新型可见光解水制氢催化剂的研究

综述了近年来出现的一些新型非TiO2光催化剂的研究情况,包括层状金属复合氧化物、金属氮氧化物、InMO4型化合物及分子筛等,并对未来的研究方向作了展望。     

A precursor route to prepare tantalum (V) nitride nanoparticles with enhanced photocatalytic activity for hydrogen evolution under visible light

Nanoparticulate Ta₃N₅ was prepared by nitridation of nanoparticulate Ta₂O₅ precursor in an attempt to improve the photocatalytic activity for H₂ evolution from aqueous methanol solution under visible light (λ > 420 nm). When platinum (Pt) was deposited in situ as a H₂ evolution cocatalyst, the as-prepared Ta₃N₅ with a primary particle size of 30–50 nm exhibited enhanced activity, three times higher than that of bulk Ta₃N₅ particles 300–500 nm in size. The improvement in activity arises from a lower density of defect sites, which is favorable for electron migration from the Ta₃N₅ bulk to the surface and/or for electron transfer from the conduction band of Ta₃N₅ to the loaded Pt.     

可见光分解水制氢催化剂研究进展

可见光分解水制氢研究主要集中在新型光催化剂的研制以及对传统光催化剂的改性。本文概述了近年来可见光分解水制氢技术的重要进展及最新研究成果,深入研究和分析了拓展光催化剂响应范围、提高其反应活性的几种技术路线,主要包括阴阳离子掺杂技术、固溶体技术、半导体复合技术以及加入助催化剂等;总结出了传统光催化剂存在可见光利用率低、光化学转化效率低等问题,提出了开发新型高效光催化剂并加强机理研究的必要性和可行性。     

A simple and environmentally friendly method of preparing sulfide photocatalyst

This paper reports the preparation of (AgIn)_xZn_2(1−x)S₂ solid solutions from acidic aqueous solutions consisting of silver nitrate, indium nitrate, zinc nitrate, and thioacetamide, without using toxic H₂S gas. The reaction sequence of this multicomponent material was investigated, as well as the post thermal treatment conditions. The formation of quaternary semiconductor solid solutions after 800 °C annealing were determined by X-ray diffraction. The peaks in the XRD patterns shifted to higher angles with an increase of [Zn]/[In] in the precursor solutions. Band gaps of the (AgIn)_xZn_2(1−x)S₂ solid solutions were estimated to be 2.11-2.45 eV by diffuse reflection UV-Vis spectra. In addition, the band gap energy increased with [Zn]/[In] accordingly. The precipitates after heat treatment had a layered structure, as revealed by SEM; the compositions were analyzed by EDS. The photocatalytic H₂ evolution rates in sacrificial reagents under a 300 W Xe lamp of Pt-loaded (AgIn)_xZn_2(1−x)S₂ solid solutions were measured. A H₂ evolution of 340 μmol/h for 0.5 g photocatalyst was obtained. The particles retained the photocatalytic activity for at least 100 h. This study demonstrates that AgInS₂-ZnS solid solution particles can be prepared from a completely aqueous route.     

可见光分解水制氢半导体催化剂的研究

直接利用太阳能光解水制氢是解决世界能源危机的重要途径,有效利用太阳能的关键是研究开发可见光化的光催化剂。介绍了光解水制氢的原理,综述了近年来半导体光催化剂在利用可见光方面研究的最新进展,并对未来的研究方向作了展望。     

Effect of electrolyte addition on activity of (Ga1−xZnx)(N1−xOx) photocatalyst for overall water splitting under visible light

