Zn掺杂CuO/CuAl<sub>2</sub>O<sub>4</sub>复合空心球的制备及光催化性能

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李小艳, 阎建辉, 张丽, 周民杰, 刘又年. Zn掺杂CuO/CuAl₂O₄复合空心球的制备及光催化性能 . 无机材料学报, 2014, 29(10): 1055-1060
LI Xiao-Yan, YAN Jian-Hui, ZHANG Li, ZHOU Ming-Jie, LIU You-Nian. Preparation and Photocatalytic Properties of Hollow Spheres-like Zn-doped CuO/CuAl₂O₄ Composite Photocatalysts . Journal of Inorganic Materials, 2014, 29(10): 1055-1060 复制到剪切板

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Zn掺杂CuO/CuAl₂O₄复合空心球的制备及光催化性能

李小艳^1,², 阎建辉^1,², 张丽^1,², 周民杰², 刘又年¹

1. 中南大学化学化工学院, 长沙410083

2. 湖南理工学院化学化工学院, 岳阳 414006

通讯作者: 刘又年, 教授. E-mail:liuyounian@csu.edu.cn; 阎建辉, 教授. E-mail:yanjh58@163.com

作者简介: 李小艳(1989-), 女, 硕士研究生. E-mail:yuyicaocao@163.com

基金:国家自然科学基金(21276285,21271071);

摘要

以葡萄糖为模板, 硝酸锌、硝酸铜和硝酸铝为原料, 采用水热法制备高比表面Zn-CuO/CuAl₂O₄复合空心球。采用XRD、SEM、HRTEM、BET、DRS和PL等手段对样品进行表征, 结果表明: 在600℃下焙烧的Zn-CuO/CuAl₂O₄复合物呈空心球状, 球体直径约为2 μm, 比表面积高达214.97 m²/g。引入Zn有助于提高样品对紫外和可见光的吸收能力, 减少光生电子空穴对的复合, 光催化活性显著提高。在模拟太阳光照下, 以甲基橙溶液为目标降解物, 考察样品的煅烧温度和Zn加入量对光催化活性的影响。当Zn加入量为0.5wt%, 煅烧温度为600℃时, 样品的光催化活性最佳。光照60 min, 0.5 g/L光催化剂用量对25 mg/L甲基橙溶液的脱色率高达97%。

关键词: Zn-CuO/CuAl2O4; 空心球; 水热法; 光催化; 降解

中图分类号:O614 文献标志码:A 文章编号:1000-324X(2014)10-1055-06

Preparation and Photocatalytic Properties of Hollow Spheres-like Zn-doped CuO/CuAl₂O₄ Composite Photocatalysts

LI Xiao-Yan^1,², YAN Jian-Hui^1,², ZHANG Li^1,², ZHOU Ming-Jie², LIU You-Nian¹

1. College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China

2. School of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang 414006, China

Fund:National Natural Science Foundation of China (21276285,21271071);

Abstract

Zn-doped CuO/CuAl₂O₄composite hollow spheres with high specific surface area were synthesized by hydrothermal method, using glucose as template and Zn(NO₃)₂·6H₂O, Cu(NO₃)₂·3H₂O, Al(NO₃)₃·9H₂O as raw materials. The samples were characterized by XRD, SEM, HRTEM, BET, DRS and PL spectra. The results showed that Zn- doped CuO/CuAl₂O₄ composites possessed hollow microspheres shape with specific surface area up to 214.97 m²/g and diameter of about 2 μm after calcined at 600℃. The Zn doped photocatalysts exhibited enhanced absorption intensity, decreased electron-hole recombination. Further photocatalytic activities of the samples were greatly increased. The influences of calcination temperature and Zn doping content on photocatalytic activities of the samples were investigated by measuring the degradation rate of methyl orange (MO) under simulated sunlight irradiation. The sample doped with 0.5wt% Zn which was calcined at 600℃ showed the highest efficiency. Under visible light irradiation for 60 min, the decolorizing efficiency of 25 mg/L MO by 0.5 g/L photocatalyst reached 97%.

Keyword: Zn-CuO/CuAl2O4; hollow sphere; hydrothermal process; photocatalysis; degradation

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尖晶石型复合物是一类重要的功能材料, 具有熔点高、硬度高、热稳定性好和耐腐蚀性等特点, 在催化、陶瓷、染料和传感等领域具有广泛应用^{[ 1, 2, 3]}。而尖晶石结构的CuAl₂O₄制备简单, 无毒, 原材料丰富, 禁带宽度小(1.92 eV), 无光腐蚀, 在紫外和可见光下具有一定的光催化活性, 是一种具有潜在应用价值的光催化剂。目前国内外对于CuAl₂O₄光催化性能的研究比较少, Naderi等^{[ 4]}以柠檬酸溶胶-凝胶法制备CuAl₂O₄纳米颗粒, 研究合成条件对光催化性能的影响; Edrisi等^{[ 5]}采用均相沉淀法制备CuAl₂O₄, 并探究CuAl₂O₄的最佳制备条件; Liang等^{[ 6]}研究铜原料、煅烧温度对NH₃-SCO反应的影响。近年来, 金属掺杂和半导体复合成为光催化领域的研究热点。相比单一的半导体结构, 金属掺杂能在接近导价带位置产生深(或浅)的杂质能级, 提高宽带隙半导体在可见光范围的响应^{[ 7]}。而复合光催化剂能形成过渡带隙, 降低带隙能, 抑制光生电子-空穴对的复合, 延长光生载流子寿命, 提高光催化活性^{[ 8, 9, 10, 11]}。本工作采用Cu、Al、Zn的硝酸盐作为原料, 以葡萄糖为模板, 制备出空心球状的Zn-CuO/CuAl₂O₄复合光催化剂。以光催化降解甲基橙来评价其光催化活性, 研究煅烧温度和Zn加入量对样品结构和光催化性能的影响。

1 实验方法

1.1 光催化剂的制备

Zn微球的制备: 15 g 葡萄糖、4.48 g 硝酸锌分别溶于120 mL蒸馏水, 在剧烈搅拌下缓慢滴加25%的氨水, 调至pH为6, 继续搅拌10 min, 转入200 mL 的聚四氟乙烯高压反应釜中, 180℃下保温24 h, 得到黑色沉淀物并进行抽滤, 用去离子水和乙醇多次洗涤, 真空干燥后即得微球。

