State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
Dalton Trans. 2023 May 22;52(20):6668-6676. doi: 10.1039/d3dt00802a.
The key to optimizing energy-consuming catalytic conversions lies in acquiring a fundamental understanding of the nature of the active sites and the mechanisms of elementary steps at an atomically precise level, while it is challenging to capture the crucial step that determines the overall temperature of a real-life catalytic reaction. Herein, benefiting from a newly-developed high-temperature ion trap reactor, the reverse water-gas shift (CO + H → CO + HO) reaction catalyzed by the Rh ( = 3-11) clusters was investigated under variable temperatures (298-783 K) and the critical temperature that each elementary step (Rh + CO and RhO + H) requires to take place was identified. The Rh cluster strikingly surpasses other Rh clusters to drive the catalysis at a mild starting temperature (∼440 K). This finding represents the first example that a specifically sized cluster catalyst that works under an optimum condition can be accurately filtered by using state-of-the-art mass spectrometric experiments and rationalized by quantum-chemical calculations.
优化耗能催化转化的关键在于在原子精度水平上获得对活性位和基元步骤机理的基本理解，然而捕捉决定实际催化反应总温度的关键步骤具有挑战性。在此，得益于新开发的高温离子阱反应器，在可变温度（298-783 K）下研究了 Rh（=3-11）团簇催化的逆水气变换（CO + H → CO + HO）反应，并确定了每个基元步骤（Rh + CO 和 RhO + H）发生所需的关键温度。Rh 团簇惊人地超越了其他 Rh 团簇，在温和的起始温度（约 440 K）下驱动催化。这一发现代表了第一个实例，即通过使用最先进的质谱实验和量子化学计算可以准确筛选在最佳条件下工作的特定尺寸团簇催化剂。
