期刊
JOURNAL OF CATALYSIS
卷 394, 期 -, 页码 273-283出版社
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcat.2020.10.029
关键词
Nickel phosphide catalysts; Hydrodeoxygenation mechanism-valerolactone; Analysis of coverage transients (ACT); In situ QXAFS; Transient studies
资金
- Japan Science and Technology Agency under the CREST program [JPMJCR16P2]
- US Department of Energy [DE-FG02-96ER14669]
- JSPS, Japan [26289301]
- U.S. Department of Energy (DOE) [DE-FG02-96ER14669] Funding Source: U.S. Department of Energy (DOE)
- Grants-in-Aid for Scientific Research [26289301] Funding Source: KAKEN
This study presents a general method for analyzing whether an adsorbed species is a reactive intermediate in hydrogenation or oxidation reactions, providing order-of magnitude estimates of the rate of reaction. The example of hydrodeoxygenation of gamma-valerolactone using a Ni2P/MCM-41 catalyst demonstrates the application of in situ infrared and X-ray absorption spectroscopy to characterize reaction intermediates.
The understanding of catalytic mechanisms is enhanced by the observation of surface intermediates at reaction conditions using spectroscopic techniques, but this is insufficient, as the observed species may not be involved in the reaction. This work describes a general method of analysis of hydrogenation or oxidation reactions which uses transient spectroscopic data to determine whether an adsorbed species is a reactive intermediate or a spectator on the surface. The assumptions and limitations of the method are summarized. Although the technique is approximate, it is easy to implement, and provides order-of magnitude estimates of the rate of reaction of an intermediate. The method consists of measuring the change of coverage of the species with time, dh/dt, during adsorption in inert gas or at reaction conditions. An example is given with the hydrodeoxygenation of the model compound gamma-valerolactone (GVL) using a Ni2P/MCM-41 catalyst, one of the most effective catalysts reported for the transformation. The reaction is relevant to the upgrading of bio-oil derived from pyrolysis of lignocellulosic feedstocks. The kinetics of the reaction and observation by in situ infrared spectroscopy of adsorbed GVL and its transformation to pentanoic acid are consistent with a Langmuir-Hinshelwood mechanism. Analysis by in situ transient X-ray absorption fine structure shows that the adsorbed GVL is a true reaction intermediate. (c) 2020 Elsevier Inc. All rights reserved.
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