Hydrodeoxygenation of gamma-valerolactone on transition metal phosphide catalysts

Gwang Nam Yun; Atsushi Takagaki; Ryuji Kikuchi; S. Ted Oyama

doi:10.1039/c6cy02252a

Hydrodeoxygenation of gamma-valerolactone on transition metal phosphide catalysts

Gwang Nam Yun, Atsushi Takagaki, Ryuji Kikuchi, S. Ted Oyama

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

36 Citations (Scopus)

Abstract

The catalytic hydrodeoxygenation (HDO) of the cyclic five-membered ester gamma-valerolactone (GVL-C₅H₈O₂) on a series of supported metal phosphide catalysts and a commercial Pd/Al₂O₃ catalyst was studied at 0.5 MPa. Comparison of activities was based on turnover frequencies calculated from surface metal atoms determined from the chemisorption of CO at 50°C. It was found that catalytic activity followed the order: Ni₂P/MCM-41 ≫ CoP/MCM-41 ≫ Pd/Al₂O₃ ≈ MoP/MCM-41 > WP/MCM-41. On all catalysts, ring opening of the lactone to produce pentanoic acid was the main initial step with subsequent hydrogenation to form pentanal. On Ni₂P/MCM-41, CoP/MCM-41 and Pd/Al₂O₃, this was followed mainly by decarbonylation to produce CO and saturated C4 hydrocarbons. On MoP/MCM-41 and WP/MCM-41, the principal subsequent step was deoxygenation to produce unsaturated C5 hydrocarbons. A possible reaction network is proposed based on product selectivity and selectivity versus conversion plots.

Original language	English
Pages (from-to)	281-292
Number of pages	12
Journal	Catalysis Science and Technology
Volume	7
Issue number	1
DOIs	https://doi.org/10.1039/c6cy02252a
Publication status	Published - 2017
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis

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title = "Hydrodeoxygenation of gamma-valerolactone on transition metal phosphide catalysts",

abstract = "The catalytic hydrodeoxygenation (HDO) of the cyclic five-membered ester gamma-valerolactone (GVL-C5H8O2) on a series of supported metal phosphide catalysts and a commercial Pd/Al2O3 catalyst was studied at 0.5 MPa. Comparison of activities was based on turnover frequencies calculated from surface metal atoms determined from the chemisorption of CO at 50°C. It was found that catalytic activity followed the order: Ni2P/MCM-41 ≫ CoP/MCM-41 ≫ Pd/Al2O3 ≈ MoP/MCM-41 > WP/MCM-41. On all catalysts, ring opening of the lactone to produce pentanoic acid was the main initial step with subsequent hydrogenation to form pentanal. On Ni2P/MCM-41, CoP/MCM-41 and Pd/Al2O3, this was followed mainly by decarbonylation to produce CO and saturated C4 hydrocarbons. On MoP/MCM-41 and WP/MCM-41, the principal subsequent step was deoxygenation to produce unsaturated C5 hydrocarbons. A possible reaction network is proposed based on product selectivity and selectivity versus conversion plots.",

author = "Yun, {Gwang Nam} and Atsushi Takagaki and Ryuji Kikuchi and {Ted Oyama}, S.",

note = "Funding Information: This work was supported by the Development of Next-generation Technology for Strategic Utilization of Biomass Energy of the New Energy and Industrial Technology Development Organization (NEDO), Japan and by the National Science Foundation under Grant No. CHE-1361842. The XAFS experiments were conducted under approval of PF-PAC (Project No. 2014G619). Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2017.",

year = "2017",

doi = "10.1039/c6cy02252a",

language = "English",

volume = "7",

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journal = "Catalysis Science and Technology",

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AU - Yun, Gwang Nam

AU - Takagaki, Atsushi

AU - Kikuchi, Ryuji

AU - Ted Oyama, S.

N1 - Funding Information: This work was supported by the Development of Next-generation Technology for Strategic Utilization of Biomass Energy of the New Energy and Industrial Technology Development Organization (NEDO), Japan and by the National Science Foundation under Grant No. CHE-1361842. The XAFS experiments were conducted under approval of PF-PAC (Project No. 2014G619). Publisher Copyright: © The Royal Society of Chemistry 2017.

PY - 2017

Y1 - 2017

N2 - The catalytic hydrodeoxygenation (HDO) of the cyclic five-membered ester gamma-valerolactone (GVL-C5H8O2) on a series of supported metal phosphide catalysts and a commercial Pd/Al2O3 catalyst was studied at 0.5 MPa. Comparison of activities was based on turnover frequencies calculated from surface metal atoms determined from the chemisorption of CO at 50°C. It was found that catalytic activity followed the order: Ni2P/MCM-41 ≫ CoP/MCM-41 ≫ Pd/Al2O3 ≈ MoP/MCM-41 > WP/MCM-41. On all catalysts, ring opening of the lactone to produce pentanoic acid was the main initial step with subsequent hydrogenation to form pentanal. On Ni2P/MCM-41, CoP/MCM-41 and Pd/Al2O3, this was followed mainly by decarbonylation to produce CO and saturated C4 hydrocarbons. On MoP/MCM-41 and WP/MCM-41, the principal subsequent step was deoxygenation to produce unsaturated C5 hydrocarbons. A possible reaction network is proposed based on product selectivity and selectivity versus conversion plots.

AB - The catalytic hydrodeoxygenation (HDO) of the cyclic five-membered ester gamma-valerolactone (GVL-C5H8O2) on a series of supported metal phosphide catalysts and a commercial Pd/Al2O3 catalyst was studied at 0.5 MPa. Comparison of activities was based on turnover frequencies calculated from surface metal atoms determined from the chemisorption of CO at 50°C. It was found that catalytic activity followed the order: Ni2P/MCM-41 ≫ CoP/MCM-41 ≫ Pd/Al2O3 ≈ MoP/MCM-41 > WP/MCM-41. On all catalysts, ring opening of the lactone to produce pentanoic acid was the main initial step with subsequent hydrogenation to form pentanal. On Ni2P/MCM-41, CoP/MCM-41 and Pd/Al2O3, this was followed mainly by decarbonylation to produce CO and saturated C4 hydrocarbons. On MoP/MCM-41 and WP/MCM-41, the principal subsequent step was deoxygenation to produce unsaturated C5 hydrocarbons. A possible reaction network is proposed based on product selectivity and selectivity versus conversion plots.

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Hydrodeoxygenation of gamma-valerolactone on transition metal phosphide catalysts

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