文献类型：期刊文献

英文题名：Realization of high-pressure dry methane reforming by suppressing coke deposition with Co-Rh intermetallic clusters

作者：Liu, Qing[1];Liu, Yang[2];Zhou, Ning;Zhang, Penghao[1];Liu, Zhicheng[3];Vovk, Evgeny I.[2];Zhu, Yi-An[1];Yang, Yong[2];Zhu, Kake[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, UNILAB, Shanghai 200237, Peoples R China;[2]ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201203, Peoples R China;[3]Shanghai Res Inst Petrochem Technol, Shanghai 201208, Peoples R China

年份：2023

卷号：339

外文期刊名：APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY

收录：;EI(收录号：20233814761470);WOS:【SCI-EXPANDED(收录号:WOS:001060285100001)】；

基金：Authors are grateful for the financial support from the National Natural Science Foundation of China (No. 22178111, 22073027, 92045301, 22072107, 22072092). YY and EV would like to thank Ministry of Science and Technology (2022YFA1503802).

语种：英文

外文关键词：Methane dry reforming; Carbon dioxide; Co -Rh alloy; Heterogeneous catalysis; Kinetics

摘要：It is economical to perform methane and carbon dioxide reforming under high-pressure and temperature con-ditions, but the harsh operation condition poses a grand challenge for coke-resistant catalyst design. We report herein that surface-segregation-free Co1Rh3 clusters are stable catalysts under 20 bars at 850 oC. Microkinetic analysis discloses that balanced and lowered surface coverages of C* and O* constitute the most abundant re-action intermediates on Co1Rh3 clusters at elevated pressures, with respect to that of the monometallic ones, thus avoiding surface carbon accumulation or surface oxidative deactivation. Moreover, density functional theory calculations of carbon atom nucleation discloses that adsorbed carbon transformation to refractory, graphene-like carbon is suppressed on Co1Rh3 cluster surface, owing to increased energetic barrier and ensemble size, hence, only CO2 gasifiable soft carbon could form. The revelation of the electronic/geometric features of Co1Rh3 is regarded to provide a guidance for future coke-resistant catalyst design.