CN110314658B - 一种吸附-光催化降解染料废水的纳米材料制备方法 - Google Patents
一种吸附-光催化降解染料废水的纳米材料制备方法 Download PDFInfo
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Abstract
本发明涉及一种吸附‑光催化降解染料废水的纳米材料制备方法，属于环境纳米材料新功能技术领域。采用喷雾热解法制备TiO2薄膜样品；将TiO2薄膜样品破碎成粉末，加入去离子水超声处理，加入NaOH溶液磁搅拌，加入AgNO3溶液得到混合溶液B；将十六烷基三甲基溴化铵溶于CCl4溶液得到有机溶液，将有机溶液缓慢加入到混合溶液B中，搅拌后在卤素灯下进行光还原，得到AgBr‑TiO2粉末；将AgBr‑TiO2粉末醋酸溶液超声，加入壳聚糖粉末后依次加入交联剂甲醛以及添加剂聚乙烯醇；静置、脱泡、流延成膜、自然风干得到膜，将膜浸入到NaOH溶液中，得到吸附‑光催化降解染料废水的纳米材料，交联壳聚糖/AgBr‑TiO2。本发明制备具有吸附和光催化双重特性的交联壳聚糖负载Ag+掺杂纳米TiO2复合材料。
Description
技术领域
本发明涉及一种吸附-光催化降解染料废水的纳米材料制备方法，属于环境纳米材料新功能技术领域。
背景技术
现代工业的崛起促进了经济的飞速发展，高速工业化进程中所引发的水污染问题日益严重。染料作为一种重要的精细化工产品，与人类的衣食住行密切相关。我国是染料大国，染料年产能约为130万吨，占全球产能的60%以上，市场份额占全球40%以上；在环保部发布的《环境保护综合名录》（2017年版）中，一共有885项产品列入“高污染、高环境风险”目录，其中涉及染料的就高达200余项。染料废水色度大，有机污染物浓度、生物需氧量(BOD)和化学需氧量(COD)高，组分复杂，实际生产中水质变动范围大，对动物乃至人类都具有毒害、致畸和致癌的潜在作用。染料废水的有效治理一直是困扰行业发展的难题。常用的染料废水处理方法比较如表1所示。
表1 各种染料废水处理方法比较
光催化技术是利用半导体材料作为催化剂，通过紫外光或可见光的辅助作用，催化氧化难降解有机废水的方法，是当今废水处理的重要研究方向。该技术的出现，有效地克服了传统方法中存在的诸如投资大、费用高、工序多、范围窄、效率低等缺点；纳米TiO2在光照下易被激发，产生光生电荷，其光生空穴的氧化电位以标准氢电位计算为3.0eV;光生电子可以使空气中的氧还原成活性氧化物质，使TiO2表现出极强的氧化还原能力。纳米TiO2不仅能氧化降解多种有机物，而且能够将有机物最终降解为CO2和H2O等无机小分子，实现有机物的彻底矿化。但是可见光利用率低和光量子效率低是限制纳米TiO2实用化的两个主要瓶颈因素，宽带隙半导体TiO2只能被紫外光激发，而太阳光中紫外光所占的比例不到5%，且90%的光生电子与空穴在10ns的时间内就发生复合，只有少量的光生电荷参与了光催化反应。
AgBr的带隙能约为2.6eV，光照过程中可以吸收光生电子，光生空穴被Br-捕获；AgBr作为一种重要的无机光敏感剂，在可见光区具有很高的感光度，能够很好地弥补纳米TiO2可见光利用率低的缺陷，使TiO2具有可见光催化活性。壳聚糖是一种天然高分子化合物，高分子链段中含有-NH2，-OH活性基团与重金属离子形成配合化合物，可制成高分子吸附剂吸附重金属离子。壳聚糖对Ni+、Zn+、Cd+以及一些稀土金属离子都与很好的吸附能力。
发明内容
针对上述现有技术存在的问题及不足，本发明提供一种吸附-光催化降解染料废水的纳米材料制备方法。本发明通过以下技术方案实现。
一种吸附-光催化降解染料废水的纳米材料制备方法，其包括以下步骤：
