The catalytic hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is a promising route towards sustainable liquid fuels with a high energy density. Herein, a novel CuCoNiAl-containing mixed metal oxide catalyst (CuCoNiAl-MMO) was prepared by calcination a layered double hydroxide (LDH) precursor in N at 500 °C, then applied for the catalytic hydrogenolysis of HMF to DMF. The effects of reaction time, reaction temperature and hydrogen pressure on DMF selectivity were investigated. Under relatively mild reaction conditions (180°C, 1.0 MPa H, 6.0 h), CuCoNiAl-MMO showed both a high initial activity and selectivity for hydrogenolysis of HMF to DMF, with HMF conversion rate of 99.8% and DMF selectivity of 95.3%. Catalysts characterization studies using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) revealed the presence of various metal oxides and metallic copper on the surface of the CuCoNiAl-MMO catalyst, with the presence of mixed metal-oxide-supported metallic Cu nanoparticles being responsible good hydrogenolysis activity of the catalyst for selective DMF synthesis.
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http://dx.doi.org/10.3389/fchem.2022.907649 | DOI Listing |
J Am Chem Soc
November 2024
Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States.
Realizing high selectivity for producing biodegradable 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) for renewable polymers from 5-hydroxymethylfurfural (HMF) biomass through ring hydrogenation on single-atom catalysts poses a considerable challenge due to the complexity of HMF functional groups and the difficulty of H dissociation. We developed a detailed reaction mechanism based on molecular dynamics (AIMD) and quantum mechanics (QM) to find that Ru single-atom catalysts can simultaneously dissociate H and perform the ring hydrogenation of biomass-derived 2,5-bis(hydroxymethyl)furan (BHMF) to produce biodegradable BHMTHF, with a free energy barrier of 0.82 eV.
View Article and Find Full Text PDFChemSusChem
December 2024
National & Local Joint Engineering Laboratory for New Petro-Chemical Materials and Fine Utilization of Resources, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, Hunan Normal University, Changsha, 410081, China.
2, 5-Dimethylfuran (DMF), which is a promising new-generation liquid biofuel, has attracted widespread attention owing to the sustainability of biomass-derived energy sources. In this study, a highly dispersed zirconia-supported nickel catalyst (CA-Ni/ZrO) was prepared via citric acid-assisted wetness impregnation for the selective hydrogenolysis of 5-hydroxymethylfurfural (HMF) to produce DMF. The characterization results confirmed the presence of Zr species in the mesoporous CA-Ni/ZrO catalyst and the formation of oxygen vacancies during its preparation, which led to the formation of a large number of catalytically active sites for the adsorption and activation of the C=O/C-O groups.
View Article and Find Full Text PDFRSC Adv
May 2024
Jiangsu Provincial Key Lab for the Chemistry and Utilization of Agro-forest Biomass, College of Chemical Engineering, Nanjing Forestry University Nanjing China +86-25-85427635.
Catalytic hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) has become a hot topic in the bioenergy field in recent years. It remains a challenge to mediate the activation/hydrogenation/hydrogenolysis of C-O and C[double bond, length as m-dash]O bonds of HMF at high temperatures. Herein, bimetallic Ru-Co/AC catalysts were prepared by the "two-step" reduction method and were used to catalyze the hydrogenolysis of HMF to DMF.
View Article and Find Full Text PDFHeliyon
March 2024
School of Mechanical, Chemical and Materials Engineering, Department of Chemical Engineering, Adama Science and Technology University, Adama, Ethiopia.
One of the most promising solutions to the current energy crisis is an efficient catalytic transformation of abundant low-cost renewable raw biomass into high-quality biofuel. Herein, a highly effective catalyst was constructed systematically for the selective synthesis of 2,5-dimethylfuran (DMF) biofuel from biomass-derived 5-hydroxymethylfurfural (HMF) via green catalytic transfer hydrogenolysis (CTH) using a nitrogen-doped ordered mesoporous carbon (N-CMK-1) decorated ruthenium (Ru)-based catalyst in -propanol as hydrogen source. The structures and properties of different catalysts were characterized by different characterization techniques such as FTIR, XRD, N-sorption, CO-sorption, TGA, TEM, ICP-AES, CHNO analysis, and acid-base back titration.
View Article and Find Full Text PDFDalton Trans
January 2024
School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin 300350, China.
Preparation of the high value-added chemical 2,5-dimethylfuran (2,5-DMF) from the biomass-derived platform molecule 5-hydroxymethylfurfural (HMF) is of great significance in the preparation of biofuels. Here, a bottom-up strategy was used to prepare a metal-organic framework (MOF) material with a two-dimensional nanosheet morphology, named CPM, in which an additive 2-methylimidazole was introduced into the hydrothermal process of Cu ions and terephthalic acid. Subsequently, CPM-700 prepared by heat treatment under an inert atmosphere showed excellent catalytic performance in the reaction of HMF hydrodeoxygenation to 2,5-DMF.
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