Structural and Mechanistic Aspects of Mn-oxo and Co-based Compounds in Water Oxidation Catalysis and Potential Applications in Solar Fuel Production

To address the issues of energy crisis and global warming, novel renewable carbon-free or carbon-neutral energy sources must be identified and developed. A deeper understanding of photosynthesis is the key to provide a solid foundation to facilitate this transformation. To mimic the water oxidation of photosystem II oxygen evolving complex, Mn-oxo complexes and Co-phosphate catalytic material were discovered in solar energy storage. Building on these discoveries, recent advances in solar energy conversion showed a compelling working principle by combing the active Mn-oxo and Co-based catalysts in water splitting with semiconductor heteronanostructures for effective solar energy harnessing. In this review the appealing systems including Mn-oxo tetramer/Nafion, Mn-oxo dimer/TiO2, Mn-oxo oligomer/WO3, Co-Pi/Fe2O3, and Co-Pi/ZnO are summarized and discussed. These accomplishments offer a promising framework and have a profound impact in the field of solar fuel production.

A low-melting-point metal doping strategy for the synthesis of small-sized intermetallic Pt_(5)Ce fuel cell catalysts

Carbon-supported platinum-lanthanum(Pt-Ln)intermetallic compound(IMC)nanoparticles with high activity and robust stability have been demonstrated as promising cathode catalysts for proton-exchange membrane fuel cells.However,the preparation of Pt-Ln IMC catalysts needs high-temperature annealing treatment that inevitably causes nanoparticle sintering,resulting in significant reduction of the electrochemical surface area and mass-based activity.Here,we prepare small-sized M-doped Pt_(5)Ce(M=Ga,Cd,and Sb)IMCs catalysts via a low-melting-point metal doping strategy.We speculate that the doping of low-melting-point metals can facilitate the generation of vacancies in the crystal lattice through thermal activation and thus reduce the kinetic barriers for the formation of intermetallic Pt_(5)Ce catalysts.The prepared Ga-doped Pt_(5)Ce catalyst exhibits a higher electrochemical active surface area(81 m^(2)·gPt^(-1))and a larger mass activity(0.45 A·mgPt^(-1)at 0.9 V)over the undoped Pt_(5)Ce and commercial Pt/C catalysts.In the membrane electrode assembly test,the Ga-doped Pt_(5)Ce cathode delivers a power density of 0.98 W·cm^(-2)at 0.67 V,along with a voltage loss of only 27 mV at 0.8 A·cm^(-2)at the end of accelerated stability test.

Highly efficient and magnetically separable nano-CuFe_2O_4 catalyzed S-arylation of thiourea by aryl/heteroaryl halides

The non-toxic and magnetically separable nano-CuFeOcatalyzed synthesis of symmetrical aryl sulfides by the reaction of thiourea with a wide variety of aryl halides,including aryl chlorides has been reported.Excellent yields of products have been obtained under ligand-free conditions and without the use of any expensive catalyst,such as palladium.