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Exploring efficient and inexpensive oxygen evolution reaction (OER) electrocatalysts is of great importance for various electrochemical energy storage and conversion technologies. Ni-based electrocatalysts have been actively pursued because of their promising activity and earth abundance. However, the OER efficiency for most of the developed Ni-based electrocatalysts has been intrinsically limited due to their low electrical conductivity and poor active site exposure yield. Herein, we report metallic Ni3N nanosheets as an efficient OER electrocatalyst for the first time. The first-principles calculations and electrical transport property measurements unravel that the Ni3N is intrinsically metallic, and the carrier concentration can be remarkably improved with dimensional confinement. The EXAFS spectra provide solid evidence that the Ni3N nanosheets have disordered structure resultant of dimensional reduction, which then could provide more active sites for OER. Benefiting from enhanced electrical conductivity with metallic behavior and atomically disordered structure, the Ni3N nanosheets realize intrinsically improved OER activity compared with bulk Ni3N and NiO nanosheets. Our finding suggests that metallic nitride nanosheets could serve as a new group of OER electrocatalysts with excellent property.

Platinum-on-palladium bimetallic heterogeneous nanostructures were prepared using a sequential synthetic method, in which 3-nm Pt particles grew on the surfaces of 5-nm Pd nanoparticles. Electrochemical study of carbon-supported Pt-on-Pd heteronanostructures shows not only enhancement in electrocatalytic activity for oxygen reduction reaction (ORR) but also much improved stability in comparison to a commercial platinum catalyst (E-TEK, 20 wt % Pt, diameter: 2.5 nm). The greatly suppressed hydroxyl adsorption on active sites by introducing Pd was attributed to the enhanced activity, while the retention of active surface area, morphology, and composition because of the large overall bimetallic particle size and unique architectures could be the key factors for the much improved stability over 30,000 cycles. Our work shows heterogeneous platinum-on-metal bimetallic nanostructures offer new opportunities to the design of hierarchically ordered multifunctional fuel cell catalysts.

This communication describes the preparation of carbon-supported truncated-octahedral Pt(3)Ni nanoparticle catalysts for the oxygen reduction reaction. Besides the composition, size, and shape controls, this work develops a new butylamine-based surface treatment approach for removing the long-alkane-chain capping agents used in the solution-phase synthesis. These Pt(3)Ni catalysts can have an area-specific activity as high as 850 muA/cm(2)(Pt) at 0.9 V, which is approximately 4 times better than the commercial Pt/C catalyst ( approximately 0.2 mA/cm(2)(Pt) at 0.9 V). The mass activity reached 0.53 A/mg(Pt) at 0.9 V, which is close to a factor of 4 increase in mass activity, the threshold value that allows fuel-cell power trains to become cost-competitive with their internal-combustion counterparts. Our results also show that the mass activities of these carbon-supported Pt(3)Ni nanoparticle catalysts strongly depend on the (111) surface fraction, which validates the results of studies based on Pt(3)Ni extended-single-crystal surfaces, suggesting that further development of catalysts with still higher mass activities is highly plausible.

Oxygen evolution reaction (OER) is a pivotal process in many energy conversion and storage techniques, such as water splitting, regenerative fuel cells, and rechargeable metal-air batteries. The synthesis of stable, efficient, non-noble metal-based electrocatalysts for OER has been a long-standing challenge. In this work, a facile and scalable method to synthesize hollow and conductive iron-cobalt phosphide (Fe-Co-P) alloy nanostructures using an Fe-Co metal organic complex as a precursor is described. The Fe-Co-P alloy exhibits excellent OER activity with a specific current density of 10 mA/cm being achieved at an overpotential as low as 252 mV. The current density at 1.5 V (vs reversible hydrogen electrode) of the Fe-Co-P catalyst is 30.7 mA/cm, which is more than 3 orders of magnitude greater than that obtained with state-of-the-art Fe-Co oxide catalysts. Our mechanistic experiments and theoretical analysis suggest that the electrochemical-induced high-valent iron stabilizes the cobalt in a low-valent state, leading to the simultaneous enhancement of activity and stability of the OER catalyst.

The preparation of ultrathin ruthenium metal nanosheets is important because these materials have unique properties originated from the unique two-dimensional (2D) structure, and yet, it remains a synthetic challenge. Herein, we report the synthesis of free-standing 2D Ru nanosheets using a facile solvothermal method, in which Ru(III) is reduced via self-decomposition of the metal precursor and grows into ultrathin nanosheets with the aid of isopropanol and urea. The 2D Ru nanosheets and their 2D oxide derivative exhibit excellent hydrogen evolution reaction and oxygen evolution reaction activities, respectively. They show much enhanced properties compared with their Ru powder counterparts and the commercial Pt in electrolytic water splitting.

Forming core-shell and alloy structures offers generally two ways to design efficient Pt-based catalysts for oxygen reduction reaction (ORR). Here, we combined these two strategies and invented a versatile aqueous route to synthesize octahedral Pd@Pt1.8Ni core-shell nanocrystals. The Pt/Ni atomic ratios in the resultant shells can be varied from 0.6 to 1.8, simply by changing the amounts of Pt and Ni precursors, with the other conditions unchanged. Experimental studies showed that the mass activities of as-prepared catalysts were 5 times higher than that of the commercial Pt/C. We believe that the ultrathin PtNi shells enclosed by {111} facets made it possible to reduce the Pt content while retaining the catalytic activity toward ORR. This strategy may be extended to the preparation of other multimetallic nanocrystals with shaped and ultrathin alloy shells, which is conducive to design highly active catalysts.

A surface hydrogen effect to modulate the pure electronic-state transition in perovskite Ca0.9 Yb0.1 MnO3 synergistically generates a more suitable eg electron filling status and better conductivity. This achieves 100 times higher catalytic activity compared to that of a pristine sample.