文献类型：期刊文献

英文题名：The Role of Convex Edge Site in Fully-Exposed Pt Cluster Catalyst for Hydrogen Production

作者：Peng, Mi[1];Li, Chengyu[1];Meng, Huaying[2];Tang, Xuan[3];Wang, Maolin[1];Zhang, Jie[1];Xie, Junzhong[1];Zhang, Qingxin[1];Tong, Fengya[4];Tian, Hao[4];Wang, Hao[4];Song, Lei[4];Liu, Hongyang[5];Dai, Sheng[3];Sun, Geng[2];Ma, Ding[1]

机构：[1]Peking Univ, Coll Chem & Mol Engn, Beijing Natl Lab Mol Engn, New Cornerstone Sci Lab, Beijing 100871, Peoples R China;[2]Chongqing Univ, Coll Chem & Chem Engn, Chongqing Key Lab Chem Theory & Mech, Chongqing 401331, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[4]SINOPEC, Shanghai Res Inst Petrochem Technol, Shanghai 201208, Peoples R China;[5]Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China

年份：2025

卷号：64

期号：25

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20252018447006);WOS:【SCI-EXPANDED(收录号:WOS:001470701400001)】；

基金：This work was supported by the National Key R&D Program of China (2023YFA1506602), and the National Natural Science Foundation of China (22232001, 22202004, 22203012, and 22376062). This work received financial support from the China Petrochemical Corporation (Sinopec Group) (30000000-22-ZC0607-0471, 33750000-22-ZC0607-0083, 14800000-22-ZC0607-0018, 32350000-22-ZC0607-0001). D.M. acknowledges support from the Tencent Foundation through the XPLORER PRIZE and the New Cornerstone Science Foundation. The XAS experiments were conducted in 1W1B beamline of Beijing Synchrotron Radiation Facility () and BL14W1 beamline of Shanghai Synchrotron Radiation Facility (). In situ IR experiment was performed with the assistance of Tianjin Xianquan Co., Ltd. DFT calculation was supported by High-performance Computing Platform of Peking University.

语种：英文

外文关键词：Active sites; Cyclohexane dehydrogenation; Density functional theory; Fully-exposed cluster catalyst; Hydrogen production

摘要：Achieving a precise understanding of the active site structure has long been an ultimate goal in fundamental heterogeneous catalysis research, yet it remains exceptionally challenging in nanocluster catalysis. In Pt-catalyzed dehydrogenation reactions, such as cyclohexane dehydrogenation for liquid organic carriers (LOHC), previous efforts have provided valuable insights into the size effects of nanoclusters. However, the optimal geometry of the active sites has remained elusive and, at times, contradictory. In this study, we investigate the geometric effect and the active site structure in fully-exposed Pt clusters supported on ceria that exhibit superior activity in cyclohexane dehydrogenation (11.4 mol molPt-(1) s-(1)), characterized by small coordination numbers, high metal utilization efficiency, and abundant convex edge sites. Through a combination of experimental and theoretical approaches, we demonstrate that the convex edge sites predominant within the fully-exposed Pt clusters outperform other active structures (e.g., terrace sites, hollow sites, etc.) in dehydrogenation reactions. These convex edge sites are not only efficient in C & horbar;H activation but, more notably, are also resistant to detrimental carbonaceous intermediates, hence enabling high and long-lived H2 production activity.