Ammonia-Induced FCC Ru Nanocrystals for Efficient Alkaline Hydrogen Electrocatalysis.

The urgent development of effective electrocatalysts for hydrogen evolution and hydrogen oxidation reaction (HER/HOR) is needed due to the sluggish alkaline hydrogen electrocatalysis. Here, an unusual face-centered cubic (fcc) Ru nanocrystal with favorable HER/HOR performance is offered. Guided by the lower calculated surface energy of fcc Ru than that of hcp Ru in NH3, the carbon-supported fcc Ru electrocatalyst is facilely synthesized in the NH3 reducing atmosphere. The specific HOR kinetic current density of fcc Ru can reach 23.4 mA cmPGM -2, which is around 20 and 21 times greater than that of hexagonal close-packed (hcp) Ru and Pt/C, respectively. Additionally, the HER specific activity is enhanced more than six times in fcc Ru electrocatalyst when compared to Pt/C. Experimental and theoretical analysis indicate that the phase transition from hcp Ru to fcc Ru can negatively shift the d band center, weaken the interaction between catalysts and key intermediates and therefore enhances the HER/HOR kinetics.

Amorphous TiOx Stabilized Intermetallic Pt3Ti Nanocatalyst for Methanol Oxidation Reaction.

Intermetallic compounds, featuring atomically ordered structures, have emerged as a class of promising electrocatalysts for fuel cells. However, it remains a formidable challenge to controllably synthesize Pt-based intermetallics during the essential high-temperature annealing process as well as stabilize the nanoparticles (NPs) during the electrocatalytic process. Herein, we demonstrated a Ketjen black supported intermetallic Pt3Ti nanocatalyst coupled with amorphous TiOx species (Pt3Ti-TiOx/KB). The TiOx can not only confine Pt3Ti NPs during the synthesis and electrocatalytic process by a strong metal-oxide interaction but also promote the water dissociation for generating more OH species, thus facilitating the conversion of COad. The Pt3Ti-TiOx/KB showed a significantly enhanced mass activity (2.15 A mgPt-1) for the methanol oxidation reaction, compared with Pt3Ti/KB and Pt/C, and presented an impressively high mass activity retention (∼71%) after the durability test. This work provides an effective strategy of coupling Pt-based intermetallics with functional oxides for developing highly performed electrocatalysts.

OH spectator at IrMo intermetallic narrowing activity gap between alkaline and acidic hydrogen evolution reaction.

The sluggish kinetics of the hydrogen evolution reaction in base has resulted in large activity gap between acidic and alkaline electrolytes. Here, we present an intermetallic IrMo electrocatalyst supported on carbon nanotubes that exhibits a specific activity of 0.95 mA cm-2 at the overpotential of 15 mV, which is 14.4 and 9.5 times of those for Ir/C and Pt/C, respectively. More importantly, its activities in base are fairly close to that in acidic electrolyte and the activity gap between acidic and alkaline media is only one fourth of that for Ir/C. DFT calculations reveal that the stably-adsorbed OH spectator at Mo site of IrMo can stabilize the water dissociation product, resulting in a thermodynamically favorable water dissociation process. Beyond offering an advanced electrocatalyst, this work provides a guidance to rationally design the desirable HER electrocatalysts for alkaline water splitting by the stably-adsorbed OH spectator.