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碱金属和碱土金属助催化剂对用于自催化CO固定的二氧化硅负载Co-Fe合金的影响

Effect of Alkali- and Alkaline-Earth-Metal Promoters on Silica-Supported Co-Fe Alloy for Autocatalytic CO Fixation.

作者信息

Song Youngdong, Beyazay Tuğçe, Tüysüz Harun

机构信息

Department of Heterogeneous Catalysis, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany.

出版信息

Angew Chem Int Ed Engl. 2024 Feb 19;63(8):e202316110. doi: 10.1002/anie.202316110. Epub 2024 Jan 11.

DOI:10.1002/anie.202316110
PMID:38127486
Abstract

Hydrothermal vents harbor numerous microbial communities rich in reduced carbon species such as formate, acetate, and hydrocarbons. Such essential chemicals for life are produced by H -dependent CO reduction, where serpentinization provides continuous H and thermal energy. Here, we show that silica-supported bimetallic Co-Fe alloys, naturally occurring minerals around serpentinite, can convert CO and H O to key metabolic intermediates of the acetyl coenzyme A pathway such as formate (up to 72 mM), acetate, and pyruvate under mild hydrothermal vent conditions. Long-chain hydrocarbons up to C including propene are also detected, just as in the Lost City hydrothermal field. The effects of promoters on structural properties and catalytic functionalities of the Co-Fe alloy are systematically investigated by incorporating a series of alkali and alkaline earth metals including Na, Mg, K, and Ca. Alkali and alkaline earth metals resulted in higher formate concentrations when dissolved in water and increased reaction pH, while alkaline earth metals also favored the formation of insoluble hydroxides and carbonates similar to the constituent minerals of the chimneys at the Lost City hydrothermal fields.

摘要

热液喷口蕴藏着众多富含甲酸、乙酸和碳氢化合物等还原态碳物种的微生物群落。生命所需的这些重要化学物质是通过依赖氢的一氧化碳还原反应产生的,其中蛇纹石化作用提供了持续的氢和热能。在此,我们表明,二氧化硅负载的双金属钴铁合金(蛇纹岩周围的天然矿物)在温和的热液喷口条件下,能够将一氧化碳和水转化为乙酰辅酶A途径的关键代谢中间体,如甲酸(高达72毫摩尔)、乙酸和丙酮酸。还检测到了包括丙烯在内的长达C的长链碳氢化合物,就像在失落之城热液区一样。通过掺入一系列碱金属和碱土金属,包括钠、镁、钾和钙,系统地研究了促进剂对钴铁合金结构性质和催化功能的影响。碱金属和碱土金属溶解于水并提高反应pH值时会产生更高浓度的甲酸,而碱土金属还有利于形成类似于失落之城热液区烟囱组成矿物的不溶性氢氧化物和碳酸盐。

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