Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei, 10607, Taiwan.
College of Material Engineering, Fujian Agriculture and Forestry University, Fuzhou, 350002, China.
Sci Rep. 2017 Aug 30;7(1):10094. doi: 10.1038/s41598-017-10705-3.
We demonstrate copper-based (Cu,M)(O,S) oxysulfide catalysts with M = Ni, Sn, and Co for the abiotic chemical synthesis of ethanol (EtOH) with the C-C bond formation by passing carbon dioxide (CO) through an aqueous dispersion bath at ambient environment. (Cu,Ni)(O,S) with 12.1% anion vacancies had the best EtOH yield, followed by (Cu,Sn)(O,S) and (Cu,Co)(O,S). The ethanol yield with 0.2 g (Cu,Ni)(O,S) catalyst over a span of 20 h achieved 5.2 mg. The ethanol yield is inversely proportional to the amount of anion vacancy. The kinetic mechanism for converting the dissolved CO into the C oxygenate is proposed. Molecular interaction, pinning, and bond weakening with anion vacancy of highly strained catalyst, the electron hopping at Cu/Cu sites, and the reaction orientation of hydrocarbon intermediates are the three critical issues in order to make the ambient chemical conversion of inorganic CO to organic EtOH with the C-C bond formation in water realized. On the other hand, Cu(O,S) with the highest amount of 22.7% anion vacancies did not produce ethanol due to its strain energy relaxation opposing to the pinning and weakening of O-H and C-O bonds.
我们展示了基于铜的（Cu，M）（O，S）氧硫化物催化剂，其中 M = Ni、Sn 和 Co，用于通过在环境温度下将二氧化碳（CO）通过水基分散浴进行非生物化学合成乙醇（EtOH），形成 C-C 键。具有 12.1%阴离子空位的（Cu，Ni）（O，S）具有最佳的乙醇产率，其次是（Cu，Sn）（O，S）和（Cu，Co）（O，S）。在 20 小时的时间内，使用 0.2g（Cu，Ni）（O，S）催化剂可获得 5.2mg 的乙醇产率。乙醇产率与阴离子空位的数量成反比。提出了将溶解的 CO 转化为 C 氧代物的动力学机制。高应变催化剂的分子相互作用、钉扎和阴离子空位导致的键变弱、Cu/Cu 位的电子跳跃以及烃中间体的反应取向是实现无机 CO 在水中与 C-C 键形成转化为有机 EtOH 的环境化学转化的三个关键问题。另一方面，具有最高 22.7%阴离子空位的 Cu（O，S）由于其应变能弛豫与 O-H 和 C-O 键的钉扎和弱化相抗衡，因此不会产生乙醇。
