiO_2-x rationally promotes the visible light absorption, and the RGO sheets present in the composites suppresses the electron-hole recombination, which accelerates the charge transfer. Hence, the noble metal-free RGO/TiO_2-x photocatalyst exhibited hydrogen production with a rate of 13.6 mmol h^?1g^?1_cat. under solar illumination. The appreciable photocatalytic hydrogen generation activity of 947.2 μmol h^?1g^?1_cat with 117 μAcm^?2 photocurrent density was observed under visible light (>450 nm).     

A composite visible-light photocatalyst for hydrogen production

A composite photocatalyst, Pd–TiO_2−xN_x–WO₃, was synthesized by the template method and characterized by energy dispersive X-ray microanalysis (EDX), X-ray diffraction (XRD), UV–vis spectrometer, and scanning electron microscope (SEM). The results of EDX analysis reveals that the molecular formula of the composite photocatalyst can be expressed as Pd–TiO_1.72N_0.28–WO₃. The UV–vis absorption spectrum indicates that the absorption edge of the catalyst red-shifts to around 600 nm. Under the irradiation with ultraviolet and visible light, the catalyst showed good performance for photocatalytic hydrogen production with a Na₂S/Na₂SO₃ system as the sacrificial agent.     

Efficient photothermal catalytic hydrogen production via plasma-induced photothermal effect of Cu/TiO2 nanoparticles

Developing appropriate photocatalyst with high efficiency is still the basic strategy for practical application of emerging technology. Herein, non-noble metal copper (Cu) nanoparticles were in situ hybrided with TiO₂ by a chemical reduction method. The crystal phase and structure were characterized by XRD, SEM, and TEM measurements. Hydrogen production results showed that Cu nanoparticles significantly improved the photocatalytic hydrogen production rate. The hydrogen production rate was as high as 24160.69 μmol g^?1 h^?1 at 100 °C, which was 36.25 and 8.46 times higher than the hydrogen production rates of pure TiO₂ and 0.13 wt% Cu/TiO₂ at room temperature, respectively. PL spectra, UV–vis spectra, IR images and photoelectrochemical measurements showed that the plasma-induced photothermal effect of Cu/TiO₂ nanoparticles, which raised the temperature of the reaction system and promoted photothermal catalytic performance. Briefly, this work provides a facile fabrication method of noble-metal-free photocatalysts featuring in low-cost and high efficiency. In the future, coupling the photothermal effect of plasmonic Cu to further speed up the kinetics should be another promising research direction for further improving hydrogen production.     

Facile synthesis of AuPd/g-C3N4 nanocomposite: An effective strategy to enhance photocatalytic hydrogen evolution activity

AuPd bimetallic nanoparticle (NP) modified ultra-thin graphitic carbon nitride nanosheet photocatalysts were synthesized via photochemical deposition-precipitation followed by hydrogen reduction. The crystal structure, chemical properties, and charge carrier behavior of these photocatalysts were characterized by X-ray diffraction (XRD), surface photovoltage spectroscopy (SPS), transient photovoltage spectroscopy (TPV), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and UV-Vis diffuse-reflectance spectroscopy (DRS). Photocatalytic H₂ evolution experiments indicate that the hydrogen treated AuPd nanoparticles can effectively promote the separation efficiency of electron-hole pairs photo-excited in the g-C₃N₄ photocatalyst, which consequently promotes photocatalytic H₂ evolution. The 1.0 wt% AuPd/g-C₃N₄ (H₂) composite photocatalyst showed the best performance with a corresponding photocatalytic H₂ evolution rate of 107 μmol h^?1. The photocatalyst can maintain most of its photocatalytic activity after four photocatalytic experiment cycles. These results demonstrate that the synergistic effect of light reduction and hydrogen reduction of AuPd and g-C₃N₄ help to greatly improve the photocatalytic activity of the composite photocatalyst.     

