p-n复合半导体光催化剂研究进展

综述了p-n复合半导体光催化剂的光催化原理及研究现状。根据p-型材料种类,将p-n复合半导体光催化剂分为4类:p-型半导体材料为镍氧化物、p-型半导体材料为钴氧化物、p-型半导体材料铜氧化物及由其它p-型半导体材料组成的"p-n结型"、"二极管"式p-n复合半导体光催化剂,分别对其研究状况进行了介绍。提出了当前p-n复合半导体光催化剂研究中存在的一些问题,并对未来的研究方向进行了探讨。     

含铋光催化材料的研究进展

含铋光催化材料因其能吸收可见光、催化活性高而具有广阔的应用前景。本文主要回顾了含铋光催化材料近年来的研究概况,详细介绍了铋氧化物、卤氧化铋及钛酸铋、钨酸铋、钒酸铋、钼酸铋、铁酸铋等光催化剂的结构、制备和光催化性能,重点对光催化性能的改进方法进行了综述,包括制备方法的改良、催化剂的掺杂改性及复合催化剂的制备等;最后针对进一步提高光催化剂整体性能、实现工业化应用两点,提出了未来可以利用多元元素掺杂、多元半导体复合进行改性和负载于某些载体制备整体催化剂进行改良的观点。     

烧绿石型复合氧化物的制备及其光催化性能

综述了近年来国内外烧绿石型复合氧化物的制备方法及其影响因素;总结了这类材料在光催化降解有机物和光催化分解水方面的研究进展;分析了烧绿石型复合氧化物的应用前景.     

天然沸石负载ZnO/SnO2复合半导体的光催化活性

利用天然沸石负载ZnO／SnO2复合半导体制备光催化材料。采用X射线衍射、红外光谱等测试方法对复合样品的结构进行了研究。讨论了材料制备过程中的焙烧条件、锌锡氧化物配比对其结构与光催化剂活性的影响。结果表明：ZnO／SnO2复合半导体与沸石间实现了一定程度的化学结合,半导体氧化物在沸石表面负载牢固,并且当ZnO／SnO2摩尔比为2：1时,与沸石复合的材料,经300℃热处理2h,对甲基橙溶液的降解效能最高。     

铁酸铜复合氧化物的制备及紫外光催化

采用一种新型燃烧剂抗坏血酸,燃烧法快速制备铁酸铜的复合氧化物。经XRD考察硝酸铁和硝酸铜摩尔比对复合氧化物的影响,采用电镜、BET、紫外光对复合氧化物进行表征。以罗丹明B为目标降解物对铁酸铜复合氧化物进行光催化研究,考察了催化剂用量、溶液酸度、双氧水用量、复合氧化物类型对光催化效果的影响。结果表明,复合氧化物最佳光催化条件为催化剂加入量为0.4g/L,pH值为9,双氧水的用量为5mL/L,硝酸铜、硝酸铁和抗坏血酸摩尔比为2∶3∶1;铁酸铜复合氧化物在紫外光下光催化效果最佳,同时复合氧化物也是较好的脱色剂。     

锌、钴氧化物及复合氧化物光催化降解活性染料的研究

研究了柠檬酸法制备的ZnO和Co3O4的单一氧化物,物理、简单化学复合氧化物和尖晶石型ZnCo2O4的光催化性能,及不同煅烧温度下ZnCo2O4的光催化活性.结果表明,催化活性顺序为物理复合氧化物＞简单化学复合氧化物＞单一氧化物＞尖晶石型复合氧化物.150 mg物理复合氧化物对20 mg/L染料的光催化降解效率可达100%.     

