Zhang Bin, Yuan Haiyang, Liu Ye, Deng Zijie, Douthwaite Mark, Dummer Nicholas F, Lewis Richard J, Liu Xingwu, Luan Sen, Dong Minghua, Wang Tianjiao, Xu Qingling, Zhao Zhijuan, Liu Huizhen, Han Buxing, Hutchings Graham J
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China.
Max Planck-Cardiff Centre on the Fundamentals of Heterogeneous Catalysis FUNCAT, Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, CF24 4HQ, UK.
Nat Commun. 2024 Sep 7;15(1):7837. doi: 10.1038/s41467-024-52163-2.
Alkoxycarbonylation reactions are common in the chemical industry, yet process sustainability is limited by the inefficient utilization of CO. In this study, we address this issue and demonstrate that significant improvements can be achieved by adopting a heterogeneously catalyzed process, using a Ru/NbO catalyst. The Ru/NbO catalyst enables the direct synthesis of methyl propionate, a key industrial commodity, with over 98% selectivity from CO, ethylene and methanol, without any ligands or acid/base promoters. Under ambient CO pressure, a high CO utilization efficiency (336 mmolmolh) is achieved. Mechanistic investigations reveal that CO undergoes a methoxycarbonyl (COOCH) intermediate pathway, attacking the terminal carbon atom of alkene and yielding linear esters. The origins of prevailing linear regioselectivity in esters are revealed. The infrared spectroscopic feature of the key COOCH species is observed at 1750 cm (C=O vibration) both experimentally and computationally. The broad substrate applicability of Ru/NbO catalyst for ester production is demonstrated. This process offers a sustainable and efficient approach with high CO utilization and atom economy for the synthesis of esters.
烷氧基羰基化反应在化学工业中很常见，但过程的可持续性受到一氧化碳利用效率低下的限制。在本研究中，我们解决了这个问题，并证明通过采用使用Ru/NbO催化剂的多相催化过程可以实现显著改进。Ru/NbO催化剂能够直接合成丙酸甲酯，这是一种关键的工业商品，从一氧化碳、乙烯和甲醇中选择性超过98%，无需任何配体或酸碱促进剂。在环境一氧化碳压力下，实现了高一氧化碳利用效率（336 mmolmolh）。机理研究表明，一氧化碳经历甲氧基羰基（COOCH）中间途径，攻击烯烃的末端碳原子并生成线性酯。揭示了酯中普遍存在的线性区域选择性的起源。通过实验和计算在1750 cm（C=O振动）处观察到关键COOCH物种的红外光谱特征。证明了Ru/NbO催化剂在酯生产中的广泛底物适用性。该过程为酯的合成提供了一种具有高一氧化碳利用率和原子经济性的可持续且高效的方法。
