TY - JOUR

T1 - Mechanistic in situ investigation of heterogeneous hydrogenation over Rh/TiO2catalysts: Selectivity, pairwise route and catalyst nature

AU - Pokochueva, Ekaterina V.

AU - Burueva, Dudari B.

AU - Kovtunova, Larisa M.

AU - Bukhtiyarov, Andrey V.

AU - Gladky, Alexei Yu

AU - Kovtunov, Kirill V.

AU - Koptyug, Igor V.

AU - Bukhtiyarov, Valerii I.

N1 - Funding Information: The ITC team thanks the Russian Ministry of Science and Higher Education for the use of NMR equipment. The BIC team thanks RSF (grant 19-13-00172) for support of the catalyst synthesis and studies of active catalytic sites via XPS. The BIC team gratefully acknowledges the assistance from Dr Igor P. Prosvirin and Dr Evgeny Yu. Gerasimov at Boreskov Institute of Catalysis. Publisher Copyright: © 2021 The Royal Society of Chemistry.

PY - 2021/2

Y1 - 2021/2

N2 - The selectivity of product formation is strongly correlated with the nature of the catalyst active centers. Therefore, the selective synthesis of active sites with certain structure is a big challenge in modern catalysis. Here synthetic procedures are adopted for the formation of 1% Rh/TiO2 catalysts with different properties. It is shown that the nature of the precursor used for catalyst preparation is important, and that the use of a solution of rhodium acetate instead of rhodium nitrate leads to the selective formation of butenes during 1,3-butadiene hydrogenation. The use of parahydrogen in the reaction results in the enhancement of NMR signals via parahydrogen-induced polarization (PHIP) for all synthesized catalysts, and this signal enhancement increases with increasing catalyst calcination temperature. This effect is explained by the decoration of rhodium nanoparticles with titania which restricts hydrogen mobility on the surface, leading to the highest reported to date selectivity toward the pairwise hydrogen addition route of 7% for supported metal catalysts. This journal is

AB - The selectivity of product formation is strongly correlated with the nature of the catalyst active centers. Therefore, the selective synthesis of active sites with certain structure is a big challenge in modern catalysis. Here synthetic procedures are adopted for the formation of 1% Rh/TiO2 catalysts with different properties. It is shown that the nature of the precursor used for catalyst preparation is important, and that the use of a solution of rhodium acetate instead of rhodium nitrate leads to the selective formation of butenes during 1,3-butadiene hydrogenation. The use of parahydrogen in the reaction results in the enhancement of NMR signals via parahydrogen-induced polarization (PHIP) for all synthesized catalysts, and this signal enhancement increases with increasing catalyst calcination temperature. This effect is explained by the decoration of rhodium nanoparticles with titania which restricts hydrogen mobility on the surface, leading to the highest reported to date selectivity toward the pairwise hydrogen addition route of 7% for supported metal catalysts. This journal is

UR - http://www.scopus.com/inward/record.url?scp=85107390370&partnerID=8YFLogxK

U2 - 10.1039/c9fd00138g

DO - 10.1039/c9fd00138g

M3 - Article

C2 - 33720219

AN - SCOPUS:85107390370

VL - 229

SP - 161

EP - 175

JO - Faraday Discussions

JF - Faraday Discussions

SN - 1364-5498

ER -