半导体复合材料光催化还原CO2的研究进展

光催化还原CO₂是实现碳循环的一种绿色的、环保的能源转化方式,该方法可以有效的将CO₂气体转化为可再生燃料,缓解能源危机和全球变暖问题。综述了半导体复合材料光催化还原CO₂为可再生碳氢燃料的研究进展,介绍了光催化还原CO₂的反应条件和光催化机理,并对已报道的不同类型半导体复合光催化材料进行分类,如“单一半导体型”、“金属/非金属掺杂半导体型”、“半导体复合型”和“碳材料–半导体复合型”。评述了各种半导体复合光催化材料的优缺点及其光催化性能的影响因素。在此基础上,进一步展望了半导体复合光催化材料催化还原CO₂的发展前景。     

二氧化硅改性二氧化钛光催化活性研究进展

二氧化钛是有代表性的一种n型半导体氧化物，其具有稳定性好、光催化效率高和不产生二次污染等特点，在很多方面有着广阔的应用前景。二氧化硅改性后的二氧化钛具有粒径小、比表面积大、吸附能力强、提高光催化效果等特点。介绍了二氧化硅改性二氧化钛的机理、制备方法以及其光催化效果。根据二氧化钛和二氧化硅的结合方式，分别从复合半导体、二氧化硅作负载、二氧化钛表面包覆二氧化硅等几方面进行总结。     

纳米氧化锌光催化剂的制备及应用

综述了纳米金属氧化锌材料半导体光催化剂的化学结构和应用性能的一些相关技术研究进展,包括影响纳米氧化锌半导体材料光催化化学结构和应用性能的一系列重要因素,如氧化锌的形貌、尺寸大小、离子掺杂、半导体复合等以及纳米氧化锌与纳米氧化锌和氧化锌复合材料的制备与应用。氧化锌作为一种宽禁频射带的新型半导体材料,具有良好的电学、光学和电子催化性能,是一种具有广阔发展空间的新型光催化材料。     

BiOI基复合光催化材料的研究进展

因其特殊的层状结构和合适的禁带宽度,BiOI显示出了优异的可见光光催化性能。通过半导体的复合制备BiOI基复合光催化材料来提高BiOI的光催化活性是当前BiOI光催化研究的主流。本文主要综述了BiOI基复合光催化材料的制备方法、结构、形貌以及光催化活性和机理的最新研究进展,并展望了其发展趋势。     

Electrochemical investigation of copper oxide films formed by oxygen plasma treatment

Linear potential sweep voltammetry was used to characterize the copper oxides grown on a metal substrate when exposed to a low pressure inductively coupled oxygen plasma. This study confirms the formation of a precursor oxide CuxO (x > 4), two copper(i) oxides Cu2-xO and Cu3O2 and copper(ii) oxide CuO. The electrochemical reduction curve of CuxO is characterized in aqueous solution (pH 9.2) by a minor peak near –0.5V vs SCE while the two Cu(i) oxides present one reduction peak at –0.8 VvsSCE and cannot be electrochemically separated; CuO is reduced to Cu(i) at –0.65V vs SCE. The reduction potentials of the copper(i) and copper(ii) oxides vary with the oxide layer thickness which increases with the time of exposure to the plasma and the injected electric power and decreases as the distance between the sample and the 1st coil increases for given treatment parameters. In addition, a mechanism is proposed for the reduction of thin films containing the copper(i) and copper(ii) oxides formed after plasma treatment.     

Hierarchical Assembly of Multifunctional Oxide-based Composite Nanostructures for Energy and Environmental Applications

Composite nanoarchitectures represent a class of nanostructured entities that integrates various dissimilar nanoscale building blocks including nanoparticles, nanowires, and nanofilms toward realizing multifunctional characteristics. A broad array of composite nanoarchitectures can be designed and fabricated, involving generic materials such as metal, ceramics, and polymers in nanoscale form. In this review, we will highlight the latest progress on composite nanostructures in our research group, particularly on various metal oxides including binary semiconductors, ABO(3)-type perovskites, A(2)BO(4) spinels and quaternary dielectric hydroxyl metal oxides (AB(OH)(6)) with diverse application potential. Through a generic template strategy in conjunction with various synthetic approaches- such as hydrothermal decomposition, colloidal deposition, physical sputtering, thermal decomposition and thermal oxidation, semiconductor oxide alloy nanowires, metal oxide/perovskite (spinel) composite nanowires, stannate based nanocompostes, as well as semiconductor heterojunction-arrays and networks have been self-assembled in large scale and are being developed as promising classes of composite nanoarchitectures, which may open a new array of advanced nanotechnologies in solid state lighting, solar absorption, photocatalysis and battery, auto-emission control, and chemical sensing.     