Effects of electrolyte addition on photocatalytic activity of (Ga_1−xZn_x)(N_1−xO_x) modified with either Rh_2−yCr_yO₃ or RuO₂ nanoparticles as cocatalysts for overall water splitting under visible light (λ > 400 nm) are investigated. The cocatalyst Rh_2−yCr_yO₃ is confirmed to selectively promote the photoreduction of H⁺, while RuO₂ functions as both H₂ evolution sites and as efficient O₂ evolution sites. The activity of Rh_2−yCr_yO₃-loaded (Ga_1−xZn_x)(N_1−xO_x) is found to be suppressed in the presence of Cl⁻, which undergoes oxidation by photogenerated holes in the valence band of (Ga_1−xZn_x)(N_1−xO_x). Alkaline- and alkaline earth-metal cations in the reactant solution compensate the negative effect of Cl⁻ to a certain extent depending on the metal cation employed. Among the electrolytes examined, the addition of an appropriate amount of NaCl or A₂SO₄ (A = Li, Na, or K) to the reactant solution without pH control is found to increase activity by up to 75% compared to the case without additives. Direct splitting of seawater to produce H₂ and O₂ is also demonstrated using Rh_2−yCr_yO₃-loaded (Ga_1−xZn_x)(N_1−xO_x) catalyst under visible light.     

Photocatalytic water splitting performance of TiO2 sensitized by metal chalcogenides: A review

Titanium dioxide (TiO₂) has been extensively studied for photocatalytic water splitting applications for more than 50 years because of its advantages, such as its low cost, abundance, good chemical stability, nontoxicity, and sufficient energy potential to oxidize and reduce water molecules. On the other hand, TiO₂ has its own set of limitations, namely its wide bandgap (Eg = ～3.2 eV), which makes it less effective in sunlight. A few methods have been reported to overcome these problems, one of which is to make a heterojunction composite with other materials. The added material can inject electrons directly into the conduction band of TiO₂ and provide a tiered band structure, which can reduce the occurrence of photogenerated electron and hole recombination. Currently, the research and development of heterojunctions consisting of TiO₂ with chalcogenide materials has attracted the attention of many researchers. Metal chalcogenides offer a number of advantages, including absorption onset tuning, a size-dependent bandgap that can lead to high theoretical quantum efficiencies, effective charge transfer to the conduction band when TiO₂ is exposed to visible light, and high photochemical stability. In this review, the performance of various TiO₂/metal chalcogenide heterojunctions for photoelectrochemical water splitting is presented. The role of most common metal chalcogenides in TiO₂ will be exposed. Finally, the review concludes with a summary and recommendations for further research on this hot issue.     

A BiVO4 photoanode grown on porous and conductive SnO2 ceramics for water splitting driven by solar energy

The transformation of solar energy into chemical energy stored as hydrogen fuel underlies the water splitting process into O₂ and H₂ in photo-electrochemical (PEC) cells. This a potentially promising technology to generate renewable and clean energy. To make this technology commercially viable, the engineering of appropriate low-cost and robust photo-electrode materials and substrates is needed. In this study, we introduce BiVO₄-photoelectrodes grown on conductive bulk SnO₂–Sb₂O₅ ceramics acting as porous substrate. For these photoelectrodes, the value of photocurrent density of 1.1 mA/cm² was achieved in 0.1 M NaOH electrolyte at 1.23 V vs. RHE (reversible hydrogen electrode) under LED light (λ = 455 nm). This PEC performance of these BiVO₄ photoelectrodes is reached in spite of using a simple and low-cost deposition technique, where the BiVO₄-precursor is delivered to the bulk porous ceramic substrate as a nebulized aerosol in air-flow at room temperature. The high porosity of the ceramic substrate permits some permeation of the aerogel into the pores to a depth of several micrometers to provide a 3D-growth of the BiVO₄-coating on conductive SnO₂ grains. The film thickness of the BiVO₄ on individual grains is approximately 100 nm. This construction of the photoelectrode leads to an effective interface with good absorption of solar radiation and good electron harvesting. The bulk ceramics assure favorable conditions for electron collection and charge transport, which results in a good PEC performance with this type of photoanode.     

