基于表面等离子体共振效应的Ag(Au)/半导体纳米复合光催化剂的研究进展

由具有表面等离子体共振(surface plasmon resonance,SPR)效应的贵金属(Ag、Au等)纳米粒子和半导体纳米结构组成的纳米复合光催化剂具有优异的可见光光催化活性,成为新型光催化材料的研究热点之一。本文综述了Ag(Au)/半导体纳米复合光催化剂的制备方法、基本性质以及光催化应用方面的一些重要研究进展;重点介绍了Ag(Au)等纳米粒子的表面等离子共振增强可见光催化活性的机理,以及Ag(Au)纳米粒子与不同类型半导体复合的光催化剂的光催化性能,其中所涉及的半导体包括金属氧化物、硫化物和其他一些半导体;本领域未来几年的研究热点将集中于新型高效的Ag(Au)/半导体纳米复合光催化剂的微结构调控及其用于可见光驱动有机反应的机理研究。本文为基于SPR效应构建Ag(Au)/半导体纳米复合光催化剂的研究提供了有力的参考依据,并且指出Ag(Au)/半导体纳米复合光催化剂的研究是发展可见光高效光催化剂的重要方向。     

Hierarchical ZnO/Ag nanocomposites for plasmon-enhanced visible-light photocatalytic performance

Surface plasmon resonance (SPR) of the noble metals improve the photocatalytic activity of semiconductor metal oxides in the visible light region. This work reports the facile preparation of SPR induced visible light active hierarchical ZnO/Ag nanocomposite photocatalysts by using environmental friendly two-step method. The prepared nanocomposites analyzed by using various techniques such as powder-XRD, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, UV–Vis spectroscopy, photoluminescence spectroscopy, and photocurrent measurements. The results indicate the formation of hierarchical ZnO/Ag nanocomposites, which shows surface plasmon absorbance and enhanced photocurrent responses. Because of the SPR effect, the nanocomposites show improved visible light photocatalytic activity by enhancing the electron-hole pair separation in Rhodamine B degradation system.     

新型三元复合可见光催化剂Au/Bi_2WO_6/RGO的制备及其性能

采用溶剂热法制备钨酸铋/石墨烯(Bi_2WO_6/RGO)光催化剂,然后利用光还原法将Au纳米颗粒沉积于该二元光催化剂表面,制备出Au/Bi_2WO_6/RGO三元复合可见光催化剂。运用X射线衍射(XRD)、紫外可见漫反射吸收光谱(UV-Vis DRS)和透射电镜(TEM)对催化剂的晶体结构、光吸收性能、形貌性能进行了分析表征。以罗丹明B (Rh B)为模拟污染物,评价了该催化剂的可见光催化性能。结果表明,RGO和Au纳米颗粒的引入,增强了Bi_2WO_6可见光吸收,同时抑制了光生载流子的复合,从而提高Bi_2WO_6可见光催化降解RhB的性能。     

Preparation of Ag@AgI-intercalated K4Nb6O17 composite and enhanced photocatalytic degradation of Rhodamine B under visible light

In this study, a novel plasmonic photocatalyst, Ag@AgI intercalated layered niobate, was synthesized via a microwave-assisted ion-exchange method. The composite materials prepared were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray fluorescence spectrometry (XRF), Brunauer–Emmett–Teller (BET) and ultraviolet–visible diffuse reflection spectra (UV–vis). The as-prepared plasmonic photocatalyst exhibited an enhanced and stable photocatalytic performance for the degradation of Rhodamine B (RhB) and up to 83% of RhB was degraded in 40 min under visible light irradiation. The mechanism of separation of the photo-generated electrons and holes at the K₄Nb₆O₁₇/Ag@AgI composite was discussed.     

Preparation and photocatalytic activity of BiOI/MnxZn1-xFe2O4 magnetic photocatalyst

BiOI/Mn_xZn_1-xFe₂O₄ magnetic photocatalysts were successfully prepared for the first time. With the degradation of simulated RhB wastewater as a pointer to the photocatalytic reaction and combined with Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–visible diffuse reflectance spectroscopy (UV–vis DRS), and vibrating sample magnetometer (VSM), the reasons influencing the photocatalytic performance of the magnetic photocatalysts were further explored. The excessive or insufficient Mn-Zn ferrite both leads to a relatively low photocatalytic activity. When the calcination temperature reaches to 200 and 400?°C, the photocatalytic activity is enhanced significantly, but the main active component in the photocatalysts has changed from BiOI to Bi₅O₇I at 400?°C. The nanocomposites prepared under alcohol water environment with hollow microspheres morphology possess a highly photocatalytic efficiency, and the RhB degradation rate within 4?h in the ethanol water environment is significantly higher than that in pure water (98% vs. 59%).     

