Tricoordinated Single-Atom Cobalt in Zeolite Boosting Propane Dehydrogenation
Ziqiang Qu1, Guangyuan He2,3, Tianjun Zhang4, Yaqi Fan5,6, Yanxia Guo7, Min Hu8, Jun Xu8, Yanhang Ma5,6, Jichao Zhang9, Weibin Fan7, Qiming Sun1,*, Donghai Mei2,3,*, and Jihong Yu10,*
1 Soochow Univ, Coll Chem Chem Engn & Mat Sci, Innovat Ctr Chem Sci, Jiangsu Key Lab Adv Negat Carbon Technol, Suzhou 215123, Peoples R China
2 Tiangong Univ, Sch Environm Sci & Engn, Tianjin 300387, Peoples R China
3 Tiangong Univ, Sch Mat Sci & Engn, State Key Lab Separat Membranes & Membrane Proc, Tianjin 300387, Peoples R China
4 Hebei Univ, Coll Chem & Mat Sci, State Key Lab New Pharmaceut Preparat & Excipients, Baoding 071002, Peoples R China
5 ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China
6 ShanghaiTech Univ, Shanghai Key Lab High resolut Electron Microscopy, Shanghai 201210, Peoples R China
7 Chinese Acad Sci, Inst Coal Chem, State Key Lab Coal Convers, Taiyuan 030001, Shanxi, Peoples R China
8 Chinese Acad Sci, Innovat Acad Precis Measurement Sci & Technol, Natl Ctr Magnet Resonance Wuhan, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan 430071, Peoples R China
9 Chinese Acad Sci, Shanghai Adv Res Inst, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China
10 Jilin Univ, Coll Chem, Int Ctr Future Sci, State Key Lab Inorgan Synth & Preparat Chem, Changchun 130012, Peoples R China
J. Am. Chem. Soc., 2024, 146, 8939-8948
Propane dehydrogenation (PDH) reaction has emerged as one of the most promising propylene production routes due to its high selectivity for propylene and good economic benefits. However, the commercial PDH processes usually rely on expensive platinum-based and poisonous chromium oxide based catalysts. The exploration of cost-effective and ecofriendly PDH catalysts with excellent catalytic activity, propylene selectivity, and stability is of great significance yet remains challenging. Here, we discovered a new active center, i.e., an unsaturated tricoordinated cobalt unit (≡Si-O)CoO(O-Mo) in a molybdenum-doped silicalite-1 zeolite, which afforded an unprecedentedly high propylene formation rate of 22.6 molC3H6 gCo-1 h-1 and apparent rate coefficient of 130 molC3H6 gCo-1 h-1 bar-1 with >99% of propylene selectivity at 550 ℃. Such activity is nearly one magnitude higher than that of previously reported Co-based catalysts in which cobalt atoms are commonly tetracoordinated, and even superior to that of most of Pt-based catalysts under similar operating conditions. Density functional theory calculations combined with the state-of-the-art characterizations unravel the role of the unsaturated tricoordinated Co unit in facilitating the C-H bond-breaking of propane and propylene desorption. The present work opens new opportunities for future large-scale industrial PDH production based on inexpensive non-noble metal catalysts.
链接：https://pubs.acs.org/doi/10.1021/jacs.3c12584