Mechano-catalytic overall water splitting on some mixed oxides

Simple transition metal oxides such as NiO, Co₃O₄, Fe₃O₄ and Cu₂O were found to catalytically decompose water into H₂ and O₂ by mechanical energy. The reaction is regarded as “mechano-catalytic” overall water splitting” and is a quite novel catalytic reaction. In this paper, some general aspects on the mechano-catalytic overall water splitting are reviewed on simple oxides. In addition, recent results on the mechano-catalytic activity of a groups of mixed oxides, wolramite-type oxides with a formula of ABO₄ (A=Fe, Co, Ni and Cu, etc., B=W, Mo), are shown. AWO₄ (A=Fe, Co, Ni and Cu) decomposed water into H₂ and O₂ under the supply of mechanical energy, indicating that mechano-catalytic overall water splitting proceeded on wolframite-type compounds containing 3d-transition metals. AMoO₄ (A=Fe, Co, Ni) also decomposed water into H₂ and O₂ under supply of mechanical energy. The reaction properties on wolframite-type oxides are discussed.     

可见光催化分解水制氢的研究进展

阐述了近五年来可见光催化分解水制氢的国内外最新研究进展。重点介绍了离子掺杂型光催化剂、价带控制型光催化剂、固溶体催化剂、Z型体系光催化剂、复合型光催化剂以及一些新型可见光催化剂。对今后可见光催化分解水制氢的研究工作进行了展望。     

Preparation of mesoporous In–Nb mixed oxides and its application in photocatalytic water splitting for hydrogen production

A series of mesoporous In–Nb mixed oxides was synthesized using NbCl₅ and In₂O₃ as the starting material and triblock copolymer P123 as template. We investigated the influence of indium content on the synthesis and characteristics of the mesoporous In–Nb mixed oxides, and their photocatalytic activities for water splitting. The materials were characterized by small angle X-ray scattering, powder X-ray diffraction, extended X-ray absorption fine structure, transmission electron microscopy, scanning electron microscopy, energy dispersive spectrometer, N₂ sorption and UV–vis spectroscopy. The surface area of mesoporous In–Nb mixed oxides was greater than 90 m²/g with a wormhole framework. The optimization of synthesis condition of the mesoporus In–Nb oxides catalyst contained a small fraction of highly dispersed indium (In/Nb = 0.13) species intercalated into the framework of mesoporous niobium oxides and exhibited a high photocatalytic activity for water splitting reaction which was about 2.7 times as compared to mesoporous Nb₂O₅ and was about 19 times higher than commercial bulk Nb₂O₅.     

Hydrothermal synthesis, characterization, and photocatalytic performances of Cr incorporated, and Cr and Ti co-incorporated MCM-41 as visible light photocatalysts for water splitting

A series of Cr incorporated, and Cr and Ti co-incorporated MCM-41 photocatalysts were synthesized by hydrothermal method. X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis), Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence analysis (XRF), N₂ adsorption–desorption isotherms and Raman spectra were used to investigate the effects of the incorporated elements on the structure of MCM-41. The experimental results for photocatalytic water splitting under visible light irradiation (λ > 430 nm) demonstrated that the photocatalytic activities of Cr-MCM-41 and Cr-Ti-MCM-41 catalysts for hydrogen production decreased with an increase in the amount of Cr incorporated. Compared with the Cr-MCM-41 which had the same amount of incorporated Cr, the Cr-Ti-MCM-41 exhibited much higher hydrogen evolution activities.     

Simple microwave synthesis of TiO2/NiS2 nanocomposite and TiO2/NiS2/Cu nanocomposite as an efficient visible driven photocatalyst

Approximately 47% of solar-terrestrial radiation is visible. It is a great achievement to produce a highly efficient visible driven photocatalyst. Here TiO₂/NiS₂/Cu nanocomposite was prepared as a highly active visible driven photocatalyst. TiO₂/NiS₂/Cu nanocomposite was prepared by microwave method. It degrades 92%, 86%, 87%, and 88% of Rhodamine B (RhB), Methyl orange (MO), Acid Black 1 (AB1), and Acid Brown 214 (AB214), respectively. Adding NiS₂ and Cu to TiO₂ dramatically increased the degradation efficiency from 17% for bare TiO₂ to 92% for TiO₂/NiS₂/Cu nanocomposite under visible light. As-prepared TiO₂/NiS₂/Cu nanocomposite was characterized by SEM, TEM, XRD, DRS, BET, and EDX.     