Cu-Mn氧化物催化N_2O直接分解性能

分别以Cu(NO_3)_2·3H_2O和50%Mn(NO_3)_2水溶液为铜源和锰源,K_2CO_3为沉淀剂,采用沉淀法和共沉淀法制备单一Cu、Mn氧化物催化剂和Cu-Mn-O复合氧化物催化剂,用于催化N_2O直接分解反应,并利用N_2物理吸附-脱附、XRD、FT-IR和TPR等进行表征。结果表明,单一Cu和Mn氧化物分别以体相CuO和Mn2O_3物相形式存在,Cu-Mn-O复合氧化物中除形成CuMn_2O_4尖晶石物相外,还有一定量小晶粒CuO,较单一氧化物具有更加优异的还原性能,表现出较高的催化N_2O直接分解活性。在空速10 000 h~(-1)和N_2O体积分数0.1%条件下,Cu-Mn-O复合氧化物催化剂可在440℃催化N_2O完全分解,分别较单一Cu和Mn氧化物催化剂降低了40℃和60℃。     

Removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound

ABSTRACT

Cu(II) is an important and typical heavy metal ion in the wastewater containing Cr(VI), and its removal during Cr(VI) reduction by zero valent iron (ZVI) may make it separately be recovered as a kind of copper resource. In this study, the removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound was investigated by atomic absorption spectrometry (AAS), X-ray powder diffractometer (XRD), scanning electron microscope-energy dispersion spectrum (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The AAS tests indicated that the ultrasound could not only obviously enhance the removal of Cu(II) but also improve the reduction rate of Cr(VI). The XRD and SEM-EDS analyses showed that Cu(II) in the solution was reduced to metallic copper and then was deposited at the surface of ZVI. The ultrasound could remove the Fe-Cr oxides and hydroxides at the ZVI surfaces, resulting in the active surfaces of iron increased. The XPS analyses demonstrated that the surface of metallic copper would be transformed into the film of copper oxide (CuO) in the ultrasound system. The obtained metallic copper and copper oxide could be recovered alone by traditional method of the acid pickling.     

Characterization of copper oxidation by linear potential sweep voltammetry and UV-Visible-NIR diffuse reflectance spectroscopy

The aim of this study was to characterize the compounds grown on copper during oxidation at low temperature (T<573 K) in air by electrochemical and optical methods. The following oxides have been characterized: a precursor Cu _x O of mixed valency character, a non stoichiometric cuprous oxide, CuO and its precursor. The mechanism of reduction has been established for layers containing CuO and a non stoichiometric copper(I) oxide. CuO is reduced before cuprous oxide. In complicated cases, it is impossible to draw conclusions from the characteristics of the electrochemical reduction (the first step of CuO reduction and the reduction of Cu(I) species specific of the non-stoichiometry are observed at the same potential). Nevertheless, the association of a non-destructive technique such as diffuse reflectance spectroscopy and electrochemical methods allows identification of the different species present in corrosion layers on copper surfaces.     

Simultaneous Gas Storage and Catalytic Gas Production Using Zeolites—A New Concept for Extending Lifetime Gas Delivery

Copper containing MCM-41 materials can be used to both store gaseous nitric oxide and to catalytically produce nitric oxide from nitrite. The active species for the reaction is copper (I). Addition of cysteine to the solution in contact with the material has different effects depending on how much Cu(I) is present. This is a new method of extending the lifetime of gas delivery from a gas storage material.     

