富含晶格畸变的多维In2O3/In2S3异质结调控用于光催化CO2转化

doi:10.1016/S1872-2067(21)63954-2

催化学报 ›› 2022, Vol. 43 ›› Issue (5): 1286-1294.DOI: 10.1016/S1872-2067(21)63954-2

富含晶格畸变的多维In₂O₃/In₂S₃异质结调控用于光催化CO₂转化

杨金曼^a, 朱兴旺^a, 于卿^a, 贺敏强^a, 张伟^a, 莫曌^a, 袁俊杰^a, 佘远斌^b, 许晖^a(), 李华明^a()

^a江苏大学化学化工学院, 能源研究院, 江苏镇江212013
^b浙江工业大学化工学院, 浙江杭州310014

收稿日期:2021-08-20 接受日期:2021-09-27 出版日期:2022-05-18 发布日期:2022-03-23
通讯作者: 许晖,李华明
基金资助:
国家自然科学基金(22075113);国家自然科学基金(22178152);国家自然科学基金(22172066);国家自然科学基金(51902138);江苏省自然科学(BK20190835);镇江市高新技术研究重点实验室(SS2018002);江苏省农业科技自主创新基金(CX(21)3067);国家自然基金重点项目(22138011);中国博士后基金(2021M691305);江苏省博士后基金(2021K079A)

Multidimensional In₂O₃/In₂S₃ heterojunction with lattice distortion for CO₂ photoconversion

Jinman Yang^a, Xingwang Zhu^a, Qing Yu^a, Minqiang He^a, Wei Zhang^a, Zhao Mo^a, Junjie Yuan^a, Yuanbin She^b, Hui Xu^a(), Huaming Li^a()

^aSchool of Chemistry and Chemical Engineering, Institute of Energy Research, Jiangsu University, Zhenjiang 212013, Jiangsu, China
^bCollege of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2021-08-20 Accepted:2021-09-27 Online:2022-05-18 Published:2022-03-23
Contact: Hui Xu, Huaming Li
Supported by:
National Natural Science Foundation of China(22075113);National Natural Science Foundation of China(22178152);National Natural Science Foundation of China(22172066);National Natural Science Foundation of China(51902138);Natural Science Foundation of Jiangsu Province(BK20190835);High-tech Research Key Laboratory of Zhenjiang(SS2018002);Jiangsu Provincial Agricultural Science and Technology Independent Innovation Fund(CX(21)3067);National Natural Science Foundation of China(22138011);China Postdoctoral Science Foundation(2021M691305);Jiangsu Postdoctoral Science Foundation(2021K079A)

摘要/Abstract

摘要：

利用光催化技术将CO₂进行有效转化是减少排放和实现可再生能源生产的理想途径之一. 然而, 较低的催化转化效率限制了其实际应用. 因此, 高效光催化剂的设计合成与改性是促进光催化CO₂还原技术发展的关键. 在众多催化剂改性策略中, 构建异质结构光催化体系是一种有效策略, 不仅有利于提高载流子分离效率, 还可以优化能级结构, 同时改善光吸收.

对于异质结材料, 有效的界面接触对电子的动态行为起着重要作用, 不仅可以为电子提供高速通道, 还可以有效抑制光催化CO₂还原反应中光生载流子的复合. 特别是载流子分离效率高和自由电子浓度增加, 可有效促进CO₂分子的吸附和活化. 此外, 构建异质结也是缓解硫化物稳定性差的有效方法. 值得注意的是, 两种半导体在匹配过程中通常会形成大量的不饱和配位键和空位缺陷, 在某种材料中甚至会发生晶格失配导致晶格畸变结构的形成. 晶格畸变结构可以为催化反应提供额外的活性位点, 并为反应进行提供温床. 除光催化剂组成设计外, 形貌的合理设计也对催化剂性能有较大影响, 因为其不仅与光吸收能力和能带结构有关, 而且在很大程度上影响着载流子的输运. 近年来, 中空结构材料因其独特的结构优势引起了光催化领域研究人员的广泛兴趣. 内部空腔为光的多次反射和折射提供机会, 进而提升光吸收和利用率. 与本体结构相比, 中空结构材料具有丰富的活性位点和较大的比表面积, 能够为电子提供高速通道, 因此, 在表面催化反应中具有广阔的应用前景. 特别是衍生的金属有机框架材料(MOFs)保留了原始材料的形貌结构, 可以通过预先设计前驱体精确控制活性位点. 因此, 设计以MOFs为前驱体的中空结构催化剂有望提高光催化CO₂还原活性.

