高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

配体功能化MIL-101(Fe)催化剂的制备及其光催化还原CO2性能

李欣, 吕泽, 钟毅, 徐红, 毛志平, 张琳萍   

  1. 东华大学化学与化工学院, 纺织染整可持续低碳技术教育部重点实验室
  • 收稿日期:2026-01-20 修回日期:2026-03-23 网络首发:2026-03-25 发布日期:2026-03-25
  • 通讯作者: 张琳萍 E-mail:zhang_lp@dhu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21872025)资助

Preparation of Ligand-Functionalized MIL-101(Fe) Catalysts and Its Photocatalytic CO2 Reduction Performance

LI Xin, LV Ze, ZHONG Yi, XU Hong, MAO Zhiping, ZHANG Linping   

  1. Key Laboratory of Sustainable Low-carbon Technologies for Textile Dyeing and Finishing, Ministry of Education, College of Chemistry and Chemical Engineering, Donghua University
  • Received:2026-01-20 Revised:2026-03-23 Online First:2026-03-25 Published:2026-03-25
  • Contact: Zhang Linping E-mail:zhang_lp@dhu.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21872025)

PDF (PC)

摘要： 将太阳能驱动的CO2光催化还原为高附加值化学品(如甲酸、甲醇等), 是缓解温室效应与实现碳资源循环利用的前沿策略之一. 采用溶剂热法引入-NH2, -OCH3, -Br和-NO2等官能团修饰的对苯二甲酸, 制备系列不同配体功能化X-MIL-101(Fe) MOFs催化材料. 利用X射线衍射(XRD)、元素分析(EA)、场发射扫描电子显微镜(FE-SEM)、紫外-可见吸收光谱(UV-Vis)、光电流响应(it)、电化学阻抗谱(EIS)和荧光光谱(PL)等手段系统表征了材料的结构、形貌与光电性质. 研究表明, 官能团的电子性质显著调控材料的光吸收、能带结构与载流子行为: 给电子基团(-NH2、-OCH3)增强光响应并促进电荷分离; 吸电子基团(-Br、-NO2)则抑制光吸收与电子转移. 在苯环取代基中, 氨基的给电子能力通常强于甲氧基, 因此在模拟太阳光下进行CO2还原性能测试, 氨基修饰的NH2-MIL-101(Fe)表现最优, 其光电流响应最强、电荷分离效率最高, 在纯水体系中甲酸生成速率达28.13 μmol g?1 h?1; 加入牺牲剂后进一步提升至42.61 μmol g?1 h?1, 较未修饰MIL-101(Fe)提升3.45倍. 该材料同时展现出良好的可重复使用性, 循环4次后活性保持率达93.92%. 本研究从配体官能团结构角度, 为设计高效稳定的MOFs基CO2光还原催化剂提供了理论依据与实验参考.

关键词: 金属有机框架, 配体, 光催化, 二氧化碳还原

Abstract: Solar-driven photocatalytic reduction of CO2 into high-value-added chemicals (e.g., formic acid, methanol) represents a cutting-edge strategy for mitigating the greenhouse effect and achieving carbon resource recycling. A series of ligand-functionalized X-MIL-101(Fe) MOFs catalytic materials were prepared by introducing functional groups such as -NH2, -OCH3, -Br and -NO2 by one-pot solvothermal method. The morphology, structure and optoelectronic properties of the catalysts were characterized by X-ray diffractometer (XRD), Element analyzer (EA), scanning electron microscope (FE-SEM), ultraviolet-visible absorption spectroscopy (UV-Vis), photocurrent response spectroscopy (it), electrochemical impedance spectroscopy (EIS) and fluorescence emission spectroscopy (PL). The study demonstrates that the electronic properties of functional groups significantly modulate the light absorption, band structure, and charge carrier behavior of material: electron-donating groups (-NH2, -OCH3) enhance light response and promote charge separation; Electron-withdrawing groups (-Br, -NO2) suppress light absorption and electron transfer. The -NH2 group exhibits a stronger electron-donating ability than the -OCH3 group bonded to the benzene ring. Consequently, under simulated sunlight, amino-modified NH2-MIL-101(Fe) demonstrated optimal CO2 reduction performance, exhibiting the strongest photocurrent response and highest charge separation efficiency. In pure water, its formic acid production rate reached 28.13 μmol g?1 h?1. This rate further increased to 42.61 μmol g?1 h?1 with the addition of a sacrificial agent, representing a 3.45-fold improvement over unmodified MIL-101(Fe). The material also demonstrated excellent reusability, maintaining 93.92% of its activity after four cycles. This study provides theoretical foundations and experimental references for designing highly efficient and stable MOF-based CO2 photoreduction catalysts from the perspectives of the ligand structure.

Key words: Metal-organic frameworks, Ligands, Photocatalyst, Carbon dioxide reduction

中图分类号: 

TrendMD: