Coupling biomass pretreatment for enzymatic hydrolysis and direct biomass-to-electricity conversion with molybdovanadophosphoric heteropolyacids as anode electron transfer carriers

Owing to their acidity,oxidizing ability and redox reversibility,molybdovanadophosphoric heteropolyacids(H_(n+3)PMo_(12-n)VnO40,abbreviated as PMo_(12-n)Vn) were employed as electron transfer carriers for coupling biomass pretreatment for enzymatic hydrolysis and direct biomass-to-electricity conversion.In this novel coupled process,PMo_(12-n)Vn pretreatment that causes deconstruction of cell wall structure with PMo_(12-n)Vn being simultaneously reduced can be considered as the "charging" process.The reduced PMo_(12-n)Vn 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 PMo_(12-n)Vn with different degree of vanadium substitution(DSV, namely n) were prepared.Compared to Keggin-type phosphomolybdic acid(PMo_(12)),PMo_(12-n)Vn(n=1-6) showed higher oxidizing ability but poorer redox reversibility.The cellulose enzymatic digestibility of PMo_(12-n)Vn pretreated wheat straw generally decreased with increase in DSV, but xylan enzymatic digestibility generally increased with DSV.PMo_(12) 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 PMo9 V3(44.7 mW/cm^(2)) when FeCl_(3) was used as a cathode electron carrier,while PMo_(12) achieved the lowest Pmax(27.4 mW/cm^(2)).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.PMo_(12) and PMo11V1 seem to be the most suitable heteropolyacids to mediate the coupled process.

Catalytic Aerobic Oxidation of Acetaldehyde over Keggin-type Molybdovanadophosphoric Acid/SBA-15 under Ambient Condition

Keggin-type molybdovanadophosphoric acids （HPA）, H4PMo11VO40 （1）, H5PMo10V2O40 （2） and H6PMo9V3O40 （3） were anchored onto γ-aminopropyltriethoxysilane （APTS） aminosilylated silica mesoporous SBA-15 through acid-base neutralization and the resulting HPA/APTS/SBA-15 were characterized by BET, TEM, XRD, ICP, FFIR and ^31p MAS NMR. The characterization results indicate that the Keggin-structure of these HPAs is preserved within the mesoporous silica host. The samples were tested for catalytic aerobic oxidation of acetaldehyde heterogeneously in liquid phase under ambient condition. The electrostatic force between heteropoly acid and amino groups grafted on the silica channel surface leads to strong immobilization of HPA inside SBA-15 which is against the leaching during the reaction. The good catalytic performance and easy recycle of these catalysts make them as potential environmental friendly catalysts for elimination of indoor air pollutants.

Inhibitory effect of H_(3+x)PMo_(12-x)V_xO_(40)-Ton the self-polymerization of methyl methacrylate

In this work,a series of molybdovanadophosphoric heteropoly acid quaternary ammonium salts H_（3＋x）PMo_（12 -x）V_xO40-T were synthesized and employed as a reaction inhibitor in the selfpolymerization of methyl methacrylate（MMA）.The polymerization inhibition effect of H_（3＋x）PMoPMo_（12 -x）V_xO40-T）with different number of vanadium atoms and reaction dosages was investigated using differential scanning calorimetry（DSC）.It shows that the inhibitory effect was improved with the increasing dosages of H_（3＋x）PMoPMo_（12 -x）V_xO40-T）,and the polymerization inhibition was also affected by the number of vanadium atoms in the H_（3＋x）PMo_（12 -x）V_xO40-T .Furthermore,cyclic voltammograms（CV）was used to probe the mechanism of the inhibition reaction with H3＋xPMo12xVxO40-T.The result of CV indicates that the inhibition reaction is an oxidation–reduction reaction.H_（3＋x）PMo_（12 -x）V_xO40-T can react directly with the MMA monomer radicals,which eliminated the MMA monomers,and therefore the self-polymerization of the MMA can be effectively inhibited by H_（3＋x）PMo_（12 -x）V_xO40-T.