Zn-CuO/CuAl₂O₄空心球的制备: 称取一定量的Zn微球分散于100 mL去离子水中, 加入1.208 g硝酸铜、3.75 g 硝酸铝、0.09 g PEG(聚乙二醇), 超声30 min, 在搅拌过程中缓慢滴加25%的氨水调至pH为8, 超声30 min, 然后在室温下搅拌5 h, 将产物进行抽滤, 沉淀物用去离子水和乙醇多次洗涤, 真空干燥得到的前驱体研磨成粉末, 置于马弗炉中经不同温度煅烧4 h, 即得不同质量百分比的Zn-CuO/ CuAl₂O₄复合光催化剂, 记为 A% Zn-CuO/CuAl₂O₄。

1.2 光催化剂的表征

采用日本理学Rigaku D/max 2550 VB/PC X射线衍射仪(Cu Kα线, 管压40 kV, 管流300 mA, 扫描范围2 θ为10°~90°, 扫描速度为10.00°/min)对催化剂的晶相结构进行分析。采用场发射Nova NanoSEM230型扫描电子显微镜和Tecnai G20ST型高分辨率电子显微镜对样品形貌和结构进行分析。采用BET比表面测试仪(ASAP2020, 美国麦克仪器公司)测定样品的比表面积及孔结构大小。采用日立U-3010紫外可见分光光度计进行紫外-可见漫反射光谱(DRS)分析样品光吸收性能。用EQCM LS-55荧光分光光度计分析样品的光致发光图谱。

1.3 光催化性能的测定

在自制的二圆筒状石英光反应器中进行降解实验, 采用150 W 氙灯为光源, 外部使用外循环水和排气双重冷却系统。在500 mL、25 mg/L 的甲基橙溶液中, 加入0.25 g 光催化剂, 在密闭的暗室搅拌吸附10 min 后, 打开氙灯, 每隔10 min 取样, 高速离心分离取其上层清液, 用紫外-可见分光光度计在波长465 nm 处测定甲基橙的吸光度( A), 换算为相关浓度。

2 结果与讨论

2.1 XRD分析

图1为0.5wt% Zn加入量的样品分别在500、600、700、800、900℃煅烧4 h后的XRD图谱。由图1可知, 随着煅烧温度的升高, 产物由过渡相CuO向CuAl₂O₄发生转变。500℃煅烧, 产物主要为CuO, 样品峰与标准图谱中CuO相(JCPDS 78-0428)匹配, 其中2 θ=35.49°、38.96°处的衍射峰分别对应于CuO相的(002)、(200)晶面。600~700℃煅烧, 产物由CuO和CuAl₂O₄两相组成。煅烧温度继续上升, CuO相基本消失, 晶形完整, 晶体结晶度高, 样品峰与标准图谱中CuAl₂O₄相(JCPDS 78-1605)匹配, 其中2 θ=31.29°、36.87°、44.86°、55.69°、59.42°、65.29°分别对应于CuAl₂O₄相的(220)、(311)、(400)、(422)、(511)、(440)晶面。

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	图1 不同温度煅烧0.5wt% Zn-CuO/CuAl₂O₄样品的XRD图谱Fig. 1 XRD patterns of 0.5wt% Zn-CuO/CuAl₂O₄ samples calcined at different temperatures

图2为煅烧温度为600℃, 不同Zn加入量样品的XRD图谱。由图2可知, Zn的引入并没有破坏样品原有的晶体结构, 产物中除了大量CuO外, 还存在少量的CuAl₂O₄。图1和图2中均未出现ZnO的特征衍射峰, 可能是因为少量掺杂的Zn已高度分散于晶格中, 使ZnO含量低于XRD检测下限。为了检测样品中是否含有Zn元素以及元素掺杂均匀性问题, 对1wt% Zn-CuO/CuAl₂O₄样品的两个区域分别进行EDS元素含量分析, 其数据结果列于表1。由表1可知, 样品中除了Cu、Al和O主要元素外, 还含有原子比为0.38%的Zn元素, 对应的质量比为0.94%, 且两区域内各元素原子、质量百分比都比较接近, 表明Zn元素掺杂成功, 并且样品中各元素分布较均匀。

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	图2 600℃煅烧Zn掺杂CuO/CuAl₂O₄样品的XRD图谱Fig. 2 XRD patterns of Zn-doped CuO/CuAl₂O₄samples calcined at 600℃(a) 0wt% Zn-CuO/CuAl₂O₄; (b) 0.5wt% Zn-CuO/CuAl₂O₄; (c) 1wt% Zn- CuO/CuAl₂O₄; (d) 2wt% Zn-CuO/CuAl₂O₄

表1 1wt% Zn-CuO/CuAl₂O₄样品的EDS分析结果 Table 1 EDS analyses of 1wt% Zn-CuO/CuAl₂O₄ samples

2.2 形貌分析

图3为不同样品的SEM和HRTEM照片。由图3(a, b)可知, Zn微球表面光滑, 球径主要分布在7~ 8 μm, 球量多而均匀。图3(a)插图为Zn微球的EDS分析, 结果显示, Zn微球主要由C、O以及少量的Zn元素组成(其中Au元素是由样品喷金处理而引入的)。图3(c)为Zn微球在500℃下煅烧所得样品的SEM照片, 由图可知, 微球煅烧后得到ZnO球体, 表明微球中含有Zn元素, 这与图3(a)分析结果一致。图3(d, e)为0.5wt% Zn-CuO/CuAl₂O₄样品的SEM照片, 由图可知, 空心球表面粗糙, 内部存在明显的中空结构, 反应过程中由于柯肯达尔效应^{[ 12, 13]}, 产物的直径减少到2 μm 左右。空心球的球壁由许多小颗粒组合而成, 小颗粒的尺寸大约在30 nm。图3(f)为0.5wt% Zn-CuO/CuAl₂O₄样品的HRTEM照片, 由图可知, CuO和CuAl₂O₄之间存在清晰的异质结结构, 表明样品由CuO和CuAl₂O₄复合而成, 这与XRD的检验结果相吻合。CuAl₂O₄的 d₍₃₁₁₎、 d₍₂₂₀₎值分别为0.2541、0.2865 nm, 而未掺杂CuAl₂O₄的 d₍₃₁₁₎、 d₍₂₂₀₎值分别为2.4360、2.8560 nm。可见, Zn掺杂CuAl₂O₄的晶面间距增大, 这是由于Zn²⁺(0.074 nm)进入四面体部分代替Cu²⁺(0.072 nm)而引起。

