缺陷态TiO2-x -Au团簇复合结构设计实现高效可见光驱动CO2还原

doi:10.16085/j.issn.1000-6613.2024-1258

化工进展 ›› 2025, Vol. 44 ›› Issue (6): 3062-3071.DOI: 10.16085/j.issn.1000-6613.2024-1258

• 专栏：化工生态环境前沿交叉新技术 • 上一篇

缺陷态TiO_2-_x -Au团簇复合结构设计实现高效可见光驱动CO₂还原

肖立¹(), 岐少鹏², 周昆²(), 薄雅楠², 王秀林¹, 姚辉超¹, 戴若云¹, 隋依言¹

^1.中海石油气电集团有限责任公司技术研发中心，北京 100028
^2.中国科学技术大学核科学技术学院，安徽合肥 230026

收稿日期:2024-07-31 修回日期:2024-11-21 出版日期:2025-06-25 发布日期:2025-07-08
通讯作者: 周昆
作者简介:肖立（1991—），男，硕士研究生，研究方向为流体力学。E-mail：xiaoli6@cnooc.com.cn。
基金资助:
中国海洋石油集团有限公司“十四五”重大科技项目CCUS专项课题三子课题“二氧化碳光电催化技术研究”(KJGG-2022-12-CCUS-030500)

Composite structure design of defect state TiO_2-_x -Au clusters for efficient visible light driven CO₂ reduction

XIAO Li¹(), QI Shaopeng², ZHOU Kun²(), BO Yanan², WANG Xiulin¹, YAO Huichao¹, DAI Ruoyun¹, SUI Yiyan¹

^1.Technology R & D Center, CNOOC Gas & Power Group, Beijing 100028, China
^2.School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2024-07-31 Revised:2024-11-21 Online:2025-06-25 Published:2025-07-08
Contact: ZHOU Kun

摘要/Abstract

摘要：

提高太阳光吸收能力和电荷分离效率对TiO₂基光催化剂实现高效CO₂光还原具有重要意义。通过在TiO₂纳米片同步引入氧空位和Au团簇，构建了TiO_2-_x -Au团簇。TiO_2-_x 与Au团簇之间的协同作用增强了可见光吸收、光诱导电荷分离和迁移过程，这对促进CO₂光转化具有重要意义。合成的TiO_2-_x -Au团簇增强了光催化CO₂还原为CO的能力，其中TiO_2-_x -Au_4.985团簇的光催化性能最好，CO产率9.45μmol/(g·h)明显优于纯TiO_2-_x 和TiO₂。本研究为开发新型TiO₂基光催化剂提供了新的见解和启示。

关键词: 复合结构, TiO_2-_x, Au团簇, 光催化CO₂还原

Abstract:

It is important to improve the absorption capacity of sunlight and charge separation efficiency to achieve efficient CO₂ photoreduction with TiO₂-based photocatalyst. In this paper, TiO_2-_x -Au clusters were constructed by introducing oxygen vacancy and Au clusters into TiO₂ nanosheets simultaneously. The synergistic interaction between TiO_2-_x and Au clusters enhanced visible light absorption, photoinduced charge separation and migration processes, which had important significance for promoting CO₂ photoconversion. The photocatalytic reduction of CO₂ to CO was enhanced by the synthesized TiO_2-_x -Au clusters. The TiO_2-_x -Au_4.985 clusters displayed the CO yield of 9.45μmol/(g·h), which was significantly better than that of pure TiO_2-_x and TiO₂. Our findings provided new insights and implications for the development of novel TiO₂-based photocatalysts.

Key words: composite structure, TiO_2-_x, Au cluster, photocatalytic CO₂ reduction

中图分类号:

O643.36

肖立, 岐少鹏, 周昆, 薄雅楠, 王秀林, 姚辉超, 戴若云, 隋依言. 缺陷态TiO_2-_x -Au团簇复合结构设计实现高效可见光驱动CO₂还原[J]. 化工进展, 2025, 44(6): 3062-3071.

XIAO Li, QI Shaopeng, ZHOU Kun, BO Yanan, WANG Xiulin, YAO Huichao, DAI Ruoyun, SUI Yiyan. Composite structure design of defect state TiO_2-_x -Au clusters for efficient visible light driven CO₂ reduction[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3062-3071.

图/表 19

图1 Au-GSH NC的紫外可见吸收光谱（插图为Au-GSH NC的光学照片）

图2 Au25(SR)18团簇的TEM图(a)、光学照片(b)、UV-Vis吸收光谱(c)

图3 TiO2纳米片(a)、(b)及TiO2-x -Au NC(c)的透射电子显微镜照片和TiO2-x -Au NC(d)的高分辨透射电子显微镜照片

图4 不同Au团簇负载量的TiO2-x -Au复合样品TiO2-x -Au1.727 NC(a)、TiO2-x -Au3.259 NC(b)、TiO2-x -Au4.262 NC(c)和TiO2-x -Au4.985 NC(d)的透射电子显微镜照片

表1 ICP对样品中Au含量的测量

样品	Au NCs(Au)投入量/mg·mL^-1	ICP结果(Au)/mg·mL^-1
TiO_2-_x -Au_1.727	1.5	1.727
TiO_2-_x -Au_3.259	3	3.259
TiO_2-_x -Au_4.265	4	4.265
Ti0_2-_x -Au_4.985	5	4.985
TiO_2-_x -Au_4.804	6	4.804

图5 TiO2-x -Au样品的X射线面分布能谱图结果

图6 TiO2-x -Au NC样品的元素总谱

图7 TiO2-x 和TiO2-x -Au NC的X射线衍射花样

图8 X射线光电子能谱图

图9 TiO2、TiO2-x 及TiO2-x -Au NC的EPR图谱

图10 可见光下催化CO2还原性能(a)、不同气氛下CO2还原性能(b)、通过复合催化剂还原13CO2产生的13CH4（m/z=17）的质谱图(c)和全谱光下的光催化CO2还原性能(d)

图11 TiO2-x -Au NC催化剂循环稳定性测试

图12 反应前(a)和反应后(b)TiO2-x -Au NC催化剂透射电子显微镜照片；催化前(c)和催化后(d)TiO2-x -Au NC催化剂粒径分布直方图

图13 反应前后样品的X射线粉末衍射花样

表2 不同催化剂进行光催化CO2转化为CO文献汇总

样品	催化剂投入量/mg	CO产率/μmol·g^-1·h^-1
TiO_2-_x -Au_4.985	20	9.45
CuGaS₂/rGO-TiO₂^[13]	200~300	0.15
m-CeO₂/g-C₃N₄^[14]	50	0.24
g-C₃N₄/MXene^[15]	50	4.985

图14 TiO2和TiO2-x -Au NC的UV-vis漫反射光谱(a)和K-M方程转换的图谱(b)

图15 样品的全谱光下的光电流图(a)、可见光下的光电流图(b)和光致发光光谱图(c)

图16 全谱光（左）和可见光（右）下的电荷转移示意图

图17 TiO2-x -Au NC光催化CO2还原过程中原位漫反射红外谱图

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缺陷态TiO_2-_x -Au团簇复合结构设计实现高效可见光驱动CO₂还原

Composite structure design of defect state TiO_2-_x -Au clusters for efficient visible light driven CO₂ reduction

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