ABSTRACT
NiMnO3 was found to be an efficient catalyst for light-driven water oxidation using [Ru(bpy)3](2+) and S2O8(2-) as a photosensitiser and a sacrificial oxidant, respectively. NiMnO3 exhibited remarkably high catalytic activity in comparison with manganese oxides and nickel oxide. For electrochemical water oxidation, the highest catalytic current was also obtained with NiMnO3 among the manganese oxides.
ABSTRACT
The addition of acetate ion to an O2-saturated mixed solution of acetonitrile and water containing oxalic acid as a reductant and 2-phenyl-4-(1-naphthyl)quinolinium ion (QuPh(+)-NA) as a photocatalyst dramatically enhanced the turnover number of hydrogen peroxide (H2O2) production. In this photocatalytic H2O2 production, a base is required to facilitate deprotonation of oxalic acid forming oxalate dianion, which acts as an actual electron donor, whereas a Brønsted acid is also necessary to protonate O2(â¢-) for production of H2O2 by disproportionation. The addition of acetate ion to a reaction solution facilitates both the deprotonation of oxalic acid and the protonation of O2(â¢-) owing to a pH buffer effect. The quantum yield of the photocatalytic H2O2 production under photoirradiation (λ = 334 nm) of an O2-saturated acetonitrile-water mixed solution containing acetate ion, oxalic acid and QuPh(+)-NA was determined to be as high as 0.34, which is more than double the quantum yield obtained by using oxalate salt as an electron donor without acetate ion (0.14). In addition, the turnover number of QuPh(+)-NA reached more than 340. The reaction mechanism and the effect of solvent composition on the photocatalytic H2O2 production were scrutinized by using nanosecond laser flash photolysis.
Subject(s)
Acetic Acid/chemistry , Hydrogen Peroxide/chemistry , Oxalic Acid/chemistry , Oxygen/chemistry , Acetonitriles/chemistry , Catalysis , Light , Photolysis , Quinolinium Compounds/chemistry , Singlet Oxygen/chemistry , Solutions , Water/chemistryABSTRACT
A simple electron donor-acceptor linked dyad, the 2-phenyl-4-(1-naphthyl)quinolinium ion (QuPh(+)-NA), was incorporated into nanosized mesoporous silica-alumina to form a composite, which is highly dispersed in water and acts as an efficient and robust photocatalyst for the reduction of O2 by oxalate to produce hydrogen peroxide with a quantum yield of 10%.
Subject(s)
Aluminum Oxide/chemistry , Quinolinium Compounds/chemistry , Silicon Dioxide/chemistry , Water/chemistry , Catalysis , Electron Transport , Electrons , Ions/chemistry , Light , Oxidation-Reduction , Oxygen/chemistryABSTRACT
Efficient photocatalytic production of hydrogen peroxide (H(2)O(2)) from O(2) and oxalate has been made possible by using a 2-phenyl-4-(1-naphthyl)quinolinium ion as a robust photocatalyst in an oxygen-saturated mixed solution of a buffer and acetonitrile with a high quantum yield of 14% (maximum 50% for the two-electron process) at λ = 334 nm and a high H(2)O(2) yield of 93% at λ > 340 nm.