title: Polyoxometalate-mediated electron transfer-oxygen transfer oxidation of cellulose and hemicellulose to synthesis gas.
abstract: Terrestrial plants contain ~70% hemicellulose and cellulose that are a significant renewable bioresource with potential as an alternative to petroleum feedstock for carbon-based fuels. The efficient and selective deconstruction of carbohydrates to their basic components, carbon monoxide and hydrogen, so called synthesis gas, is an important key step towards the realization of this potential, because the formation of liquid hydrocarbon fuels from synthesis gas are known technologies. Here we show that by using a polyoxometalate as an electron transfer-oxygen transfer catalyst, carbon monoxide is formed by cleavage of all the carbon-carbon bonds through dehydration of initially formed formic acid. In this oxidation-reduction reaction, the hydrogen atoms are stored on the polyoxometalate as protons and electrons, and can be electrochemically released from the polyoxometalate as hydrogen. Together, synthesis gas is formed. In a hydrogen economy scenario, this method can also be used to convert carbon monoxide to hydrogen.
authors.affiliation: Department of Organic Chemistry, Weizmann Institute of Science, 234 Herzyl Street, Rehovot 76100, Israel.
authors.forename: Bidyut Bikash
authors.initials: BB
authors.lastname: Sarma
authors.affiliation: Department of Organic Chemistry, Weizmann Institute of Science, 234 Herzyl Street, Rehovot 76100, Israel.
authors.forename: Ronny
authors.initials: R
authors.lastname: Neumann
mesh_terms: D002248:Carbon Monoxide / Q000138:chemical synthesis*; D002384:Catalysis; D002482:Cellulose / Q000737:chemistry*; D055664:Electrochemical Techniques; D004579:Electron Transport; D004583:Electrons; D005561:Formates / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D011134:Polysaccharides / Q000737:chemistry*; D011522:Protons; D059205:Renewable Energy; D017973:Tungsten Compounds / Q000737:chemistry*; D000099294:Polyoxometalates
chemical_list: D002248:Carbon Monoxide; D002482:Cellulose; D005561:Formates; D006859:Hydrogen; D010100:Oxygen; D011134:Polysaccharides; D011522:Protons; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates; C030544:formic acid; C007916:hemicellulose