Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Pairwise hydrogen addition in the selective semihydrogenation of alkynes on silica-supported Cu catalysts. / Salnikov, Oleg G.; Liu, Hsueh Ju; Fedorov, Alexey и др.
в: Chemical Science, Том 8, № 3, 01.03.2017, стр. 2426-2430.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Pairwise hydrogen addition in the selective semihydrogenation of alkynes on silica-supported Cu catalysts
AU - Salnikov, Oleg G.
AU - Liu, Hsueh Ju
AU - Fedorov, Alexey
AU - Burueva, Dudari B.
AU - Kovtunov, Kirill V.
AU - Copéret, Christophe
AU - Koptyug, Igor V.
N1 - Publisher Copyright: © The Royal Society of Chemistry.
PY - 2017/3/1
Y1 - 2017/3/1
N2 - Mechanistic insight into the semihydrogenation of 1-butyne and 2-butyne on Cu nanoparticles supported on partially dehydroxylated silica (Cu/SiO2-700) was obtained using parahydrogen. Hydrogenation of 1-butyne over Cu/SiO2-700 yielded 1-butene with ≥97% selectivity. The surface modification of this catalyst with tricyclohexylphosphine (PCy3) increased the selectivity to 1-butene up to nearly 100%, although at the expense of reduced catalytic activity. Similar trends were observed in the hydrogenation of 2-butyne, where Cu/SiO2-700 provided a selectivity to 2-butene in the range of 72-100% depending on the reaction conditions, while the catalyst modified with PCy3 again demonstrated nearly 100% selectivity. Parahydrogen-induced polarization effects observed in hydrogenation reactions catalyzed by copper-based catalysts demonstrate the viability of pairwise hydrogen addition over these catalysts. Contribution of pairwise hydrogen addition to 1-butyne was estimated to be at least 0.2-0.6% for unmodified Cu/SiO2-700 and ≥2.7% for Cu/SiO2-700 modified with PCy3, highlighting the effect of surface modification with the tricyclohexylphosphine ligand.
AB - Mechanistic insight into the semihydrogenation of 1-butyne and 2-butyne on Cu nanoparticles supported on partially dehydroxylated silica (Cu/SiO2-700) was obtained using parahydrogen. Hydrogenation of 1-butyne over Cu/SiO2-700 yielded 1-butene with ≥97% selectivity. The surface modification of this catalyst with tricyclohexylphosphine (PCy3) increased the selectivity to 1-butene up to nearly 100%, although at the expense of reduced catalytic activity. Similar trends were observed in the hydrogenation of 2-butyne, where Cu/SiO2-700 provided a selectivity to 2-butene in the range of 72-100% depending on the reaction conditions, while the catalyst modified with PCy3 again demonstrated nearly 100% selectivity. Parahydrogen-induced polarization effects observed in hydrogenation reactions catalyzed by copper-based catalysts demonstrate the viability of pairwise hydrogen addition over these catalysts. Contribution of pairwise hydrogen addition to 1-butyne was estimated to be at least 0.2-0.6% for unmodified Cu/SiO2-700 and ≥2.7% for Cu/SiO2-700 modified with PCy3, highlighting the effect of surface modification with the tricyclohexylphosphine ligand.
KW - ADSORPTION
KW - DNP
KW - DYNAMIC NUCLEAR-POLARIZATION
KW - ENHANCED NMR-SPECTROSCOPY
KW - HETEROGENEOUS HYDROGENATION
KW - HYPERPOLARIZATION
KW - ION-EXCHANGED COPPER
KW - PARAHYDROGEN-INDUCED POLARIZATION
KW - PROPYNE
KW - STATE NMR
UR - http://www.scopus.com/inward/record.url?scp=85014199716&partnerID=8YFLogxK
U2 - 10.1039/c6sc05276b
DO - 10.1039/c6sc05276b
M3 - Article
C2 - 28451349
AN - SCOPUS:85014199716
VL - 8
SP - 2426
EP - 2430
JO - Chemical Science
JF - Chemical Science
SN - 2041-6520
IS - 3
ER -
ID: 10278152