Cobalt and Copper Composite Oxides as Efficient Catalysts for Preferential Oxidation of CO in H2-Rich Stream

A series of Co–Cu composite oxides with different Co/Cu atomic ratios were prepared by a co-precipitation method. XRD, N₂ sorption, TEM, XPS, H₂-TPR, CO-TPR, CO-TPD and O₂-TPD were used to characterize the structure and redox properties of the composite oxides. Only spinel structure of Co₃O₄ phase was confirmed for the Co–Cu composite oxides with Co/Cu ratios of 4/1 and 2/1, but the particle sizes of these composite oxides decreased evidently compared with Co₃O₄. These composite oxides could be reduced at lower temperatures than Co₃O₄ by either H₂ or CO. CO and O₂ adsorption amounts over the composite oxides were significantly higher than those over Co₃O₄. These results indicated a strong interaction between cobalt and copper species in the composite samples, possibly suggesting the formation of Cu _x Co_3?x O₄ solid solution. For the preferential oxidation of CO in a H₂-rich stream, the Co–Cu composite oxides (Co/Cu = 4/1–1/1) showed distinctly higher catalytic activities than both Co₃O₄ and CuO, and the formation of Cu _x Co_3?x O₄ solid solution was proposed to contribute to the high catalytic activity of the composite catalysts. The Co–Cu composite oxide was found to exhibit higher catalytic activity than several other Co₃O₄-based binary oxides including Co–Ce, Co–Ni, Co–Fe and Co–Zn oxides.     

NO decomposition and reduction by C3H6 over transition metal oxides supported on MgF2

The monooxides copper, manganese, molybdenum and chromium catalysts supported on MgF₂ were tested in NO decomposition and reduction by propene. The effect of the oxides content, time on stream and O₂ concentration in reaction mixture during NO reduction on their catalytic activity was investigated. All the catalysts showed the optimum active phase concentration corresponding to 2–4 wt.% of the metal. For the best copper catalyst an effect of introduction of another oxide (manganese or chromium oxide) on the catalytic performance was studied. The double copper-manganese oxide sample containing 2 wt.% Cu and 4 wt.% Mn was proved to ensure the best catalytic performance.     

Recyclable Carbon Supported Copper‐Manganese Oxide for Selective Aerobic Oxidation of Alcohols in Combination with 2,2,6,6‐Tetramethylpiperidyl‐1‐oxyl under Neutral Condition

Due to the promotion of the surface area and the dispersion of active components upon supporting mixed metal oxides on the porous material active carbon, the copper‐manganese oxide on carbon system has been proven to be much more efficient than the co‐precipitation prepared Cu‐Mn oxide in mediating the 2,2,6,6‐tetramethylpiperidyl‐1‐oxyl (TEMPO)‐catalyzed aerobic oxidation of alcohols. Even at 30 °C and with a 0.1 mol% load of TEMPO, the oxidations proceeded smoothly. Upon catalysis with the Cu‐Mn oxide/C (10 wt%) and TEMPO (0.5–5 mol%), various alcohols were oxidized selectively to the corresponding aldehydes or ketones with molecular oxygen at 80 °C. Such a stable, recyclable heterogeneous cocatalyst permits alcohols to be oxidized under neutral and mild conditions.     

Production of nanoparticles of copper compounds by anodic dissolution of copper in organic solvents

The anodic behaviour of copper was investigated in ethanol solution containing LiClO₄, LiCl electrolyte and water. The type of electrolyte and the water content influences the mechanism of the anodic process and the formation of anodic products. In LiClO₄ electrolyte the dissolution of copper is related to the oxidation of Cu(I) to Cu(II). In solutions of LiCl the etching of copper begins with the creation of soluble complexes of Cu(I) with chloride ions and solvent molecules. At potentials above 0.4 V the formation of alkoxides was observed in both solutions, characterized by a yellow tint. On the other hand, above 0.8 V (i.e. above the equilibrium potential of alcohol oxidation) copper dissolution is accompanied by the formation of a blue colloidal suspension of Cu (II) copper salt. Anodic etching of copper in solutions containing 3% H₂O at potentials higher than 0.4 V leads to the formation of colloidal suspension of copper oxide nanoparticles.