Affiliation:
1. Hefei National Research Center for Physical Sciences at the Microscale Department of Chemistry University of Science and Technology of China Hefei Anhui 230026 P. R. China
2. State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structural of Matter Chinese Academy of Sciences Fuzhou Fujian 35000 P. R. China
3. University of Chinese Academy of Sciences Beijing 100049 P. R. China
4. School of Energy and Power Engineering North China Electric Power University Baoding Hebei 071003 P. R. China
Abstract
AbstractThe selectivity control of Pd nanoparticles (NPs) in the direct CO esterification with methyl nitrite toward dimethyl oxalate (DMO) or dimethyl carbonate (DMC) remains a grand challenge. Herein, Pd NPs are incorporated into isoreticular metal–organic frameworks (MOFs), namely UiO‐66‐X (X=‐H, ‐NO2, ‐NH2), affording Pd@UiO‐66‐X, which unexpectedly exhibit high selectivity (up to 99 %) to DMC and regulated activity in the direct CO esterification. In sharp contrast, the Pd NPs supported on the MOF, yielding Pd/UiO‐66, displays high selectivity (89 %) to DMO as always reported with Pd NPs. Both experimental and DFT calculation results prove that the Pd location relative to UiO‐66 gives rise to discriminated microenvironment of different amounts of interface between Zr‐oxo clusters and Pd NPs in Pd@UiO‐66 and Pd/UiO‐66, resulting in their distinctly different selectivity. This is an unprecedented finding on the production of DMC by Pd NPs, which was previously achieved by Pd(II) only, in the direct CO esterification.
Funder
National Key Research and Development Program of China
National Natural Science Foundation of China
Fundamental Research Funds for the Central Universities
Subject
General Chemistry,Catalysis
Cited by
17 articles.
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