Chen Jiawen, Xia Yongming, Ling Yuxuan, Liu Xuehui, Li Shuyuan, Yin Xiong, Zhang Lipeng, Liang Minghui, Yan Yi-Ming, Zheng Qiang, Chen Wenxing, Guo Yan-Jun, Yuan En-Hui, Hu Gaofei, Zhou Xiaole, Wang Leyu
State Key Laboratory of Chemical Resource Engineering, Innovation Centre for Soft Matter Science and Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China.
State Key Laboratory of Organic-Inorganic Composites, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China.
Nano Lett. 2024 May 1;24(17):5197-5205. doi: 10.1021/acs.nanolett.4c00512. Epub 2024 Apr 18.
Highly active nonprecious-metal single-atom catalysts (SACs) toward catalytic transfer hydrogenation (CTH) of α,β-unsaturated aldehydes are of great significance but still are deficient. Herein, we report that Zn-N-C SACs containing Zn-N moieties can catalyze the conversion of cinnamaldehyde to cinnamyl alcohol with a conversion of 95.5% and selectivity of 95.4% under a mild temperature and atmospheric pressure, which is the first case of Zn-species-based heterogeneous catalysts for the CTH reaction. Isotopic labeling, FT-IR spectroscopy, and DFT calculations indicate that reactants, coabsorbed at the Zn sites, proceed CTH via a "Meerwein-Ponndorf-Verley" mechanism. DFT calculations also reveal that the high activity over Zn-N moieties stems from the suitable adsorption energy and favorable reaction energy of the rate-determining step at the Zn active sites. Our findings demonstrate that Zn-N-C SACs hold extraordinary activity toward CTH reactions and thus provide a promising approach to explore the advanced SACs for high-value-added chemicals.
用于α,β-不饱和醛催化转移氢化（CTH）的高活性非贵金属单原子催化剂（SAC）具有重要意义，但仍存在不足。在此，我们报道含Zn-N基团的Zn-N-C SAC在温和温度和大气压下可催化肉桂醛转化为肉桂醇，转化率为95.5%，选择性为95.4%，这是基于锌物种的多相催化剂用于CTH反应的首例。同位素标记、傅里叶变换红外光谱和密度泛函理论计算表明，共吸附在锌位点的反应物通过“Meerwein-Ponndorf-Verley”机制进行CTH反应。密度泛函理论计算还表明，Zn-N基团的高活性源于锌活性位点上速率决定步骤的合适吸附能和有利反应能。我们的研究结果表明，Zn-N-C SAC对CTH反应具有非凡活性，从而为探索用于高附加值化学品的先进SAC提供了一种有前景的方法。
