Earth-abundant Metal Complexes Research Articles

Hydrogen photogeneration from water on the biomimetic hybrid artificial photocatalytic systems of semiconductors and earth-abundant metal complexes: progress and challenges

This perspective summarizes the advances and challenges in hybrid artificial photocatalytic systems comprising semiconductors and biomimetic metal complexes for the photogeneration of hydrogen from water.

Selective and efficient photocatalytic CO2 reduction to CO using visible light and an iron-based homogeneous catalyst.

Converting CO2 into valuable compounds using sunlight as the energy input and an earth-abundant metal complex as the catalyst is an exciting challenge related to contemporary energy issues as well as to climate change. By using an inexpensive organic photosensitizer under visible-light excitation (λ > 400 nm) and a substituted iron(0) tetraphenylporphyrin as a homogeneous catalyst, we have been able to generate carbon monoxide from CO2 selectively with high turnover numbers. Sustained catalytic activity over a long time period (t > 50 h) did not lead to catalyst or sensitizer deactivation. A catalytic mechanism is proposed.

Electrochemical and Photoelectrochemical Water Oxidation by Supported Cobalt–Oxo Cubanes

Cobalt–oxo cubane clusters were immobilized on a Nafion film-coated fluorine-doped tin oxide (FTO) electrode and an α-Fe2O3 photoanode as surface catalysts for water oxidation. The performance of electrochemical water splitting indicated that these earth-abundant metal complexes retain their homogeneous reactivity on the electrode. Furthermore, efficient visible light-driven water oxidation was realized by coupling a molecular electrocatalyst with an inorganic semiconductor as a noble metal-free photoanode, showing a stability significantly improved with respect to that of the homogeneous system.

Recent progress in electrochemical hydrogen production with earth-abundant metal complexes as catalysts

This perspective article reviews the recent important progress in electrocatalytic hydrogen production catalyzed by earth-abundant metal complexes. The catalysts are divided into two categories depending on the media used in the hydrogen-evolving reactions, with an emphasis on the types of acids employed. The catalysts used in the first category, which work in organic solutions, include nickel and cobalt complexes with base-containing diphosphine ligands, cobaloximes, cobalt tetrapyridine complexs, and [NiFe]- and [FeFe]-hydrogenase mimics. Molybdenum and cobalt pentapyridine complexes, as well as the cobalt bis(iminopyridine) complex reported very recently, are the most important examples of catalysts used in the second category, which work in aqueous solutions. The advantages and disadvantages of the different types of catalysts are discussed and the hydrogen-evolving mechanisms for the well-studied catalysts are illustrated. In addition, several molecular catalyst-modified electrodes for hydrogen production are described.