Preparation of direct Z-scheme Bi2WO6/TiO2 heterojunction by one-step solvothermal method and enhancement mechanism of photocatalytic H2 production

Direct Z-scheme Bi₂WO₆/TiO₂ heterojunction photocatalyst was prepared by one-step solvothermal method. The catalyst was characterized by XRD, TEM, XPS, UV–Vis DRS, photoluminescence spectroscopy and photoelectrochemical studies. The photocatalytic hydrogen production experiments show that Bi₂WO₆ did not generate H₂ and the H₂-production rate of TiO₂ is only 0.1 mmol⋅g⁻¹h⁻¹. The hydrogen production rate of the Bi₂WO₆/TiO₂ heterojunction photocatalyst reaches 12.9 mmol⋅g⁻¹h⁻¹, which is 129 times that of TiO₂. Compared with TiO₂, the enhanced H₂-production activity of the heterojunction catalyst can be attributed to the wider light absorption range and the efficient separation and migration of carriers at the close contact interface between Bi₂WO₆ and TiO₂. Based on the work functions of Bi₂WO₆, TiO₂ and their heterojunctions, combined with the results of electron paramagnetic resonance spectroscopy and Mott-Schottky measurements, the photocatalytic H₂ production mechanism of Z-scheme heterojunction Bi₂WO₆/TiO₂ was proposed. This work provides an easy and simple way to design a binary Z-scheme photocatalyst with efficient catalytic H₂-production activity without electron mediators.     

CoNi bimetallic alloy cocatalyst-modified TiO2 nanoflowers with enhanced photocatalytic hydrogen evolution

In terms of improving photocatalytic hydrogen production performance, inexpensive and earth-rich cocatalysts have become promising alternatives to precious metals. Herein, a novel CoNi–TiO₂ photocatalyst composed of TiO₂ nanoflowers and CoNi alloy was prepared by hydrothermal and chemical reduction methods. Various characterizations and test results have confirmed that the further improvement of the photocatalytic performance of the CoNi–TiO₂ photocatalyst is mainly due to the fact that the bimetallic CoNi alloy can accelerate charge transfer and inhibit the recombination of photo-induced carriers. The hydrogen production rate of the prepared CoNi–TiO₂ is about 24 times higher than that of the pristine TiO₂, and its hydrogen production rate value can reach 6580.9 μmol g^?1 h^?1, and showing comparable photocatalytic performance to 0.5 wt% Pt–TiO₂. In addition, combined with the characterization results, a probable mechanism for enhanced photocatalytic performance was proposed. This study provides favorable enlightenment for the design of a series of highly efficient non-precious metal TiO₂-based photocatalysts.     

Ag-doped TiO2 photocatalysts with effective charge transfer for highly efficient hydrogen production through water splitting

The development of efficient metal doped semiconductors for solar energy harvesting to produce hydrogen has attracted significant attention. Herein, the H₂ generation over Ag-doped TiO₂ photocatalyst, synthesized using a simple and cost-effective method based on chemical reduction, was reported. The Ag/TiO₂ exhibited an absorption peak in the visible region and the reduction of the bandgap to 2.5 eV due to surface plasmonic resonance (SPR). X-ray photoelectron spectroscopy revealed the presence of oxygen vacancies and 11% of Ag in Ti–Ag–O phase. The effect of reaction time and photocatalyst loading in the absence and presence of sacrificial reagents (alcohols and sulfur) on water splitting was studied and compared the activity of Ag/TiO₂ with that of bare TiO₂. The H₂ production rate of 23.5 mmol g⁻¹ h⁻¹ (with an apparent quantum yield of 19%), over 1.5Ag/TiO₂, was the highest ever reported so far. The observed higher activity could mainly be attributed to the existence of oxygen vacancies and the Ti–Ag–O phase. The photocatalyst was stable for three consecutive cycles in both the presence and absence of sacrificial reagents. This study offers new insights into the rational design of metal-support hybrid structures for hydrogen production through photocatalytic water splitting.     

