通过金属空位工程促进CO2光还原

doi:10.1016/S1872-2067(24)60074-4

催化学报 ›› 2024, Vol. 63: 202-212.DOI: 10.1016/S1872-2067(24)60074-4

通过金属空位工程促进CO₂光还原

王金龙^a^,^b^,¹, 刘东妮^a^,^b^,¹, 李铭洋^a^,^b, 谷骁一^a^,^b, 吴仕群^a^,^b^,^*(), 张金龙^a^,^b^,^*()

^a华东理工大学化学与分子工程学院, 结构可控先进功能材料及其制备教育部重点实验室, 费林加诺贝尔奖科学家联合研究中心, 上海 200237
^b华东理工大学上海市多介质环境催化与资源化工程技术研究中心, 上海 200237

收稿日期:2024-04-26 接受日期:2024-06-06 出版日期:2024-08-18 发布日期:2024-08-19
通讯作者: *电子信箱: wushiqun@ecust.edu.cn (吴仕群),jlzhang@ecust.edu.cn (张金龙).
作者简介:
¹共同第一作者.
基金资助:
国家重点研发计划(2022YFE0107900);国家重点研发计划(2022YFB3803600);国家自然科学基金(22202070);上海市教委创新计划(2021-01-07-00-02-E00106);上海市科委项目(22230780200);上海市科委项目(20DZ2250400);博士后创新人才支持计划(BX20220107);中国博士后科学基金(2022M720050);上海市科技启明星扬帆计划(22YF1410200);中央高校基本科研业务费(222201717003)

Boosting CO₂ photoreduction by synergistic optimization of multiple processes through metal vacancy engineering

Jinlong Wang^a^,^b^,¹, Dongni Liu^a^,^b^,¹, Mingyang Li^a^,^b, Xiaoyi Gu^a^,^b, Shiqun Wu^a^,^b^,^*(), Jinlong Zhang^a^,^b^,^*()

^aKey Laboratory for Advanced Materials, Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science & Technology, Shanghai 200237, China
^bShanghai Engineering Research Center for Multi-media Environmental Catalysis and Resource Utilization, East China University of Science and Technology, Shanghai 200237, China

Received:2024-04-26 Accepted:2024-06-06 Online:2024-08-18 Published:2024-08-19
Contact: *E-mail: wushiqun@ecust.edu.cn (S. Wu), jlzhang@ecust.edu.cn (J. Zhang).
About author:
¹Contributed equally to this work.
Supported by:
National Key Research and Development Program of China(2022YFE0107900);National Key Research and Development Program of China(2022YFB3803600);National Natural Science Foundation of China(22202070);Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-02-E00106);Science and Technology Commission of Shanghai Municipality(22230780200);Science and Technology Commission of Shanghai Municipality(20DZ2250400);Postdoctoral Innovative Talent Support Program(BX20220107);China Postdoctoral Science Foundation(2022M720050);Shanghai Rising-Star Program(22YF1410200);Fundamental Research Funds for the Central Universities(222201717003)

摘要/Abstract

摘要：

随着化石燃料不断消耗, 世界面临着严重的能源危机和环境恶化, 迫切需要可持续的解决方案. 利用太阳能将CO₂光还原成可燃和可利用的化学物质, 是可持续和清洁能源转换的有效途径之一. In₂O₃是一种n型半导体, 具有光学特性、化学稳定性、成本效益、无毒性质, 在CO₂光还原中广泛应用. 但In₂O₃光还原CO₂的效果还不能令人满意, 这主要是由于CO₂与光催化剂的相互作用弱, In₂O₃的电荷分离效率相对较差. 催化剂的缺陷工程是提高CO₂光催化活性的关键策略, 目前, 大部分研究聚焦于金属氧化物催化剂的阴离子空位的构建, 但对金属空位及其效应的探索仍然不足.

