Tuning Photoactive MIL-68(In) by Functionalized Ligands for Boosting Visible-Light Nitrogen Fixation

Sun, Qiufan1; Zhu, Yuxiang1; Zhong, Xiang1; Jiang, Meng1; Fan, Yanchen2,3; Yao, Jianfeng1

2022-11-01

10.1021/acsami.2c17007

ACS Applied Materials & Interfaces   Impact Factor & Quartile

1944-8244

1944-8252

In this work, MIL-68(In) functionalized with various ligand substitutions including amine, hydroxyl, bromine, nitro, and methyl groups was prepared, via a one-pot solvothermal reaction for visible-light photocatalytic ammonia synthesis. The diversity of ligands tunes the morphology, geometry, pore environment, and electronic structure of MIL-68(In)-based photocatalysts due to the polarity and intraframework interactions. Amine-inserted MIL-68(In) outperforms its counterparts, presenting a boosted nitrogen photofixation rate of 140.34 mu mol gcat-1 h-1 with an apparent quantum efficiency of 5.69% at 420 nm. Further, the size of the batch solvothermal reactor and the amine group content also influence the photocatalytic activity. The combined experimental and theoretical results reveal that amine substituents improve the chemisorption of nitrogen molecules and the conversion of nitrogen into ammonia follows a dual pathway, i.e., a Mars-van Krevelen process and a ligand-to-metal charge transfer mechanism. This work provides a molecular engineering strategy via dual catalysis toward efficient ammonia production.

amine group ligand design indium-organic frameworks dual catalysis pathway ammonia synthesis photocatalysis

SCI

English

Others

[52002186]

Science & Technology - Other Topics ; Materials Science

Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:000890011400001

AMER CHEMICAL SOC

Web of Science

1.Nanjing Forestry Univ, Coll Chem Engn, Jiangsu Coinnovat Ctr Efficient Proc & Utilizat Fo, Jiangsu Prov Key Lab Green Biomass Based Fuels & C, Nanjing 210037, Jiangsu, Peoples R China
2.Southern Univ Sci & Technol, SUSTech Acad Adv Interdisciplinary Studies, Shenzhen 518055, Guangdong, Peoples R China
3.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Guangdong, Peoples R China

Sun, Qiufan,Zhu, Yuxiang,Zhong, Xiang,et al. Tuning Photoactive MIL-68(In) by Functionalized Ligands for Boosting Visible-Light Nitrogen Fixation[J]. ACS Applied Materials & Interfaces,2022.

Sun, Qiufan,Zhu, Yuxiang,Zhong, Xiang,Jiang, Meng,Fan, Yanchen,&Yao, Jianfeng.(2022).Tuning Photoactive MIL-68(In) by Functionalized Ligands for Boosting Visible-Light Nitrogen Fixation.ACS Applied Materials & Interfaces.

Sun, Qiufan,et al."Tuning Photoactive MIL-68(In) by Functionalized Ligands for Boosting Visible-Light Nitrogen Fixation".ACS Applied Materials & Interfaces (2022).