Photocatalytic hydrogen production by flower-like graphene supported ZnS composite photocatalysts

Flower-like graphene (FG) prepared by a transformer coupled plasma enhanced chemical vapor deposition method was used as support for the preparation of composite photocatalysts. Small ZnS particles were formed on the surface of FG by a hydrothermal process with ZnCl₂ and Na₂S precursors. The surface morphology, surface area, surface chemistry, crystalline property, optical properties, photogenerated current and photocatalytic hydrogen production activity of the FG-ZnS photocatalysts were investigated by using the X-ray diffraction, scanning electron microscope, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectra, photocurrent response, photoluminescence spectra, electrochemical impedance spectra and photocatalytic hydrogen production tests. The maximum hydrogen production rate of FG-ZnS composite photocatalyst ZS-G0.02 was 11600 μmol g^?1h^?1 under UV light irradiation at a graphene/ZnCl₂ precursor weight ratio of 0.02. The flower-like structure of FG may help the light absorption, adsorption of sacrificing agents in the solution, and separation of photogenerated carriers. In comparison with pristine ZnS photocatalyst, the FG-ZnS nanocomposites exhibits enhanced photocatalytic hydrogen production activity.     

Construction of ternary Z-scheme covalent triazine framework@Au@TiO2 for enhanced visible-light-driven hydrogen evolution activity

One key challenge in photocatalytic hydrogen production is how to construct high-performance photocatalyst. Covalent triazine framework (CTF) based polymers as photocatalysts show great application potential because of their good photocatalytic activity, high chemical stability, tunable electronic and optical properties, and easy synthesis process. In this paper, we designed the ternary Z-scheme heterojunction Au@TiO₂-X%TrTh based on CTF polymer TrTh, TiO₂ and Au nanoparticle, which exhibit higher photocatalytic hydrogen production rate compared with the corresponding binary heterojunction Au@TiO₂ and TiO₂-12%TrTh. The results of photocatalytic hydrogen production show that the optimized Au@TiO₂-12%TrTh has a remarkable hydrogen production rate of 4288.54 μmol g^?1 h^?1, which is about 312.3 times of Au@TiO₂ and 9.1 times of the TiO₂-12%TrTh. The enhanced hydrogen production activity of the ternary heterojunction comes from the local surface plasmonic resonance effect of Au nanoparticle, lower recombination efficiency of photogenerated electron-holes pairs and Z-scheme electron transfer pathway of Au@TiO₂-12%TrTh. The work provides a new strategy for designing efficient and practical photocatalyst.     

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.     

Effect of polystyrene characteristic on photocatalytic hydrogen production by porous polystyrene photocatalyst film under simulated solar light irradiation

In this study, we developed a polystyrene-platinum/nitrogen-doped titanium dioxide/strontium titanate composite-polyvinylpyrrolidone (PS-PNS-PVP) photocatalyst film, which is applied in the process of photocatalytic hydrolysis under simulated sunlight to produce hydrogen, is developed. PS, which is cheap, non-toxic, with high UV resistance, and chemical inertness, is used as a carrier, and a highly effective hydrogen production of Pt/N–TiO₂/SrTiO₃ as a photocatalyst. The influence of the PS concentration on the stability, optical, and electrical properties of the photocatalyst film is discussed. In addition, the influence of the photocatalyst dispersion in the film on the activity under various photocatalyst concentrations was investigated. A polyvinylpyrrolidone pore-forming agent was then used to examine the effect on the photocatalyst film structure and optical properties, and the subsequent influence on photocatalytic hydrogen energy activity. Adjusting the PS concentration to 20 wt% produced good film-forming stability, and the photocatalyst dispersibility in the film under different photocatalyst concentrations. A photocatalyst concentration of 2.5 wt% resulted in good film dispersibility and the realization of added pore-forming agent. The modified photocatalyst film changed the film from a blind pore structure to a connecting void structure, increasing the film's porosity and hydrophilicity. This increased the number of photocatalytic sites, and the optimal hydrogen production of the photocatalyst film reached 21,333 μmol h^?1 g^?1.