Confined Pyrolysis within Metal-Organic Frameworks To Form Uniform Ru3 Clusters for Efficient Oxidation of Alcohols

Shufang Ji; Yuanjun Chen; Qiang Fu; Yifeng Chen; Juncai Dong; Wenxing Chen; Zhi Li; Yu Wang; Lin Gu; Wei He; Chen Chen; Qing Peng; Yu Huang; Xiangfeng Duan; Dingsheng Wang; Claudia Draxl; Yadong Li

doi:10.1021/jacs.7b05018

Confined Pyrolysis within Metal-Organic Frameworks To Form Uniform Ru₃ Clusters for Efficient Oxidation of Alcohols

J Am Chem Soc. 2017 Jul 26;139(29):9795-9798. doi: 10.1021/jacs.7b05018. Epub 2017 Jul 13.

Authors

Shufang Ji¹, Yuanjun Chen¹, Qiang Fu², Yifeng Chen³, Juncai Dong⁴, Wenxing Chen¹, Zhi Li¹, Yu Wang⁵, Lin Gu⁶, Wei He³, Chen Chen¹, Qing Peng¹, Yu Huang^{1

7}, Xiangfeng Duan⁷, Dingsheng Wang¹, Claudia Draxl², Yadong Li¹

Affiliations

¹ Department of Chemistry, Tsinghua University , Beijing 100084, China.
² Institut für Physik and IRIS Adlershof, Humboldt-Universität zu Berlin , Berlin 12489, Germany.
³ School of Pharmaceutical Sciences, Tsinghua University , Beijing 100084, China.
⁴ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
⁵ Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences , Shanghai 201204, China.
⁶ Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences , Beijing 100190, China.
⁷ Department of Materials Science & Engineering, University of California , Los Angeles, California 90095, United States.

PMID: 28696113
DOI: 10.1021/jacs.7b05018

Abstract

Here we report a novel approach to synthesize atomically dispersed uniform clusters via a cage-separated precursor preselection and pyrolysis strategy. To illustrate this strategy, well-defined Ru₃(CO)₁₂ was separated as a precursor by suitable molecular-scale cages of zeolitic imidazolate frameworks (ZIFs). After thermal treatment under confinement in the cages, uniform Ru₃ clusters stabilized by nitrogen species (Ru₃/CN) were obtained. Importantly, we found that Ru₃/CN exhibits excellent catalytic activity (100% conversion), high chemoselectivity (100% for 2-aminobenzaldehyde), and significantly high turnover frequency (TOF) for oxidation of 2-aminobenzyl alcohol. The TOF of Ru₃/CN (4320 h^-1) is about 23 times higher than that of small-sized (ca. 2.5 nm) Ru particles (TOF = 184 h^-1). This striking difference is attributed to a disparity in the interaction between Ru species and adsorbed reactants.

Publication types

Research Support, Non-U.S. Gov't