Ag/AgX（X=Cl,Br,I）等离子共振光催化剂的研究进展

银/卤化银[Ag/AgX（X=Cl,Br,I）]光催化剂作为一种新型光催化剂,由于在可见光区域具有明显的等离子共振效应从而显示了优异的可见光催化降解有机污染物的活性,引起了人们的极大重视。本文主要对Ag/AgX（X=Cl,Br,I）等离子体光催化剂的结构、光催化降解有机物机理、催化剂制备等进行了综述。Ag/AgX（X=Cl,Br,I）的活性普遍较高,通过半导体复合及形貌尺寸的控制,光催化性能得到进一步改善。进而论述了Ag/AgX体系等离子体共振光催化剂在工业染料废水处理上的应用现状,并对Ag/AgX（X=Cl,Br,I）等离子体光催化剂在高浓度、成分复杂污水体系处理中的应用进行了展望。     

Facile one-step synthesis of BiOCl/BiOI heterojunctions with exposed {001} facet for highly enhanced visible light photocatalytic performances

Flowers-like structure BiOCl/BiOI heterojunctions with exposed {001} facets have been prepared by a facile one-step hydrothermal method. The 70% BiOCl/BiOI heterojunction exhibited the highest photocatalytic activity. The highly enhanced visible light photocatalytic performance was mainly ascribed to the synergistic effect of {001} crystal facets, sensitization of RhB, increasing photo absorption and heterojunctions. The synergistic effect of coupled system could open up new opportunities to develop high-performance photocatalysts for degradation of organic pollutants in water.     

g-C3N4/Bi2MoO6复合光催化剂的制备及性能研究

结合热缩聚法和水热法制备了g-C₃N₄/Bi₂MoO₆复合光催化剂,利用X射线衍射（XRD）、傅里叶红外光谱（FT-IR）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、氮气吸附-脱附曲线、紫外-可见漫反射光谱（UV-Vis DRS）、光致发光光谱（PL）等分析测试技术对材料的结构和性能进行了表征,研究了材料光催化降解罗丹明B（RhB）的效果。结果表明,与纯Bi₂MoO₆相比,g-C₃N₄/Bi₂MoO₆复合材料提高了对可见光的吸收能力,减小了带隙宽度,在可见光激发下提高了降解RhB的光催化活性。其中,5% g-C₃N₄/Bi₂MoO₆复合材料对RhB的降解率最高,在可见光照射180 min对RhB的降解率为93%;而同样条件下Bi₂MoO₆对RhB的降解率为58%。重复性实验表明,复合材料在RhB光降解过程中是稳定的,具有较好的应用潜力。     

磷钨酸/SiC复合材料的制备及光催化性能研究

以磷钨酸(PTA)和SiC为原料,采用浸渍法制备了4种不同比例PTA的PTA-SiC光催化剂.采用紫外可见漫反射光谱、傅里叶红外变换光谱、X射线衍射光谱、扫描电镜进行表征,并以罗丹明B(RhB)为降解底物,考察光催化剂的光催化降解性能.结果表明,制备的光催化剂既保持了SiC的载体结构,又保持了PTA的Keggin型结构...     

One-step hydrothermal synthesis of N-doped TiO2/C nanocomposites with high visible light photocatalytic activity