本文通过直接溶剂热和煅烧法成功合成了具有高密度铟空位(V_In)的In₂O₃. 高角度环形暗场扫描透射电镜结果表明, 合成的In₂O₃材料均表现出高度结晶的颗粒结构. 紫外-可见光漫反射光谱结果表明, V_In的引入显著提高了催化剂的光吸收能力, 结合莫特肖特基(Mott-Schottky)曲线结果, 说明催化剂的能带结构合理, 导带位置满足光催化还原CO₂的最低要求, V_In的引入有效地降低了禁带宽度且导带位置更负, In₂O₃的还原能力更强. 采用光致发光光谱、时间分辨光致发光光谱、光电流强度曲线和电化学阻抗曲线研究了催化剂的载流子分离行为, 结果表明, V_In的引入显著提高了光生载流子分离率和电子寿命. Rama光谱、高分辨率X射线光电子能谱、密度泛函理论(DFT)计算结果佐证了V_In的存在. V_In的引入明显提高了催化效率、表观量子效率和太阳能转化为化学能的效率. 原位漫反射红外傅里叶变换光谱和DFT计算结果表明, V_In作为CO₂活化的活性位点, 有利于CO₂吸附和关键中间体*COOH的形成, 且V_In可以降低CO₂转化速率决定步骤的能垒, 促进CO产量的增加. 结果表明, 该催化剂的CO产率为841.32 μmol g^‒1 h^‒1, 是不含V_In的In₂O₃催化剂的7.4倍.

综上所述, 本文提供了一种构建金属空位的方法, 有效地提高了In₂O₃的光还原CO₂活性, 丰富了金属空位对光催化CO₂还原影响机制的理解, 为设计更有效的CO₂还原光催化剂提供参考.

关键词: 光催化, 二氧化碳光还原, 氧化铟, 金属空位, 缺陷

Abstract:

The photoreduction of greenhouse gas CO₂ using photocatalytic technologies not only benefits environmental remediation but also facilitates the production of raw materials for chemicals. However, the efficiency of CO₂ photoreduction remains generally low due to the challenging activation of CO₂ and the limited light absorption and separation of charge. Defect engineering of catalysts represents a pivotal strategy to enhance the photocatalytic activity for CO₂, with most research on metal oxide catalysts focusing on the creation of anionic vacancies. The exploration of metal vacancies and their effects, however, is still underexplored. In this study, we prepared an In₂O₃ catalyst with indium vacancies (V_In) through defect engineering for CO₂ photoreduction. Experimental and theoretical calculations results demonstrate that V_In not only facilitate light absorption and charge separation in the catalyst but also enhance CO₂ adsorption and reduce the energy barrier for the formation of the key intermediate *COOH during CO₂ reduction. Through metal vacancy engineering, the activity of the catalyst was 7.4 times, reaching an outstanding rate of 841.32 µmol g^‒1 h^‒1. This work unveils the mechanism of metal vacancies in CO₂photoreduction and provides theoretical guidance for the development of novel CO₂ photoreduction catalysts.

Key words: Photocatalyst, CO₂ photoreduction, Indium oxide, Metal vacancy, Defect

王金龙, 刘东妮, 李铭洋, 谷骁一, 吴仕群, 张金龙. 通过金属空位工程促进CO₂光还原[J]. 催化学报, 2024, 63: 202-212.

Jinlong Wang, Dongni Liu, Mingyang Li, Xiaoyi Gu, Shiqun Wu, Jinlong Zhang. Boosting CO₂ photoreduction by synergistic optimization of multiple processes through metal vacancy engineering[J]. Chinese Journal of Catalysis, 2024, 63: 202-212.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60074-4

https://www.cjcatal.com/CN/Y2024/V63/I8/202

图/表 8

Scheme 1. Scheme depicting the synthesis of In2O3 with In vacancies.

