期刊
ACS CATALYSIS
卷 11, 期 2, 页码 682-690出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.0c03933
关键词
heterogeneous methanol carbonylation; single site Rh catalyst; accommodation site; electronic interaction; carbonyl groups
资金
- National Key R&D Program of China [2017YFB0602203]
- Natural Science Foundation of Zhejiang Province, China [LY18B060007]
- State Key Laboratory of Molecular Reaction Dynamics in DICP, CAS
- Strategic Priority Research Program of the Chinese Academy of Sciences [XDA21020300, XDB17020400]
- National Natural Science Foundation of China [22002156]
Heterogeneous single-metal-site catalyst Rh-1/AC exhibits superior catalytic activity and lower activation energy compared to homogeneous catalyst, achieved through atomic dispersion and electronic interaction.
Heterogeneous single-metal-site catalysts have been drawing increasing interests in the field of academy and industry because of the comparable catalytic activity with homogeneous catalyst and easy separation. Here, an efficiently heterogeneous single-site Rh catalyst on activated carbon (Rh-1/AC) was constructed, which performs three times activity than the corresponding homogeneous catalyst for methanol carbonylation. Experimental data reveals that the apparent activation energy on the Rh-1/AC catalyst is 0.91 eV, far less than 1.54 eV of its homogeneous counterpart. Ex situ EXAFS confirms the molecular configuration of a single Rh site. DFT calculation demonstrates that the electron-donating carbonyl group on the surface of the support possesses the precedence to accommodate the single-site Rh ions. Furthermore, difference charge density verifies that the coordinative bond between a single metal ion and a carbonyl group enhances the electronic density of the central Rh atom, consequently lowering the energy barrier of the rate-determining step of CH3I oxidative addition. Together with the atomic dispersion, as well as the electronic interaction between a single Rh ion and carbonyl groups, the Rh-1/AC catalyst performs superior activity than homogeneous systems.
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