催化学报

催化学报

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内建电场耦合非贵金属等离基元效应助推MIL-125光催化二氧化碳还原活性

姜晓康a,1, 高永泽a,1, 张博闻a,1, 杨晓东a, 袁之敏b,*, 许兆宁a, 孙彬c,*, 姜在勇b, 周国伟c,*, 周恩龙a,*   

  1. a山东农业大学化学与材料科学学院, 山东泰安 271018;
    b潍坊学院化学化工与环境工程学院, 山东潍坊 261061;
    c齐鲁工业大学(山东省科学院)化学与化工学院, 山东济南 250353
  • 收稿日期:2025-12-01 接受日期:2026-01-12
  • 通讯作者: *电子信箱: yuanzhiminjinan@163.com (袁之敏), binsun@qlu.edu.cn (孙彬), gwzhou@qlu.edu.cn (周国伟), chemelzhou@sdau.edu.cn (周恩龙).
  • 作者简介:1共同第一作者.
  • 基金资助:
    国家自然科学基金(22502145, 22572148, 52202102, 52472215, 61804075); 山东省自然科学基金(ZR2023MB049, ZR2023QB285).

Built-in electric field coupled with non-noble metal plasma cocatalyst boosts photocatalytic CO2 reduction of MIL-125

Xiaokang Jianga,1, Yongze Gaoa,1, Bowen Zhanga,1, Xiaodong Yanga, Zhimin Yuanb,*, Zhaoning Xua, Bin Sunc,*, Zaiyong Jiangb, Guowei Zhouc,*, Enlong Zhoua,*   

  1. aCollege of Chemistry and Material Science, Shandong Agricultural University, Taian 271018, Shandong, China;
    bSchool of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, Shandong, China;
    cSchool of Chemistry and Chemical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, Shandong, China
  • Received:2025-12-01 Accepted:2026-01-12
  • Contact: *E-mail: yuanzhiminjinan@163.com (Z. Yuan), binsun@qlu.edu.cn (B. Sun), gwzhou@qlu.edu.cn (G. Zhou), chemelzhou@sdau.edu.cn (E. Zhou).
  • About author:1Contributed equally to this work.
  • Supported by:
    National Natural Science Foundation of China (22502145, 22572148, 52202102, 52472215, 61804075) and the Natural Science Foundation of Shandong Province, China (ZR2023MB049, ZR2023QB285).

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摘要： 利用太阳能驱动半导体光催化还原CO2是实现碳循环与可再生能源转化的重要途径. 金属有机框架(MOF)材料因其高比表面积和优异的CO2吸附能力而备受关注, 但光吸收范围窄、光生载流子分离效率低等问题限制了其光催化性能. 等离子体助催化剂修饰被认为是提升无机半导体材料光吸收能力和载流子分离效率的有效策略, 现也开始在MOF基光催化剂中被探索和应用. 由于金属与MOF之间存在常规的晶格失配和大的生长差别, 导致它们之间存在较大的界面势垒, 阻碍光电子有效传输, 限制了其光催化应用. 构筑内建电场可作为驱动力克服界面势垒, 促进电荷分离与迁移的有效策略, 而这在金属/MOF光催化领域鲜有报道. 基于此, 如果在非贵金属等离子体金属/MOF复合材料界面构筑内建电场, 将有效地拓宽MOF的光吸收范围、促进光生载流子分离, 为突破MOF基材料光催化性能瓶颈、提升光催化还原CO2活性提供关键解决方案.
本文采用溶剂热法, 以Bi(NO3)3·5H2O为铋源, 在MIL-125表面原位还原沉积Bi纳米颗粒, 制备了一系列具有内建电场和等离激元效应的BM-X复合光催化剂. 在模拟太阳光照射, 无外加牺牲试剂条件下, 最优的BM-110光催化还原CO2的CO产率达96.63 μmol g‒1 h‒1, 为原始MIL-125的10.4倍, 选择性高达97%. X-射线粉末衍射、扫描电镜、透射电镜、电子顺磁共振光谱、比表面积等结果证实Bi纳米颗粒成功负载于MIL-125表面, 并发现Bi3+的蚀刻作用可引入氧空位和介孔结构, 有利于增强CO2和H2O的传质. 紫外-可见吸收光谱、莫特-肖特基测试、电化学阻抗谱、荧光光谱等光电化学测试表明, BM-110具有更宽的光吸收范围、更高的载流子浓度与更有效的电荷分离效率. 密度泛函理论计算与原位X-射线光电子能谱揭示了Bi与MIL-125之间形成由Bi指向MIL-125的内置电场, 促进光生电子从MIL-125向Bi转移, 同时Bi表面发生动态Bi3+/Bi0氧化还原循环, 进一步增强等离子体效应与光催化活性.
综上, 该体系光催化还原CO2性能的显著提升可归因于Bi的等离子体效应拓宽光吸收、内建电场驱动界面电子迁移、氧空位促进载流子捕获与反应物活化等多重机制的协同作用赋予了Bi/MIL-125光催化剂优异的光吸收能力、高效的光生载流子空间分离与转移效率. 本研究通过非贵金属等离基元效应与内建电场的协同设计, 为构建高效MOF基光催化还原二氧化碳催化剂提高了新思路, 对高效人工光合作用系统的开发具有重要借鉴价值.

关键词: 金属铋, MIL-125, 等离子体效应, 内建电场, 光催化还原CO2

Abstract: In recent years, metal-organic frameworks (MOFs) based materials have garnered significant interest for photocatalytic CO2 reduction, owing to their unique structural features coupled with exceptional CO2 capture capacities. Due to the insufficient light absorption capacity and low efficiency of photogenerated electron-hole separation, their catalytic activities still need to be further improved. Plasma cocatalyst is considered as a promising strategy to expand light absorption range and facilitate separation efficiency of photogenerated charges for inorganic semiconductor photocatalysts, thereby also beginning to be explored and applied in the MOFs-based photocatalysts. However, due to the usual lattice mismatch or large growth differences between metals and MOFs, interface barriers exist, which to some extent hinders the effective transmission of photogenerated electrons. Build-in electric field (IEF) of the interface could be used as the driving force to overcome the interface barriers, promoting the transfer of charge carriers. Herein, the non-noble metal Bi and ordinary MIL-125 are chosen as plasma cocatalyst and MOF object, respectively, forming Bi/MIL-125 composite via an in-situ reduction strategy. The experimental results and theoretical calculation demonstrate that an IEF is formed and pointed from Bi to MIL-125. And metal Bi possesses obvious plasma light absorption and carrier capture capabilities. Built-in electric field in coordination with Bi plasma co-catalytic effect realizes the highly efficient photocatalytic CO2 reduction. The optimized BM-110 demonstrates a 10.4-fold higher CO production rate relative to the initial MIL-125, recording a yield of 96.63 µmol g‒1 h‒1. This work demonstrated a new insight to design MOF-based photocatalysts for photocatalytic CO2 reduction.

Key words: Metal Bi, MIL-125, Plasma effect, Built-in electric field, Photocatalytic CO2 reduction