后合成法构建Ni-Ti双金属MOF及其光催化CO2还原性能

doi:10.15541/jim20260307

摘要/Abstract

摘要： 光催化CO₂还原为高价值燃料是缓解能源危机与温室效应的有效途径,但传统单金属光催化剂中光生电子-空穴对的快速复合及CO₂活化不足严重制约了其效率。本研究采用后合成修饰策略,以预合成的NH₂-MIL-125(Ti)为前驱体,构建了一系列稳定的金属有机框架(MOF)双金属光催化剂(MTV-TiM,M=Co、Ni、Fe、Mn)。异金属簇与光敏有机连接体为光生电荷转移和CO₂还原提供了结构基础。在所合成的材料中,MTV-TiNi₂在无牺牲剂条件下表现出13.59 μmol·g⁻¹·h⁻¹的CO生成速率和93%的CO选择性;当引入[Ru(bpy)₃]²⁺光敏剂和三乙醇胺牺牲电子供体后,CO生成速率提升至39.2 μmol·g⁻¹·h⁻¹,CO选择性达97%,其CO生成速率高于其他双金属对照样品。MTV-TiNi₂的性能提升与高效的电荷分离和传输、有利的能带结构及增强的CO₂吸附亲和力。此外,归属于COOH*、CO*、CHO*和CH₃O*的表面物种信号为所提出的双金属簇光催化CO₂还原路径提供了支持。本研究为设计具有可调电子结构的双金属MOF光催化剂、实现高效选择性CO₂还原提供了新策略。

关键词: 异金属MOFs, Ni-Ti双金属簇, 后合成修饰, 光催化CO₂还原

Abstract: Photocatalytic CO₂ reduction into valuable fuels is a promising route to mitigate the energy crisis and greenhouse effect, yet it remains severely hampered by the rapid recombination of photogenerated electron-hole pairs and insufficient CO₂ activation in traditional single-metal photocatalysts. A series of stable bimetallic metal-organic framework (MOF) photocatalysts (MTV-TiM, M=Co, Ni, Fe, Mn) were constructed using preformed NH₂-MIL-125(Ti) as the precursor via a post-synthetic modification strategy. The heterometallic clusters and photosensitive organic linkers provide a platform for photoinduced charge transfer and CO₂ reduction. Among the synthesized materials, MTV-TiNi₂ exhibits a CO evolution rate of 13.59 μmol·g⁻¹·h⁻¹ with 93% CO selectivity without any sacrificial agent. When coupled with the [Ru(bpy)₃]²⁺ photosensitizer, the CO evolution rate is boosted to 39.2 μmol·g^–1·h^–1 with an enhanced CO selectivity of 97%, outperforming the other bimetallic counterparts. The improved performance of MTV-TiNi₂ is associated with efficient charge separation and transport, favorable band alignment, and CO₂ adsorption at the framework surface. Furthermore, surface species assigned to COOH*, CO*, CHO*, and CH₃O* support proposed photocatalytic CO₂ reduction pathways. This work provides a new strategy for designing bimetallic MOF photocatalysts with tailored electronic structures for efficient and selective CO₂ reduction.

Key words: heterometallic MOFs, Ni-Ti bimetallic cluster, post-synthetic modification, photocatalytic CO₂ reduction

中图分类号:

嵇子凡, 王自豪, 朱建华. 后合成法构建Ni-Ti双金属MOF及其光催化CO₂还原性能[J]. 无机材料学报, DOI: 10.15541/jim20260307.

JI Zifan, WANG Zihao, ZHU Jianhua. Post-synthetic Construction of Ni-Ti Bimetallic MOF for Photocatalytic CO₂ Reduction[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260307.

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后合成法构建Ni-Ti双金属MOF及其光催化CO₂还原性能

Post-synthetic Construction of Ni-Ti Bimetallic MOF for Photocatalytic CO₂ Reduction

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