Single atoms of Pt-group metals stabilized by N-doped carbon nanofibers for efficient hydrogen production from formic acid

Bulushev, D. A., Zacharska, M., Lisitsyn, A. S., Podyacheva, O. Y., Hage, F. S., Ramasse, Q. M., Bangert, U. and Bulusheva, L. G. (2016) Single atoms of Pt-group metals stabilized by N-doped carbon nanofibers for efficient hydrogen production from formic acid. ACS Catalysis, 6(6), pp. 3442-3451. (doi: 10.1021/acscatal.6b00476)

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Abstract

Formic acid is a valuable chemical derived from biomass, as it has a high hydrogen-storage capacity and appears to be an attractive source of hydrogen for various applications. Hydrogen production via formic acid decomposition is often based on using supported catalysts with Pt-group metal nanoparticles. In the present paper, we show that the decomposition of the acid proceeds more rapidly on single metal atoms (by up to 1 order of magnitude). These atoms can be obtained by rather simple means through anchoring Pt-group metals onto mesoporous N-functionalized carbon nanofibers. A thorough evaluation of the structure of the active site by aberration-corrected scanning transmission electron microscopy (ac-STEM) in high-angle annular dark field (HAADF) mode and by CO chemisorption, X-ray photoelectron spectroscopy (XPS), and quantum-chemical calculations reveals that the metal atom is coordinated by a pair of pyridinic nitrogen atoms at the edge of graphene sheets. The chelate binding provides an ionic/electron-deficient state of these atoms that prevents their aggregation and thereby leads to an excellent stability under the reaction conditions. Catalysts with single atoms have also shown very high selectivity. Evidently, the findings can be extended to hydrogen production from other chemicals and can be helpful for improving other energy-related and environmentally benign catalytic processes.

Item Type:Articles
Additional Information:This publication has emanated from research conducted with the financial support of the Russian Science Foundation (Grant 16-13-00016). M.Z. acknowledges the support of the Earth and Natural Sciences (ENS) Doctoral Studies Programme, funded by the Higher Education Authority (HEA) through the Programme of Research at Third Level Institutions, Cycle 5 (PRTLI − 5), cofunded by the European Regional Development Fund (ERDF).
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Hage, Dr Fredrik Sydow
Authors: Bulushev, D. A., Zacharska, M., Lisitsyn, A. S., Podyacheva, O. Y., Hage, F. S., Ramasse, Q. M., Bangert, U., and Bulusheva, L. G.
College/School:College of Science and Engineering > School of Physics and Astronomy
Journal Name:ACS Catalysis
Publisher:American Chemical Society
ISSN:2155-5435
ISSN (Online):2155-5435
Published Online:15 April 2016
Copyright Holders:Copyright © 2016 American Chemical Society
First Published:First published in ACS Catalysis 6(6): 3442-3451
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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