Catalytic hydrodeoxygenation of m-cresol over Ni2P/hierarchical ZSM-5

Antonio Berenguer; James A. Bennett; James Hunns; Inés Moreno; Juan M. Coronado; Adam F. Lee; Patricia Pizarro; Karen Wilson; David P. Serrano

doi:10.1016/j.cattod.2017.08.032

Catalytic hydrodeoxygenation of m-cresol over Ni₂P/hierarchical ZSM-5

Antonio Berenguer, James A. Bennett, James Hunns, Inés Moreno, Juan M. Coronado, Adam F. Lee, Patricia Pizarro, Karen Wilson, David P. Serrano^*

^*Corresponding author for this work

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

Abstract

Bifunctional catalysts comprising Ni₂P supported over a hierarchical ZSM-5 zeolite (h-ZSM-5) were synthesized and applied to the hydrodeoxygenation (HDO) of m-cresol, a model pyrolysis bio-oil compound. Surface and bulk characterization of Ni₂P/h-ZSM-5 catalysts by XRD, TEM, DRIFTS, TPR, porosimetry and propylamine temperature-programmed desorption reveal that Ni₂P incorporation modifies the zeolite textural properties through pore blockage of the mesopores by phosphide nanoparticles, but has negligible impact of the micropore network. Ni₂P nanoparticles introduce new, strong Lewis acid sites, whose density is proportional to the Ni₂P loading, accompanied by new Brönsted acid sites attributed to the presence of Psingle bondOH moieties. Ni₂P/h-ZSM-5 is ultraselective (>97%) for m-cresol HDO to methylcyclohexane, significantly outperforming a reference Ni₂P/SiO₂ catalyst and highlighting the synergy between metal phosphide and solid acid support. m-Cresol conversion was proportional to Ni2P loading reaching 80 and 91% for 5 and 10 wt% Ni respectively. Turnover frequencies for m-cresol HDO are a strong function of Ni₂P dispersion, evidencing a structure sensitivity, with optimum activity observed for 4 nm particles.

Original language	English
Pages (from-to)	72-79
Journal	Catalysis Today
Volume	304
Early online date	24 Aug 2017
DOIs	https://doi.org/10.1016/j.cattod.2017.08.032
Publication status	Published - 15 Apr 2018

Bibliographical note

© 2017, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/

Funding: Spanish Ministry of Economy and Competitiveness (CTQ2014-60209-R); Regional Government of Madrid (S2013/MAE-2882); EPSRC (EP/K036548/2 and EP/N009924/1).

Keywords

hydrodeoxygenation
m-cresol
nickel phosphide
hierarchical ZSM-5

Access to Document

10.1016/j.cattod.2017.08.032

Catalytic hydrodeoxygenation of m-cresol over Ni2P-hierarchical ZSM-5
© 2017, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/
Accepted author manuscript, 997 KBLicence: CC BY-NC-ND 3.0

Cite this

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title = "Catalytic hydrodeoxygenation of m-cresol over Ni2P/hierarchical ZSM-5",

abstract = "Bifunctional catalysts comprising Ni2P supported over a hierarchical ZSM-5 zeolite (h-ZSM-5) were synthesized and applied to the hydrodeoxygenation (HDO) of m-cresol, a model pyrolysis bio-oil compound. Surface and bulk characterization of Ni2P/h-ZSM-5 catalysts by XRD, TEM, DRIFTS, TPR, porosimetry and propylamine temperature-programmed desorption reveal that Ni2P incorporation modifies the zeolite textural properties through pore blockage of the mesopores by phosphide nanoparticles, but has negligible impact of the micropore network. Ni2P nanoparticles introduce new, strong Lewis acid sites, whose density is proportional to the Ni2P loading, accompanied by new Br{\"o}nsted acid sites attributed to the presence of Psingle bondOH moieties. Ni2P/h-ZSM-5 is ultraselective (>97%) for m-cresol HDO to methylcyclohexane, significantly outperforming a reference Ni2P/SiO2 catalyst and highlighting the synergy between metal phosphide and solid acid support. m-Cresol conversion was proportional to Ni2P loading reaching 80 and 91% for 5 and 10 wt% Ni respectively. Turnover frequencies for m-cresol HDO are a strong function of Ni2P dispersion, evidencing a structure sensitivity, with optimum activity observed for 4 nm particles.",

keywords = "hydrodeoxygenation, m-cresol, nickel phosphide, hierarchical ZSM-5",

author = "Antonio Berenguer and Bennett, {James A.} and James Hunns and In{\'e}s Moreno and Coronado, {Juan M.} and Lee, {Adam F.} and Patricia Pizarro and Karen Wilson and Serrano, {David P.}",

note = "{\textcopyright} 2017, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ Funding: Spanish Ministry of Economy and Competitiveness (CTQ2014-60209-R); Regional Government of Madrid (S2013/MAE-2882); EPSRC (EP/K036548/2 and EP/N009924/1).",

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month = apr,

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doi = "10.1016/j.cattod.2017.08.032",

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AU - Berenguer, Antonio

AU - Bennett, James A.

AU - Hunns, James

AU - Moreno, Inés

AU - Coronado, Juan M.

AU - Lee, Adam F.

AU - Pizarro, Patricia

AU - Wilson, Karen

AU - Serrano, David P.

N1 - © 2017, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ Funding: Spanish Ministry of Economy and Competitiveness (CTQ2014-60209-R); Regional Government of Madrid (S2013/MAE-2882); EPSRC (EP/K036548/2 and EP/N009924/1).

PY - 2018/4/15

Y1 - 2018/4/15

N2 - Bifunctional catalysts comprising Ni2P supported over a hierarchical ZSM-5 zeolite (h-ZSM-5) were synthesized and applied to the hydrodeoxygenation (HDO) of m-cresol, a model pyrolysis bio-oil compound. Surface and bulk characterization of Ni2P/h-ZSM-5 catalysts by XRD, TEM, DRIFTS, TPR, porosimetry and propylamine temperature-programmed desorption reveal that Ni2P incorporation modifies the zeolite textural properties through pore blockage of the mesopores by phosphide nanoparticles, but has negligible impact of the micropore network. Ni2P nanoparticles introduce new, strong Lewis acid sites, whose density is proportional to the Ni2P loading, accompanied by new Brönsted acid sites attributed to the presence of Psingle bondOH moieties. Ni2P/h-ZSM-5 is ultraselective (>97%) for m-cresol HDO to methylcyclohexane, significantly outperforming a reference Ni2P/SiO2 catalyst and highlighting the synergy between metal phosphide and solid acid support. m-Cresol conversion was proportional to Ni2P loading reaching 80 and 91% for 5 and 10 wt% Ni respectively. Turnover frequencies for m-cresol HDO are a strong function of Ni2P dispersion, evidencing a structure sensitivity, with optimum activity observed for 4 nm particles.

AB - Bifunctional catalysts comprising Ni2P supported over a hierarchical ZSM-5 zeolite (h-ZSM-5) were synthesized and applied to the hydrodeoxygenation (HDO) of m-cresol, a model pyrolysis bio-oil compound. Surface and bulk characterization of Ni2P/h-ZSM-5 catalysts by XRD, TEM, DRIFTS, TPR, porosimetry and propylamine temperature-programmed desorption reveal that Ni2P incorporation modifies the zeolite textural properties through pore blockage of the mesopores by phosphide nanoparticles, but has negligible impact of the micropore network. Ni2P nanoparticles introduce new, strong Lewis acid sites, whose density is proportional to the Ni2P loading, accompanied by new Brönsted acid sites attributed to the presence of Psingle bondOH moieties. Ni2P/h-ZSM-5 is ultraselective (>97%) for m-cresol HDO to methylcyclohexane, significantly outperforming a reference Ni2P/SiO2 catalyst and highlighting the synergy between metal phosphide and solid acid support. m-Cresol conversion was proportional to Ni2P loading reaching 80 and 91% for 5 and 10 wt% Ni respectively. Turnover frequencies for m-cresol HDO are a strong function of Ni2P dispersion, evidencing a structure sensitivity, with optimum activity observed for 4 nm particles.

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KW - nickel phosphide

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DO - 10.1016/j.cattod.2017.08.032

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JO - Catalysis Today

JF - Catalysis Today

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