Carboxyl-Functionalized Graphene for Highly Efficient H<sub>2</sub>-Evolution Activity of TiO<sub>2</sub> Photocatalyst

Citation: Ping Wang, Haitao Li, Yanjie Cao, Huogen Yu. Carboxyl-Functionalized Graphene for Highly Efficient H₂-Evolution Activity of TiO₂ Photocatalyst[J]. Acta Physico-Chimica Sinica, 2021, 37(6): 200804. doi: 10.3866/PKU.WHXB202008047 shu

羧基功能化石墨烯增强TiO₂光催化产氢性能

王苹 ^{1,
,} ,
李海涛 ^1, ,
曹艳洁 ^1, ,
余火根 ^{1, 2,
,}

1.
武汉理工大学化学化工与生命科学学院，武汉 430070
2.
武汉理工大学硅酸盐建筑材料国家重点实验室，武汉 430070

通讯作者: 王苹, wangping0904@whut.edu.cn
余火根, yuhuogen@whut.edu.cn

基金项目:
国家自然科学基金 21771142

国家自然科学基金 51872221

中央高校基本科研业务费 WUT2019IB002

摘要: 利用半导体光催化剂(CdS、g-C₃N₄、TiO₂等)产氢是将太阳能转换为氢能以满足未来能源需求的前瞻性策略之一。在众多光催化剂中，TiO₂因其合适的还原电位和出色的化学稳定性而备受关注。然而，TiO₂受光激发产生的电子和空穴容易发生猝灭而表现出有限的光催化性能。由于具备优异的导电性和稳定性，石墨烯可以作为一种有效的电子助剂加速光生电子的传输，进而提高TiO₂的产氢性能。但是，在光催化反应中，除了光生电子的快速转移外，石墨烯表面的界面产氢反应也非常重要。因此，有必要进一步优化石墨烯的微观结构(功能化石墨烯)，以提高石墨烯基TiO₂光催化剂的产氢性能。通常，石墨烯的功能化是一个可以在石墨烯表面上引入产氢活性位点的有效策略。与非共价功能化(例如在石墨烯表面上加载Pt，MoS_x和CoS_x)相比，石墨烯的共价功能化可以通过化学反应将产氢活性位点与石墨烯表面的官能团相结合，并形成强相互作用，有利于界面的产氢反应。本文将开环和酯化反应制备的羧基功能化石墨烯(rGO-COOH)成功地通过超声辅助自组装法修饰TiO₂得到高活性的TiO₂/rGO-COOH光催化剂。傅立叶变换红外(FTIR)光谱显著增强的―COOH官能团特征峰、X射线光电子能谱(XPS)中的峰面积变化和热重(TG)曲线的质量变化证实了GO向rGO-COOH的成功转变。X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、XPS和紫外可见漫反射光谱(UV-Vis)等一系列表征可证明TiO₂/rGO-COOH光催化剂的成功合成。光催化产氢测试结果表明TiO₂/rGO-COOH样品表现出较高的产氢活性(254.2 μmol·h^-1·g^-1)，分别是TiO₂/GO和TiO₂的2.06和4.48倍。光催化活性提高可归因于羧基功能化石墨烯中具有优异亲核性的羧基可以富集氢离子，并作为有效的产氢活性位点，显著地提高TiO₂的界面产氢反应速率。这项研究为我们在光催化产氢领域中开发高活性石墨烯负载的光催化剂提供了新的思路。

关键词:

English

Carboxyl-Functionalized Graphene for Highly Efficient H₂-Evolution Activity of TiO₂ Photocatalyst

Ping Wang ^{1,
,} ,
Haitao Li ^1, ,
Yanjie Cao ^1, ,
Huogen Yu ^{1, 2,
,}

1.
School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, China
2.
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China

Corresponding author: Ping Wang, wangping0904@whut.edu.cn Huogen Yu, yuhuogen@whut.edu.cn

Received Date: 17 August 2020
Accepted Date: 22 September 2020
Revised Date: 21 September 2020
Available Online: 15 June 2021
Fund Project:

