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Owing to their acidity,oxidizing ability and redox reversibility,molybdovanadophosphoric heteropolyacids (Hn+3PMo12-nVnO40,abbreviated as PMo12-nVn) were employed as electron transfer carriers for coupling biomass pretreatment for enzymatic hydrolysis and direct biomass-to-electricity conversion.In this novel coupled process,PMo12-nVn pretreatment that causes deconstruction of cell wall structure with PMo12-nVn being simultaneously reduced can be considered as the “charging” process.The reduced PMo12-nVn are further re-oxidized with release of electrons in a liquid flow fuel cell (LFFC) to generate electricity is the “discharging” process.Several Keggin-type PMo12-nVn with different degree of vanadium substitution (DSv,namely n) were prepared.Compared to Keggin-type phosphomolybdic acid (PMo12),PMo12-nVn (n =1-6) showed higher oxidizing ability but poorer redox reversibility.The cellulose enzymatic digestibility of PMo12-nVn pretreated wheat straw generally decreased with increase in DSv,but xylan enzymatic digestibility generally increased with DSv.PMo12 pretreatment of wheat straw at 120 ℃ obtained the highest enzymatic glucan conversion (EGC) reaching 95%,followed by PMo11V1 pretreatment (85%).Discharging of the reduced heteropolyacids in LFFC showed that vanadium substitution could improve the maximum output power density (Pmax).The highest Pmax was obtained by PMogV3 (44.7 mW/cm2) when FeCl3 was used as a cathode electron carrier,while PMo12 achieved the lowest Pmax (27.4 mW/cm2).All the heteropolyacids showed good electrode Faraday efficiency (>95%) and cell discharging efficiency (>93%).The energy efficiency of the coupled process based on the heat values of the products and generated electric energy was in the range of 18%-25% depending on DSv.PMo12 and PMo11V1 seem to be the most suitable heteropolyacids to mediate the coupled process.