步骤1、以无水乙醇、乙酰丙酮及钛酸丁酯液体混合均匀为混合溶液A，采用喷雾热解法制备TiO2薄膜样品；
步骤2、将步骤1制备得到的TiO2薄膜样品破碎成粉末，然后按照液固比为4:800g/mL加入去离子水超声处理，按照粉末与NaOH溶液质量比为4:2加入NaOH溶液磁搅拌，再按照粉末质量与AgNO3溶液体积比为0.4:20~60mL加入AgNO3溶液得到混合溶液B；将十六烷基三甲基溴化铵溶于CCl4溶液得到浓度为0.1/20g/mL的有机溶液，将有机溶液缓慢加入到混合溶液B中，搅拌后在卤素灯下进行光还原，过滤、洗涤、干燥得到AgBr-TiO2粉末；
步骤3、将步骤2得到的AgBr-TiO2粉末溶于体积分数为4%的醋酸溶液超声，加入壳聚糖粉末后依次加入交联剂甲醛以及添加剂聚乙烯醇；静置、脱泡、流延成膜、自然风干得到膜，将膜浸入到2mol/L的NaOH溶液中浸泡12h，用去离子水反复洗涤至溶液呈中性，冷却干燥后得到吸附-光催化降解染料废水的纳米材料，交联壳聚糖/AgBr-TiO2。
所述步骤1中向无水乙醇中按照体积比为4：1：1依次加入乙酰丙酮和钛酸丁酯，混合均匀为混合溶液A；将洁净的载玻片基板加热至温度为450～600℃，控制混合溶液A液流量为300mL/h，高压载气流量为40mL/h，在温度为700℃下两路开始沉积薄膜，喷雾0.5h，待基板冷却至室温后，得到TiO2薄膜样品。
所述步骤3中AgBr-TiO2粉末与体积分数为4%的醋酸溶液的固液比为0.2～0.4：80～100g/mL。
所述步骤3中AgBr-TiO2粉末、壳聚糖粉末、甲醛和聚乙烯醇质量比为3.5：7：1：6。
上述没有提及到具体浓度的均为分析纯试剂。
本发明的有益效果是：
（1）采用喷雾热解法制备TiO2，薄膜致密均匀，相较于传统方法，制备过程中不需要使用真空设备，实验条件简单、成本低廉；
（2）采用油水自组装法（油包水法）将AgBr沉积在TiO2表面，提高TiO2对可见光的利用率，大幅度提高光催化活性。
（3）利用交联壳聚糖良好的吸附性，与AgBr-TiO2进行杂化，制备具有吸附和光催化双重特性的交联壳聚糖负载Ag+掺杂纳米TiO2复合材料，提高对染料废水的净化去除效率。
附图说明
图1是实施例1制备纳米材料应用甲基橙（MO）溶液中不同光照时间甲基橙溶液的UV--vis吸收光谱图；
图2是实施例2制备纳米材料应用甲基橙（MO）溶液中不同光照时间甲基橙溶液的UV--vis吸收光谱图；
图3是实施例3制备纳米材料应用甲基橙（MO）溶液中不同光照时间甲基橙溶液的UV--vis吸收光谱图。
具体实施方式
下面结合附图和具体实施方式，对本发明作进一步说明。
实施例1
该吸附-光催化降解染料废水的纳米材料制备方法，其包括以下步骤：
步骤1、以无水乙醇、乙酰丙酮及钛酸丁酯液体混合均匀为混合溶液A，采用喷雾热解法制备TiO2薄膜样品；具体为：无水乙醇中按照体积比为4：1：1依次加入乙酰丙酮和钛酸丁酯，混合均匀为混合溶液A；将洁净的载玻片基板加热至温度为450℃，控制混合溶液A液流量为300mL/h，高压载气流量为40mL/h，在温度为700℃下两路开始沉积薄膜，喷雾0.5h，待基板冷却至室温后，得到TiO2薄膜样品；
步骤2、将步骤1制备得到的0.4gTiO2薄膜样品破碎成粉末（2目），然后按照液固比为4:800g/mL加入去离子水超声处理，按照粉末与NaOH溶液质量比为4:2加入NaOH溶液磁搅拌，再按照粉末质量与AgNO3溶液体积比为0.4:20g/mL加入AgNO3溶液得到混合溶液B；将0.1g十六烷基三甲基溴化铵溶于20mLCCl4溶液得到有机溶液，将有机溶液缓慢加入到混合溶液B中，搅拌后在卤素灯下进行光还原，过滤、洗涤、干燥得到AgBr-TiO2粉末；
