原位还原的WO3负载的第VIII族金属催化剂上光热协同甲烷二氧化碳重整

doi:10.1016/S1872-2067(21)63835-4

催化学报 ›› 2021, Vol. 42 ›› Issue (11): 1976-1982.DOI: 10.1016/S1872-2067(21)63835-4

原位还原的WO₃负载的第VIII族金属催化剂上光热协同甲烷二氧化碳重整

刘会敏^a^,^b^,^*(), 孟宪光^b, 杨维维^c, 赵桂霞^b, 贺德华^c, 叶金花^b^,^#()

^a辽宁工业大学化学与环境工程学院, 辽宁锦州121001, 中国
^b日本国立材料研究机构, 国际材料纳米结构中心, 日本
^c清华大学化学系, 有机光电及分子工程教育部重点实验室, 北京100084, 中国

收稿日期:2021-03-10 接受日期:2021-03-10 出版日期:2021-11-18 发布日期:2021-05-18
通讯作者: 刘会敏,叶金花
基金资助:
国家自然科学基金(21902116)

Photo-thermal CO₂ reduction with methane on group VIII metals: In situ reduced WO₃ support for enhanced catalytic activity

Huimin Liu^a^,^b^,^*(), Xianguang Meng^b, Weiwei Yang^c, Guixia Zhao^b, Dehua He^c, Jinhua Ye^b^,^#()

^aSchool of chemical and environmental engineering, Liaoning University of Technology, Jinzhou 121001, Liaoning, China
^bInternational Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
^cInnovative Catalysis Program, Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China

Received:2021-03-10 Accepted:2021-03-10 Online:2021-11-18 Published:2021-05-18
Contact: Huimin Liu,Jinhua Ye
About author:^*Tel: +86-15810724205; E-mail: liuhuimin08@tsinghua.org.cn;
Supported by:
National Natural Science Foundation of China(21902116)

摘要/Abstract

摘要：

将廉价的碳源(CO₂)转化为化石燃料可缓解由于温室气体引起的气候问题. CH₄/CO₂重整(CRM)是CO₂转化利用的有效途径之一, 要实现这个过程的关键是研制高效的光响应催化剂.
本文采用WO₃负载的第VIII族金属催化剂、引入光照能量来活化CO₂, 利用光热协同催化CRM. 研究结果表明, 光学材料WO₃负载的第VIII族金属催化剂在可见光辅助下的催化活性是热驱动条件下的1.4~2.4倍, 与等离子体金催化剂的活性增强率(1.7倍)相当. 进一步以不同波段的可见光为光源, 对WO₃负载的第VIII族金属催化剂上催化活性提高的原因进行了研究. 结果表明, 活性增强率与WO₃在可见光区域的吸光趋势并不吻合, 说明并非WO₃提高了其负载的第VIII族金属催化剂上CRM活性.
除WO₃外, WO_3-_x亦可作为光催化剂吸收可见光, 因此, 本文通过X射线光电子能谱、X射线衍射及紫外-可见分光光度法等进行表征. 结果表明, 在还原型CRM反应气氛下, WO₃部分原位还原为WO_3-_x, 并且活性增强率与WO_3-_x在可见光区域的吸光趋势相吻合, 说明导致可见光辅助下活性增强的是WO_3-_x而不是WO₃. 热力学分析及原位电子顺磁共振波谱法结果表明, CO₂的活化是CRM的速控步,该步骤吸热, 在500^oC时不能自发进行. 在可见光的辅助下, CO₂可以被WO_3-_x通过Mars-van Krevelen机理进行活化, 提高速控步的反应速率, 进而提高了催化活性. 综上, 本文为提高光催化活性提供了一条有效途径.

关键词: 氧化钨, 可见光, 原位还原, 光催化, 二氧化碳还原

Abstract:

Photo-thermal CO₂ reduction with methane (CRM) is beneficial for solar energy harvesting and energy storage. The search for efficient photo-thermal catalysts is of great significance. Here, we reveal that group VIII metal catalysts supported by optical material WO₃ are more effective for photo-thermal CRM, giving catalytic activities with visible light assistance that are 1.4-2.4 times higher than that achieved under thermal conditions. The activity enhancement (1.4-2.4 times) was comparable to that achieved with plasmonic-Au-promoted catalysts (1.7 times). Characterization results indicated that WO₃ was partially reduced to WO_3-_x in situ under the reductive CRM reaction atmosphere, and that WO_3-_x rather than WO₃ enhanced the activities with visible light assistance. Our method provides a promising approach for improving the activity of catalysts under light irradiation.

Key words: Tungsten oxide, Visible light, In situ reduction, Photocatalysis, CO₂ reduction

刘会敏, 孟宪光, 杨维维, 赵桂霞, 贺德华, 叶金花. 原位还原的WO₃负载的第VIII族金属催化剂上光热协同甲烷二氧化碳重整[J]. 催化学报, 2021, 42(11): 1976-1982.

Huimin Liu, Xianguang Meng, Weiwei Yang, Guixia Zhao, Dehua He, Jinhua Ye. Photo-thermal CO₂ reduction with methane on group VIII metals: In situ reduced WO₃ support for enhanced catalytic activity[J]. Chinese Journal of Catalysis, 2021, 42(11): 1976-1982.

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图/表 6

Fig. 1. Catalytic performances of Rh/WO3 and Rh/TiO2 in CRM. (a) CO2 conversion; (b) CH4 conversion; (c) CO yield; (d) H2 yield. Reaction conditions: 500 °C, CH4/CO2 = 1, flow rate = 20.0 mL min-1, 0.050 g of catalyst, with or without visible light irradiation (500 nm < λ < 800 nm).

Fig. 2. XRD patterns (a), enlarged XRD patterns in the range of 32°-36° (b), UV-visible spectra (c), XPS spectra (d), and HRTEM images of Rh/WO3 (e) and Rh/TiO2 (f).

Table 1 Physicochemical properties of the supports and catalysts.

Catalyst	Rh loading^a (wt%)	A_BET^b (m² g^-1)
WO₃	—	5.1
Rh/WO₃	0.93	5.5
TiO₂	—	8.6
Rh/TiO₂	1.00	8.3

Fig. 3. (a) Wavelength ranges obtained with different filter sets; CH4 and CO2 conversions (b) and H2 and CO yields (c) obtained with Rh/WO3 without and with light irradiation with different wavelength ranges; (d) UV-visible spectra of fresh Rh/WO3 and spent Rh/WO3 (400-1000 nm) and AE/photon. Reaction conditions: 500 °C, CH4/CO2 = 1, flow rate = 20.0 mL min-1, 0.050 g of catalyst.

Fig. 4. (a) W 4f XPS spectra of Rh/WO3 and spent Rh/WO3, with the blue and orange lines denoting the peaks of W6+ and W5+, respectively; (b) H2-TPR profiles of WO3 and Rh/WO3; XRD pattern (c) and UV-visible spectrum (d) of spent Rh/WO3.

Fig. 5. In situ ESR profiles of fresh and spent Rh/WO3 in CO2 atmosphere with and without visible light irradiation.

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原位还原的WO₃负载的第VIII族金属催化剂上光热协同甲烷二氧化碳重整

Photo-thermal CO₂ reduction with methane on group VIII metals: In situ reduced WO₃ support for enhanced catalytic activity

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