Single Isolated Pd2+ Cations Supported on N-Doped Carbon as Active Sites for Hydrogen Production from Formic Acid Decomposition | Sciact - CRIS-system of Boreskov Institute of Catalysis

Single Isolated Pd2+ Cations Supported on N-Doped Carbon as Active Sites for Hydrogen Production from Formic Acid Decomposition Full article

Journal

ACS Catalysis
ISSN: 2155-5435

Output data

Year: 2016, Volume: 6, Number: 2, Pages: 681-691 Pages count : 11 DOI: 10.1021/acscatal.5b02381

Tags

DFT, formic acid decomposition, hydrogen production, mesoporous carbon, N-doping, Pd/C catalyst, single-site catalysis

Authors

Bulushev Dmitri A. ^1,2 , Zacharska Monika ³ , Shlyakhova Elena V. ² , Chuvilin Andrey L. ^6,7 , Guo Yina ⁴ , Beloshapkin Sergey ⁴ , Okotrub Alexander V. ^2,5 , Bulusheva Lyubov G. ^2,5

Affiliations

1	Boreskov Institute of Catalysis, SB RAS, 630090 Novosibirsk, Russia
2	Novosibirsk State University, 630090 Novosibirsk, Russia
3	Chemical & Environmental Sciences Department, University of Limerick, Limerick, Ireland
4	Materials & Surface Science Institute, University of Limerick, Limerick, Ireland
5	Nikolaev Institute of Inorganic Chemistry, SB RAS, 630090 Novosibirsk, Russia
6	CIC nanoGUNE Consolider, E-20018 San Sebastian, Spain
7	IKERBASQUE, Basque Foundation for Science, Bilbao, Spain

Funding (5)

1	Russian Foundation for Basic Research	13-03-00884
2	Russian Science Foundation	16-13-00016
3	European Commission	295180 FP7-PEOPLE-2011-IRSES
4	European Commission
5	FEI Company

Single-site heterogeneous catalysis with isolated Pd atoms was reported earlier, mainly for oxidation reactions and for Pd catalysts supported on oxide surfaces. In the present work, we show that single Pd atoms on nitrogen-functionalized mesoporous carbon, observed by aberration-corrected scanning transmission electron microscopy (ac STEM), contribute significantly to the catalytic activity for hydrogen production from vapor-phase formic acid decomposition, providing an increase by 2-3 times in comparison to Pd catalysts supported on nitrogen-free carbon or unsupported Pd powder. Some gain in selectivity was also achieved. According to X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) studies after ex situ reduction in hydrogen at 573 K, these species exist in a Pd2+ state coordinated by nitrogen species of the support. Extended density functional theory (DFT) calculations confirm that an isolated Pd atom can be the active site for the reaction, giving decomposition of the formic acid molecule into an adsorbed hydrogen atom and a carboxyl fragment, but only if it is coordinated by a pair of pyridinic-type nitrogen atoms located on the open edge of the graphene sheet. Hence, the role of the N-doping of the carbon support is the formation and stabilization of the new active Pd sites. A long-term experiment performed for more than 30 h on stream indicated an excellent stability of these Pd species in the reaction

Bulushev D.A. , Zacharska M. , Shlyakhova E.V. , Chuvilin A.L. , Guo Y. , Beloshapkin S. , Okotrub A.V. , Bulusheva L.G.
Single Isolated Pd2+ Cations Supported on N-Doped Carbon as Active Sites for Hydrogen Production from Formic Acid Decomposition

ACS Catalysis. 2016. V.6. N2. P.681-691. DOI: 10.1021/acscatal.5b02381 WOS Scopus РИНЦ ANCAN OpenAlex

Full text from publisher

Submitted:	Oct 22, 2015
Accepted:	Dec 3, 2015
Published online:	Dec 29, 2015
Published print:	Feb 5, 2016

Web of science:	WOS:000369774900024
Scopus:	2-s2.0-84957555860
Elibrary:	26873807
Chemical Abstracts:	2015:2007103
Chemical Abstracts (print):	164:189634
OpenAlex:	W2282371201

DB	Citing
Web of science	248
Scopus	253
Elibrary	250
OpenAlex	269