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Chemical Structure| 3857-25-8 Chemical Structure| 3857-25-8
Chemical Structure| 3857-25-8

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Synonyms: 5-Methylfurfuryl alcohol

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Xin Yuan ; Kwanpyung Lee ; J. R. Schmidt ; Kyoung-Shin Choi ;

Abstract: Reductive upgrading of 5-hydroxymethylfurfural (HMF), a biomass-derived platform molecule, to 2,5-dimethylfuran (DMF), a biofuel with an energy density 40% greater than that of ethanol, involves hydrogenolysis of both the aldehyde (C═O) and the alcohol (C–OH) groups of HMF. It is known that when hydrogenation of the aldehyde occurs to form 2,5-bis(hydroxymethyl)furan (BHMF), BHMF cannot be further reduced to DMF. Thus, aldehyde hydrogenation must be suppressed to increase the selectivity for DMF production. Previously, it was shown that on a Cu electrode hydrogenolysis occurs mainly through proton-coupled electron transfer (PCET), where a proton from the solution and an electron from the electrode are transferred to the organic species. In contrast, hydrogenation occurs not only through PCET but also through hydrogen atom transfer (HAT), where a surface-adsorbed hydrogen atom (H*) is transferred to the organic species. This study shows that halide adsorption on Cu can effectively suppress HAT by decreasing the steady-state H* coverage on Cu during HMF reduction. As HAT enables only aldehyde hydrogenation, a striking suppression of BHMF is observed, thereby enhancing DMF production. We discuss how the identity and concentration of the halide, along with the reduction conditions (i.e., potential and pH), affect halide adsorption on Cu and identify when optimal halide coverages are achieved to maximize DMF selectivity. Our experimental results are presented alongside computational results that elucidate how halide adsorption affects the adsorption energy of hydrogen and the steady-state H* coverage on Cu, which provide an atomic-level understanding of all experimentally observed effects.

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Xin Yuan ; Kwanpyung Lee ; Michael T. Bender ; J. R. Schmidt ; Kyoung-Shin Choi ;

Abstract: Hydrogenation and hydrogenolysis are two important reactions for electrochemical reductive valorization of biomass-derived oxygenates such as 5-hydroxymethylfurfural (HMF). In general, hydrogenolysis (which combines hydrogenation and deoxygenation) is more challenging than hydrogenation (which does not involve the cleavage of carbon–oxygen bonds). Thus, identifying factors and conditions that can promote hydrogenolysis is of great interest for reductive valorization of biomass-derived oxygenates. For the electrochemical reduction of HMF and its derivatives, it is known that aldehyde hydrogenation is not a part of aldehyde hydrogenolysis but rather a competing reaction; however, no atomic-level understanding is currently available to explain their electrochemical mechanistic differences. In this study, combined experimental and computational investigations were performed using Cu electrodes to elucidate the key mechanistic differences between electrochemical hydrogenation and hydrogenolysis of HMF. The results revealed that hydrogenation and hydrogenolysis of HMF involve the formation of different surface-adsorbed intermediates via different reduction mechanisms and that lowering the pH promoted the formation of the intermediates required for aldehyde and alcohol hydrogenolysis. This study for the first time explains the origins of the experimentally observed pH-dependent selectivities for hydrogenation and hydrogenolysis and offers a new mechanistic foundation upon which rational strategies to control electrochemical hydrogenation and hydrogenolysis can be developed.

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Product Details of 5-Methyl-2-furanmethanol

CAS No. :3857-25-8
Formula : C6H8O2
M.W : 112.13
SMILES Code : OCC1=CC=C(C)O1
Synonyms :
5-Methylfurfuryl alcohol
MDL No. :MFCD00130134
InChI Key :VOZFDEJGHQWZHU-UHFFFAOYSA-N
Pubchem ID :520911

Safety of 5-Methyl-2-furanmethanol

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302
Precautionary Statements:P280-P305+P351+P338
 

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