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Heterogeneous Hydrogenation of Phenylalkynes with Parahydrogen: Hyperpolarization, Reaction Selectivity, and Kinetics Full article

Общее Language: Английский, Genre: Full article,
Status: Published, Source type: Original
Journal PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084
Output data Year: 2019, Volume: 21, Number: 48, Pages: 26477-26482 Pages count : 6 DOI: 10.1039/c9cp02913c
Tags LIQUID-PHASE HYDROGENATION; INDUCED POLARIZATION; Pd-NANOPARTICLES; NMR; CATALYSTS; ACETYLENE; EFFICIENT
Authors Pokochueva Ekaterina V. 1,2 , Kovtunov Kirill V. 1,2 , Salnikov Oleg G. 1,2 , Gemeinhardt Max E. 3 , Kovtunova Larisa M. 2,4 , Bukhtiyarov Valerii I. 4 , Chekmenev Eduard Y. 5,6 , Goodson Boyd M. 3,7 , Koptyug Igor V. 1,2
Affiliations
1 International Tomography Center SB RAS, 3A Institutskaya St., Novosibirsk, 630090, Russia
2 Novosibirsk State University, 2 Pirogova St., Novosibirsk, 630090, Russia
3 Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, IL 62901, USA
4 Boreskov Institute of Catalysis SB RAS, 5 Acad. Lavrentiev Pr., Novosibirsk, 630090, Russia
5 Department of Chemistry, Integrative Biosciences (Ibio), Wayne State University, Karmanos Cancer Institute (KCI), Detroit, MI 48202, USA
6 Russian Academy of Sciences, 14 Leninskiy Pr., Moscow, 119991, Russia
7 Materials Technology Center, Southern Illinois University, Carbondale, IL 62901, USA

Funding (7)

1 National Science Foundation CHE-1416432
2 National Science Foundation CHE-1836308
3 Russian Foundation for Basic Research 18-33-20019 (АААА-А18-118101090008-1)
4 Federal Agency for Scientific Organizations 0333-2016-0002 (АААА-А16-116121510087-5)
5 Russian Foundation for Basic Research 18-43-543023 (АААА-А18-118060990008-2)
6 Russian Science Foundation 19-13-00172
7 National Science Foundation CHE-1904780

Abstract: Parahydrogen-induced polarization (PHIP) is a powerful technique for studying hydrogenation reactions in gas and liquid phases. Pairwise addition of parahydrogen to the hydrogenation substrate imparts nuclear spin order to reaction products, manifested as enhanced 1H NMR signals from the nascent proton sites. Nanoscale metal catalysts immobilized on supports comprise a promising class of catalysts for producing PHIP effects; however, on such catalysts the percentage of substrates undergoing the pairwise addition route - a necessary condition for observing PHIP - is usually low. In this paper, we present a systematic study of several metal catalysts (Rh, Pt, Pd, and Ir) supported on TiO2 in liquid-phase hydrogenation of different prototypical phenylalkynes (phenylacetylene, 1-phenyl-1-propyne, and 3-phenyl-1-propyne) with parahydrogen. Catalyst activity and selectivity were found to be affected by both the nature of the active metal and the percentage of metal loading. It was demonstrated that the optimal catalyst for production of hyperpolarized products is Rh/TiO2 with 4 wt% metal loading, whereas Pd/TiO2 provided the greatest selectivity for semihydrogenation of phenylalkynes. In a study of liquid-phase hydrogenation reaction kinetics, it was shown that reaction order with respect to hydrogen is nearly the same for pairwise and non-pairwise H2 addition - consistent with a similar nature of the catalytically active sites for these reaction pathways. This journal is © the Owner Societies.
Cite: Pokochueva E.V. , Kovtunov K.V. , Salnikov O.G. , Gemeinhardt M.E. , Kovtunova L.M. , Bukhtiyarov V.I. , Chekmenev E.Y. , Goodson B.M. , Koptyug I.V.
Heterogeneous Hydrogenation of Phenylalkynes with Parahydrogen: Hyperpolarization, Reaction Selectivity, and Kinetics
PCCP: Physical Chemistry Chemical Physics. 2019. V.21. N48. P.26477-26482. DOI: 10.1039/c9cp02913c publication_identifier_short.wos_identifier_type publication_identifier_short.scopus_identifier_type publication_identifier_short.rinz_identifier_type
Dates:
Submitted: May 23, 2019
Accepted: Nov 19, 2019
Published online: Nov 20, 2019
Published print: Dec 28, 2019
Identifiers:
publication_identifier.wos_identifier_type WOS:000502767400017
publication_identifier.scopus_identifier_type 2-s2.0-85076386069
publication_identifier.rinz_identifier_type 43213270
publication_identifier.accession_number_identifier_type 2019:2188948
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