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	图3 Zn微球(a, b), 500℃煅烧Zn微球(c)和0.5wt% Zn-CuO/CuAl₂O₄样品(d, e)的SEM照片, 0.5wt% Zn-CuO/CuAl₂O₄样品(f)的HRTEM照片Fig. 3 SEM images of Zn microspheres (a, b), Zn microspheres calcined at 500℃(c), 0.5wt% Zn-CuO/CuAl₂O₄ samples (d, e) andHRTEM images of 0.5wt% Zn-CuO/CuAl₂O₄ samples (f)

2.3 BET比表面积及孔结构分析

当煅烧温度为600℃时, 不同Zn加入量样品的比表面积和孔结构参数列于表2。由表2可知, 随着Zn加入量的增加, 样品比表面积和孔体积先增大后减小, 说明少量引入Zn可以促进CuO/CuAl₂O₄样品的分散, 当Zn加入量为0.5 wt%时, 产物的比表面积和孔体积最大, 分别为214.97 m²/g和0.71 cm³/g。图4为Zn掺杂CuO/CuAl₂O₄样品的N₂吸附-脱附等温线及孔径分布图。根据BDDT分类, 图4(A)吸附等温线属于Ⅳ类、H₂滞后环, 表明Zn-CuO/CuAl₂O₄复合空心球上存在孔结构^{[ 14, 15]}。曲线a、b、c、d在低压和相对较高压力(0.8< p/ p₀<1.0)范围内均具有一定的吸附性, 可见滞后环不仅与初级粒子之间聚合形成的小孔有关, 也与次级粒子之间聚合形成的大孔有关^{[ 16, 17, 18]}。这一点可以通过图3(d, e)证实。随着Zn加入量的增大, 孔径的大小发生明显变化, 当Zn加入量为0.5wt%时, 曲线b的平均孔径为9.2 nm, 高于其他加入量的孔径, 这可能与复合空心球的中空内部结构有关。

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	图4 Zn掺杂CuO/CuAl₂O₄样品的(a)N₂吸附-脱附等温线和(b)孔径分布图Fig. 4 (A) N₂ adsorption-desorption isotherms and (B) pore size distribution curves of Zn-doped CuO/CuAl₂O₄ samples(a) 0wt% Zn-CuO/CuAl₂O₄; (b) 0.5wt% Zn-CuO/CuAl₂O₄; (c) 1wt% Zn-CuO/CuAl₂O₄; (d) 2wt% Zn-CuO/CuAl₂O₄

2.4 UV-Vis DRS分析

图5为Zn掺杂CuO/CuAl₂O₄样品在600℃煅烧下的紫外-可见漫反射光谱, 由图可以看出, 当Zn加入量为0.5wt%时, 样品的光吸收性能最大, 掺杂后的样品在紫外和可见光范围内的光吸收能力大大增加, 并伴随着紫外可见吸收边带的红移, 这可能是由于Zn掺杂引入了杂质能级, 使得带隙能降低, 因而可见光利用率高。此外, 随着Zn加入量的增大, 样品颜色由抹茶绿-墨绿-灰绿发生变化。CuO/CuAl₂O₄样品在400~800 nm处也具有一定的吸收能力, 表明CuO/CuAl₂O₄本身具有一定的可见光吸收性能。根据公式 E_g =1240 /λ_g可以估算产物的禁带宽度, E_g表示能带宽度(单位: eV), λ_g表示半导体材料吸收边界延长线与横轴交点处的波长值(单位: nm)。如图5所示, 可以估算0.5wt% Zn-CuO/CuAl₂O₄复合物的禁带宽度为1.55 eV, 小于CuAl₂O₄(1.92 eV)的禁带宽度。

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	图5 Zn掺杂CuO/CuAl₂O₄样品的UV-Vis DRS图谱Fig. 5 UV-Vis DRS spectra of Zn-doped CuO/CuAl₂O₄ samples(a) 0wt% Zn-CuO/CuAl₂O₄; (b) 0.5wt% Zn-CuO/CuAl₂O₄; (c) 1wt% Zn-CuO/CuAl₂O₄ calcined at 600℃

表2 Zn掺杂CuO/CuAl₂O₄样品的物理性质 Table 2 Physical property of Zn-doped CuO/CuAl₂O₄ samples

2.5 PL光谱分析

图6为0wt% Zn-CuO/CuAl₂O₄和0.5wt% Zn-CuO/ CuAl₂O₄样品的PL图谱, 激发波长为233 nm。通常光致发光光谱是由光生电子空穴对的复合而产生^{[ 19]}。从图6可以看出, 引入Zn并没有引发新的发光现象, 掺杂Zn后, CuO/CuAl₂O₄光谱强度明显减弱, 表明Zn掺杂可以抑制电子和空穴的复合。因此在光催化降解中0.5wt% Zn-CuO/CuAl₂O₄有可能会表现出更好的光催化活性。

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	图6 0wt% Zn-CuO/CuAl₂O₄和0.5wt% Zn-CuO/CuAl₂O₄样品的光致发光图谱Fig. 6 PL spectra of 0wt% Zn-CuO/CuAl₂O₄ and 0.5wt% Zn- CuO/CuAl₂O₄ samples

2.6 光催化活性的评价

2.6.1 煅烧温度的影响

图7为经500、600、700、800、900℃煅烧后0.5wt% Zn-CuO/CuAl₂O₄样品对甲基橙溶液的降解效果。由图7可知, 煅烧温度由500℃升高到600℃, 光催化活性显著增强, 600℃煅烧样品的光催化活性最高, 继续升高煅烧温度, 样品的光催化活性反而降低。由XRD图谱(图1)可知, 500℃煅烧, 样品中只有CuO相生成, 衍射峰弥散, 晶体发育不完整。随着煅烧温度的升高, 产物的组成成分和粒径大小均发生很大变化, CuO相衍射峰逐渐减小, CuAl₂O₄相衍射峰逐渐增大, 在600、700℃煅烧产物为CuO/ CuAl₂O₄复合物。继续升高温度, CuO相消失, 产物主要为CuAl₂O₄, 并且晶粒尺寸增大, 光催化活性减小。样品经600℃煅烧的活性最高, 此时达到最佳CuO/ CuAl₂O₄复合比例。

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	图7 煅烧温度对0.5wt% Zn-CuO/CuAl₂O₄样品降解甲基橙的影响Fig. 7 Effect of calcination temperatures on methyl orange degradation of 0.5wt% Zn-CuO/CuAl₂O₄ samples(a) 500℃; (b) 600℃; (c) 700℃; (d) 800℃; (e) 900℃

