CuO和Au纳米结构协同增强Cu<sub>2</sub>O立方体光催化活性和稳定性

引用本文: 蒋登辉, 张跃钢, 李鑫恒. CuO和Au纳米结构协同增强Cu₂O立方体光催化活性和稳定性[J]. 催化学报, 2019, 40(1): 105-113. doi: 10.1016/S1872-2067(18)63164-X shu

Citation: Denghui Jiang, Yuegang Zhang, Xinheng Li. Synergistic effects of CuO and Au nanodomains on Cu₂O cubes for improving photocatalytic activity and stability[J]. Chinese Journal of Catalysis, 2019, 40(1): 105-113. doi: 10.1016/S1872-2067(18)63164-X shu

CuO和Au纳米结构协同增强Cu₂O立方体光催化活性和稳定性

a 中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室和苏州研究院, 江苏苏州 215123;
b 中南大学资源加工与生物工程学院, 湖南长沙 410083;
c 中国科学院苏州纳米技术与纳米仿生研究所国际实验室, 江苏苏州 215123
基金项目:
国家自然科学基金（21573263，21872157，51402346）；科技部国家重点研发计划（2016YFE0105700）；江苏省基础研究计划（BK20151236）；河南省合作开放基金（60）；中国博士后科学基金资助项目（2018M632984）.

摘要: 氧化亚铜（Cu₂O）是一种重要的P型半导体，并且具有无毒、廉价和易于控制合成等优点，被广泛应用于光催化领域.然而，低的光催化性能极大地限制了它的应用，特别是氧化亚铜立方体表面存在的障碍层严重阻碍了光生载流子传输，导致其几乎没有光催化活性.构建异质结构是提高氧化亚铜光催化性能的有效手段，然而，目前氧化亚铜异质结构的光催化性能和稳定性仍然需要大幅地提高.我们的前期研究发现，通过乙二胺在氧化亚铜表面轻微氧化刻蚀形成CuO/Cu₂O异质结构，在提高一定的光催化活性的同时能够大幅提高其稳定性.另外，在氧化亚铜表面负载金纳米颗粒也能够有效地增强氧化亚铜的光催化性能.因此，协同氧化铜和金纳米颗粒应该能够同时大幅地提高氧化亚铜的光催化活性和稳定性.
本文利用乙二胺对氧化亚铜立方体进行轻微的氧化刻蚀，然后光还原负载金纳米颗粒，成功地制备了Au/CuO/Cu₂O异质结构.TEM和SEM结果表明，氧化铜和金纳米结构随机均匀地分散在氧化亚铜表面.XPS数据表明，Au/CuO/Cu₂O异质结构表面的二价铜主要来自生成的氧化铜纳米结构.表面残存的N元素表明，氧化铜由一价铜与乙二胺形成的配合物转变而来.在可见光下光催化降解甲基橙实验结果显示，Au/CuO/Cu₂O异质结构的光降解速率大幅地提高.通过表观量子效率的估算发现，Au/CuO/Cu₂O异质结构光催化活性是纯Cu₂O的123倍，Au/Cu₂O的5.4倍.光电流测试中，Au/CuO/Cu₂O异质结构的光电流也都明显高于Cu₂O，Au/Cu₂O和CuO/Cu₂O.不仅如此，Au/CuO/Cu₂O异质结构在8个循环后还能维持80%的光催化活性，远高于Au/Cu₂O的5个循环.由此可见，Au/CuO/Cu₂O异质结构具有增强的光催化活性和稳定性.
通过电子顺磁共振（ESR）自由基测试发现，光催化降解过程中，羟基自由基是主要的氧化物种，而且Au/CuO/Cu₂O异质结构的自由基信号强度明显高于Cu₂O和CuO/Cu₂O，这也说明金和氧化铜的双异质结构提高了体系载流子分离效率.PL数据进一步证实了这一结论.另外，比表面积和暗吸附实验数据表明，轻微的表面积增加不会显著地改变三元异质结构的吸附和光催化性能.根据UV-Vis和价带XPS数据，我们认为轻微光吸收变化和价带改变不会显著影响异质结构的光催化活性.因此，金和氧化铜纳米结构协同增强光生载流子分离效率，是提高氧化亚铜光催化活性的主要原因.首先，Au/Cu₂O异质结构通过肖特基结和金颗粒的表面等离子共振效应提高光生载流子的分离效率.其次，氧化铜纳米结构不仅能与氧化亚铜形成Ⅱ型异质结构，而且还能够作为保护层提高氧化亚铜的稳定性.另外，氧化铜纳米结构生成过程中去除了表面障碍层，减少空穴在氧化亚铜上的累积，进而提高氧化亚铜的稳定性.总之，氧化铜和金纳米结构的协同效应显著提高了体系的光催化活性和稳定性.

关键词:

English

Synergistic effects of CuO and Au nanodomains on Cu₂O cubes for improving photocatalytic activity and stability

a State Key Laboratory for Oxo Synthesis and Selective Oxidation and Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics(LICP), Chinese Academy of Sciences, Suzhou 215123, Jiangsu, China;
b Centre for Mineral Materials, School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, Hunan, China;
c i-Lab, Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou 215123, Jiangsu, China
Received Date: 31 August 2018
Revised Date: 15 September 2018
Fund Project:
This work was supported by National Natural Science Foundation of China (21573263, 21872157, 51402346), National Key Research and Development Program of China from Ministry of Science and Technology of China (2016YFE0105700), Jiangsu Provincial Fundamental Research Foundation of China (BK20151236), Henan provincial co-operation and open foundation (60), and China Postdoctoral Science Foundation (2018M632984).

Abstract: Cu₂O is a promising photocatalyst, but it suffers from poor photocatalytic activity and stability, especially for Cu₂O cubes. Herein, we report the deposition of CuO and Au nanodomains on Cu₂O cubes to form dual surface heterostructures (HCs) to improve photocatalytic activity and stability. The apparent quantum efficiency of Au/CuO/Cu₂O HCs was ca. 123 times that of pristine Cu₂O. In addition, the Au/CuO/Cu₂O HCs maintained nearly 80% of its original activity after eight cycles in contrast to five cycles for the Au/Cu₂O material. Therefore, CuO and Au domains greatly improved the photocatalytic activity and stability of the Cu₂O cubes due to the synergistic effect of the HCs.

Key words:

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CuO和Au纳米结构协同增强Cu₂O立方体光催化活性和稳定性

English

Synergistic effects of CuO and Au nanodomains on Cu₂O cubes for improving photocatalytic activity and stability

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