The hydrolysis and subsequent acidic dehydration of biomass leads to the production of smaller oxygenates, including furfural, which can undergo subsequent reactions such as hydrogenation to produce value-added products. Palladium has been found to be an active catalyst for this process. As a result, the surface chemistry of furfural is investigated on a Pd(111) single-crystal surface using reflection-absorption infrared spectroscopy as a basis for understanding the catalytic conversion of furfural to value-added products. Following adsorption at 90 K, furfural adopts a flat-lying geometry at low coverages, but converts to a tilted species as the coverage approaches saturation. Heating to ∼175 K forms a tilted η1(O) species that appears to deprotonate on heating to above 200 K to form an intermediate with a tilted furyl ring and a carbonyl group close to parallel to the surface. Further heating to ∼250 K and above caused this species to decarbonylate to form adsorbed carbon monoxide and an infrared invisible furyl intermediate. This can then undergo a ring-opening reaction to produce further CO and form a C3H3 intermediate that can hydrogenate to produce propylene. This reaction sequence is in good agreement with previous density functional theory calculations and with the products observed in temperature-programmed desorption.
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January 2022
Research Article|
December 01 2021
Reflection absorption infrared spectroscopy of the surface chemistry of furfural on Pd(111)
Special Collection:
Commemorating the Career of Pat Thiel
Robert Bavisotto
;
Robert Bavisotto
Department of Chemistry and Biochemistry, Laboratory for Surface Studies, University of Wisconsin-Milwaukee
, Milwaukee, Wisconsin 53211
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Sree Pradipta Roy;
Sree Pradipta Roy
Department of Chemistry and Biochemistry, Laboratory for Surface Studies, University of Wisconsin-Milwaukee
, Milwaukee, Wisconsin 53211
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Wilfred T. Tysoe
Wilfred T. Tysoe
a)
Department of Chemistry and Biochemistry, Laboratory for Surface Studies, University of Wisconsin-Milwaukee
, Milwaukee, Wisconsin 53211a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is a part of the Special Collection Commemorating the Career of Pat Thiel.
J. Vac. Sci. Technol. A 40, 013203 (2022)
Article history
Received:
August 12 2021
Accepted:
October 26 2021
Citation
Robert Bavisotto, Sree Pradipta Roy, Wilfred T. Tysoe; Reflection absorption infrared spectroscopy of the surface chemistry of furfural on Pd(111). J. Vac. Sci. Technol. A 1 January 2022; 40 (1): 013203. https://doi.org/10.1116/6.0001355
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