2.6.2 Zn加入量的影响

图8为经600℃煅烧后不同Zn加入量的样品对甲基橙溶液的降解效果。0wt% Zn-CuO/CuAl₂O₄、0.3wt% Zn-CuO/CuAl₂O₄、0.5wt% Zn-CuO/CuAl₂O₄、1wt% Zn-CuO/CuAl₂O₄、2wt% Zn-CuO/CuAl₂O₄样品对应的降解率依次为78%、90%、97%、76%、60%。随着Zn加入量的增加, 样品的光催化活性先增大后减小。这是由于随着Zn加入量的增加, 样品所对应的比表面积先增大后减小, 当Zn加入量为0.5wt%时, 样品的比表面积和孔体积最大。比表面积越大, 提供的活性位点越多, 更有利于反应物的吸附和内部电荷的转移, 因而催化效果越好^{[ 20, 21]}。

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	图 8 Zn加入量对CuO/CuAl₂O₄样品降解甲基橙的影响Fig. 8 Effect of Zn doped content on methyl orange degradation of Zn-CuO/CuAl₂O₄samples(a) 0wt% Zn-CuO/CuAl₂O₄; (b) 0.3wt% Zn-CuO/CuAl₂O₄; (c) 0.5wt% Zn-CuO/CuAl₂O₄; (d) 1wt% Zn-CuO/CuAl₂O₄; (e) 2wt% Zn-CuO/ CuAl₂O₄ calcined at 600℃

3 结论

1) 煅烧温度对样品的晶体结构有较大影响。随着温度的升高, CuO相衍射峰逐渐减小, CuAl₂O₄相衍射峰逐渐增强, 600~700℃煅烧产物为CuO和CuAl₂O₄复合物, 煅烧温度继续升高, 产物主要为CuAl₂O₄相。

2) 引入Zn不改变样品原有的晶体结构, 随着Zn加入量的增加, 样品的比表面积先增大后减小, 当Zn加入量为0.5wt%时, 样品比表面积最大, 为214.97 cm²/g; Zn掺杂CuO/CuAl₂O₄样品在紫外和可见光区域的光吸收性能显著提高, 光致发光强度减弱, 表明光生电子-空穴对复合几率降低, 因而光催化活性有所提高。

3) 当煅烧温度为600℃, Zn加入量为0.5wt%时, 样品的光催化活性最高, 在模拟太阳光下照射60 min, 0.5 g/L催化剂用量对浓度为25 mg/L的甲基橙溶液的脱色率达到97%。

参考文献

View Option

[1]	LI F H, LIN H, LI J F, et al. Influence of LiF on the infrared transmissivity of magnesia alumina spinel transparent ceramics. Journal of Inorganic Materials, 2012, 27(4): 417-421. [本文引用:1] [JCR: 0.531] [CJCR: 1.106]
[2]	TORKIAN L, AMINI M M, BAHRAMI Z. Synthesis of nano crystalline MgAl₂O₄ spinel powder by microwave assisted combustion. Journal of Inorganic Materials, 2011, 26(5): 550-554. [本文引用:1] [JCR: 0.531] [CJCR: 1.106]
[3]	BAYAL N, JEEVANANDAM P. Synthesis of metal aluminate nanoparticles by Sol-Gel method and studies on their reactivity. J. Alloys Compd. , 2012, 516: 27-32. [本文引用:1] [JCR: 2.39]
[4]	NADERI M, SHAMIRIAN A, EDRISI M. Synthesis, characterization and photocatalytic properties of nanoparticles CuAl₂O₄ by pechini method using taguchi statistical design. J. Sol-Gel Sci. Technol. , 2011, 58(2): 557-563. [本文引用:1]
[5]	EDRISI M, TAJIK S, SOLEYMANI M. Synthesis of CuAl₂O₄ nanoparticles by mixed chelates thermolysis and homogeneous precipitation using solubility difference reactions; taguchi optimization and photocatalytic application. Journal of Materials Science: Materials in Electronics, 2013, 24(10): 3914-3920. [本文引用:1] [JCR: 1.486]
[6]	LIANG C X, LI X Y, QU Z P, et al. The role of copper species on Cu/γ-Al₂O₃ catalysts for NH₃-SCO reaction. Applied Surface Science, 2012, 258(8): 3738-3743. [本文引用:1] [JCR: 2.112]
[7]	SHANG H X, TIAN Y, WANG X T, et al. Photocatalytic H₂ evolution from glycerol solution over Bi³+-doped TiO₂ nanoparti-cles. Journal of Inorganic Materials, 2012, 27(12): 1283-1288. [本文引用:1] [JCR: 0.531] [CJCR: 1.106]
[8]	YIN J, ZANG Y S, YUE C, et al. Ag nanoparticle/ZnO hollow nanosphere arrays: large scale synthesis and surface plasmon resonance effect induced Raman scattering enhancement. J. Mater. Chem. , 2012, 22(16): 7902-7909. [本文引用:1] [JCR: 5.968]
[9]	ZHAO G, LIU S W, LU Q F. Synthesis of TiO₂/Bi₂WO₆ nanofibers with electrospinning technique for photocatalytic methyl blue degradation. J. Sol-Gel Sci. Technol. , 2013, 66(3): 406-412. [本文引用:1]
[10]	LI Z Q, CHEN X T, XUE Z L. Microwave-assisted synthesis and photocatalytic properties of flower-like Bi₂WO₆ and Bi₂O₃-Bi₂WO₆ composite. J. Colloid Interface sci. , 2013, 394: 69-77. [本文引用:1] [JCR: 3.172]
[11]	TIAN G H, CHEN Y J, MENG X Y, et al. Hierarchical composite of Ag/AgBr nanoparticles supported on Bi₂MoO₆ hollow spheres for enhanced visible-light photocatalytic performance. ChemPlusChem, 2013, 78(1): 117-123. [本文引用:1]
[12]	BAO Y, YANG Y Q, MA J Z. Research progress of hollow structural materials prepared via templating method. Journal of Inorganic Materials, 2013, 28(5): 459-468. [本文引用:1] [JCR: 0.531] [CJCR: 1.106]
[13]	ZHAO B, LIN L, CHEN C, et al. Research progress on crystal growth mechanism of titania/titanate nano-powder materials. Journal of Inorganic Materials, 2013, 28(7): 683-690. [本文引用:1] [JCR: 0.531] [CJCR: 1.106]
[14]	MENG H X, WANG B B, LIU S, et al. Hydrothermal preparation, characterization and photocatalytic activity of TiO₂/Fe-TiO₂ composite catalysts. Ceram. Int. , 2013, 39(5): 5785-5793. [本文引用:1] [JCR: 1.789]
[15]	YIN B, WANG J T, XU W, et al. Preparation of TiO₂/mesoporous carbon composites and their photocatalytic performance for methyl orange degradation. New Carbon Materials, 2013, 28(1): 47-54. [本文引用:1] [JCR: 0.981] [CJCR: 1.397]
[16]	ZHANG L, YAN J H, ZHOU M J, et al. Fabrication and photocatalytic properties of spheres-in-spheres ZnO/ZnAl₂O₄ composite hollow microspheres. Appl. Surf. Sci. , 2013, 268: 237-245. [本文引用:1] [JCR: 2.112]
[17]	ZHANG L, YAN J H, ZHOU M J, et al. Preparation and photocatalytic property of hollow sphere-like ZnO/ZnAl₂O₄ composite photocatalysts with high specific surface area. Journal of Inorganic Chemistry, 2012, 28(9): 1827-1834. [本文引用:1]
[18]	LV K, YU J, DENG K, et al. Synergistic effects of hollow structure and surface fluorination on the photocatalytic activity of titania. Journal of Hazardous Materials, 2010, 173(1): 539-543. [本文引用:1] [JCR: 3.925]
[19]	ZHANG Y J, XU Y, LI T, et al. Preparation of ternary Cr₂O₃-SiC-TiO₂ composites for the photocatalytic production of hydrogen. Particuology, 2012, 10(1): 46-50. [本文引用:1] [JCR: 1.419] [CJCR: 0.4971]
[20]	DONG F, SUN Y J, FU M, et al. Room temperature synthesis and highly enhanced visible light photocatalytic activity of porous BiOI/BiOCl composites nanoplates microflowers. Journal of Hazardous Materials, 2012, 219: 26-34. [本文引用:1] [JCR: 3.925]
[21]	LEE S S, BAI H W, LIU Z Y, et al. Novel-structured electrospun TiO₂/CuO composite nanofibers for high efficient photocatalytic cogeneration of clean water and energy from dye wastewater. Water Research, 2013, 47(12): 4059-4073. [本文引用:1] [JCR: 4.655]

