Highly effective Ir-based catalysts for benzoic acid hydrogenation: experiment- and theory-guided catalyst rational design
Highly effective Ir-based catalysts for benzoic acid hydrogenation: experiment- and theory-guided catalyst rational design
复制标题
用于苯甲酸加氢的高效铱基催化剂：实验和理论指导的催化剂合理设计
DOI：
10.1039/c7gc00387k
复制
发表时间：
2017
期刊：
影响因子：
9.8
通讯作者：
Wang Yong
中科院分区：
文献类型：
--
作者：
Tang Minghui;Mao Shanjun;Li Xuefeng;Chen Chunhong;Li Mingming;Wang Yong
在探索上级加氢催化剂的过程中，已经成功开发了在温和的反应条件（85 °C，0.1 MPa H2，在水中）下将苯甲酸加氢为环己烷羧酸的具有创纪录催化活性（高达40 h-1）的Ir基催化剂。在排除各种因素的情况下，实验结果表明，影响Ir基催化剂活性差异的主要因素实际上是载体（如掺氮碳、活性炭、SBA-15和各种金属氧化物）在反应溶液中的分散稳定性，而不是Ir活性组分与载体之间的相互作用。结合第一性原理的理论研究，首次提出了考虑反应物（H2）和溶剂（H2O）竞争吸附的芳环水溶液加氢活性火山曲线。Ir的高活性可以通过H_2和H_2O在催化剂上的解离能或吸附能的适当差异来推断。该活性火山曲线为进一步合理设计苯甲酸加氢催化剂乃至芳环加氢催化剂提供了指导。
On the way to exploring superior hydrogenation catalysts, Ir-based catalysts with a record catalytic activity (up to 40 h−1) for the hydrogenation of benzoic acid to cyclohexanecarboxylic acid under mild reaction conditions (85 °C, 0.1 MPa H2, in water) have been successfully developed. By excluding various factors, the experimental results showed that the main factor governing the activity discrepancy between the Ir-based catalysts is actually the dispersion stability of the supports (such as N-doped carbon, active carbon, SBA-15 and various metal oxides) in the reaction solution, rather than the interaction between the Ir active component and the supports. Combined with theoretical investigation from first principles, an activity volcano curve considering the competing adsorption between the reactants (H2) and solvent (H2O) for aqueous aromatic ring hydrogenation was presented for the first time. The high activity of Ir can be deduced by the proper discrepancy of dissociation energies or adsorption energies between H2 and H2O on the catalysts. This activity volcano curve provides guidance for further rational design of promising catalysts for benzoic acid or even aromatic ring hydrogenation under true reaction conditions for practical applications.