具有超快电子传输能力的金/薄层氮化碳等离子光催化剂用于光催化产氢

引用本文: 莫曌, 许晖, 陈志刚, 佘小杰, 宋艳华, 严鹏程, 徐远国, 雷玉成, 袁寿其, 李华明. 具有超快电子传输能力的金/薄层氮化碳等离子光催化剂用于光催化产氢[J]. 催化学报, 2018, 39(4): 760-770. doi: 10.1016/S1872-2067(17)62978-4 shu

Citation: Zhao Mo, Hui Xu, Zhigang Chen, Xiaojie She, Yanhua Song, Pengcheng Yan, Yuanguo Xu, Yucheng Lei, Shouqi Yuan, Huaming Li. Gold/monolayer graphitic carbon nitride plasmonic photocatalyst for ultrafast electron transfer in solar-to-hydrogen energy conversion[J]. Chinese Journal of Catalysis, 2018, 39(4): 760-770. doi: 10.1016/S1872-2067(17)62978-4 shu

具有超快电子传输能力的金/薄层氮化碳等离子光催化剂用于光催化产氢

莫曌 ^a, ,
许晖 ^a, ,
陈志刚 ^a, ,
佘小杰 ^a, ,
宋艳华 ^b, ,
严鹏程 ^a, ,
徐远国 ^a, ,
雷玉成 ^a, ,
袁寿其 ^a, ,
李华明 ^a,

a 江苏大学材料科学与工程学院, 能源研究院, 江苏镇江 212003;
b 江苏科技大学环境与化工学院, 江苏镇江 212003
基金项目:
国家自然科学基金（21476097，21776118）；江苏省六大人才高峰项目（2014-JNHB-014）；江苏省自然科学基金（BK20161363）；江苏省研究生培养创新工程（KYCX17-1769）；江苏高校优势学科建设资助项目.

摘要: 光催化产氢可以直接将太阳能转化为化学能，是非常有前景的产氢技术之一.然而，光催化产氢的瓶颈在于如何提高光催化产氢效率和光催化剂的稳定性，以及降低产氢成本.因此，开发廉价、易于制备的产氢光催化剂引起人们广泛关注.作为一种非金属半导体光催化剂，石墨相氮化碳（g-C₃N₄）具有良好的物理化学性质，如良好的化学和热稳定性、极佳的光电性能、强的抗氧化能力等.更为重要的是，g-C₃N₄具有合适的能带结构，能够利用可见光.因此，g-C₃N₄已广泛应用于光催化降解、空气净化、光解水和光催化CO₂还原等领域.然而，体相g-C₃N₄仍然暴露出一些缺点，例如比表面积小、光生电子-空穴对的复合率高和反应动力学差等.将体相g-C₃N₄剥离成g-C₃N₄纳米薄片是提高光催化效率的有效方法.薄层g-C₃N₄纳米片具有较高的比表面积，比体相的g-C₃N₄有更好的光生电子-空穴对分离效率.
为了进一步提高g-C₃N₄的光催化性能，本文通过在薄层g-C₃N₄表面均匀分散Au纳米颗粒来控制电荷载流子的流动.并通过光催化产氢和污染物降解来评估金/薄层氮化碳（Au/monolayer g-C₃N₄）复合材料的光催化性能.所有的Au/薄层g-C₃N₄复合材料均显示出优于体相g-C₃N₄的光催化性能，其中1% Au/薄层g-C₃N₄复合光催化剂具有最高的产氢速率（565μmol g^-1 h^-1），且具有最佳的污染物降解能力.这主要归结于热电子的注入，而不是肖特基结.Au纳米颗粒的成功引入带来了表面等离子共振（SPR）效应，SPR效应不仅能够提高光吸收效率，而且能够带来高效的热电子转移途径.热电子是从Au纳米颗粒表面注入到薄层g-C₃N₄纳米片的导带上.因此，Au/薄层g-C₃N₄复合光催化剂具有更高的光生电子-空穴对迁移和分离效率，以及更低的光生电子-空穴对复合几率.
采用紫外可见光谱（UV-Vis）、光致发光光谱（PL）、光电流和阻抗等表征手段研究了Au/薄层g-C₃N₄复合光催化剂性能提升的原因.结果表明，相比于薄层g-C₃N₄纳米片，Au/薄层g-C₃N₄复合光催化剂具有更好的光电性能，因而光催化活性更高.此外，与薄层g-C₃N₄纳米片的光电流强度相比，Au/薄层g-C₃N₄复合光催化剂的光电流强度没有发生改变，这表明薄层g-C₃N₄纳米片导带上的光生电子不可能转移到Au纳米颗粒的表面.也就是说，肖特基结并没有参与到电子转移过程中，因此推测出整个光催化反应是热电子注入在起作用.

关键词:

English

Gold/monolayer graphitic carbon nitride plasmonic photocatalyst for ultrafast electron transfer in solar-to-hydrogen energy conversion

a School of Materials Science & Engineering, Institute for Energy Research, Jiangsu University, Zhenjiang 212013, Jiangsu, China;
b School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, Jiangsu, China
Received Date: 30 November 2017
Revised Date: 31 December 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21476097, 21776118), the Six Talent Peaks Project in Jiangsu Province (2014-JNHB-014), the Natural Science Foundation of Jiangsu Province (BK20161363), the Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX17-1769), and the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

Abstract: Gold (Au) plasmonic nanoparticles were grown evenly on monolayer graphitic carbon nitride (g-C₃N₄) nanosheets via a facile oil-bath method. The photocatalytic activity of the Au/monolayer g-C₃N₄ composites under visible light was evaluated by photocatalytic hydrogen evolution and environmental treatment. All of the Au/monolayer g-C₃N₄ composites showed better photocatalytic performance than that of monolayer g-C₃N₄ and the 1% Au/monolayer g-C₃N₄ composite displayed the highest photocatalytic hydrogen evolution rate of the samples. The remarkable photocatalytic activity was attributed largely to the successful introduction of Au plasmonic nanoparticles, which led to the surface plasmon resonance (SPR) effect. The SPR effect enhanced the efficiency of light harvesting and induced an efficient hot electron transfer process. The hot electrons were injected from the Au plasmonic nanoparticles into the conduction band of monolayer g-C₃N₄. Thus, the Au/monolayer g-C₃N₄ composites possessed higher migration and separation efficiencies and lower recombination probability of photogenerated electron-hole pairs than those of monolayer g-C₃N₄. A photocatalytic mechanism for the composites was also proposed.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

具有超快电子传输能力的金/薄层氮化碳等离子光催化剂用于光催化产氢

English

Gold/monolayer graphitic carbon nitride plasmonic photocatalyst for ultrafast electron transfer in solar-to-hydrogen energy conversion

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

具有超快电子传输能力的金/薄层氮化碳等离子光催化剂用于光催化产氢

English

Gold/monolayer graphitic carbon nitride plasmonic photocatalyst for ultrafast electron transfer in solar-to-hydrogen energy conversion

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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