2012

0.531

1.106

Journal of Inorganic Materials. 2012, 27(4):417-421 DOI:10.3724/SP.J.1077.2012.00417

Influence of LiF on the infrared transmissivity of magnesia alumina spinel transparent ceramics

(1. The State Key Lab of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China; 2. Research Institute of Synthetic Crystals, Beijing 100018, China; 3. Bright Crystals Technology, Inc., Beijing 100018, China; 4. Key Laboratory of Ministry of Education for Application Technology of Chemical Materials in Hainan Superior Resources, School of Materials Science and Chemical Engineering, Hainan University, Haikou 570228, China)

The influence of LiF as a sintering aidditive on the infrared transmissivity of magnesia alumina spinel (MgAl 2 O 4 ; spinel, briefly) transparent ceramics was investigated. Spinel powders prepared by Sol-Gel method, were mixed with LiF of 0-2.5wt%, and then ball milled, tested by XRD for their phase compositions. Hot press (HP) or hot press combined with hot isostatic press (HP/HIP) technique was applied to sintering the powder mixtures into spinel ceramics, while HP under 32 MPa at 1550℃, and HIP under 150 MPa at 1700℃. The structures and infrared transmissions of the ceramic bodies were examined by SEM and IR spectrometer, respectively. Li contents in the spinel powder mixtures and in the resulted ceramics were detected by inductively coupled plasma (ICP) technique. The incorporation of LiF in the starting spinel powders facilitates the growth of grains and the expulsion of pores during sintering. And it shows LiF promotes the sintering of spinel ceramics. Spinel ceramics with LiF contents of 1.0wt%-1.5wt% exhibit optimal infrared transmissivity. While excess LiF acts adversly on the optical performances of spinel ceremics due likely to its remnant or derivative in the ceramic bodies.

以溶胶-凝胶法制备镁铝尖晶石(以下简称“尖晶石”)粉末, 掺入0~2.5wt%的LiF, 经球磨后, 测试混合粉末的物相组成. 采用热压(HP; 32 MPa/1550℃)及热压结合热等静压(HP/HIP; 热等静压工艺条件为150 MPa/1700℃)工艺制备出尖晶石透明陶瓷. 分析测试了掺入不同LiF的尖晶石陶瓷的结构和红外透过率, 采用感应耦合等离子体(Inductively Coupled Plasma, 或ICP)方法测定了LiF掺杂后的粉料和透明陶瓷中的Li离子含量. 实验显示, LiF的加入促进了尖晶石晶粒长大和气孔的排除, 并促进了尖晶石陶瓷烧结的致密化进程. 添加1.0wt%~1.5wt% LiF的尖晶石透明陶瓷具有最高的红外透过率. LiF在尖晶石陶瓷中形成残余物质, 添加过量的LiF对尖晶石陶瓷的光学性能会产生不利影响.

... 尖晶石型复合物是一类重要的功能材料, 具有熔点高、硬度高、热稳定性好和耐腐蚀性等特点, 在催化、陶瓷、染料和传感等领域具有广泛应用^[1,2,3] ...

2011

0.531

1.106

Journal of Inorganic Materials. 2011, 26(5):550-554 DOI:10.3724/SP.J.1077.2011.10815

Synthesis of nano crystalline MgAl₂O₄ spinel powder by microwave assisted combustion

(1. Department of Applied Chemistry, Islamic Azad University, South Tehran Branch, Tehran, Iran; 2. Department of Chemistry, Shahid Beheshti University, G.C., Tehran, Iran; 3. School of Chemistry, Collage of Science, University of Tehran, Tehran, Iran)

Stoichiometric MgAl 2 O 4 spinel nanoparticles were synthesized by microwave assisted combustion reaction from aluminium nitrate nanohydrate (Al(NO 3 )3·9H 2 O) and Sol-Gel prepared magnesium hydroxide (Mg(OH) 2 ) in the presence of urea ((NH 2 ) 2 CO) as a fuel, in about 20 min of irradiation. X-ray diffraction (XRD) studies reveal that microwave assisted combustion synthesis route yields single-phase spinel nanoparticles with larger crystalline size (around 75 nm) than other conventional heating methods. Scanning electronic microscope (SEM) images show nanoparticles with spherical shape and homogenous morphology. The surface area measurements (SBET) show crystals with 2.11 m 2 /g and 0.0033 mL/g pore volume.

