A Non‐Heme Iron Photocatalyst for Light‐Driven Aerobic Oxidation of Methanol

Abstract

Non‐heme (L)FeIII and (L)FeIII‐O‐FeIII(L) complexes (L=1,1‐di(pyridin‐2‐yl)‐N,N‐bis(pyridin‐2‐ylmethyl)ethan‐1‐amine) underwent reduction under irradiation to the FeII state with concomitant oxidation of methanol to methanal, without the need for a secondary photosensitizer. Spectroscopic and DFT studies support a mechanism in which irradiation results in charge‐transfer excitation of a FeIII−μ‐O−FeIII complex to generate [(L)FeIV=O]2+ (observed transiently during irradiation in acetonitrile), and an equivalent of (L)FeII. Under aerobic conditions, irradiation accelerates reoxidation from the FeII to the FeIII state with O2, thus closing the cycle of methanol oxidation to methanal.

Direct and Selective Photocatalytic Oxidation of CH4 to Oxygenates with O2 on Cocatalysts/ZnO at Room Temperature in Water

“…The concentration of liquid product HCHO was quantified by the colorimetric method. 37 Typically, 100 mL of reagent aqueous solution was first prepared by dissolving 15 g of ammonium acetate, 0.3 mL of acetic acid, and 0.2 mL of pentane-2,4-dione in water. Then, 0.5 mL of liquid product was mixed with 2.0 mL of water and 0.5 mL of reagent solution.…”

Selective Photo-oxidation of Methane to Methanol with Oxygen over Dual-Cocatalyst-Modified Titanium Dioxide

“…27 The amount of formaldehyde was quantified using colorimetric method. 29 Briefly, 2.0 mL colorimetric reagent (0.3 mL acetic acid, 15 g ammonium acetate, 0.2 mL acetylacetone in 100 mL water) was mixed with 0.5 mL product solution. The mixed solution was held 35 °C for around 0.5 h. The absorption intensity of the solution was detected using UV-visible absorption spectroscopy.…”

Synergy of Single Atoms Pd and Oxygen Vacancies on In2O3 for Highly Selective C1 Oxygenates Production from Methane under Visible Light

“…Thus, CH 3 OOH could be quanti ed. HCHO was measured through the colorimetric method[57] on the UV-3600 Plus spectrometer (Shimadzu Co., Ltd). After the reactor being degassed for 30 min, 1 bar 18 O 2 or16 O 2 and 5 bar CH 4 were injected into the reactor.…”