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Heterogeneous hydrogenation of phenylalkynes with parahydrogen : Hyperpolarization, reaction selectivity, and kinetics. / Pokochueva, Ekaterina V.; Kovtunov, Kirill V.; Salnikov, Oleg G. et al.

In: Physical Chemistry Chemical Physics, Vol. 21, No. 48, 11.12.2019, p. 26477-26482.

Research output: Contribution to journal › Article › peer-review

Harvard

Pokochueva, EV, Kovtunov, KV, Salnikov, OG, Gemeinhardt, ME, Kovtunova, LM, Bukhtiyarov, VI, Chekmenev, EY, Goodson, BM & Koptyug, IV 2019, 'Heterogeneous hydrogenation of phenylalkynes with parahydrogen: Hyperpolarization, reaction selectivity, and kinetics', Physical Chemistry Chemical Physics, vol. 21, no. 48, pp. 26477-26482. https://doi.org/10.1039/c9cp02913c

APA

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. (2019). Heterogeneous hydrogenation of phenylalkynes with parahydrogen: Hyperpolarization, reaction selectivity, and kinetics. Physical Chemistry Chemical Physics, 21(48), 26477-26482. https://doi.org/10.1039/c9cp02913c

Vancouver

Pokochueva EV, Kovtunov KV, Salnikov OG, Gemeinhardt ME, Kovtunova LM, Bukhtiyarov VI et al. Heterogeneous hydrogenation of phenylalkynes with parahydrogen: Hyperpolarization, reaction selectivity, and kinetics. Physical Chemistry Chemical Physics. 2019 Dec 11;21(48):26477-26482. doi: 10.1039/c9cp02913c

Author

Pokochueva, Ekaterina V. ; Kovtunov, Kirill V. ; Salnikov, Oleg G. et al. / Heterogeneous hydrogenation of phenylalkynes with parahydrogen : Hyperpolarization, reaction selectivity, and kinetics. In: Physical Chemistry Chemical Physics. 2019 ; Vol. 21, No. 48. pp. 26477-26482.

BibTeX

@article{ebe228ae23ed42438b8cf7b427b605c6,
title = "Heterogeneous hydrogenation of phenylalkynes with parahydrogen: Hyperpolarization, reaction selectivity, and kinetics",
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.",
keywords = "LIQUID-PHASE HYDROGENATION, INDUCED POLARIZATION, PD-NANOPARTICLES, NMR, CATALYSTS, ACETYLENE, EFFICIENT",
author = "Pokochueva, {Ekaterina V.} and Kovtunov, {Kirill V.} and Salnikov, {Oleg G.} and Gemeinhardt, {Max E.} and Kovtunova, {Larisa M.} and Bukhtiyarov, {Valerii I.} and Chekmenev, {Eduard Y.} and Goodson, {Boyd M.} and Koptyug, {Igor V.}",
note = "Publisher Copyright: This journal is {\textcopyright} the Owner Societies. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",
year = "2019",
month = dec,
day = "11",
doi = "10.1039/c9cp02913c",
language = "English",
volume = "21",
pages = "26477--26482",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "48",

}

RIS

TY - JOUR

T1 - Heterogeneous hydrogenation of phenylalkynes with parahydrogen

T2 - Hyperpolarization, reaction selectivity, and kinetics

AU - Pokochueva, Ekaterina V.

AU - Kovtunov, Kirill V.

AU - Salnikov, Oleg G.

AU - Gemeinhardt, Max E.

AU - Kovtunova, Larisa M.

AU - Bukhtiyarov, Valerii I.

AU - Chekmenev, Eduard Y.

AU - Goodson, Boyd M.

AU - Koptyug, Igor V.

N1 - Publisher Copyright: This journal is © the Owner Societies. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2019/12/11

Y1 - 2019/12/11

N2 - 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.

AB - 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.

KW - LIQUID-PHASE HYDROGENATION

KW - INDUCED POLARIZATION

KW - PD-NANOPARTICLES

KW - NMR

KW - CATALYSTS

KW - ACETYLENE

KW - EFFICIENT

UR - http://www.scopus.com/inward/record.url?scp=85076386069&partnerID=8YFLogxK

U2 - 10.1039/c9cp02913c

DO - 10.1039/c9cp02913c

M3 - Article

C2 - 31776540

AN - SCOPUS:85076386069

VL - 21

SP - 26477

EP - 26482

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 48

ER -

ID: 22982691