本文通过简单的MOFs衍生策略和原位硫化法构筑了多维中空结构的In₂O₃/In₂S₃异质结. 通过光反射和折射提高了其对光子的利用率; 高度匹配的能级结构实现了电子-空穴对的有效分离; 紧密的界面接触为进一步快速的光生电子转移到活性位提供了高速通道. 此外, 大量晶格畸变的形成和氧原子逃逸造成的氧空位, 也为光生载流子的分离提供了驱动力; 增加的自由电子浓度促进CO₂在催化剂表面的吸附和活化, 使关键中间体*COOH处于较低的能垒. In₂O₃/In₂S₃异质结表现出较好的CO生成速率(12.2 μmol g^-1 h^-1), 分别为In₂O₃和In₂S₃的4倍左右. 本文为异质结光催化剂的构建提供有效策略.

关键词: 光催化, CO₂转化, In₂O₃/In₂S₃异质结, 界面, 晶格畸变

Abstract:

Photocatalytic CO₂ reduction to sustainably product of fuels is a potential route to achieve clean energy conversion. Unfortunately, the sluggish charge transport dynamics and poor CO₂ activation performance result in a low CO₂ conversion efficiency. Herein, we develop a multidimensional In₂O₃/In₂S₃ (IO/IS) heterojunction with abundant lattice distortion structure and high concentration of oxygen defects. The close contact interfaces between the junction of the two phases ensure undisturbed transmission of electrons with high-speed. The increased free electron concentration promotes the adsorption and activation of CO₂ on the catalyst surface, leaving the key intermediate *COOH at a lower energy barrier. The perfect combination of the band matching oxide and sulfide effectively reduces the internal energy barrier of the CO₂ reduction reaction. Furthermore, the lattice distortion structure not only provides additional active sites, but also optimizes the kinetics of the reaction through microstructural regulation. Remarkably, the optimal IO/IS heterojunction exhibits superior CO₂ reduction performance with CO evolution rate of 12.22 μmol g^-1 h^-1, achieving about 4 times compared to that of In₂O₃ and In₂S₃, respectively. This work emphasizes the importance of tight interfaces of heterojunction in improving the performance of CO₂ photoreduction, and provides an effective strategy for construction of heterojunction photocatalysts.

Key words: Photocatalysis, CO₂ conversion, In₂O₃/In₂S₃ heterojunction, Interface, Lattice distortion

杨金曼, 朱兴旺, 于卿, 贺敏强, 张伟, 莫曌, 袁俊杰, 佘远斌, 许晖, 李华明. 富含晶格畸变的多维In₂O₃/In₂S₃异质结调控用于光催化CO₂转化[J]. 催化学报, 2022, 43(5): 1286-1294.

Jinman Yang, Xingwang Zhu, Qing Yu, Minqiang He, Wei Zhang, Zhao Mo, Junjie Yuan, Yuanbin She, Hui Xu, Huaming Li. Multidimensional In₂O₃/In₂S₃ heterojunction with lattice distortion for CO₂ photoconversion[J]. Chinese Journal of Catalysis, 2022, 43(5): 1286-1294.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63954-2

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图/表 6

Fig. 1. (a) Schematic illustration of the photocatalyst formation process; SEM images of MIL-68 (b), In2O3 (c) and 50% IO/IS (d); TEM image (e) and EDX mapping images of In (f), O (g) and S (h) for 50% IO/IS.

Fig. 2. (a?c) HR-TEM images of 50% IO/IS; O 1s (d), S 2p (e) in XPS and EPR spectra (f) of In2O3 and 50% IO/IS.

Fig. 3. (a) Average CO production rates of In2O3, IO/ISs and In2S3 under light irradiation; (b) evolution of product under various reaction conditions; (c) mass spectra of product CO from the photocatalytic reaction of 13CO2 over 50% IO/IS; (d) cycling runs for the CO2 photoreduction in the presence of 50% IO/IS.

Fig. 4. PL spectra (a), SPV spectra (b), transient photocurrent responses (c) and EIS (d) of In2O3, IO/IS and In2S3.

Fig. 5. UPS (a,b), Tauc plots (c) and trivial band structure diagram (d) of In2O3 and In2S3.

Fig. 6. (a) The in-situ FTIR for 50% IO/IS in the atmosphere of H2O vapor and CO2 with light irradiation; (b) Gibbs free energy diagrams of photocatalytic CO2 reduction into CO for In2O3, IO/IS and In2S3; (c) the models of In2O3, IO/IS and In2S3 for DFT calculation.

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富含晶格畸变的多维In₂O₃/In₂S₃异质结调控用于光催化CO₂转化

Multidimensional In₂O₃/In₂S₃ heterojunction with lattice distortion for CO₂ photoconversion

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