步骤3、将步骤2得到的0.2gAgBr-TiO2粉末溶于体积分数为4%的醋酸溶液超声（AgBr-TiO2粉末与体积分数为4%的醋酸溶液的固液比为0.4：100g/mL），加入壳聚糖粉末后依次加入交联剂甲醛以及添加剂聚乙烯醇（AgBr-TiO2粉末、壳聚糖粉末、甲醛和聚乙烯醇质量比为3.5：7：1：6）；静置、脱泡、流延成膜、自然风干得到膜，将膜浸入到2mol/L的NaOH溶液中浸泡12h，用去离子水反复洗涤至溶液呈中性，冷却干燥后得到吸附-光催化降解染料废水的纳米材料，交联壳聚糖/AgBr-TiO2。
本实施例制备得到的交联壳聚糖/AgBr-TiO2记为标号TA-20/壳聚糖。本实施例制备得到的TA-20/壳聚糖应用甲基橙（MO）溶液中不同光照时间甲基橙溶液的UV--vis吸收光谱图如图1所示，从图1中可以看出，将TA-20/壳聚糖应用甲基橙（MO）溶液在黑暗中反应30min甲基橙的吸收度最高，而在光照30min后甲基橙的吸收度最低，甲基橙的吸收度越低证明TA-20/壳聚糖降解甲基橙的降解率越高。
本实施例制备得到的交联壳聚糖/AgBr-TiO2，经光照30min后，对甲基橙的降解率为88.53%。
实施例2
该吸附-光催化降解染料废水的纳米材料制备方法，其包括以下步骤：
步骤1、以无水乙醇、乙酰丙酮及钛酸丁酯液体混合均匀为混合溶液A，采用喷雾热解法制备TiO2薄膜样品；具体为：无水乙醇中按照体积比为4：1：1依次加入乙酰丙酮和钛酸丁酯，混合均匀为混合溶液A；将洁净的载玻片基板加热至温度为450℃，控制混合溶液A液流量为300mL/h，高压载气流量为40mL/h，在温度为700℃下两路开始沉积薄膜，喷雾0.5h，待基板冷却至室温后，得到TiO2薄膜样品；
步骤2、将步骤1制备得到的0.4gTiO2薄膜样品破碎成粉末（2目），然后按照液固比为4:800g/mL加入去离子水超声处理，按照粉末与NaOH溶液质量比为4:2加入NaOH溶液磁搅拌，再按照粉末质量与AgNO3溶液体积比为0.4:40g/mL加入AgNO3溶液得到混合溶液B；将0.1g十六烷基三甲基溴化铵溶于20mLCCl4溶液得到有机溶液，将有机溶液缓慢加入到混合溶液B中，搅拌后在卤素灯下进行光还原，过滤、洗涤、干燥得到AgBr-TiO2粉末；
步骤3、将步骤2得到的0.3gAgBr-TiO2粉末溶于体积分数为4%的醋酸溶液超声（AgBr-TiO2粉末与体积分数为4%的醋酸溶液的固液比为0.4：100g/mL），加入壳聚糖粉末后依次加入交联剂甲醛以及添加剂聚乙烯醇（AgBr-TiO2粉末、壳聚糖粉末、甲醛和聚乙烯醇质量比为3.5：7：1：6）；静置、脱泡、流延成膜、自然风干得到膜，将膜浸入到2mol/L的NaOH溶液中浸泡12h，用去离子水反复洗涤至溶液呈中性，冷却干燥后得到吸附-光催化降解染料废水的纳米材料，交联壳聚糖/AgBr-TiO2。
本实施例制备得到的交联壳聚糖/AgBr-TiO2记为标号TA-40/壳聚糖。本实施例制备得到的TA-40/壳聚糖应用甲基橙（MO）溶液中不同光照时间甲基橙溶液的UV--vis吸收光谱图如图2所示，从图2中可以看出，将TA-40/壳聚糖应用甲基橙（MO）溶液在黑暗中反应30min甲基橙的吸收度最高，而在光照30min后甲基橙的吸收度最低，甲基橙的吸收度越低证明TA-40/壳聚糖降解甲基橙的降解率越高。
本实施例制备得到的交联壳聚糖/AgBr-TiO2，经光照30min后，对甲基橙的降解率为99.28%。
实施例3
该吸附-光催化降解染料废水的纳米材料制备方法，其包括以下步骤：
步骤1、以无水乙醇、乙酰丙酮及钛酸丁酯液体混合均匀为混合溶液A，采用喷雾热解法制备TiO2薄膜样品；具体为：无水乙醇中按照体积比为4：1：1依次加入乙酰丙酮和钛酸丁酯，混合均匀为混合溶液A；将洁净的载玻片基板加热至温度为450℃，控制混合溶液A液流量为300mL/h，高压载气流量为40mL/h，在温度为700℃下两路开始沉积薄膜，喷雾0.5h，待基板冷却至室温后，得到TiO2薄膜样品；
