Modulating the band gap of a pyrazinoquinoxaline-based metal-organic framework through orbital hybridization for enhanced visible light-driven C=N bond construction

被引:0
|
作者
Chen, Zitong [2 ]
Cao, Linghui [2 ]
Liu, Aogang [2 ]
Liu, Pengda [2 ]
Chen, Yuan [2 ]
Yan, Juntao [1 ]
Li, Bao [1 ,2 ]
机构
[1] Wuhan Polytech Univ, Coll Chem & Environm Engn, Wuhan 430023, Peoples R China
[2] Huazhong Univ Sci & Technol, Sch Chem & Chem Engn, Key Lab Mat Chem Energy Convers & Storage, Hubei Key Lab Bioinorgan Chem & Mat Med,Semicond C, Wuhan 430074, Peoples R China
基金
中国国家自然科学基金;
关键词
EFFICIENT;
D O I
10.1039/d4ta06282e
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Massive efforts have been devoted to developing photocatalysts based on metal-organic frameworks (MOFs), which are expected to play a significant role in the fields of energy conversion and environmental remediation. Nevertheless, further research is still required to better design the photoactive ligands and select suitable metal nodes to optimize the band gap and electron transfer pathways of MOFs in order to improve their photocatalytic efficiency. To this end, pyrazinoquinoxaline tetracarboxylic acid with a highly conjugated and electron-rich structure was synthesized to function as a photoactive ligand. However, the large energy difference between the metal nodes and ligands requires strong energy excitation, which hinders visible light-driven photocatalytic reactions from occurring. To identify the influence of energy-level matching and orbital hybridization between the metal nodes and ligands on the photocatalytic performance, an indium-based MOF was consequently prepared. In this way, efficient orbital hybridization between the metal nodes and photoactive ligands was established, and hence, the metal-to-ligand charge-transfer (MLCT) process could be triggered with visible light irradiation. Here, the combination of colorless In(3+ )ions and brown ligands gave rise to dark red crystalline materials, which effectively promoted visible light-energy utilization. As a result, the In-MOF exhibited a wide visible light absorption range with a relatively narrow band gap (1.474 eV), and it could facilitate two reactions under visible light irradiation concerning the construction of CN bonds, which is significant in the fine chemicals and pharmaceuticals industries. In-depth theoretical calculations were conducted to clarify the mechanism of the reactions and the catalytic activity of In-MOF. It turns out that two approaches of charge transfer, namely MLCT and intra-ligand charge-transfer (ILCT), and the interaction between the host and intermediates played a crucial role in these transformations. In this way, this study has established a template strategy for modulating the orbital hybridization between the components to control the band structure of MOFs.
引用
收藏
页码:30582 / 30590
页数:9
相关论文
共 50 条
  • [41] Coating BiOCl@g-C3N4 nanocomposite with a metal organic framework: Enhanced visible light photocatalytic activities
    Zhu, Yu
    Zhu, Min
    Lv, Hua
    Zhao, Suya
    Shen, Xinru
    Zhang, Qiyuan
    Zhu, Wenfei
    Li, Bingdong
    JOURNAL OF SOLID STATE CHEMISTRY, 2020, 292
  • [42] Highly Efficient Visible-Light-Driven H2 Production via an Eosin Y-Based Metal-Organic Framework
    Wang, Jian
    Liu, Yanhong
    Li, Yang
    Xia, Lingling
    Jiang, Min
    Wu, Pengyan
    INORGANIC CHEMISTRY, 2018, 57 (13) : 7495 - 7498
  • [43] A CuI Cluster-Based Covalent Metal-Organic Framework as a Photocatalyst for Efficient Visible-Light-Driven Reduction of CO2
    Cui, Jinxian
    Fu, Yaomei
    Song, Jian
    Meng, Bo
    Zhou, Jie
    Zhou, Ziyan
    Su, Zhongmin
    CHEMSUSCHEM, 2023, 16 (06)
  • [44] Copper-Based Metal-Organic Framework with a Tetraphenylethylene-Tetrazole Linker for Visible-Light-Driven CO2 Photoconversion
    Han, Xu
    Chu, Yun-Jie
    Dong, Man
    Chen, Weichao
    Ding, Guanyu
    Wen, Li-Li
    Shao, Kui-Zhan
    Su, Zhongmin
    Zhang, Min
    Wang, Xinlong
    Shan, Guo-Gang
    INORGANIC CHEMISTRY, 2022, 61 (15) : 5869 - 5877
  • [45] Engineering a multivariate cobalt metal-organic framework for high photocatalytic activity: the impact of mixed ligands and metal incorporation in a visible light-driven heterogeneous photo-Fenton reaction for water treatment
    Rodriguez-Sanchez, Noelia
    Bhattacharya, Biswajit
    Emmerling, Franziska
    Prinz, Carsten
    Prieto-Laria, Paula
    Ruiz-Salvador, A. Rabdel
    Ballesteros, Menta
    NANOSCALE ADVANCES, 2025, 7 (08): : 2255 - 2265
  • [46] Enhanced visible-light-driven hydrogen evolution of ultrathin narrow-band-gap g-C3N4 nanosheets
    Yu, Tao
    Hu, Zhimin
    Wang, Hongmei
    Tan, Xin
    JOURNAL OF MATERIALS SCIENCE, 2020, 55 (05) : 2118 - 2128
  • [47] Visible-LED-light-driven photocatalytic synthesis of N-heterocycles mediated by a polyoxometalate-containing mesoporous zirconium metal-organic framework
    Karamzadeh, Samireh
    Sanchooli, Esmael
    Oveisi, Ali Reza
    Daliran, Saba
    Luque, Rafael
    APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY, 2022, 303
  • [48] Enhanced visible-light-driven hydrogen evolution of ultrathin narrow-band-gap g-C3N4 nanosheets
    Tao Yu
    Zhimin Hu
    Hongmei Wang
    Xin Tan
    Journal of Materials Science, 2020, 55 : 2118 - 2128
  • [49] Thiazolo[5,4-d]Thiazole-Linked Conjugated Porous Organic Polymers for Visible Light-Driven C-N Bond Formation Reactions
    He, Yuan-Yuan
    Ma, Zhang-Peng
    Liu, Chun-Hua
    Zhu, Yuan-Yuan
    CHEMCATCHEM, 2024,