N-doped TiO(2) nanoparticles modified with carbon (denoted N-TiO(2)/C) were successfully prepared by a facile one-pot hydrothermal treatment in the presence of L-lysine, which acts as a ligand to control the nanocrystal growth and as a source of nitrogen and carbon. As-prepared nanocomposites were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), electron paramagnetic resonance (EPR) spectra, and N(2) adsorption-desorption analysis. The photocatalytic activities of the as-prepared photocatalysts were measured by the degradation of methyl orange (MO) under visible light irradiation at λ≥ 400 nm. The results show that N-TiO(2)/C nanocomposites increase absorption in the visible light region and exhibit a higher photocatalytic activity than pure TiO(2), commercial P25 and previously reported N-doped TiO(2) photocatalysts. We have demonstrated that the nitrogen was doped into the lattice and the carbon species were modified on the surface of the photocatalysts. N-doping narrows the band gap and C-modification enhances the visible light harvesting and accelerates the separation of the photo-generated electrons and holes. As a consequence, the photocatalytic activity is significantly improved. The molar ratio of L-lysine/TiCl(4) and the pH of the hydrothermal reaction solution are important factors affecting the photocatalytic activity of the N-TiO(2)/C; the optimum molar ratio of L-lysine/TiCl(4) is 8 and the optimum pH is ca. 4, at which the catalyst exhibits the highest reactivity. Our findings demonstrate that the as-obtained N-TiO(2)/C photocatalyst is a better and more promising candidate than well studied N-doped TiO(2) alternatives as visible light photocatalysts for potential applications in environmental purification.     

可见光驱动溴化银/溴氧化铋复合纳米 材料制备及活性评价*

室温沉淀法合成溴氧化铋（BiOBr）纳米片,然后通过离子交换法制备溴化银/溴氧化铋（AgBr/BiOBr）复合纳米材料,采用X射线衍射（XRD）、场发射扫描电子显微镜（FE-SEM）及紫外可见分光光度计（UV-Vis）对其进行表征,并进行了光催化降解实验。以节能、绿色的LED灯为可见光光源,AgBr/BiOBr复合材料光催化降解罗丹明B（RhB）和甲基橙（MO）的效率均高于BiOBr。AgBr/BiOBr降解RhB的活性强于MO。在AgBr/BiOBr光催化系统中,超氧自由基和空穴是主要的活性物种。不同pH条件下,AgBr/BiOBr对RhB均表现出理想的光催化降解效果,酸性条件下降解效率最佳;碱性环境下AgBr/BiOBr光催化降解MO的活性最高。经过循环利用,AgBr/BiOBr可见光催化活性呈现出一定程度的降低,归因于降解过程中产生了金属银。     

Improved photocatalytic performance of Gd and Nd co-doped ZnO nanorods for the degradation of methylene blue

This paper reports the synthesis of pure ZnO, Gd and Nd co-doped ZnO nanorods based nanocomposites via simple hydrothermal method. Subsequently, the prepared photocatalysts were characterized using XRD, SEM/EDX, TEM, UV–visible and PL spectroscopy. The XRD results demonstrate that Gd and Nd ions were incorporated into ZnO lattice in the synthesized ZnO based nanocomposites and showed hexagonal wurtzite structure. The SEM and TEM results show that nanorods having nanoscale diameter and length were successfully synthesized by hydrothermal method. The UV–visible spectroscopy verified that the band gap of ZnO was reduced due to incorporation of Gd and Nd into ZnO photocatalyst. Similarly, Gd and Nd incorporation into ZnO was found effective to reduce the recombination of electrons and holes as confirmed by PL spectroscopy. Moreover, the prepared nanocomposites with various atomic ratios (0.5–2%) were tested for photocatalytic degradation of methylene blue (MB), under visible light irradiation. The highly efficient and optimized 1.5% Nd/ZnO nanocomposite demonstrated enhanced photocatalytic performance for the degradation of methylene blue compared to pure ZnO and other nanocomposites. Furthermore, the recycling results show that the 1.5% Nd/ZnO nanocomposites displayed good stability and long-term durability. These finding suggest that the ZnO based nanocomposite could be efficiently used in various energy and environmental applications.     

Photocatalytic degradation of organic compounds diluted in water using visible light-responsive metal ion-implanted TiO2 catalysts: Fe ion-implanted TiO2

The application of metal ion-implantation method has been made to improve the electronic properties of the TiO₂ photocatalyst to realize the utilization of visible light. The photocatalytic properties of these unique TiO₂ photocatalysts for the purification of water have been investigated. By the metal ion-implantation method, metal ions (Fe⁺, Mn⁺, V⁺, etc.) are accelerated enough to have the high kinetic energy (150 keV) and can be implanted into the bulk of TiO₂. TiO₂ photocatalysts which can absorb visible light and work as a photocatalyst efficiently under visible light irradiation were successfully prepared using this advanced technique. The UV-Vis absorption spectra of these metal ion-implanted TiO₂ photocatalysts were found to shift toward visible light regions depending on the amount and the kind of metal ions implanted. They were found to exhibit an effective photocatalytic reactivity for the liquid-phase degradation of 2-propanol diluted in water at 295 K under visible light (λ>450 nm) irradiation. The investigation using XAFS analysis suggested that the substitution of Ti ions in TiO₂ lattice with implanted metal ions is important to modify TiO₂ to be able to adsorb visible light.     

