Zeolite-Encaged Single-Atom Rhodium Catalysts: Highly-Efficient Hydrogen Generation and Shape-Selective Tandem Hydrogenation of Nitroarenes

Qiming Sun; Ning Wang; Tianjun Zhang; Risheng Bai; Alvaro Mayoral; Peng Zhang; Qinghong Zhang; Osamu Terasaki; Jihong Yu

doi:10.1002/anie.201912367

Zeolite-Encaged Single-Atom Rhodium Catalysts: Highly-Efficient Hydrogen Generation and Shape-Selective Tandem Hydrogenation of Nitroarenes

Angew Chem Int Ed Engl. 2019 Dec 16;58(51):18570-18576. doi: 10.1002/anie.201912367. Epub 2019 Nov 19.

Authors

Qiming Sun¹, Ning Wang¹, Tianjun Zhang¹, Risheng Bai¹, Alvaro Mayoral², Peng Zhang³, Qinghong Zhang⁴, Osamu Terasaki², Jihong Yu^{1

5}

Affiliations

¹ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, P. R. China.
² Center for High-resolution Electron Microscopy (CħEM), School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, P. R. China.
³ Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
⁴ State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
⁵ International Center of Future Science, Jilin University, Qianjin Street 2699, Changchun, 130012, P. R. China.

PMID: 31657875
DOI: 10.1002/anie.201912367

Abstract

Single-atom catalysts are emerging as a new frontier in heterogeneous catalysis because of their maximum atom utilization efficiency, but they usually suffer from inferior stability. Herein, we synthesized single-atom Rh catalysts embedded in MFI-type zeolites under hydrothermal conditions and subsequent ligand-protected direct H₂ reduction. C_s -corrected scanning transmission electron microscopy and extended X-ray absorption analyses revealed that single Rh atoms were encapsulated within 5-membered rings and stabilized by zeolite framework oxygen atoms. The resultant catalysts exhibited excellent H₂ generation rates from ammonia borane (AB) hydrolysis, up to 699 min^-1 at 298 K, representing the top level among heterogeneous catalysts for AB hydrolysis. The catalysts also showed superior catalytic performance in shape-selective tandem hydrogenation of various nitroarenes by coupling with AB hydrolysis, giving >99 % yield of corresponding amine products.

Keywords: hydrogen generation; rhodium; single-atom catalysts; tandem reactions; zeolites.

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Review

Abstract

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