铜上CO2加氢的模式特异性动力学：分子旋转的隐藏作用
Mode-Specific Dynamics of $\text{CO}_2$ Hydrogenation on Copper: The Hidden Role of Molecular Rotation
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中文总结 AI 辅助
该研究基于全维第一性原理神经网络势能面，揭示铜表面CO2加氢反应中分子旋转激发的主导作用，修正了传统机理解释，为CO2加氢的精准控制提供了基础。
中文摘要 AI 辅助
铜上CO2催化加氢生成甲酸盐是CO2利用的关键基元步骤。此前实验和理论研究表明该反应遵循Eley-Rideal机理，由弯曲振动激发促进，但仍缺乏直接的态分辨证据。本文基于全维第一性原理神经网络势能面，给出Cu(111)表面CO2加氢的精确动力学预测。计算结果近定量复现了测得的反应概率，包括其喷嘴温度和入射能量的依赖关系。态分辨结果显示，尽管弯曲模式的振动激发可提升反应性，但仅靠该激发无法解释观测到的反应性随喷嘴温度升高的现象；相反，旋转激发起主导作用，主要源于CO2到达过渡态时分子极性取向各向异性的显著变化。这种模式特异性机理见解修正了传统解释，为催化剂上CO2加氢的精准控制奠定基础。
英文摘要
Catalytic hydrogenation of $\text{CO}_2$ to formate on copper is a key elementary step for $\text{CO}_2$ utilization. Previous experimental and theoretical studies suggested an Eley-Rideal mechanism for this reaction, promoted by bending vibrational excitation, yet direct state resolved evidence remains lacking. Here, we present first-principles dynamical predictions for $\text{CO}_2$ hydrogenation on Cu(111) based on an accurate full-dimensional neural network potential energy surface. Our calculations near-quantitatively reproduce the measured reaction probabilities, including their nozzle-temperature and incidence-energy dependence. Our state-resolved results indicate that while vibrational excitation of the bending mode enhances reactivity, it alone cannot account for the observed reactivity increase with nozzle temperature. Instead, rotational excitation plays a dominant role, mainly attributable to the significant change in anisotropy of the molecular polar orientation as $\text{CO}_2$ accesses the transition state. This mode-specific insight reinforces the hidden role of rotation in surface reactivity, opening new avenues for state-selective control of $\text{CO}_2$ hydrogenation on heterogenous catalysts.
发表机构
- State Key Laboratory of Precision and Intelligent Chemistry, Department of Chemical Physics, University of Science and Technology of China（中国科学技术大学精密与智能化学国家重点实验室化学物理系）
- State Key Laboratory of Petroleum Molecular and Process Engineering, SINOPEC Research Institute of Petroleum Processing Co., Ltd.（中国石化石油化工科学研究院石油分子与工艺工程国家重点实验室）
- Department of Chemistry and Chemical Biology, Center for Computational Chemistry, University of New Mexico（新墨西哥大学化学与化学生物学系计算化学中心）
- Hefei National Laboratory, University of Science and Technology of China（中国科学技术大学合肥国家实验室）
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