整体式三氧化钨/氧化石墨烯气凝胶增强可见光光催化氧化NO性能

引用本文: 杨荔, 刘旸, 张瑞阳, 李伟, 李璞, 王星, 周莹. 整体式三氧化钨/氧化石墨烯气凝胶增强可见光光催化氧化NO性能[J]. 催化学报, 2018, 39(4): 646-653. doi: 10.1016/S1872-2067(17)62974-7 shu

Citation: Li Yang, Yang Liu, Ruiyang Zhang, Wei Li, Pu Li, Xin Wang, Ying Zhou. Enhanced visible-light photocatalytic performance of a monolithic tungsten oxide/graphene oxide aerogel for nitric oxide oxidation[J]. Chinese Journal of Catalysis, 2018, 39(4): 646-653. doi: 10.1016/S1872-2067(17)62974-7 shu

整体式三氧化钨/氧化石墨烯气凝胶增强可见光光催化氧化NO性能

杨荔 ^a, ,
刘旸 ^a, ,
张瑞阳 ^a, ,
李伟 ^b, ,
李璞 ^c, ,
王星 ^c, ,
周莹 ^a,

a 西南石油大学材料科学与工程学院, 新能源材料与技术研究中心, 四川成都 610500;
b 四川旭航新材料有限公司, 四川成都 610041;
c 中国测试技术研究院, 四川成都 610021
基金项目:
四川省青年科技创新研究团队（2016TD0011）；四川省杰出青年科技基金（2014JQ0017）；国家自然科学基金（21403172）.

摘要: 近年来，光催化技术在去除以NO为代表的诸多室内气体污染物方面展现出巨大的潜力.单质铋和铋系氧化物，非金属氧化物以及钙钛矿等众多半导体光催化材料均具有优异的NO降解效率，但很难控制氧化产物.因而会生成大量毒性更强的中间产物NO₂造成二次污染.因此，寻求一种清洁、高效，且具有良好选择性的光催化材料成为了亟待解决的问题.六方相三氧化钨（h-WO₃）的价带位置较正，氧化电位较高，具有很强的氧化能力，是一种良好的氧化性光催化半导体材料.然而，WO₃催化材料多为粉末状，不仅容易团聚，难以回收利用并且会堵塞检测气路.同时，WO₃本身存在的电子-空穴复合率高，弱的可见光响应性等问题使其光催化活性较低.因而，制备具有良好可见光响应，高电子-空穴分离效率的一体化WO₃材料是其广泛应用前急需解决的问题.而石墨烯气凝胶是理想的催化剂载体，其较高的比表面积以及多孔状结构可有效地增加催化剂的暴露面积，提升催化剂利用率；更重要的是，氧化石墨烯（GO）具有极高的导电率，可作为电子受体加速电子-空穴对的分离而提升光催化活性.因此，以GO作为基体材料，构建WO₃/GO气凝胶一体化材料有良好的应用前景.然而，现在还鲜见有关宏观WO₃/GO气凝胶光催化降解NO的报道.
本文以偏钨酸铵为钨源，利用体积分数为25%的冰醋酸在180℃条件下制备六方相三氧化钨.通过机械搅拌以及冷冻干燥法制备WO₃/GO气凝胶.经光催化氧化NO测试发现其可见光下降解率可达51%，是WO₃粉体的3.3倍，并且NO₂生成率仅为0.5%，远远低于其他相关光催化材料.采用了X射线衍射（XRD），透射电镜（TEM），X射线光电子能谱（XPS），紫外-漫反射分光光度计（UV-DRS），傅里叶红外光谱（FTIR）和荧光光谱（PL）等手段研究了其光催化性能提高的原因.
XRD测试显示，复合材料主体为h-WO₃，说明GO的引入并未破坏材料晶体结构；TEM和BET测试发现，在加入GO之后h-WO₃分散性变好，比表面积变大，从而可暴露更多的光催化活性位点.UV-DRS吸收光谱可以看到WO₃/GO气凝胶材料的吸收边发生了显著的红移，其禁带宽度从3.44eV减小到3.16eV，这可能是GO影响了WO₃的能带结构所致.同时PL结果表明，引入了GO之后，气凝胶材料的非辐射跃迁程度明显减小表明其电子-空穴对的复合得到了显著抑制，电子迁移显著加强.
综合以上结果，可以得到WO₃/GO光催化性能提升以及良好的产物选择性的原因.首先，三维气凝胶材料的结构提升了催化剂的有效利用率，较大的比表面积暴露了更多的活性位点.其次，GO的引入减小了复合材料的禁带宽度，并使其吸光性能有所改善，产生了更多的光生电子和空穴.最后，GO本身极高的导电性，使光生电子-空穴对得以有效的分离，一方面，电子通过GO迅速转移到材料表面来参与光催化反应；另一方面，电子的快速转移抑制了电子-空穴对的复合，进而提高光催化性能，而且较正的价带位置保证了NO较为彻底的氧化为NO₃^-.因此，相比传统粉末WO₃催化材料，一体化的WO₃/GO气凝胶不仅显著提升了NO降解率，同时严格抑制了毒副产物NO₂的生成，同时更具有容易回收利用，不存在二次污染的优点.综上所述，WO₃/GO一体化气凝胶光催化材料有望在环境净化与能源领域表现出良好的应用前景.

关键词:

English

Enhanced visible-light photocatalytic performance of a monolithic tungsten oxide/graphene oxide aerogel for nitric oxide oxidation

Li Yang ^a, ,
Yang Liu ^a, ,
Ruiyang Zhang ^a, ,
Wei Li ^b, ,
Pu Li ^c, ,
Xin Wang ^c, ,
Ying Zhou ^a,

a The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China;
b Sichun Xuhang New Materials Co., Itd, Chengdu 610041, Sichuan, China;
c National Institute of Measurement and Testing Technology, Chengdu 610021, Sichuan, China
Received Date: 20 November 2017
Revised Date: 13 December 2017
Fund Project:
This work was supported by the Innovative Research Team of Sichuan Province (2016TD0011), the Sichuan Youth Science and Technology Foundation (2014JQ0017) and the National Natural Science Foundation of China (21403172).

Abstract: Photocatalysis is considered a promising technique for removal of pollutants from indoor air. However, the low selectivity and limited recyclability of photocatalysts in powder form currently limit their practical application. In this work, we reported the successful preparation of a monolithic tungsten oxide (WO₃)/graphene oxide (GO) aerogel photocatalyst through a cost-effective freeze-drying method. GO not only acts as a macroscopic support, but also increases the catalyst surface area from 46 to 57 m²/g, enhances the light absorption in the visible-light region, and raises the separation efficiency of photogenerated electron-hole pairs. The Obtained WO₃/GO aerogel exhibited an outstanding visible-light photocatalytic degradation rate of nitric oxide of 51%, which was 3.3 times that of pristine WO₃ powder. In addition, the aerogel displayed excellent selectivity, with a generation fraction of toxic nitrogen dioxide of as low as 0.5%. This work presents a facile synthesis route to fabricate a monolithic WO₃/GO aerogel photocatalyst with great promise for air purification.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

整体式三氧化钨/氧化石墨烯气凝胶增强可见光光催化氧化NO性能

English

Enhanced visible-light photocatalytic performance of a monolithic tungsten oxide/graphene oxide aerogel for nitric oxide oxidation

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中国化学会秘书处

整体式三氧化钨/氧化石墨烯气凝胶增强可见光光催化氧化NO性能

English

Enhanced visible-light photocatalytic performance of a monolithic tungsten oxide/graphene oxide aerogel for nitric oxide oxidation

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

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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

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