WO_3/BiOBr复合催化剂的制备及可见光催化降解甲基橙

以Bi(NO_3)5·5H_2O、Na Br、H_2WO_4为原料,采用一步水热合成法合成不同n(W)∶n(Br)的WO_3/BiOBr复合催化剂,并通过SEM和TEM对催化剂进行表征分析。以甲基橙为探针污染物,考察前驱液pH、水热温度、水热时间和n(W)∶n(Br)对WO_3/BiOBr复合催化剂活性的影响。结果表明,在pH为10.2、100℃水热时间6 h合成n(W)∶n(Br)为0.02的WO_3/BiOBr复合催化剂活性最好,光照120 min后,对目标污染物的降解率达99.39%,较BiOBr催化剂(合成条件为原始pH值,100℃水热反应6 h)提高了30.85%。采用水热合成法制备的WO_3/BiOBr复合催化剂具有良好的可见光活性。     

Synthesis and characterization of visible light driven N—Fe-codoped TiO2/SiO2 for simultaneous photoremoval of Cr (VI) and azo dyes in a novel fixed bed continuous flow photoreactor

N─Fe-codoped TiO₂/SiO₂ nanocomposites were prepared and stabilized onto glass beads by coupling two methods of dip coating and heat attachment. The prepared nanocomposites were characterized by DRS-UV/vis, FTIR, XRD, FESEM, EDX, TEM, XPS, and N₂ adsorption/desorption analyses. The operational parameters of pH, flow rate, and the photoreactor's angle against sunlight were optimized to achieve the highest degradation efficiency. Then, the photocatalytic efficacy of the prepared substrates was examined in a novel fabricated photoreactor on a complex pollutant mixture consisting of Cr (VI), BR-29, BB-41, and BY-51, under two irradiation sources of visible light and sunlight. Moreover, to virtualize the process under natural irradiation conditions, the effectiveness of the performance was evaluated in various outdoor climate circumstances. Consequently, the results demonstrated the enhanced photocatalytic activity of the prepared nanocomposites under visible and solar irradiations. The removal percentages were also considerable under a partly cloudy sky and were 91.73%, 85.64%, 87.23%, and 58.59% for Cr (VI), BR-29, BB-41, and BY-51, respectively. The results showed the promising activity of the innovative photoreactor and the as-prepared nanocomposites for photocatalytic remediation of the water pollutants under natural climate conditions.     

LED可见光下Au/TiO2光催化氧化甲醛表观动力学

甲醛是室内空气中典型的挥发性有机化合物（VOCs）之一。等离子激元型光催化剂可吸收可见光,可在室温常压下利用太阳光驱动光催化氧化脱除室内空气中甲醛的反应,其表观反应动力学研究对设计等离子激元型光催化剂及应用于脱除VOCs等污染物具有重要意义。研究了LED可见光下等离子激元型Au/TiO₂光催化脱除气相中甲醛的表观反应动力学,考察不同波长的可见光源、光强及反应气相对湿度对表观反应动力学的影响,根据对实验数据的分析求得LED可见光催化氧化甲醛表观反应速率常数k（I,H）。结果表明,在13%相对湿度、蓝光光强为38.5 mW·cm^-2的条件下,光反应的甲醛转化率达77%,是暗反应的近5倍。在LED红、绿、蓝、白光照射下,随着光强增加,甲醛转化率快速增加后缓慢增至基本不变。相同光强（低于42 mW·cm^-2）和湿度条件下,红、绿、蓝光源的甲醛转化率相近,白光略低于其他光源。干气氛下,光反应和暗反应的甲醛转化率几乎为0。湿气氛下,光反应和暗反应均有甲醛转化率,光反应的甲醛转化率更高。不同光源条件下甲醛转化率随相对湿度变化规律相似。相对湿度为21.9%时甲醛转化率最高,而后保持不变,基本在80%左右。通过对红、绿、蓝、白光的数据拟合计算,得到表观动力学参数k（I）_H、k（H）_I、k（I,H）以及速率方程。     