步骤2、将步骤1制备得到的0.4gTiO2薄膜样品破碎成粉末（2目），然后按照液固比为4:800g/mL加入去离子水超声处理，按照粉末与NaOH溶液质量比为4:2加入NaOH溶液磁搅拌，再按照粉末质量与AgNO3溶液体积比为0.4:60g/mL加入AgNO3溶液得到混合溶液B；将0.1g十六烷基三甲基溴化铵溶于20mLCCl4溶液得到有机溶液，将有机溶液缓慢加入到混合溶液B中，搅拌后在卤素灯下进行光还原，过滤、洗涤、干燥得到AgBr-TiO2粉末；
步骤3、将步骤2得到的0.4gAgBr-TiO2粉末溶于体积分数为4%的醋酸溶液超声（AgBr-TiO2粉末与体积分数为4%的醋酸溶液的固液比为0.4：100g/mL），加入壳聚糖粉末后依次加入交联剂甲醛以及添加剂聚乙烯醇（AgBr-TiO2粉末、壳聚糖粉末、甲醛和聚乙烯醇质量比为3.5：7：1：6）；静置、脱泡、流延成膜、自然风干得到膜，将膜浸入到2mol/L的NaOH溶液中浸泡12h，用去离子水反复洗涤至溶液呈中性，冷却干燥后得到吸附-光催化降解染料废水的纳米材料，交联壳聚糖/AgBr-TiO2。
本实施例制备得到的交联壳聚糖/AgBr-TiO2记为标号TA-60/壳聚糖。本实施例制备得到的TA-60/壳聚糖应用甲基橙（MO）溶液中不同光照时间甲基橙溶液的UV--vis吸收光谱图如图3所示，从图3中可以看出，将TA-60/壳聚糖应用甲基橙（MO）溶液在黑暗中反应30min甲基橙的吸收度最高，而在光照30min后甲基橙的吸收度最低，甲基橙的吸收度越低证明TA-60/壳聚糖降解甲基橙的降解率越高。
本实施例制备得到的交联壳聚糖/AgBr-TiO2，经光照30min后，对甲基橙的降解率为94.14%。
实施例4
该吸附-光催化降解染料废水的纳米材料制备方法，其包括以下步骤：
步骤1、以无水乙醇、乙酰丙酮及钛酸丁酯液体混合均匀为混合溶液A，采用喷雾热解法制备TiO2薄膜样品；具体为：无水乙醇中按照体积比为4：1：1依次加入乙酰丙酮和钛酸丁酯，混合均匀为混合溶液A；将洁净的载玻片基板加热至温度为550℃，控制混合溶液A液流量为300mL/h，高压载气流量为40mL/h，在温度为700℃下两路开始沉积薄膜，喷雾0.5h，待基板冷却后，得到TiO2薄膜样品；
步骤2、将步骤1制备得到的0.4gTiO2薄膜样品破碎成粉末（2目），然后按照液固比为4:800g/mL加入去离子水超声处理，按照粉末与NaOH溶液质量比为4:2加入NaOH溶液磁搅拌，再按照粉末质量与AgNO3溶液体积比为0.4:60g/mL加入AgNO3溶液得到混合溶液B；将0.1g十六烷基三甲基溴化铵溶于20mLCCl4溶液得到有机溶液，将有机溶液缓慢加入到混合溶液B中，搅拌后在卤素灯下进行光还原，过滤、洗涤、干燥得到AgBr-TiO2粉末；
步骤3、将步骤2得到的0.4gAgBr-TiO2粉末溶于体积分数为4%的醋酸溶液超声（AgBr-TiO2粉末与体积分数为4%的醋酸溶液的固液比为0.2：80g/mL），加入壳聚糖粉末后依次加入交联剂甲醛以及添加剂聚乙烯醇（AgBr-TiO2粉末、壳聚糖粉末、甲醛和聚乙烯醇质量比为3.5：7：1：6）；静置、脱泡、流延成膜、自然风干得到膜，将膜浸入到2mol/L的NaOH溶液中浸泡12h，用水反复洗涤至溶液呈中性，冷却干燥后得到吸附-光催化降解染料废水的纳米材料，交联壳聚糖/AgBr-TiO2。
实施例5
该吸附-光催化降解染料废水的纳米材料制备方法，其包括以下步骤：