2012

2.39

0.0

Journal of Alloys and Compounds. 2012, 516:null-null

Synthesis of metal aluminate nanoparticles by Sol-Gel method and studies on their reactivity

2011

0.0

Journal of Sol-Gel Science and Technology. 2011, 58(2):557-563

Synthesis, characterization and photocatalytic properties of nanoparticles CuAl₂O₄ by Pechini method using Taguchi statistical design

Mahnaz Naderi (1) , Armen Shamirian (1) , Mohammad Edrisi (1)

1. Department of chemistry, Amirkabir University of Technology, Hafez Ave, P. O. Box 15875-4413, Tehran, Iran

In the present work nano crystalline copper aluminate (CuAl 2 O 4 ) has been synthesized by the Pechini method using aqueous solutions containing corresponding metal nitrates. A Taguchi L 4 statistical design was employed for investigating the most effective factors on the synthesis conditions and their interactions and production optimization. Nano crystalline CuAl 2 O 4 particles with crystal size between 17 and 26 nm were obtained. The product characterized by XRD, FT-IR, DLS and TGA. The morphological properties have investigated using SEM. The photocatalytic degradation was investigated using methyl orange under the irradiation of visible light.

... 目前国内外对于CuAl₂O₄光催化性能的研究比较少, Naderi等^[4]以柠檬酸溶胶-凝胶法制备CuAl₂O₄纳米颗粒, 研究合成条件对光催化性能的影响 ...

2013

1.486

0.0

Journal of Materials Science: Materials in Electronics. 2013, 24(10):3914-3920 DOI:10.1007/s10854-013-1338-4

Synthesis of CuAl₂O₄ nanoparticles by mixed chelates thermolysis and homogeneous precipitation using solubility difference reactions; taguchi optimization and photocatalytic application

1. Faculty of Chemical Engineering, Amirkabir University of Technology, Hafez Ave, P.O. Box 15875-4413, Tehran, Iran

Abstract In the present study two novel methods are reported for preparation of nano crystalline copper aluminate (CuAl 2 O 4 ).The first one is based on the pyrolysis of mixed Aluminum and Copper chelates of cupferron. The nanoparticles prepared by the first method were spherical with high specific surface area and smaller size in respect to the particles of second method. The nano crystals of CuAl 2 O 4 at optimum conditions were spherical, with average particle size of 15.2 nm. In the second method the CuAl 2 O 4 nano spindles with high purity were synthesized by a novel homogeneous solubility difference reactions using magnesium hydroxide as initial material. The Taguchi L 8 statistical design was employed for procedure optimization of the chelates thermolysis method. The structure and morphological properties of products have been investigated using X-ray diffraction, Thermogravimetric Analysis, scanning electron microscopy, transmission electron microscopy, fourier transform infra-red, Brunauer-Emmett-Teller, Dynamic laser light scattering and elemental micro analysis. The photocatalytic activity of nanocrystalline CuAl 2 O 4 obtained by first procedure was investigated for degradation of crystal violet (C 25 N 3 H 30 Cl) as a model pollutant and UV lamp as energy source. The results revealed that about 98 % degradation of crystal violet could be achieved at 120 min.

... Edrisi等^[5]采用均相沉淀法制备CuAl₂O₄, 并探究CuAl₂O₄的最佳制备条件 ...

2012

2.112

0.0

Applied Surface Science. 2012, 258(8):null-null

The role of copper species on Cu/#cod#x003b3;-Al₂O₃ catalysts for NH₃-SCO reaction

... Liang等^[6]研究铜原料、煅烧温度对NH₃-SCO反应的影响 ...

2012

0.531

1.106

Journal of Inorganic Materials. 2012, 27(12):1283-1288 DOI:10.3724/SP.J.1077.2012.12142

Photocatalytic H₂ evolution from glycerol solution over Bi³+-doped TiO₂ nanoparti-cles

(1. College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China; 2. Tianjin Academy of Environmental Sciences, Tianjin 300191, China)

TiO 2 and Bi 3+ -doped TiO 2 semiconductors were prepared by using Sol-Gel method. Their pore size distribution, crystal structure, surface composition, photo absorption properties and photocatalytic performance for H 2 evolution from glycerol solution were investigated by techniques of N 2 adsorption-desorption, XRD, FT-Raman, SEM, UV-Vis DRS and photocatalytic reaction. The results show that Bi 3+ -doped TiO 2 appears anatase phase nanoparticles with mesoporous structure and has a much smaller crystallite size and much higher BET surface area than bare TiO 2 . These samples exhibit a visible-light absorption capability much higher than bare TiO 2 , which mainly originates from the doping process with the formation of new energy level of Bi 3+ between conduction band and valence band of TiO 2 to reduce the energy gap and the electron–hole recombination rate. The Bi 3+ -doped TiO 2 samples display improved photocatalytic H 2 production from glycerol solution, and 2%Bi-doped TiO 2 shows a maximum H 2 production rate of 3534.8 μmol/(h·gcat) under UV irradiation and 455.7 μmol/(h·gcat) under simulated-solar irradiation, respectively.

采用溶胶–凝胶法制备了TiO 2 和Bi掺杂的TiO 2 纳米颗粒, 用N2吸附-脱附、SEM、XRD、FT-Raman、UV-Vis DRS对光催化材料的孔结构、表面构造、能带结构、吸光特性进行了表征, 并考查了其光催化甘油水溶液制氢反应的活性. 结果表明: Bi掺杂后的TiO 2 为介孔结构的锐钛矿晶型纳米颗粒, 其分散度明显增加, 晶粒变小, 比表面积增大; Bi掺杂使得TiO 2 禁带内形成杂质能级, 降低了禁带能量, 增加了光生电子和空穴的分离效率, 有利于将TiO2的吸光带边界扩展至可见光区; Bi掺杂的TiO 2 样品表现出了远高于纯TiO 2 的光催化甘油水溶液制氢性能, 2mol%Bi掺杂的样品在紫外光和模拟太阳光辐射下表现出了最高产氢活性, 其速率分别为3534.8 μmol/(h·gcat)和 455.7 μmol/(h·gcat).

