The present invention relates to methods of preparing carbon monoxide (CO) and hydrogen (H2) by reacting biomass, a biomass component (e.g., lignin, ligno-cellulose, cellulose, hemiceullose or combination thereof) or a carbohydrate from any source with a polyoxometalate catalyst such as H5PV2Mo10O40, or solvates thereof, in the presence of a concentrated acid, under conditions sufficient to yield carbon monoxide (CO); followed by electrochemical release of hydrogen (H2). The carbon monoxide (CO) and hydrogen (H2) may be combined in any desired proportion to yield synthesis gas (Syngas). The present invention further relates to methods for preparing H2, CO and formic acid/formaldehyde from biomass, a biomass component and/or from carbohydrates.