构建MoS2/Fe-g-C3N4异质结催化剂以促进其可见光催化产氢性能

以g-C_3N_4为基底,通过掺杂Fe元素,复合MoS_2的方法制备了具有多孔异质结结构的MoS_2/Fe-g-C_3N_4半导体材料,并测量了其光解水产氢性能,发现MoS_2含量为3%(以g-C_3N_4的质量为基准,下同)时,MoS_2/Fe-g-C_3N_4的光催化性能优异,其产氢速率达到48.2μmol/h,为g-C_3N_4的5.48倍。利用XRD、FTIR、SEM、TEM、XPS表征了催化剂的物化性质;利用PL、UV-Vis等方法表征了催化剂的光学性质。结果发现,Fe元素的掺杂使g-C_3N_4结晶度降低,并呈现一种交叉孔道结构,极大增加了催化剂的比表面积。同时,MoS_2可以与g-C_3N_4形成异质结结构,提高了MoS_2/Fe-g-C_3N_4的可见光吸收率以及光生电子-空穴对的分离效率,从而有效提高了MoS_2/Fe-g-C_3N_4光解水产氢的能力。     

Enhanced visible light response of heterostructured Cr2O3 incorporated two-dimensional mesoporous TiO2 framework for H2 evolution

Mesoporous TiO₂ frameworks incorporated with diverse percentages of Cr₂O₃ nanoparticles (NPs) were achieved through the one-step sol-gel approach for photocatalytic H₂ evolution under visible-light exposure. The obtained isotherms could be classified as type IV, indicating mesopore 2D-hexagonal symmetry. The H₂ evolution rate over mesoporous Cr₂O₃/TiO₂ photocatalyst was observably promoted employing glycerol as a sacrificial agent, providing a comparatively high H₂ yield of 14300 μmolg^?1. The highest photocatalytic efficiency was achieved with an optimal 4% Cr₂O₃/TiO₂ photocatalyst, and the evolution rate was enhanced 1430-fold compared to pristine TiO₂. The eminent photocatalytic performance of mesoporous Cr₂O₃/TiO₂ was ascribable to different key factors such as the narrow bandgap, wide visible light photoresponse, Cr₂O₃ as photosensitizer, synergistic effect and high surface area. The recycle tests for five times over synthesized photocatalyst revealed excellent durability and stability without loss in H₂ evolution. The photocatalytic mechanisms for H₂ evolution over Cr₂O₃/TiO₂ photocatalyst were proposed according to the photocurrent transient and photoluminescence measurements and photocatalytic H₂ evolution results.     

Perspective of hydrogen energy and recent progress in electrocatalytic water splitting

As a secondary energy with great commercialization potential, hydrogen energy has been widely studied due to the high calorific value, clean combustion products and various reduction methods. At present, the blueprint of hydrogen energy economy in the world is gradually taking shape. Compared with the traditional high-energy consuming methane steam reforming hydrogen production method, the electrocatalytic water splitting hydrogen production stands out among other process of hydrogen production owning to the mild reaction conditions, high-purity hydrogen generation and sustainable production process. Basing on current technical economy situation, the highly electric power cost limits the further promotion of electrocatalytic water splitting hydrogen production process. Consequently, the rational design and development of low overpotential and high stability electrocatalytic water splitting catalysts are critical toward the realization of low-cost hydrogen production technology. In this review, we summarize the existing hydrogen production methods, elaborate the reaction mechanism of the electrocatalytic water splitting reaction under acidic and alkaline conditions and the recent progress of the respective catalysts for the two half-reactions. The structure–activity relationship of the catalyst was deep-going discussed, together with the prospects of electrocatalytic water splitting and the current challenges, aiming at provide insights for electrocatalytic water splitting catalyst development and its industrial applications.     