溶胶-凝胶-微波法制备银掺杂TiO_2光催化剂及其光催化性能

用硝酸银和钛酸正丁酯为原料,采用溶胶-凝胶-微波辐射干燥法合成银掺杂TiO_2光催化剂TiO_2-Ag。为了提高催化剂的光催化活性和降解有机污染物的速率,用微波辅助Ti O2-Ag光催化剂降解有机污染物。通过扫描电子显微镜、红外光谱法、紫外可见光谱法和荧光光谱法对TiO_2-Ag催化剂进行测试和表征。以甲基橙为有机污染物,分别在太阳光照射和微波、紫外、紫外-微波条件下降解甲基橙以考察催化剂的光催化活性。结果表明,TiO_2-Ag光催化剂最佳制备条件为:银掺杂量n(Ag+)∶n(Ti~(4+))=0.003,离子液体用量3.0 m L,微波干燥功率210 W,微波干燥时间20 min,焙烧温度650℃,焙烧时间3 h,此条件下制备的TiO_2-Ag光催化剂在太阳光照射4 h下,紫外光照、微波辐射和紫外光照-微波辐射分别辐射55 min后,甲基橙降解率分别为98.70%、98.79%和99.05%。     

氧化亚铜光催化剂性能提升及增强机制的研究进展

Cu₂O是目前最有潜力的可见光光催化剂之一,在太阳能电池、一氧化碳氧化、光催化剂、传感器、化学模板等方面有着广泛的应用。然而,Cu₂O光生电子-空穴对具有容易复合、易发生光腐蚀、稳定性不好等特性,使其在实际应用上面临很大的挑战,因此如何有效地提高Cu₂O的光催化性能成为国内外研究者关注的焦点。首先,本文围绕Cu₂O半导体的形貌控制、杂原子掺杂以及构建半导体异质结这三方面对Cu₂O光催化性能的提升进行系统阐述,其中构建半导体异质结是提升Cu₂O光催化性能最有效的方法,Cu₂O与贵金属、金属氧化物以及碳材料构成的复合半导体异质结均有效地提高了Cu₂O的光催化活性;其次,从复合半导体异质结、肖特基结以及Z-scheme机制三方面分析并讨论了Cu₂O光催化增强机制;最后对Cu₂O基纳米复合材料在电子结构、界面性质以及表面负载的成分和厚度等方面的研究进行了展望。     

Preparation of transparent PVA/TiO2 nanocomposite films with enhanced visible-light photocatalytic activity

Polymer/semiconductor oxide nanocomposite films have been intensively investigated for various applications. In this work, we reported a simple hydrothermal method to fabricate highly transparent poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposite films with enhanced visible-light photocatalytic activity. The as-prepared PVA/TiO₂ nanocomposite films showed high optical transparency in the visible region even at a high TiO₂ content (up to 40 wt.%). The determination of photocatalytic activity by photodegradation of methyl orange (MO) and colorless phenol showed that PVA/TiO₂ nanocomposite films exhibited enhanced visible-light photocatalytic activity and excellent recycle stability. This work provided new insights into fabrication of polymer/TiO₂ nanocomposites as high performance photocatalysts in waste water treatment.     

Co9S8/CdS heterostructures as efficient photocatalysts for degradation of organic pollutant

Because of its superior coupling and composition matching, narrow band gap semiconductor heterojunction can increase redox activity, reduce carrier recombination, and enhance light absorption. When heterojunction photocatalysts are constructed properly, it is thought to be an efficient technique to boost photocatalytic activity. The Co₉S₈/CdS heterostructures in this study were created using a two-step solvothermal technique. The as-prepared Co₉S₈/CdS heterostructures exhibit outstanding photocatalytic degradation performance of methyl orange (MO) owing to their unique structure and compositional properties. Co₉S₈/CdS heterostructures can offer a remarkable MO degradation rate that can reach 97% in 25 min when illuminated by visible light. In addition to demonstrating better long-term stability after numerous cycling photocatalytic tests, experiments with radical trapping have shown that ·O₂⁻ is crucial for the photocatalytic degradation of MO. The pertinent photogenerated charge transfer and catalytic mechanisms of Co₉S₈/CdS heterostructures are suggested and examined.