TY - JOUR
T1 - Catalytic Transformation of Biomass-Derived 5-Hydroxymethylfurfural over Supported Bimetallic Iridium-Based Catalysts
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
N1 - Publisher Copyright:
©
PY - 2021/5/13
Y1 - 2021/5/13
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.
UR - http://www.scopus.com/inward/record.url?scp=85106454201&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.1c00958
DO - 10.1021/acs.jpcc.1c00958
M3 - Article
AN - SCOPUS:85106454201
SN - 1932-7447
VL - 125
SP - 9657
EP - 9678
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 18
ER -