中国科学技术大学江海龙团队报道了Na⁺修饰的微环境促进单原子Cu位点上CO₂加氢制甲醇。相关研究成果于2024年3月22日发表在《国家科学评论》。

尽管单原子Cu位点在CO₂氢化为甲醇中表现出高效率，但由于在反应条件下，特别是在高温下的还原和聚集，它们易于形成Cu纳米颗粒。

该文中，在金属有机框架（MOF）基催化剂，即MOF-808-NaCu中，成功构建了由相邻Na⁺离子稳定的单原子Cu位点。研究发现，在CO₂氢化过程中，即使在高达275°C的温度下，Na⁺和H^δ-物种之间的静电相互作用，也在维持MOF-808-NaCu中Cu的原子分散方面发挥着关键作用。

这种特殊的稳定效果使催化剂具有优异的活性（306 g·kg_cat^-1·h^-1）、对甲醇的高选择性（93%）和在升高的反应温度下的长期稳定性，远远超过了在没有Na⁺的情况下的催化剂（表示为MOF-808-Cu）。

该项工作开发了一种通过在附近创建碱修饰的微环境，来制造用于高级催化的稳定单原子位点的有效策略。

附：英文原文

Title: Promoted hydrogenation of CO2 to methanol over single-atom Cu sites with Na+ decorated microenvironment

Author: Ling, Li-Li, Guan, Xinyu, Liu, Xiaoshuo, Lei, Xiao-Mei, Lin, Zhongyuan, Jiang, Hai-Long

Issue&Volume: 2024-03-22

Abstract: Although single-atom Cu sites exhibit high efficiency in CO2 hydrogenation to methanol, they are prone to form Cu nanoparticles due to reduction and aggregation under reaction conditions, especially at high temperatures. Herein, single-atom Cu sites stabilized by adjacent Na+ ions have been successfully constructed within a metal-organic framework (MOF)-based catalyst, namely MOF-808-NaCu. It is found that the electrostatic interaction between the Na+ and Hδ species plays a pivotal role in upholding the atomic dispersion of Cu in MOF-808-NaCu during CO2 hydrogenation, even at temperatures up to 275°C. This exceptional stabilization effect endows the catalyst with excellent activity (306 g·kgcat1·h1), high selectivity to methanol (93%), and long-term stability at elevated reaction temperatures, far surpassing the counterpart in the absence of Na+ (denoted as MOF-808-Cu). This work develops an effective strategy to the fabrication of stable single-atom sites for advanced catalysis by creating alkali-decorated microenvironment in close proximity.

DOI: 10.1093/nsr/nwae114

Source: https://dx.doi.org/10.1093/nsr/nwae114