Catalytic Transformation of Biomass-Derived 5-Hydroxymethylfurfural over Supported Bimetallic Iridium-Based Catalysts

Ricardo J. Chimentão; Héctor Oliva; Vincenzo Russo; Jordi Llorca; José L.G. Fierro; Päivi Mäki-Arvela; D. Yu Murzin; Doris Ruiz

doi:10.1021/acs.jpcc.1c00958

Catalytic Transformation of Biomass-Derived 5-Hydroxymethylfurfural over Supported Bimetallic Iridium-Based Catalysts

Ricardo J. Chimentão
, Héctor Oliva
, Vincenzo Russo
, Jordi Llorca
, José L.G. Fierro
, Päivi Mäki-Arvela
, D. Yu Murzin
, Doris Ruiz^*

^*Corresponding author for this work

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

14 Citations (Scopus)

77 Downloads (Pure)

Abstract

5-Hydroxymethylfurfural (HMF) is a biobased platform chemical that can be valorized into a spectrum of valuable products. In this report, supported Ir, Ir-Co, Ir-Ni, and Ir-Ru catalysts were investigated for this purpose. Only hydrogenation of HMF to 2,5-bis-(hydroxymethyl)furan (BHMF) occurred over all catalysts. The effect of the second metal (Co, Ni, and Ru) on Ir/SiO2 was reflected by the kinetic constants being in the order Ir-Ni/SiO2 > Ir-Co/SiO2 > Ir-Ru/SiO2. The oxophilic nature of the secondary metal improved the catalytic performance of the bimetallic catalysts compared to the monometallic iridium catalyst (Ir/SiO2). Addition of HCOOH and H2SO4 as cocatalysts is a strategy to reach one-pot conversion of HMF to 2,5-di-methylfuran (DMF). Over-hydrogenolysis products such as 2,5-dimethyltetrahydrofuran were formed when only H2SO4 was added, giving higher activity compared to addition of HCOOH. Simultaneous presence of acids gave the highest HMF conversion, promoting esterification to 5-formyloxymethyl furfural and allowing the one-pot transformation of HMF to DMF. Thermodynamic analysis of HMF transformations revealed that both hydrogenation and dehydration steps are feasible.

Original language	English
Pages (from-to)	9657-9678
Journal	Journal of Physical Chemistry C
Volume	125
Issue number	18
Early online date	28 Apr 2021
DOIs	https://doi.org/10.1021/acs.jpcc.1c00958
Publication status	Published - 13 May 2021
MoE publication type	A1 Journal article-refereed

Funding

The authors are grateful to FONDECYT 1201936 and FONDECYT 1180243 for the financial support. J.L. is a Serra Húnter fellow and is grateful to the ICREA Academia program and project 2017 SGR 128 (Generalitat de Catalunya). Authors would like to thank to our wonderful colleague J.L.G. Fierro for his contribution in this work related to analysis techniques, specifically for his brilliant contribution in the XPS field. This paper is dedicated to his memory.

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https://urn.fi/URN:NBN:fi-fe202201148411

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title = "Catalytic Transformation of Biomass-Derived 5-Hydroxymethylfurfural over Supported Bimetallic Iridium-Based Catalysts",

abstract = "5-Hydroxymethylfurfural (HMF) is a biobased platform chemical that can be valorized into a spectrum of valuable products. In this report, supported Ir, Ir-Co, Ir-Ni, and Ir-Ru catalysts were investigated for this purpose. Only hydrogenation of HMF to 2,5-bis-(hydroxymethyl)furan (BHMF) occurred over all catalysts. The effect of the second metal (Co, Ni, and Ru) on Ir/SiO2 was reflected by the kinetic constants being in the order Ir-Ni/SiO2 > Ir-Co/SiO2 > Ir-Ru/SiO2. The oxophilic nature of the secondary metal improved the catalytic performance of the bimetallic catalysts compared to the monometallic iridium catalyst (Ir/SiO2). Addition of HCOOH and H2SO4 as cocatalysts is a strategy to reach one-pot conversion of HMF to 2,5-di-methylfuran (DMF). Over-hydrogenolysis products such as 2,5-dimethyltetrahydrofuran were formed when only H2SO4 was added, giving higher activity compared to addition of HCOOH. Simultaneous presence of acids gave the highest HMF conversion, promoting esterification to 5-formyloxymethyl furfural and allowing the one-pot transformation of HMF to DMF. Thermodynamic analysis of HMF transformations revealed that both hydrogenation and dehydration steps are feasible. ",

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AU - Chimentão, Ricardo J.

AU - Oliva, Héctor

AU - Russo, Vincenzo

AU - Llorca, Jordi

AU - Fierro, José L.G.

AU - Mäki-Arvela, Päivi

AU - Murzin, D. Yu

AU - Ruiz, Doris

PY - 2021/5/13

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N2 - 5-Hydroxymethylfurfural (HMF) is a biobased platform chemical that can be valorized into a spectrum of valuable products. In this report, supported Ir, Ir-Co, Ir-Ni, and Ir-Ru catalysts were investigated for this purpose. Only hydrogenation of HMF to 2,5-bis-(hydroxymethyl)furan (BHMF) occurred over all catalysts. The effect of the second metal (Co, Ni, and Ru) on Ir/SiO2 was reflected by the kinetic constants being in the order Ir-Ni/SiO2 > Ir-Co/SiO2 > Ir-Ru/SiO2. The oxophilic nature of the secondary metal improved the catalytic performance of the bimetallic catalysts compared to the monometallic iridium catalyst (Ir/SiO2). Addition of HCOOH and H2SO4 as cocatalysts is a strategy to reach one-pot conversion of HMF to 2,5-di-methylfuran (DMF). Over-hydrogenolysis products such as 2,5-dimethyltetrahydrofuran were formed when only H2SO4 was added, giving higher activity compared to addition of HCOOH. Simultaneous presence of acids gave the highest HMF conversion, promoting esterification to 5-formyloxymethyl furfural and allowing the one-pot transformation of HMF to DMF. Thermodynamic analysis of HMF transformations revealed that both hydrogenation and dehydration steps are feasible.

AB - 5-Hydroxymethylfurfural (HMF) is a biobased platform chemical that can be valorized into a spectrum of valuable products. In this report, supported Ir, Ir-Co, Ir-Ni, and Ir-Ru catalysts were investigated for this purpose. Only hydrogenation of HMF to 2,5-bis-(hydroxymethyl)furan (BHMF) occurred over all catalysts. The effect of the second metal (Co, Ni, and Ru) on Ir/SiO2 was reflected by the kinetic constants being in the order Ir-Ni/SiO2 > Ir-Co/SiO2 > Ir-Ru/SiO2. The oxophilic nature of the secondary metal improved the catalytic performance of the bimetallic catalysts compared to the monometallic iridium catalyst (Ir/SiO2). Addition of HCOOH and H2SO4 as cocatalysts is a strategy to reach one-pot conversion of HMF to 2,5-di-methylfuran (DMF). Over-hydrogenolysis products such as 2,5-dimethyltetrahydrofuran were formed when only H2SO4 was added, giving higher activity compared to addition of HCOOH. Simultaneous presence of acids gave the highest HMF conversion, promoting esterification to 5-formyloxymethyl furfural and allowing the one-pot transformation of HMF to DMF. Thermodynamic analysis of HMF transformations revealed that both hydrogenation and dehydration steps are feasible.

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ER -

Catalytic Transformation of Biomass-Derived 5-Hydroxymethylfurfural over Supported Bimetallic Iridium-Based Catalysts

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