Yttrium -barium oxide as a robust photocatalyst for photocatalytic degradation of organic dyes under visible light

Based on the structure related to the high-temperature superconductor yttrium-barium-copper oxide, two novel high-efficiency visible light photocatalysts were created in this study. The yttrium-barium oxide (YBO) semiconductors Y₂Ba₃O₆ (YB3O) and Y₂Ba₄O₇ (YB4O) were prepared by a copper-free solid-phase sintering method. They were applied for the effective treatment of dye-containing wastewater by photocatalysis under visible light irradiation. The degradation efficiency of methylene blue (MB) reached more than 95% within 10 min. Stable visible light degradation of methyl orange (MO) was achieved in the presence of YB3O and YB4O. The electron spin resonance technique and active substance capture technique confirmed the presence of superoxide radicals (·O₂^?), hydroxyl radicals (·OH) and holes (h_VB⁺) under visible light illumination. UV–Vis diffuse reflectance spectroscopy analysis showed that the direct optical band gaps of YB3O and YB4O were 2.550 eV and 2.583 eV, respectively, which resulted in their high visible absorption at 486.27 nm and 480.06 nm. After five cycles, the recoveries of YB3O and YB4O reached 67.15% and 72.98%. Therefore, YB3O and YB4O are considered as powerful semiconductor catalysts for the photocatalytic degradation of organic dyes in wastewater.     

微波加热法制备TiO2/膨润土复合光催化材料

提出了一种制备TiO₂/膨润土复合光催化材料的新方法-微波加热法，并通过改变微波加热功率、微波加热时间、焙烧温度和焙烧时间等得到最佳制备条件。在模拟染料废水中，对催化材料的光催化性能进行了研究，结果发现微波加热法制备的复合光催化材料具有同常规法相当的光催化降解性能。     

Surfactant-free synthesis of homogeneous nano-grade cadmium sulfide grafted reduced graphene oxide composite as a high-activity photocatalyst in visible light

Zero-dimensional cadmium sulfide (CdS) nanoparticles with small size (∼50 nm) were grafted on the two-dimensional reduced graphene oxide (RGO) nanosheet via a facile hydrothermal method without any surfactant to synthesize CdS@RGO nanocomposites in this paper. The structural analysis confirms the strong attachment and interaction between CdS and RGO in CdS@RGO photocatalyst, which leads to a higher photocatalytic efficiency (95.3%) with superior anti-corrosion stability (almost no change of efficiency over three repeated experiments) to that of pure CdS in visible light. The unique hybrid nanostructure of CdS@RGO can effectively prevent the self-corrosion of CdS and facilitate the separation of electron-hole pairs. Consequently, these outstanding photocatalytic performances of CdS@RGO endow it with a promising prospect for the degradation of organic pollutants and this work can be extended to other graphene-based inorganic semiconductor composites.     

The role of graphene and europium on TiO2 performance for photocatalytic hydrogen evolution

Highly efficient Eu-TiO₂/graphene composites were synthesized by a two-step method such as sol-gel and hydrothermal process. The synthesized photocatalysts were characterized by XRD, TEM, XPS, UV–vis diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy. The results confirmed that anatase Eu-TiO₂ nanoparticles with average 10 nm sizes were successfully deposited on two-dimensional graphene sheets. The UV–visible spectroscopy showed a red shift in the absorption edge of TiO₂ due to Eu doping and graphene incorporation. Moreover, effective charge separation in Eu-TiO₂/graphene composites was confirmed by PL emission spectroscopy compared to TiO₂/graphene, Eu-TiO₂ and pure TiO₂. The photocatalytic activity for H₂ evolution over prepared composites was studied under visible light irradiation (λ ≥ 400 nm). The results demonstrate that photocatalytic performance of the photocatalysts for hydrogen production increases with increasing doping concentration of Eu upto 2 at%. However, further increase in doping content above this optimum level has decreased the performance of photocatalyst. The enhanced photocatalytic performance for H₂ evolution is attributed to extended visible light absorption, suppressed recombination of electron-hole pairs due to synergistic effects of Eu and graphene.