Fig. 1. HRTEM images of In2O3 (a) and In2?xO3-20 (e). HAADF-STEM (b) and corresponding elemental mapping of In (c) and O (d) of In2O3. (f) HAADF-STEM and corresponding elemental mapping of In (g) and O (h) of In2?xO3-20.

Fig. 2. (a) XRD patterns of In2O3 and In2?xO3 samples. (b) Raman spectra of In2O3 and In2?xO3 samples. (c) FTIR spectra of In2O3 and In2?xO3-20. (d) In 3d high resolution XPS spectra of In2O3 and In2?xO3-20.

Fig. 3. (a) The UV-vis DRS spectra. (b) Corresponding Tauc plotsusing (αhν)1/2 (Kubelka-Munk parameter) as a function versus the photon energy. Mott-Schottky plots (c) and VB and CB edge potentials and bandgap values (d) of In2O3, In2?xO3-10, In2?xO3-20 and In2?xO3-30.

Fig. 4. (a) Time dependent conversion rates of CO2 to CO of In2O3, In2?xO3-10, In2?xO3-20, In2?xO3-30. (b) Carbon monoxide generation rate of the samples. (c) Reusability of In2?xO3-20 during the process of photocatalytic CO2 reduction. (d) Comparative testing of In2?xO3-20 under different conditions.

Fig. 5. (a) PL spectra of In2O3, In2?xO3-10, In2?xO3-20, In2?xO3-30. Time-resolved fluorescence decay spectra (b), transient photocurrent response density (c) and Nyquist plots of EIS (d) of the samples.

Fig. 6. In situ DRIFTS spectra of CO2 and H2O interaction with In2O3 (a), In2?xO3-20 (b) in the dark and light.

Fig. 7. (a) CO2 adsorption energy on different sites. (b) C=O bond length of adsorbed CO2 on different sites. (c) Bond angle of adsorbed CO2 on different sites. (d,e) Top and side view of charge density difference of In2O3 with CO2 adsorption. (f,g) Top and side view of Charge density difference of In2?xO3 with CO2 adsorption, the topological construction represents electron accumulation (purple) and depletion (green), and the isosurface level is 0.002 e ??3. (h) Gibbs free energy diagrams for the conversion of CO2 into CO on In2O3 and In2?xO3. The blue, and yellow ball represent In, O atom, respectively.