步骤1、以无水乙醇、乙酰丙酮及钛酸丁酯液体混合均匀为混合溶液A，采用喷雾热解法制备TiO2薄膜样品；具体为：无水乙醇中按照体积比为4：1：1依次加入乙酰丙酮和钛酸丁酯，混合均匀为混合溶液A；将洁净的载玻片基板加热至温度为600℃，控制混合溶液A液流量为300mL/h，高压载气流量为40mL/h，在温度为700℃下两路开始沉积薄膜，喷雾0.5h，待基板冷却后，得到TiO2薄膜样品；
步骤2、将步骤1制备得到的0.4gTiO2薄膜样品破碎成粉末（2目），然后按照液固比为4:800g/mL加入去离子水超声处理，按照粉末与NaOH溶液质量比为4:2加入NaOH溶液磁搅拌，再按照粉末质量与AgNO3溶液体积比为0.4:60g/mL加入AgNO3溶液得到混合溶液B；将0.1g十六烷基三甲基溴化铵溶于20mLCCl4溶液得到有机溶液，将有机溶液缓慢加入到混合溶液B中，搅拌后在卤素灯下进行光还原，过滤、洗涤、干燥得到AgBr-TiO2粉末；
步骤3、将步骤2得到的0.4g AgBr-TiO2粉末溶于体积分数为4%的醋酸溶液超声（AgBr-TiO2粉末与体积分数为4%的醋酸溶液的固液比为0.3：90g/mL），加入壳聚糖粉末后依次加入交联剂甲醛以及添加剂聚乙烯醇（AgBr-TiO2粉末、壳聚糖粉末、甲醛和聚乙烯醇质量比为3.5：7：1：6）；静置、脱泡、流延成膜、自然风干得到膜，将膜浸入到2mol/L的NaOH溶液中浸泡12h，用水反复洗涤至溶液呈中性，冷却干燥后得到吸附-光催化降解染料废水的纳米材料，交联壳聚糖/AgBr-TiO2。
以上结合附图对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (4)
1.一种吸附-光催化降解染料废水的纳米材料制备方法，其特征在于包括以下步骤：
步骤1、以无水乙醇、乙酰丙酮及钛酸丁酯液体混合均匀为混合溶液A，采用喷雾热解法制备TiO2薄膜样品；
步骤2、将步骤1制备得到的TiO2薄膜样品破碎成粉末，然后按照固液比为4:800g/mL加入去离子水超声处理，按照粉末与NaOH溶液质量比为4:2加入NaOH溶液磁搅拌，再按照粉末质量与AgNO3溶液体积比为0.4:20~60g/mL加入AgNO3溶液得到混合溶液B；将十六烷基三甲基溴化铵溶于CCl4溶液得到浓度为0.1/20g/mL的有机溶液，将有机溶液缓慢加入到混合溶液B中，搅拌后在卤素灯下进行光还原，过滤、洗涤、干燥得到AgBr-TiO2粉末；
步骤3、将步骤2得到的AgBr-TiO2粉末溶于体积分数为4%的醋酸溶液超声，加入壳聚糖粉末后依次加入交联剂甲醛以及添加剂聚乙烯醇；静置、脱泡、流延成膜、自然风干得到膜，将膜浸入到2mol/L的NaOH溶液中浸泡10~12h，用去离子水反复洗涤至溶液呈中性，冷却干燥后得到吸附-光催化降解染料废水的纳米材料，交联壳聚糖/AgBr-TiO2。
2.根据权利要求1所述的吸附-光催化降解染料废水的纳米材料制备方法，其特征在于：所述步骤1中向无水乙醇中按照体积比为4：1：1依次加入乙酰丙酮和钛酸丁酯，混合均匀为混合溶液A；将洁净的载玻片基板加热至温度为450～600℃，控制混合溶液A液流量为300mL/h，高压载气流量为40mL/h，在温度为700℃下两路开始沉积薄膜，喷雾0.5h，待基板冷却至室温后，得到TiO2薄膜样品。
3.根据权利要求1所述的吸附-光催化降解染料废水的纳米材料制备方法，其特征在于：所述步骤3中AgBr-TiO2粉末与体积分数为4%的醋酸溶液的固液比为0.2～0.4：80～100g/mL。
4.根据权利要求1所述的吸附-光催化降解染料废水的纳米材料制备方法，其特征在于：所述步骤3中AgBr-TiO2粉末、壳聚糖粉末、甲醛和聚乙烯醇质量比为3.5：7：1：6。
