CuNi双金属MOFs串联催化促进硝酸盐还原合成氨

doi:10.15541/jim20250321

摘要/Abstract

摘要： 电催化硝酸盐还原反应(NO₃RR)是一种生产氨和净化废水的绿色技术,但是其反应过程会与析氢反应竞争,并且造成亚硝酸盐中间体积累。设计和构筑具有不同催化特性的双活性位点可以提高反应活性,进而通过串联催化策略(NO₃^-→NO₂^-→NH₃)显著提升氨的生成速率与选择性。本研究以结构明确的金属有机框架(MOFs)为模板,通过简单的水热法构筑了CuNi双金属MOFs串联催化体系。研究结果表明,Cu活性位点可高效催化NO₃^-还原为NO₂^-,Ni位点展现出优异的活性氢物种^*H供应能力及NO₂^-转化效率,二者形成高效的串联催化机制,实现了高达90.1%的氨合成法拉第效率和28.8 mg·h^-1·mg_cat^-1的氨产率。经过多次循环测试后,双金属MOFs催化剂的合成氨性能未出现衰减, 表现出优异的循环稳定性。本研究可为高性能串联催化剂的设计与优化提供新的见解。

关键词: 合成氨, 硝酸盐还原反应, 双金属, 金属有机框架, 串联催化

Abstract: Electrocatalytic nitrate reduction reaction (NO₃RR), as a green technology for producing ammonia and purifying wastewater, faces challenges in terms of nitrite intermediate accumulation and competitive hydrogen evolution reactions. Tandem catalytic strategy (NO₃^-→NO₂^-→NH₃) is expected to significantly improve the rate and selectivity of ammonia production. Therefore, designing and constructing dual active sites with different catalytic properties contributes to improving reaction activity. Herein, a CuNi bimetallic metal organic frameworks (MOFs) tandem catalytic system using well-defined MOFs as templates was constructed through simple hydrothermal synthesis. The research results indicated that Cu active sites could efficiently catalyze the reduction of NO₃^- to NO₂^-, while Ni sites exhibited excellent active hydrogen species ^*H supply capacity and NO₂^- conversion efficiency, forming an efficient tandem catalytic mechanism with Cu sites, achieving a Faraday efficiency of up to 90.1% for ammonia synthesis and an ammonia yield of 28.8 mg·h^-1·mg_cat^-1. In addition, the bimetallic MOFs catalyst showed excellent cycling stability without any degradation in ammonia synthesis after multiple cycling tests. This work provides new insights for the design and optimization of high-performance tandem catalysts.

Key words: ammonia production, nitrate reduction reaction, bimetallic, metal organic framework, tandem catalysis

中图分类号:

O646

王萌, 曹磊磊, 苟王燕, 程娅伊, 战琪, 原孟磊. CuNi双金属MOFs串联催化促进硝酸盐还原合成氨[J]. 无机材料学报, DOI: 10.15541/jim20250321.

WANG Meng, CAO Leilei, GOU Wangyan, CHENG Yayi, ZHAN Qi, YUAN Menglei. Tandem Catalysis of CuNi Bimetallic MOFs Boosting Nitrate Reduction for Ammonia Production[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250321.

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