Atomically Dispersed Ruthenium Species Inside Metal-Organic Frameworks: Combining the High Activity of Atomic Sites and the Molecular Sieving Effect of MOFs

Shufang Ji; Yuanjun Chen; Shu Zhao; Wenxing Chen; Lijun Shi; Yu Wang; Juncai Dong; Zhi Li; Fuwei Li; Chen Chen; Qing Peng; Jun Li; Dingsheng Wang; Yadong Li

doi:10.1002/anie.201814182

Atomically Dispersed Ruthenium Species Inside Metal-Organic Frameworks: Combining the High Activity of Atomic Sites and the Molecular Sieving Effect of MOFs

Angew Chem Int Ed Engl. 2019 Mar 22;58(13):4271-4275. doi: 10.1002/anie.201814182. Epub 2019 Feb 25.

Authors

Shufang Ji¹, Yuanjun Chen¹, Shu Zhao², Wenxing Chen¹, Lijun Shi³, Yu Wang⁴, Juncai Dong⁵, Zhi Li¹, Fuwei Li³, Chen Chen¹, Qing Peng¹, Jun Li¹, Dingsheng Wang¹, Yadong Li¹

Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing, 100084, China.
² Beijing Guyue New Materials Research Institute, Beijing University of Technology, Beijing, 100124, China.
³ State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, 730000, China.
⁴ Shanghai Synchrotron Radiation Facilities, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China.
⁵ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China.

PMID: 30730605
DOI: 10.1002/anie.201814182

Abstract

Incorporating atomically dispersed metal species into functionalized metal-organic frameworks (MOFs) can integrate their respective merits for catalysis. A cage-controlled encapsulation and reduction strategy is used to fabricate single Ru atoms and triatomic Ru₃ clusters anchored on ZIF-8 (Ru₁ @ZIF-8, Ru₃ @ZIF-8). The highly efficient and selective catalysis for semi-hydrogenation of alkyne is observed. The excellent activity derives from high atom-efficiency of atomically dispersed Ru active sites and hydrogen enrichment by the ZIF-8 shell. Meanwhile, ZIF-8 shell serves as a novel molecular sieve for olefins to achieve absolute regioselectivity of catalyzing terminal alkynes but not internal alkynes. Moreover, the size-dependent performance between Ru₃ @ZIF-8 and Ru₁ @ZIF-8 is detected in experiment and understood by quantum-chemical calculations, demonstrating a new and promising approach to optimize catalysts by controlling the number of atoms.

Keywords: cluster compounds; composites; heterogeneous catalysis; metal-organic frameworks; ruthenium.

Abstract

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