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| CN112169379B (zh) * | 2020-10-22 | 2022-04-12 | 陕西师范大学 | 一种具有漂浮吸油性的生物质气囊/TiO2复合材料 |
| CN113042077B (zh) * | 2021-03-12 | 2023-07-18 | 南京林业大学 | 一种光热-光化学协同转换的水凝胶材料及其制备方法和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210081A (zh) * | 2007-12-20 | 2008-07-02 | 江汉大学 | 壳聚糖/二氧化钛复合材料的制备 |
| CN102583637A (zh) * | 2012-01-17 | 2012-07-18 | 同济大学 | 一种吸附-光催化联合高效去除高浓度染料废水的方法 |
| CN104607214A (zh) * | 2015-01-19 | 2015-05-13 | 上海交通大学 | 一种可见光响应的AgBr/TiO2催化剂的制备方法 |
| KR20160088557A (ko) * | 2015-01-16 | 2016-07-26 | 박케빈 | 광촉매 TiO2와 ZnO의 효율적인 코팅 방법 연구 |
| CN109422888A (zh) * | 2017-08-23 | 2019-03-05 | 张家港市六福新材料科技有限公司 | 一种壳聚糖-二氧化钛复合膜的制备方法 |
-
2019
- 2019-06-20 CN CN201910535740.8A patent/CN110314658B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210081A (zh) * | 2007-12-20 | 2008-07-02 | 江汉大学 | 壳聚糖/二氧化钛复合材料的制备 |
| CN102583637A (zh) * | 2012-01-17 | 2012-07-18 | 同济大学 | 一种吸附-光催化联合高效去除高浓度染料废水的方法 |
| KR20160088557A (ko) * | 2015-01-16 | 2016-07-26 | 박케빈 | 광촉매 TiO2와 ZnO의 효율적인 코팅 방법 연구 |
| CN104607214A (zh) * | 2015-01-19 | 2015-05-13 | 上海交通大学 | 一种可见光响应的AgBr/TiO2催化剂的制备方法 |
| CN109422888A (zh) * | 2017-08-23 | 2019-03-05 | 张家港市六福新材料科技有限公司 | 一种壳聚糖-二氧化钛复合膜的制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| Photocatalytic activity of AgBr/TiO2 in water under simulated sunlight irradiation;Yujing Zang et al.;《Applied Catalysis B: Environmental》;20071025;第79卷;334-340 * |
| TiO2 薄膜的火焰喷雾热分解法制备与自清洁研究;武光明等;《石油化工高等学校学报》;20100615;第23卷(第2期);5-8 * |
| 油水自组装制备Ag@AgBr/BiOBr高效可见光催化剂;安伟佳等;《无机化学学报》;20150210;第31卷(第2期);329-337 * |
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