Much effort has been devoted to photocatalytic production of hydrogen peroxide (H 2 O 2 )a sa na lternative to fossil fuels.F roma ne conomic point of view,r eductive synthesis of H 2 O 2 from O 2 coupled with the oxidative synthesis of value-added products is particularly interesting.W eh erein report application of MIL-125-NH 2 ,aphotoactive metalorganic framework (MOF), to ab enzylalcohol/water twophase system that realized photocatalytic production and spontaneous separation of H 2 O 2 and benzaldehyde.H ydrophobization of the MOF enabled its separation from the aqueous phase.T his resulted in enhanced photocatalytic efficiency and enabled application of various aqueous solutions including extremely low pH solution which is favorable for H 2 O 2 production but fatal to MOF structure.I na ddition, ah ighly concentrated H 2 O 2 solution was obtained by simply reducing the volume of the aqueous phase.

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Photocatalytic H2O2 production via two-electron reduction of O2 was realized by visible-light irradiation of a metal-organic framework, MIL-125-NH2, in the presence of TEOA and benzylalcohol. Deposition of NiO nanoparticles onto MIL-125-NH2 dramatically enhanced the catalytic activity. Further studies suggested that fast disproportionation of the O2˙- intermediate to H2O2 resulted in the enhancement.

A water-soluble iridium(iii)–hydroxo complex catalyses the production of H2from paraformaldehyde in water under basic conditions at 298 K.

† Electronic Supplementary Information (ESI) available: Experimental section, X-ray diffraction patterns ( Fig. S1 and S10b), X-ray fluorescence data (Table S1), DLS data ( Fig. S2 and S10c), IR spectra ( Fig. S3 and S10a), time courses of H2O2 production under various conditions (Figs. S4, S7, S8, and S9), time courses of O2 evolution amount (Fig. S5 and S6) and estimation of the amount of evolved O2. See

The photocatalytic activity of a cluster-alkylated MOF for H2O2 production far exceeded that of a linker-alkylated MOF in a benzyl alcohol/water two-phase system.

Hydrogen peroxide (H2O2) was produced from H2O and O2via semiconductor-photocatalysed oxidation of H2O in combination with photocatalytic two-electron reduction of O2 with [RuII((MeO)2bpy)3]2+ ((MeO)2bpy = 4,4′-dimethoxy-2,2′-bipyridine) in water.

Much effort has been devoted to photocatalytic production of hydrogen peroxide (H2O2) as an alternative to fossil fuels. From an economic point of view, reductive synthesis of H2O2 from O2 coupled with the oxidative synthesis of value‐added products is particularly interesting. We herein report application of MIL‐125‐NH2, a photoactive metal–organic framework (MOF), to a benzylalcohol/water two‐phase system that realized photocatalytic production and spontaneous separation of H2O2 and benzaldehyde. Hydrophobization of the MOF enabled its separation from the aqueous phase. This resulted in enhanced photocatalytic efficiency and enabled application of various aqueous solutions including extremely low pH solution which is favorable for H2O2 production but fatal to MOF structure. In addition, a highly concentrated H2O2 solution was obtained by simply reducing the volume of the aqueous phase.