参考文献

[1]	R. Zeng, K. Lian, B. Su, L. Lu, J. Lin, D. Tang, S. Lin, X. Wang, Angew. Chem. Int. Ed., 2021, 60, 25055-25062.
[2]	C. He, S. Wu, Q. Li, M. Li, J. Li, L. Wang, J. Zhang, Chem, 2023, 9, 3224-3244.
[3]	Y. Bian, H. He, G. Dawson, J. Zhang, K. Dai, Sci. China Mater., 2024, 67, 514-523.
[4]	Y. Chen, L. Tan, H. Zhang, X. Zhang, Q. Chen, H. Jiang, F. Ge, S. Wei, X. Gao, P. Wang, Res. Chem. Intermed., 2021, 47, 3349-3362.
[5]	M. Li, Z. Liu, S. Wu, J. Zhang, ACS EST Engg., 2022, 2, 942-956.
[6]	A. Kumar, L. Kumar, Res. Chem. Intermed., 2024, 50, 195-217.
[7]	S. Zhu, S. Liang, J. Bi, M. Liu, L. Zhou, L. Wu, X. Wang, Green Chem., 2016, 18, 1355-1363.
[8]	C. Tan, M. Qi, Z. Tang, Y. Xu, ACS Catal., 2023, 13, 8317-8329.
[9]	S. Hu, Z. Deng, M. Xing, S. Wu, J. Zhang, Res. Chem. Intermed., 2022, 48, 3275-3287.
[10]	F. Xu, K. Meng, B. Cheng, S. Wang, J. Xu, J. Yu, Nat. Commun., 2020, 11, 4613.
[11]	K. Lu, Y. Li, F. Zhang, M. Qi, X. Chen, Z. Tang, Y. M. A. Yamada, M. Anpo, M. Conte, Y. Xu, Nat. Commun., 2020, 11, 5181.
[12]	Z. Liu, Z. Chen, M. Li, J. Li, W. Zhuang, X. Yang, S. Wu, J. Zhang, ACS Catal., 2023, 13, 6630-6640.
[13]	Y. Horiuchi, K. Miyazaki, M. Tachibana, K. Nishigaki, M. Matsuoka, Res. Chem. Intermed., 2023, 49, 1131-1146.
[14]	S. Wu, Z. Chen, W. Yue, S. Mine, T. Toyao, M. Matsuoka, X. Xi, L. Wang, J. Zhang, ACS Catal., 2021, 11, 4362-4371.
[15]	Y. Yu, X. Dong, P. Chen, Q. Geng, H. Wang, J. Li, Y. Zhou, F. Dong, ACS Nano, 2021, 15, 14453-14464.
[16]	S. Wu, X. Tan, J. Lei, H. Chen, L. Wang, J. Zhang, J. Am. Chem. Soc., 2019, 141, 6592-6600.
[17]	M. Li, C. He, X. Yang, Z. Liu, J. Li, L. Wang, S. Wu, J. Zhang, Chem Catal., 2023, 3, 100737.
[18]	L. Wang, J. Wan, Y. Zhao, N. Yang, D. Wang, J. Am. Chem. Soc., 2019, 141, 2238-2241.
[19]	S. Gong, Y. Niu, X. Liu, C. Xu, C. Chen, T. J. Meyer, Z. Chen, ACS Nano, 2023, 17, 4922-4932.
[20]	X. Xu, C. Shao, J. Zhang, Z. Wang, K. Dai, Acta Phys.-Chim. Sin., 2024, 40, 2309031.
[21]	G. Han, C. Liu, Y. Pan, W. Macyk, S. Wageh, A. A. Al-Ghamdi, F. Xu, Adv. Sustain. Syst., 2023, 7, 2200381.
[22]	X. Bai, L. Wang, Y. Zhu, ACS Catal., 2012, 2, 2769-2778.
[23]	J. Li, C. He, J. Wang, X. Gu, Z. Zhang, H. Li, M. Li, L. Wang, S. Wu, J. Zhang, Green Chem., 2023, 25, 8826-8837.
[24]	J. Sheng, Y. He, J. Li, C. Yuan, H. Huang, S. Wang, Y. Sun, Z. Wang, F. Dong, ACS Nano, 2020, 14, 13103-13114.
[25]	S. Li, M. Qi, Y. Fan, Y. Yang, M. Anpo, Y. M. A. Yamada, Z. Tang, Y. Xu, Appl. Catal. B, 2021, 292, 120157.
[26]	M. Zhou, S. Wang, P. Yang, C. Huang, X. Wang, ACS Catal., 2018, 8, 4928-4936.
