Copper on Carbon Materials: Stabilization by Nitrogen Doping
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Journal of Materials Chemistry A, Materials for Energy and Sustainability
ISSN: 2050-7488
, E-ISSN: 2050-7496
|
| Output data |
Year: 2017,
Volume: 5,
Number: 21,
Pages: 10574-10583
Pages count
: 10
DOI:
10.1039/c7ta02282d
|
| Tags |
FORMIC-ACID DECOMPOSITION; X-RAY PHOTOELECTRON; N-DOPED CARBON; HYDROGEN-PRODUCTION; CU CATALYSTS; NANOPARTICLES; REDUCTION; NICKEL; NANOFIBERS; PARTICLES |
| Authors |
Bulushev Dmitri A.
1,2,3
,
Chuvilin Andrey L.
4,5
,
Sobolev Vladimir I.
1,2
,
Stolyarova Svetlana G.
2
,
Shubin Yury V.
2,3
,
Asanov Igor P.
2,3
,
Ishchenko Arcady V.
1,3
,
Magnani Giacomo
6
,
Riccò Mauro
6
,
Okotrub Alexander V.
2,3
,
Bulusheva Lyubov G.
2,3
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis, SB RAS, Novosibirsk, 630090, Russia
|
| 2 |
Novosibirsk State University, Novosibirsk, 630090, Russia
|
| 3 |
Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk, 630090, Russia
|
| 4 |
CIC nanoGUNE Consolider, San Sebastian, 20018, Spain
|
| 5 |
IKERBASQUE, Basque Foundation for Science, Bilbao, 20013, Spain
|
| 6 |
Dipartimento di Scienze Matematiche, Fisiche e Informatiche, Universita di Parma, `
43124 Parma, Italy
|
|
Funding (1)
|
1
|
Russian Science Foundation
|
16-13-00016
|
The applicability of Cu/C catalysts is limited by sintering of Cu leading to deactivation in catalytic reactions. We show that the problem of sintering could be resolved by N-doping of the carbon support. Cu nanocatalysts with 1 at% of metal were synthesized by Cu acetate decomposition on N-free and N-doped (5.7 at% N) mesoporous carbon supports as well as on thermally expanded graphite oxide. Catalytic properties of these samples were compared in hydrogen production from formic acid decomposition. The N-doping leads to a strong interaction of the Cu species with the support providing stabilization of Cu in the form of clusters of less than 5 nm in size and single Cu atoms, which were observed in a significant ratio by atomic resolution HAADF/STEM even after testing the catalyst under harsh conditions of the reaction at 600 K. The mean size of the obtained Cu clusters was by a factor of 7 smaller than that of the particles in the N-free catalyst. The N-doped Cu catalyst possessed good stability in the formic acid decomposition at 478 K for at least 7 h on-stream and a significantly higher catalytic activity than the N-free Cu catalysts. The nature of the strongly interacting Cu species was studied by XPS, XRD and other methods as well as by DFT calculations. The presence of single Cu atoms in the N-doped catalysts should be attributed to their strong coordination by pyridinic nitrogen atoms at the edge of the graphene sheets of the support. We believe that the N-doping of the carbon support will allow expanding the use of Cu/C materials for different applications avoiding sintering and deactivation.