Abstract: The use of semiconductor photocatalysts (CdS, g-C₃N₄, TiO₂, etc.) to generate hydrogen (H₂) is a prospective strategy that can convert solar energy into hydrogen energy, thereby meeting future energy demands. Among the numerous photocatalysts, TiO₂ has attracted significant attention because of its suitable reduction potential and excellent chemical stability. However, the photoexcited electrons and holes of TiO₂ are easily quenched, leading to limited photocatalytic performance. Furthermore, graphene has been used as an effective electron cocatalyst in the accelerated transport of photoinduced electrons to enhance the H₂-production performance of TiO₂, owing to its excellent conductivity and high charge carrier mobility. For an efficient graphene-based photocatalyst, the rapid transfer of photogenerated electrons is extremely important along with an effectual interfacial H₂-production reaction on the graphene surface. Therefore, it is necessary to further optimize the graphene microstructures (functionalized graphene) to improve the H₂-production performance of graphene-based TiO₂ photocatalysts. The introduction of H₂-evolution active sites onto the graphene surface is an effective strategy for the functionalization of graphene. Compared with the noncovalent functionalization of graphene (such as loading Pt, MoS_x, and CoS_x on the graphene surface), its covalent functionalization can provide a strong interaction between graphene and organic molecules in the form of H₂-evolution active sites that are produced by chemical reactions. In this study, carboxyl-functionalized graphene (rGO-COOH) was successfully modified via ring-opening and esterification reactions on the TiO₂ surface by using an ultrasound-assisted self-assembly method to prepare a high-activity TiO₂/rGO-COOH photocatalyst. The Fourier transform infrared (FTIR) spectra, X-ray photoelectron spectroscopy (XPS), and thermogravimetric (TG) curves revealed the successful covalent functionalization of GO to rGO-COOH by significantly enhanced ―COOH groups in FTIR and increased peak area of carboxyl groups in XPS. A series of characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), XPS, and UV-Vis adsorption spectra, were performed to demonstrate the successful synthesis of TiO₂/rGO-COOH photocatalysts. The experimental data for the hydrogen-evolution rate showed that the TiO₂/rGO-COOH displayed an extremely high hydrogen-generation activity (254.2 μmol∙h⁻¹∙g⁻¹), which was 2.06- and 4.48-fold higher than those of TiO₂/GO and TiO₂, respectively. The enhanced photocatalytic activity of TiO₂/rGO-COOH is ascribed to the carboxyl groups of carboxyl-functionalized graphene, which act as effective hydrogen-generation active sites and enrich hydrogen ions owing to their excellent nucleophilicity that facilitates the interfacial hydrogen production reaction of TiO₂. This study provides novel insights into the development of high-activity graphene-supported photocatalysts in the hydrogen-generation field.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

羧基功能化石墨烯增强TiO₂光催化产氢性能

通讯作者: 王苹, wangping0904@whut.edu.cn
余火根, yuhuogen@whut.edu.cn

English

Carboxyl-Functionalized Graphene for Highly Efficient H₂-Evolution Activity of TiO₂ Photocatalyst

Corresponding author: Ping Wang, wangping0904@whut.edu.cn Huogen Yu, yuhuogen@whut.edu.cn

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

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

羧基功能化石墨烯增强TiO2光催化产氢性能

通讯作者: 王苹, wangping0904@whut.edu.cn 余火根, yuhuogen@whut.edu.cn

English

Carboxyl-Functionalized Graphene for Highly Efficient H2-Evolution Activity of TiO2 Photocatalyst

Corresponding author: Ping Wang, wangping0904@whut.edu.cn Huogen Yu, yuhuogen@whut.edu.cn

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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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

羧基功能化石墨烯增强TiO₂光催化产氢性能

通讯作者: 王苹, wangping0904@whut.edu.cn
余火根, yuhuogen@whut.edu.cn

Carboxyl-Functionalized Graphene for Highly Efficient H₂-Evolution Activity of TiO₂ Photocatalyst

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs