太阳能驱动WO3‒x光热催化CO2还原的C‒C偶联机制

doi:10.1016/S1872-2067(21)63868-8

催化学报 ›› 2022, Vol. 43 ›› Issue (5): 1230-1237.DOI: 10.1016/S1872-2067(21)63868-8

太阳能驱动WO_3‒_x光热催化CO₂还原的C‒C偶联机制

邓宇^a^,^†, 李珏^a^,^†, 张如梦^a, 韩春秋^b, 陈亿^b, 周莹^b, 刘维^a, Po Keung Wong^c, 叶立群^a()

^a三峡大学材料与化学工程学院, 无机非金属晶体与能量转换材料重点实验室, 湖北宜昌443002
^b西南石油大学材料科学与工程学院, 油气藏地质与开发国家重点实验室, 四川成都610500
^c香港中文大学生命科学学院, 香港沙田

收稿日期:2021-05-18 接受日期:2021-06-11 出版日期:2022-05-18 发布日期:2022-03-23
通讯作者: 叶立群
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(51872147);111计划(D20015);河南省高校科技创新团队支持计划(19IRTSTHN025);三峡大学学位论文培优基金项目

Solar-energy-driven photothermal catalytic C-C coupling from CO₂ reduction over WO_3-_x

Yu Deng^a^,^†, Jue Li^a^,^†, Rumeng Zhang^a, Chunqiu Han^b, Yi Chen^b, Ying Zhou^b, Wei Liu^a, Po Keung Wong^c, Liqun Ye^a()

^aCollege of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002, Hubei, China
^bState Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, School of Materials Science and Engineering, Southwest Petroleum University, Chengdu, 610500, Sichuan, China
^cSchool of Life Sciences, The Chinese University of Hong Kong, Shatin, Hong Kong SAR, China

Received:2021-05-18 Accepted:2021-06-11 Online:2022-05-18 Published:2022-03-23
Contact: Liqun Ye
About author:First author contact:
^†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(51872147);111 Project(D20015);Program for Innovative Research Team of Science and Technology in the University of Henan Province(19IRTSTHN025);Research Fund for Excellent Dissertation of China Three Gorges University

摘要/Abstract

摘要：

氧化钨(WO₃)一直是太阳能驱动CO₂减排领域的一种备受关注的催化剂. 作为一种无毒、廉价的n型半导体, WO₃可以吸收大约12%的太阳光, 因此被认为是最具吸引力的光催化候选材料之一. 然而, WO₃的红外响应性能受到带宽(E_g = 2.5‒2.8 eV)的限制, 从而影响其光热催化条件下CO₂的还原活性. 因此, 在太阳能驱动的WO₃催化CO₂还原反应中, 主要生成C1产物(包括CO, CH₄), 很少有C2烃类产物的报道.

本文采用一锅法合成了WO_3‒_x纳米片, 并利用X射线衍射、X射线光电子能谱、透射电镜、电子自旋共振和拉曼光谱表征了其基本结构. 光致发光光谱表明, WO_3‒_x比WO₃有更强的光生载流子分离能力和更弱的载流子复合能力, 这与WO_3‒_x更强的光电流响应和更小的阻抗一致. 此外, CO₂吸附和程序升温脱附结果表明, 氧空位的存在使WO_3‒_x具有更强的CO₂吸附能力和更弱的CO₂脱附能力, 这为CO₂高效参与反应并实现C‒C偶联生成C2产物提供了条件.

另一方面, 氧空位的引入有效地拓宽了WO₃材料的光响应范围, 漫反射光谱结果表明, WO_3‒_x材料对红外光的吸收能力更强. 由此造成的热效应通过热成像数据显示出来, WO₃的光热平衡温度为92.3 °C, WO_3‒_x的平衡温度可达177 °C. 在光热协同催化下, 辐照4 h后, WO_3‒_x产生的C₂H₄和C₂H₆分别达到5.30和0.93 μmol·g^-1, 生成C2产物的选择性大于34%. 采用光热催化CO₂还原生成产物的产量远高于同样温度下热催化反应结果, 说明WO_3‒_x较好的CO₂还原性能得益于光诱导的光热催化性能.

最后, 通过原位傅里叶红外光谱以及理论计算, 进一步考察了WO_3‒_x光热催化得到C2产物的反应路径: 催化剂吸附CO₂后, 光生电子还原CO₂得到-COOH, -CHO, -CH₃中间体, WO₃上的中间体容易发生脱附, 并生成CH₄和CO产物; 而WO_3‒_x表面存在的大量氧空位为-CH₂/-CH₃进一步偶联生成C₂H₄/C₂H₆提供了条件. 具体反应路径为: CO₂ → COOH → CHO → CH₂/CH₃ → C₂H₄/C₂H₆.

综上, 本文采用WO_3‒_x光热催化CO₂还原可高效制备C2产物, 分析了反应机理, 为设计太阳能驱动的高活性CO₂还原C‒C偶联催化剂提供了新思路.

关键词: 氧化钨, 氧空位, CO₂还原, 光热, C?C偶联

Abstract:

Solar-energy-driven catalytic CO₂ reduction for the production of value-added carbon-based materials and chemical raw materials has attracted great interest to alleviate the global climate change and energy crisis. The production of multicarbon (C2) products through CO₂ reduction is extremely attractive, however, the yield and selectivity of C2 products remain low because of the low reaction temperature required and the low photoelectron density of the substrate. Here, we introduce WO_3-_x, which contains oxygen vacancies and exhibits an excellent photothermal conversion efficiency, to improve the generation of C2 products (C₂H₄ and C₂H₆) under simulated sunlight (UV-Vis-IR) irradiation. WO_3-_x produced 5.30 and 0.93 μmol·g^-1 C₂H₄ and C₂H₆, respectively, after 4 h, with a selectivity exceeding 34%. In situ Fourier transform infrared spectra and theoretical calculations showed that the oxygen vacancies enhanced the water activation and hydrogenation of adsorbed CO for the formation of C2 products via C-C coupling from CH₂/CH₃ intermediates. The findings of this study could assist in the design of highly active solar-energy-driven catalysts to produce C-C coupling products through CO₂ reduction.

Key words: WO₃, Oxygen vacancy, CO₂ reduction, Photothermal, C-C coupling

邓宇, 李珏, 张如梦, 韩春秋, 陈亿, 周莹, 刘维, Po Keung Wong, 叶立群. 太阳能驱动WO_3‒_x光热催化CO₂还原的C‒C偶联机制[J]. 催化学报, 2022, 43(5): 1230-1237.

Yu Deng, Jue Li, Rumeng Zhang, Chunqiu Han, Yi Chen, Ying Zhou, Wei Liu, Po Keung Wong, Liqun Ye. Solar-energy-driven photothermal catalytic C-C coupling from CO₂ reduction over WO_3-_x[J]. Chinese Journal of Catalysis, 2022, 43(5): 1230-1237.

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图/表 5

Fig. 1. The characterization results of different samples. (a) XRD patterns of WO3 and WO3?x; (b) HRTEM images of WO3?x; (c) Intensity profiles along the arrows in b and the corresponding elemental mapping of W and O of WO3?x; (d) ESR spectra; (e) O 1s XPS spectra; (f) Raman spectra of WO3 and WO3?x.

Fig. 2. (a) UV-Vis-IR DRS spectra of WO3 and WO3-x. (b) Temperature-time variation curve under UV-Vis-IR irradiation; Photothermal images after 5 min of UV-Vis-IR irradiation: blank (c), WO3 (d), and WO3-x (e).

Fig. 3. Light-induced catalytic performance of WO3 and WO3-x; (a) CO, (b) CH4, (c) C2H4, and (d) C2H6 generation; (e) Comparison between the hydrocarbon fuel production rates over WO3-x under UV-Vis, IR, and UV-Vis-IR irradiation, and 73, 106, and 177 °C; (f) On-line gas chromatography mass spectrum of the WO3-x catalyzed CO2 reduction under UV-Vis-IR light irradiation.

Fig. 4. CO2 adsorption (a) and TPD (b) of WO3 and WO3-x; Photocurrent responses (c), electrochemical impedance spectra (d), PL spectra (e), and time-resolved PL spectra (f) of WO3 and WO3-x.

Fig. 5. In-situ FTIR spectra indicating the adsorption and activation of CO2 in the presence of H2O on WO3-x between 1000 and 1800 cm-1 (a) and 2900 and 3400 cm-1 (b). Differential charge density diagrams (0.04 electrons/Å3) of C1 adsorbed on the material surface: (c) CO2 adsorbed on WO3, (d) CO adsorbed on WO3, (e) CO2 adsorbed on WO3-x, and (f) CO adsorbed on WO3-x. Differential charge density diagrams (0.003 electrons/Å3) of C2 adsorbed on the material surface: (g) CH3 + CH3 adsorbed on WO3, (h) CH2 + CH2 adsorbed on WO3, (i) CH3 + CH3 adsorbed on WO3-x, (j) and CH2 + CH2 adsorbed on WO3-x.

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太阳能驱动WO_3‒_x光热催化CO₂还原的C‒C偶联机制

Solar-energy-driven photothermal catalytic C-C coupling from CO₂ reduction over WO_3-_x

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