Performance, structure and mechanism of Pd-Ag alloy catalyst for selective oxidation of glycerol to dihydroxyacetone

Shota Hirasawa; Hideo Watanabe; Tokushi Kizuka; Yoshinao Nakagawa; Keiichi Tomishige

doi:10.1016/j.jcat.2013.01.014

Performance, structure and mechanism of Pd-Ag alloy catalyst for selective oxidation of glycerol to dihydroxyacetone

Shota Hirasawa, Hideo Watanabe, Tokushi Kizuka, Yoshinao Nakagawa, Keiichi Tomishige

ENG - Applied Chemistry

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

112 Citations (Scopus)

Abstract

The mechanism of the oxidation of glycerol to dihydroxyacetone over Pd-Ag catalysts was discussed. Characterization results suggest that the metal composition of the surface of the crystalline Pd-Ag alloy particles is almost the same as the bulk composition. The synergetic effects of Pd and Ag appear on the oxidation of the secondary OH group of vic-diols. The reaction order with respect to glycerol concentration over Pd-Ag/C was zero, suggesting the strong interaction between glycerol and the catalyst surface. The reaction order with respect to O₂ pressure was 0.4, suggesting that the rate-determining step is the reaction involving oxygen species. These reaction trends and characterization results support the mechanism where the terminal OH group of glycerol is adsorbed on the Ag site and the neighboring secondary OH group (CH-OH) is attacked by the oxygen species dissociatively adsorbed on the Pd site.

Original language	English
Pages (from-to)	205-216
Number of pages	12
Journal	Journal of Catalysis
Volume	300
DOIs	https://doi.org/10.1016/j.jcat.2013.01.014
Publication status	Published - 2013 Apr

Keywords

Biomass
Glycerol
Oxidation
Palladium
Silver

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry

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10.1016/j.jcat.2013.01.014

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title = "Performance, structure and mechanism of Pd-Ag alloy catalyst for selective oxidation of glycerol to dihydroxyacetone",

abstract = "The mechanism of the oxidation of glycerol to dihydroxyacetone over Pd-Ag catalysts was discussed. Characterization results suggest that the metal composition of the surface of the crystalline Pd-Ag alloy particles is almost the same as the bulk composition. The synergetic effects of Pd and Ag appear on the oxidation of the secondary OH group of vic-diols. The reaction order with respect to glycerol concentration over Pd-Ag/C was zero, suggesting the strong interaction between glycerol and the catalyst surface. The reaction order with respect to O2 pressure was 0.4, suggesting that the rate-determining step is the reaction involving oxygen species. These reaction trends and characterization results support the mechanism where the terminal OH group of glycerol is adsorbed on the Ag site and the neighboring secondary OH group (CH-OH) is attacked by the oxygen species dissociatively adsorbed on the Pd site.",

keywords = "Biomass, Glycerol, Oxidation, Palladium, Silver",

author = "Shota Hirasawa and Hideo Watanabe and Tokushi Kizuka and Yoshinao Nakagawa and Keiichi Tomishige",

note = "Funding Information: This research is supported by the JSPS KAKENHI (23760737) and the Cabinet Office, Government of Japan, through its {\textquoteleft}{\textquoteleft}Funding Program for Next Generation World-Leading Researchers{\textquoteright}{\textquoteright}. ",

year = "2013",

month = apr,

doi = "10.1016/j.jcat.2013.01.014",

language = "English",

volume = "300",

pages = "205--216",

journal = "Journal of Catalysis",

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T1 - Performance, structure and mechanism of Pd-Ag alloy catalyst for selective oxidation of glycerol to dihydroxyacetone

AU - Hirasawa, Shota

AU - Watanabe, Hideo

AU - Kizuka, Tokushi

AU - Nakagawa, Yoshinao

AU - Tomishige, Keiichi

N1 - Funding Information: This research is supported by the JSPS KAKENHI (23760737) and the Cabinet Office, Government of Japan, through its ‘‘Funding Program for Next Generation World-Leading Researchers’’.

PY - 2013/4

Y1 - 2013/4

N2 - The mechanism of the oxidation of glycerol to dihydroxyacetone over Pd-Ag catalysts was discussed. Characterization results suggest that the metal composition of the surface of the crystalline Pd-Ag alloy particles is almost the same as the bulk composition. The synergetic effects of Pd and Ag appear on the oxidation of the secondary OH group of vic-diols. The reaction order with respect to glycerol concentration over Pd-Ag/C was zero, suggesting the strong interaction between glycerol and the catalyst surface. The reaction order with respect to O2 pressure was 0.4, suggesting that the rate-determining step is the reaction involving oxygen species. These reaction trends and characterization results support the mechanism where the terminal OH group of glycerol is adsorbed on the Ag site and the neighboring secondary OH group (CH-OH) is attacked by the oxygen species dissociatively adsorbed on the Pd site.

AB - The mechanism of the oxidation of glycerol to dihydroxyacetone over Pd-Ag catalysts was discussed. Characterization results suggest that the metal composition of the surface of the crystalline Pd-Ag alloy particles is almost the same as the bulk composition. The synergetic effects of Pd and Ag appear on the oxidation of the secondary OH group of vic-diols. The reaction order with respect to glycerol concentration over Pd-Ag/C was zero, suggesting the strong interaction between glycerol and the catalyst surface. The reaction order with respect to O2 pressure was 0.4, suggesting that the rate-determining step is the reaction involving oxygen species. These reaction trends and characterization results support the mechanism where the terminal OH group of glycerol is adsorbed on the Ag site and the neighboring secondary OH group (CH-OH) is attacked by the oxygen species dissociatively adsorbed on the Pd site.

KW - Biomass

KW - Glycerol

KW - Oxidation

KW - Palladium

KW - Silver

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DO - 10.1016/j.jcat.2013.01.014

M3 - Article

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SN - 0021-9517

VL - 300

SP - 205

EP - 216

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Performance, structure and mechanism of Pd-Ag alloy catalyst for selective oxidation of glycerol to dihydroxyacetone

Abstract

Keywords

ASJC Scopus subject areas

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