Disentangling Electronic and Geometric Effects in Electrocatalysis through Substitution in Isostructural Intermetallic Compounds.

Efficient development of catalytic materials requires knowledge of the decisive parameters defining the catalytic properties. In multicomponent metallic catalysts, these are categorized as electronic and geometric effects, yet they are strongly interrelated. A systematic disentanglement can be achieved by fixing one parameter while altering the other, which becomes possible through the substitution in isostructural intermetallic compounds. This approach enables the evaluation of electronic or geometric contributions both individually and combined. Herein, this is achieved by substitution of indium (three valence electrons) with tin (four valence electrons) in the series In1-xSnxPd2, which allows for a systematic variation of the total number of electrons per unit cell with only a minor variation of the unit cell parameters and thus the evaluation of the electronic effect. Geometric effects were evaluated by substitution of indium with gallium in the Ga1-xInxPd2 series, which allows for a systematic variation of the interatomic distances while maintaining the same number of valence electrons per unit cell and close atomic coordinates. By substituting gallium with tin in the Ga1-xSnxPd2 series, both effects are combined and addressed simultaneously. The activity enhancement of the methanol oxidation reaction on the Ga1-xSnxPd2 series is attributed to the synergy of the combined effects.

Interfacial Electron Transfer Strategy to Improve the Hydrogen Evolution Catalysis of CrP Heterostructure.

Though several Pt-free hydrogen evolution reaction (HER) catalysts have been reported, their employment for industry is challenging. Here, a facile pyrolysis method to obtain phase-pure CrP nanoparticles supported on N, P dual-doped carbon (CrP/NPC) is reported to be tuned toward industrial HER. Interestingly, CrP/NPC exhibits excellent HER activity that requires an overpotential of 34 mV to attain a current density of 10 mA cm-2 , which is only 1 mV positive to commercial Pt/C and a potential of 55 mV to achieve a current density of 200 mA cm-2 which is better than Pt/C. In addition, the long-term durability of CrP/NPC is far superior to Pt/C due to the strong interaction between CrP and C support, restricting any agglomeration or leaching. Density functional theory (DFT) calculations suggest that electronic modulation at the interface (CrP/NPC) optimizes the hydrogen adsorption energy. The Cr-Cr bridge site with required density of states near the Fermi level is found to be the active site. Overall, this report provides a practical scheme to synthesize rarely investigated CrP based materials along with a computational mechanistic guideline for electrocatalysis that can be utilized to explore other phosphides for various applications.

Pd-coated Ru nanocrystals supported on N-doped graphene as HER and ORR electrocatalysts.

Here, Pd-coated Ru nanocrystals supported on N-doped graphene (Pd-Ru@NG) are obtained via electroless deposition of Pd on Ru nanocrystals. We have demonstrated that Pd boosts the electrocatalytic performance of Pd-Ru@NG towards the hydrogen evolution reaction (HER) and alcohol tolerant oxygen reduction reaction (ORR) as compared to Pt/C.