Concurrent Ammonia Synthesis and Alcohol Oxidation Boosted by Glutathione-Capped Quantum Dots under Visible Light.

Mother nature accomplishes efficient ammonia synthesis via cascade N oxidation by lightning strikes followed with enzyme-catalyzed nitrogen oxyanion (NO , x = 2,3) reduction. The protein environment of enzymatic centers for NO -to-NH process greatly inspires the design of glutathione-capped (GSH) quantum dots (QDs) for ammonia synthesis under visible light (440 nm) in tandem with plasma-enabled N oxidation. Mechanistic studies reveal that GSH induces positive shift of surface charge to strengthen the interaction between NO and QDs.

Photochemistry Journey to Multielectron and Multiproton Chemical Transformation.

The odyssey of photochemistry is accompanied by the journey to manipulate "electrons" and "protons" in time, in space, and in energy. Over the past decades, single-electron (1e) photochemical transformations have brought marvelous achievements. However, as each photon absorption typically generates only one exciton pair, it is exponentially challenging to accomplish multielectron and proton photochemical transformations.

Mechanistic Insights Into Iron(II) Bis(pyridyl)amine-Bipyridine Skeleton for Selective CO Photoreduction.

A bis(pyridyl)amine-bipyridine-iron(II) framework (Fe(BPAbipy)) of complexes 1-3 is reported to shed light on the multistep nature of CO reduction. Herein, photocatalytic conversion of CO to CO even at low CO concentration (1 %), together with detailed mechanistic study and DFT calculations, reveal that 1 first undergoes two sequential one-electron transfer affording an intermediate with electron density on both Fe and ligand for CO binding over proton. The following 2 H -assisted Fe-CO formation is rate-determining for selective CO -to-CO reduction.

Identifying a Real Catalyst of [NiFe]-Hydrogenase Mimic for Exceptional H Photogeneration.

Inspired by the natural [NiFe]-H ase, we designed mimic 1, (dppe)Ni(μ-pdt)(μ-Cl)Ru(CO) Cl to realize effective H evolution under photocatalytic conditions. However, a new species 2 was captured in the course of photo-, electro-, and chemo- one-electron reduction. Experimental studies of in situ IR spectroscopy, EPR, NMR, X-ray absorption spectroscopy, and DFT calculations corroborated a dimeric structure of 2 as a closed-shell, symmetric structure with a Ru center.

Self-assembled inorganic clusters of semiconducting quantum dots for effective solar hydrogen evolution.

Owing to promoted electron-hole separation, the catalytic activity of semiconducting quantum dots (QDs) towards solar hydrogen (H2) production has been significantly enhanced by forming self-assembled clusters with ZnSe QDs made ex situ. Taking advantage of the favored interparticle hole transfer to ZnSe QDs, the rate of solar H2 evolution of CdSe QDs can be increased to ∼30 000 μmol h-1 g-1 with ascorbic acid as the sacrificial reagent, ∼150-fold higher than that of bare CdSe QDs clusters under the same conditions.