... 相比单一的半导体结构, 金属掺杂能在接近导价带位置产生深(或浅)的杂质能级, 提高宽带隙半导体在可见光范围的响应^[7] ...

2012

5.968

0.0

... 而复合光催化剂能形成过渡带隙, 降低带隙能, 抑制光生电子-空穴对的复合, 延长光生载流子寿命, 提高光催化活性^[8,9,10,11] ...

2013

0.0

Journal of Sol-Gel Science and Technology. 2013, 66(3):406-412

Synthesis of TiO₂/Bi₂WO₆ nanofibers with electrospinning technique for photocatalytic methyl blue degradation

Gang Zhao (1) , Suwen Liu (1) , Qifang Lu (1) , Fengxiu Xu (1) , Haiyan Sun (2) , Jiaoxian Yu (1)

1. Shandong Provincial Key Laboratory of Processing and Testing Technology of Glass & Functional Ceramics, Jinan, 250353, People’s Republic of China 2. Analytical Center, Shandong Polytechnic University, Jinan, 250353, People’s Republic of China

TiO 2 /Bi 2 WO 6 composite nanofibers have been successfully synthesized by a simple electrospinning process. XRD, SEM, HR-TEM, nitrogen adsorption–desorption isotherms and UV–visible diffuse reflectance spectra were used to characterize the composite nanofibers. The composite fibers with diameters about 100 nm was composed of nanoparticles and possessed of high specific surface area (49.6 m 2 g −1 ) and porous structure. Besides, the TiO 2 /Bi 2 WO 6 composite nanofibers exhibited excellent visible photocatalytic property in the photodegradation of methylene blue (MB), and over 97.2 % of MB was degraded within 5.5 h.

... 而复合光催化剂能形成过渡带隙, 降低带隙能, 抑制光生电子-空穴对的复合, 延长光生载流子寿命, 提高光催化活性^[8,9,10,11] ...

2013

3.172

0.0

Journal of Colloid and Interface Science. 2013, 394:null-null

Microwave-assisted synthesis and photocatalytic properties of flower-like Bi₂WO₆ and Bi₂O₃-Bi₂WO₆ composite

... 而复合光催化剂能形成过渡带隙, 降低带隙能, 抑制光生电子-空穴对的复合, 延长光生载流子寿命, 提高光催化活性^[8,9,10,11] ...

2013

0.0

ChemPlusChem. 2013, 78(1):117-123

Hierarchical Composite of Ag/AgBr Nanoparticles Supported on Bi₂MoO₆ Hollow Spheres for Enhanced Visible-Light Photocatalytic Performance

Dr. Guohui Tian 1,2 ,Dr. Yajie Chen 1 ,Dr. Xiangying Meng 1 ,Dr. Juan Zhou 1 ,Wei Zhou 1 ,Dr. Kai Pan 1 ,Dr. Chungui Tian 1 ,Dr. Zhiyu Ren 1 andProf. Honggang Fu 1,*

1 Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People's Republic of China, Heilongjiang University, Harbin 150080 (P. R. China), Fax: (+86) 451-8667-3647 2 Key Laboratory of Chemical Engineering Process & Technology for High-efficiency Conversion, College of Heilongjiang Province, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080 (P. R. China) * Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People's Republic of China, Heilongjiang University, Harbin 150080 (P. R. China), Fax: (+86) 451-8667-3647

> The fabrication of multicomponent composite systems may provide benefits in terms of charge separation and the retardation of charge pair recombination. For this purpose, a hierarchical Ag/AgBr/Bi 2 MoO 6 composite was fabricated by using prepared hierarchical floriated Bi 2 MoO 6 hollow spheres as a supporting material. The interleaved nanoflakes assembled in the hierarchical floriated Bi 2 MoO 6 hollow spheres contributed to the stable deposition of Ag/AgBr nanoparticles and the formation of effective nanojunctions, which led to the low recombination rates of the photoinduced electron–hole pairs. The presence of double visible-light-active components in the Ag/AgBr/Bi 2 MoO 6 nanojunction system further broadened the visible-light photoresponse range. As a result, the hierarchical Ag/AgBr/Bi 2 MoO 6 composite exhibited a higher photocatalytic activity than both photocatalysts containing single visible-light-active components and crushed Ag/AgBr/Bi 2 MoO 6 nanoparticles for the degradation of alizarin red S (ARS) and phenol. X-ray photoelectron spectroscopy (XPS) analyses indicated that both AgBr and Ag 0 components coexist in the system, and the as-prepared composite is relatively stable. The improved photoinduced charge-transfer properties of the hierarchical Ag/AgBr/Bi 2 MoO 6 composite were investigated by using the transient photovoltage (TPV) technique.

... 而复合光催化剂能形成过渡带隙, 降低带隙能, 抑制光生电子-空穴对的复合, 延长光生载流子寿命, 提高光催化活性^[8,9,10,11] ...

2013

0.531

1.106

Journal of Inorganic Materials. 2013, 28(5):459-468 DOI:10.3724/SP.J.1077.2013.12506

Research progress of hollow structural materials prepared via templating method

(College of Resources and Environment, Shaanxi University of Science and Technology, Xi’an 710021, China)

Hollow structural materials with low density and high surface area which can encapsulate small molecules, are widely used in environmental protection, drug delivery system, electronic and other fields. Because templating method is simple, and owns high repeat rate, good prediction and many other advantages, it is particularly interesting and frequently used to fabricate hollow structural materials with homogeneous, dense layers. Templating methods can be divided broadly into two classes according to the properties of templates used in synthesis, which can be called traditional templating methods and self-templating methods, respectively. In this review, a comprehensive overview of the preparation of hollow structural materials via templating methods was provided. The progress of two traditional templating methods: hard templates and soft templates were firstly summarized. The research and development of hollow structural materials prepared via four self-templating methods: Ostwald ripening, Kirkendall effect, galvanic replacement and chemical etching were mainly reviewed and commented in the later. At last, perspective on the future research and development of hollow structural materials prepared by templating methods were also discussed.

