Hydrogenation of levulinic acid to γ-valerolactone over Fe-Re/TiO2 catalysts

Xiaoming Huang; Kaituo Liu; Wilbert L. Vrijburg; Xianhong Ouyang; A. Iulian Dugulan; Yingxin Liu; M. W.G.M. Tiny Verhoeven; Nikolay A. Kosinov; Evgeny A. Pidko; Emiel J.M. Hensen

doi:10.1016/j.apcatb.2020.119314

Hydrogenation of levulinic acid to γ-valerolactone over Fe-Re/TiO₂ catalysts

Xiaoming Huang
, Kaituo Liu
, Wilbert L. Vrijburg
, Xianhong Ouyang
, A. Iulian Dugulan
, Yingxin Liu
, M. W.G.M. Tiny Verhoeven
, Nikolay A. Kosinov
, Evgeny A. Pidko
, Emiel J.M. Hensen (Corresponding author)

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

82 Citations (Scopus)

Abstract

Hydrogenation of levulinic acid to γ-valerolactone is a key reaction in the valorization of carbohydrates to renewable fuels and chemicals. State-of-the-art catalysts are based on supported noble metal nanoparticle catalysts. We report the utility of a bimetallic Fe-Re supported on TiO₂ for this reaction. A strong synergy was observed between Fe and Re for the hydrogenation of levulinic acid in water under mild conditions. Fe-Re/TiO₂ shows superior catalytic performance compared to monometallic Fe and Re catalysts at similar metal content. The hydrogenation activity of the bimetallic catalysts increased with Re content. H₂-TPR, XPS, XANES, EXAFS, Mössbauer spectroscopy, TEM, and low-temperature CO IR spectroscopy show that the bimetallic catalysts contain metallic Re nanoparticles covered by FeO_x species and small amounts of a Fe-Re alloy. Under reaction conditions, the partially reduced surface FeO_x species adsorb water and form Brønsted acidic OH groups, which are involved in dehydration of reaction intermediates. Under optimized conditions, nearly full conversion of levulinic acid with a 95 % yield of γ-valerolactone could be achieved at a temperature as low as 180 °C in water at a H₂ pressure of 40 bar.

Original language	English
Article number	119314
Number of pages	13
Journal	Applied Catalysis. B, Environmental
Volume	278
DOIs	https://doi.org/10.1016/j.apcatb.2020.119314
Publication status	Published - 5 Dec 2020

Funding

This work was performed in the framework of the European Union FP7 NMP project NOVACAM (“Novel Cheap and Abundant Materials for Catalytic Biomass Conversion”, FP7‐NMP‐2013‐EU‐Japan‐604319). E.A.P. thanks the Government of the Russian Federation (Grant 074‐U01 ) and the Ministry of Education and Science of the Russian Federation (Project 11.1706.2017/4.6) for supporting his research in the framework of his personal ITMO professorship. The authors would like to thank Rim van de Poll and Alexander Parastaev for helping with the XAS measurements, Bart Zijlstra for the FEFF calculations and Miao Yu for the useful discussions about EXAFS fitting.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

Bimetallic
Characterization
Fe-Re
Hydrogenation
Levulinic acid

Access to Document

10.1016/j.apcatb.2020.119314

Cite this

@article{090c9998414044e3964878b6fddde500,

title = "Hydrogenation of levulinic acid to γ-valerolactone over Fe-Re/TiO2 catalysts",

abstract = "Hydrogenation of levulinic acid to γ-valerolactone is a key reaction in the valorization of carbohydrates to renewable fuels and chemicals. State-of-the-art catalysts are based on supported noble metal nanoparticle catalysts. We report the utility of a bimetallic Fe-Re supported on TiO2 for this reaction. A strong synergy was observed between Fe and Re for the hydrogenation of levulinic acid in water under mild conditions. Fe-Re/TiO2 shows superior catalytic performance compared to monometallic Fe and Re catalysts at similar metal content. The hydrogenation activity of the bimetallic catalysts increased with Re content. H2-TPR, XPS, XANES, EXAFS, M{\"o}ssbauer spectroscopy, TEM, and low-temperature CO IR spectroscopy show that the bimetallic catalysts contain metallic Re nanoparticles covered by FeOx species and small amounts of a Fe-Re alloy. Under reaction conditions, the partially reduced surface FeOx species adsorb water and form Br{\o}nsted acidic OH groups, which are involved in dehydration of reaction intermediates. Under optimized conditions, nearly full conversion of levulinic acid with a 95 \% yield of γ-valerolactone could be achieved at a temperature as low as 180 °C in water at a H2 pressure of 40 bar.",

