配体功能化 MIL-101(Fe)金属有机骨架的制备及光催化还原 CO₂性能

Preparation of Ligand-functionalized MIL-101（Fe） MOFs and Their Photocatalytic Performance for CO₂ Reduction

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. 本文采用溶剂热法引入-NH₂, -OCH₃, -Br 和-NO₂等官能团修饰的对苯二甲酸, 制备了系列不同配体功能化的X-MIL-101(Fe) 金属有机骨架(MOFs)催化材料. 通过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)、 光电流响应谱(I-t)、 电化学阻抗谱(EIS)和荧光光谱(PL)等手段表征了材料的结构、 形貌与光电性质. 研究结果表明, 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)可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光催化还原CO₂性能测试时, 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, 较未修饰的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.

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 was 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(I-t), 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(-NH ₂, -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 photocatalytic performance for CO₂ reduction, 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, which 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.

关键词

金属有机骨架 / 配体 / 光催化 / 二氧化碳还原

Key words

Metal-organic framework / Ligand / Photocatalysis / Carbon dioxide reduction

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基金资助

国家自然科学基金(21872025)