中空结构材料具有低密度、高比表面积、可以容纳客体分子等特点被广泛用于环境保护、生物医药、电子等领域。模板法具有简单、重复率高、预见性好等诸多优点, 在制备中空结构材料的过程中被广泛采用。根据所使用模板性质的不同, 模板法又可分为传统模板法和自模板法两类。本文对模板法制备中空结构材料的研究进行了综述, 首先阐述了硬模板法和软模板法两种传统模板法制备中空结构材料的研究进展, 并在此基础上重点综述和评价了奥斯特瓦尔德熟化法、柯肯达尔效应法、电化学置换法和化学刻蚀法四种自模板法制备中空结构材料的研究进展, 最后, 对模板法制备中空结构材料的发展前景进行了展望。

... 5wt% Zn-CuO/CuAl₂O₄样品的SEM照片, 由图可知, 空心球表面粗糙, 内部存在明显的中空结构, 反应过程中由于柯肯达尔效应^[12,13], 产物的直径减少到2 #cod#x003bc ...

2013

0.531

1.106

Journal of Inorganic Materials. 2013, 28(7):683-690 DOI:10.3724/SP.J.1077.2013.12690

Research progress on crystal growth mechanism of titania/titanate nano-powder materials

(1. National Engineering Research Center for Nanotechnology, Shanghai 200241, China; 2. School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China)

Chemical and physical properties of titania/titanate nanomaterials should be strongly influenced by their crystalline phases, grain sizes, morphologies and microstructures. The process of crystal growth contains phase transition and morphological evolution behavior. In this review, the crystal phase transition mechanisms and morphology evolution models were elucidated based on the recent research works of crystal phase and morphology controlled synthesis of titania/titanate nano-powder materials, which included Ostwald Ripening, Ostwald’s step rule, Oriented Attachment Growth, Kirkendall Effect, etc. These phase transition mechanisms and morphology evolution models not only offer explanations for the formation of titania/titanate nano-powder materials with different phases and morphologies, but also give a guidance of phase and morphology controlled synthesis of titania/titanate nano-powder materials.

二氧化钛/钛酸盐纳米材料的晶型、尺寸、形貌和微结构等特征对物理化学性能有着至关重要的影响。晶体生长过程包括晶型转变和形貌演化等行为。本文综述了近年来在二氧化钛/钛酸盐纳米粉体材料晶型与形貌的控制合成工作中, 材料晶型转变和形貌演化行为方面的研究进展。对奥斯特瓦尔德规则、奥斯特瓦尔德熟化机制、柯肯达尔效应和定向附着生长模式等重要的机理进行了阐述, 并将晶体生长机理应用于二氧化钛/钛酸盐纳米粉体材料的合成过程中。不仅利用上述晶体生长机理解释了不同晶型、不同形貌二氧化钛/钛酸盐纳米粉体材料的生成原因, 并且利用晶体生长机理指导二氧化钛/钛酸盐纳米粉体材料晶型与形貌的控制合成工作。

2013

1.789

0.0

Ceramics International. 2013, 39(5):null-null

Hydrothermal preparation, characterization and photocatalytic activity of TiO₂/Fe-TiO₂ composite catalysts

... 类、H₂滞后环, 表明Zn-CuO/CuAl₂O₄复合空心球上存在孔结构^[14,15] ...

2013

0.981

1.397

New Carbon Materials. 2013, 28(1):47-54

Preparation of TiO₂/mesoporous carbon composites and their photocatalytic performance for methyl orange degradation

1.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China|2.Key Laboratory of Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

Mesoporous carbon (MC) prepared using colloidal silica templates was used as a support to synthesize TiO2/MC composites using a sol-gel method. The TiO2 content and the crystalline structure of TiO2/MC photocatalysts can be tuned by the precursor composition and calcination temperature, respectively. MC and TiO2/MC composites were characterized by nitrogen adsorption, XRD, TG, SEM, TEM and electron energy dispersive spectroscopy. Results showed that the anatase TiO2 nanoparticles were highly dispersed on the surface of the carbon framework. As-prepared composites exhibited high photocatalytic activities for methyl orange (MO) degradation under UV irradiation, and a synergistic effect of adsorption and photocatalytic degradation was observed. The MO removal rate reached 89% after UV irradiation for 75 min. The kinetics of MO degradation can be well fitted with a first-order reaction model and the largest rate constant observed was 0.015 min-1.

以模板法制备的中孔炭为载体，通过溶胶凝胶法制备了二氧化钛/中孔炭复合光催化剂，并考察了其对甲基橙的光催化去除能力。复合材料中二氧化钛含量及其晶型结构分别通过改变前驱体组成及煅烧温度进行调节。材料的结构性能通过氮气吸附、X射线衍射（XRD）、能谱分析仪（EDS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、热重分析仪（TG）等测试技术进行了表征。结果表明，由于中孔炭的纳米孔限域作用，锐钛矿型的二氧化钛以纳米颗粒形式均匀分散在炭的网络骨架界面，从而形成了高度分散的二氧化钛/中孔炭纳米复合材料。另外，复合材料中的中孔吸附作用协同纳米二氧化钛的高效光催化作用，明显提高了复合材料在紫外光照射下对于水溶液中甲基橙的去除能力。在光照射下反应75min时样品对甲基橙的去除率可达89%。甲基橙光降解反应遵循一级反应动力学，其最大反应速率为0.015min-1。

... 类、H₂滞后环, 表明Zn-CuO/CuAl₂O₄复合空心球上存在孔结构^[14,15] ...

2013

2.112

0.0

Applied Surface Science. 2013, 268:null-null

Fabrication and photocatalytic properties of spheres-in-spheres ZnO/ZnAl₂O₄ composite hollow microspheres

... 8p/p₀[16,17,18] ...

2012

0.0

... 8p/p₀[16,17,18] ...

2010

3.925

0.0

Journal of Hazardous Materials. 2010, 173(1):null-null

Synergistic effects of hollow structure and surface fluorination on the photocatalytic activity of titania

... 8p/p₀[16,17,18] ...

2012

1.419

0.4971

Particuology. 2012, 10(1):null-null

Preparation of ternary Cr₂O₃-SiC-TiO₂ composites for the photocatalytic production of hydrogen

... 通常光致发光光谱是由光生电子空穴对的复合而产生^[19] ...

2012

3.925

0.0

... 比表面积越大, 提供的活性位点越多, 更有利于反应物的吸附和内部电荷的转移, 因而催化效果越好^[20,21] ...

2013

4.655

0.0

Water Research. 2013, 47(12):null-null

Novel-structured electrospun TiO₂/CuO composite nanofibers for high efficient photocatalytic cogeneration of clean water and energy from dye wastewater

... 比表面积越大, 提供的活性位点越多, 更有利于反应物的吸附和内部电荷的转移, 因而催化效果越好^[20,21] ...