keywords = "Bimetallic, Characterization, Fe-Re, Hydrogenation, Levulinic acid",

author = "Xiaoming Huang and Kaituo Liu and Vrijburg, \{Wilbert L.\} and Xianhong Ouyang and \{Iulian Dugulan\}, A. and Yingxin Liu and \{Tiny Verhoeven\}, \{M. W.G.M.\} and Kosinov, \{Nikolay A.\} and Pidko, \{Evgeny A.\} and Hensen, \{Emiel J.M.\}",

year = "2020",

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doi = "10.1016/j.apcatb.2020.119314",

language = "English",

volume = "278",

journal = "Applied Catalysis. B, Environmental",

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AU - Huang, Xiaoming

AU - Liu, Kaituo

AU - Vrijburg, Wilbert L.

AU - Ouyang, Xianhong

AU - Iulian Dugulan, A.

AU - Liu, Yingxin

AU - Tiny Verhoeven, M. W.G.M.

AU - Kosinov, Nikolay A.

AU - Pidko, Evgeny A.

AU - Hensen, Emiel J.M.

PY - 2020/12/5

Y1 - 2020/12/5

N2 - Hydrogenation of levulinic acid to γ-valerolactone is a key reaction in the valorization of carbohydrates to renewable fuels and chemicals. State-of-the-art catalysts are based on supported noble metal nanoparticle catalysts. We report the utility of a bimetallic Fe-Re supported on TiO2 for this reaction. A strong synergy was observed between Fe and Re for the hydrogenation of levulinic acid in water under mild conditions. Fe-Re/TiO2 shows superior catalytic performance compared to monometallic Fe and Re catalysts at similar metal content. The hydrogenation activity of the bimetallic catalysts increased with Re content. H2-TPR, XPS, XANES, EXAFS, Mössbauer spectroscopy, TEM, and low-temperature CO IR spectroscopy show that the bimetallic catalysts contain metallic Re nanoparticles covered by FeOx species and small amounts of a Fe-Re alloy. Under reaction conditions, the partially reduced surface FeOx species adsorb water and form Brønsted acidic OH groups, which are involved in dehydration of reaction intermediates. Under optimized conditions, nearly full conversion of levulinic acid with a 95 % yield of γ-valerolactone could be achieved at a temperature as low as 180 °C in water at a H2 pressure of 40 bar.

AB - Hydrogenation of levulinic acid to γ-valerolactone is a key reaction in the valorization of carbohydrates to renewable fuels and chemicals. State-of-the-art catalysts are based on supported noble metal nanoparticle catalysts. We report the utility of a bimetallic Fe-Re supported on TiO2 for this reaction. A strong synergy was observed between Fe and Re for the hydrogenation of levulinic acid in water under mild conditions. Fe-Re/TiO2 shows superior catalytic performance compared to monometallic Fe and Re catalysts at similar metal content. The hydrogenation activity of the bimetallic catalysts increased with Re content. H2-TPR, XPS, XANES, EXAFS, Mössbauer spectroscopy, TEM, and low-temperature CO IR spectroscopy show that the bimetallic catalysts contain metallic Re nanoparticles covered by FeOx species and small amounts of a Fe-Re alloy. Under reaction conditions, the partially reduced surface FeOx species adsorb water and form Brønsted acidic OH groups, which are involved in dehydration of reaction intermediates. Under optimized conditions, nearly full conversion of levulinic acid with a 95 % yield of γ-valerolactone could be achieved at a temperature as low as 180 °C in water at a H2 pressure of 40 bar.

KW - Bimetallic

KW - Characterization

KW - Fe-Re

KW - Hydrogenation

KW - Levulinic acid

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