[27]	J. Xu, Z. Wang, Y. Zhu, ACS Appl. Mater. Interfaces, 2017, 9, 27727-27735.
[28]	W. Yu, J. Zhang, T. Peng, Appl. Catal. B, 2016, 181, 220-227.
[29]	M. Nasirian, Y. P. Lin, C. F. Bustillo-Lecompte, M. Mehrvar, Int. J. Environ. Sci. Technol., 2018, 15, 2009-2032.
[30]	Z. Zhao, Z. Wang, J. Zhang, C. Shao, K. Dai, K. Fan, C. Liang, Adv. Funct. Mater., 2023, 33, 2214470.
[31]	J. Ran, M. Jaroniec, S. Qiao, Adv. Mater., 2018, 30, 1704649.
[32]	Z. Deng, S. Hu, J. Ji, S. Wu, H. Xie, M. Xing, J. Zhang, Appl. Catal. B, 2022, 316, 121621.
[33]	D. Jiang, Y. Zhou, Q. Zhang, Q. Song, C. Zhou, X. Shi, D. Li, ACS Appl. Mater. Interfaces, 2021, 13, 46772-46782.
[34]	J. Low, B. Cheng, J. Yu, Appl. Surf. Sci., 2017, 392, 658-686.
[35]	B. Lei, W. Cui, P. Chen, L. Chen, J. Li, F. Dong, ACS Catal., 2022, 12, 9670-9678.
[36]	P. Xia, M. Antonietti, B. Zhu, T. Heil, J. Yu, S. Cao, Adv. Funct. Mater., 2019, 29, 1900093.
[37]	H. He, Z. Wang, K. Dai, S. Li, J. Zhang, Chin. J. Catal., 2023, 48, 267-278.
[38]	B. Yang, X. Li, Q. Zhang, X. Yang, J. Wan, G. Liao, J. Zhao, R. Wang, J. Liu, R.D. Rodriguez, X. Jia, Appl. Catal. B, 2022, 314, 121521.
[39]	Y. Cao, L. Guo, M. Dan, D. E. Doronkin, C. Han, Z. Rao, Y. Liu, J. Meng, Z. Huang, K. Zheng, P. Chen, F. Dong, Y. Zhou, Nat. Commun., 2021, 12, 1675.
[40]	T. Yang, J. Wang, Z. Wang, J. Zhang, K. Dai, Chin. J. Catal., 2024, 58, 157-167.
[41]	Y. He, J. Sheng, Q. Ren, Y. Sun, W. Hao, F. Dong, ACS Catal., 2023, 13, 191-203.
[42]	P. Yang, H. Zhuzhang, R. Wang, W. Lin, X. Wang, Angew. Chem. Int. Ed., 2019, 58, 1134-1137.
[43]	X. Zhu, J. Yang, X. Zhu, J. Yuan, M. Zhou, X. She, Q. Yu, Y. Song, Y. She, Y. Hua, H. Li, H. Xu, Chem. Eng. J., 2021, 422, 129888.
[44]	Q. Zhang, P. Yang, H. Zhang, J. Zhao, H. Shi, Y. Huang, H. Yang, Appl. Catal. B, 2022, 300, 120729.
[45]	R. Zhang, Y. Zhang, L. Pan, G. Shen, N. Mahmood, Y. Ma, Y. Shi, W. Jia, L. Wang, X. Zhang, W. Xu, J. Zou, ACS Catal., 2018, 8, 3803-3811.
[46]	L. Pan, M. Ai, C. Huang, L. Yin, X. Liu, R. Zhang, S. Wang, Z. Jiang, X. Zhang, J. Zou, W. Mi, Nat. Commun., 2020, 11, 418.
[47]	Y. Qi, L. Song, S. Ouyang, X. Liang, S. Ning, Q. Zhang, J. Ye, Adv. Mater., 2020, 32, 1903915.
[48]	L. Wang, Y. Dong, T. Yan, Z. Hu, F. M. Ali, D. Meira, P. N. Duchesne, J. Loh, C. Qiu, E. E. Storey, Y. Xu, W. Sun, M. Ghoussoub, N. P. Kherani, A. S. Helmy, G. A. Ozin, Nat. Commun., 2020, 11, 2432.
[49]	P. Chang, Y. Wang, Y. Wang, Y. Zhu, Chem. Eng. J., 2022, 450, 137804.
[50]	J. Sheng, Y. He, M. Huang, C. Yuan, S. Wang, F. Dong, ACS Catal., 2022, 12, 2915-2926.

通过金属空位工程促进CO₂光还原

Boosting CO₂ photoreduction by synergistic optimization of multiple processes through metal vacancy engineering

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 8

参考文献

相关文章 15

编辑推荐

Metrics

[1]	张棋祺, 苗慧, 王俊, 孙涛, 刘恩周. In_2.77S₄/K⁺掺杂g-C₃N₄自组装S型异质结光催化H₂O和O₂合成H₂O₂[J]. 催化学报, 2024, 63(8): 176-189.
[2]	厉超, 王朔, 刘媛, 黄细河, 庄严, 吴舒鸿, 汪颖, 温娜, 吴凯丰, 丁正新, 龙金林. 共价有机框架双电场叠加实现高效光催化产氢[J]. 催化学报, 2024, 63(8): 164-175.
[3]	陈春光, 张金锋, 褚海亮, 孙立贤, Graham Dawson, 代凯. 硫族化物基S型异质结光催化剂[J]. 催化学报, 2024, 63(8): 81-108.
[4]	梅子雯, 陈克军, 谭耀, 刘秋文, 陈琴, 王其忧, 汪喜庆, 蔡超, 刘康, 傅俊伟, 刘敏. 从富含缺陷的碳载体到酞菁钴的质子供给用于增强CO₂电还原[J]. 催化学报, 2024, 62(7): 190-197.
[5]	任卫杰, 李宁, 常青, 武杰, 杨金龙, 胡胜亮, 康振辉. 通过碳点从共价三嗪框架中提取光生空穴用于光合作用产过氧化氢[J]. 催化学报, 2024, 62(7): 178-189.
[6]	刘高雄, 陈润东, 夏兵全, 吴珍, 刘善堂, 冉景润. 共价有机框架基光催化剂合成过氧化氢和高价值化学品的最新进展[J]. 催化学报, 2024, 61(6): 97-110.
[7]	杜仕文, 章福祥. 密度泛函理论在光催化中的普遍应用[J]. 催化学报, 2024, 61(6): 1-36.
[8]	任梦真, 刘天府, 董媛媛, 李正, 杨嘉新, 刁振恒, 吕红金, 杨国昱. CdS纳米棒/含Ni多钨氧酸盐光催化苯硫酚氧化偶联耦合制氢[J]. 催化学报, 2024, 61(6): 312-321.
[9]	陈朝辉, 邓军, 郑燕梅, 张文君, 董琳, 陈祖鹏. 通过调节碳自由基的反应活性调控偶联反应产物和羰基化合物的选择性合成[J]. 催化学报, 2024, 61(6): 135-143.
[10]	邵韵航, 张亚宁, 陈潮锋, 窦帅, 娄阳, 董玉明, 朱永法, 潘成思. 通过晶面调控产生强内建电场以提高卟啉光催化剂的H₂O₂生成速率[J]. 催化学报, 2024, 61(6): 205-214.
[11]	毛海舫, 刘洋, 许振民, 卞振锋. 缺陷诱导电子-金属载体相互作用加速固液界面Fenton反应[J]. 催化学报, 2024, 61(6): 247-258.
[12]	徐伟, 甄超, 朱华泽, 姚婷婷, 邱建航, 梁艳, 白朔, 陈春林, 成会明, 刘岗. 六氟钽酸氨拓扑转变制备低深能级缺陷Ta₃N₅光阳极实现超低偏压光电化学分解水[J]. 催化学报, 2024, 61(6): 144-153.
[13]	房文健, 严嘉玮, 韦之栋, 刘军营, 郭伟琦, 江治, 上官文峰. 光解水制氢催化剂的掺杂改性[J]. 催化学报, 2024, 60(5): 1-24.
[14]	杜晨宇, 盛剑平, 钟丰忆, 何烨, 孙艳娟, 董帆. 光催化二氧化碳还原制多碳产物的先进光催化剂设计与机制: 现状与挑战[J]. 催化学报, 2024, 60(5): 25-41.
[15]	丁婕婷, 王浩帆, 沈葵, 韦小明, 陈立宇, 李映伟. 具有丰富活性位点和高电子传导性的非晶MOF用于高效肼氧化[J]. 催化学报, 2024, 60(5): 351-359.