Research output: Contribution to journal › Article › peer-review
Copper on carbon materials : Stabilization by nitrogen doping. / Bulushev, Dmitri A.; Chuvilin, Andrey L.; Sobolev, Vladimir I. et al.
In: Journal of Materials Chemistry A, Vol. 5, No. 21, 07.06.2017, p. 10574-10583.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Copper on carbon materials
T2 - Stabilization by nitrogen doping
AU - Bulushev, Dmitri A.
AU - Chuvilin, Andrey L.
AU - Sobolev, Vladimir I.
AU - Stolyarova, Svetlana G.
AU - Shubin, Yury V.
AU - Asanov, Igor P.
AU - Ishchenko, Arcady V.
AU - Magnani, Giacomo
AU - Riccò, Mauro
AU - Okotrub, Alexander V.
AU - Bulusheva, Lyubov G.
PY - 2017/6/7
Y1 - 2017/6/7
N2 - 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.
AB - 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.
KW - FORMIC-ACID DECOMPOSITION
KW - X-RAY PHOTOELECTRON
KW - N-DOPED CARBON
KW - HYDROGEN-PRODUCTION
KW - CU CATALYSTS
KW - NANOPARTICLES
KW - REDUCTION
KW - NICKEL
KW - NANOFIBERS
KW - PARTICLES
UR - http://www.scopus.com/inward/record.url?scp=85021627317&partnerID=8YFLogxK
U2 - 10.1039/c7ta02282d
DO - 10.1039/c7ta02282d
M3 - Article
AN - SCOPUS:85021627317
VL - 5
SP - 10574
EP - 10583
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
SN - 2050-7488
IS - 21
ER -
ID: 10098435