Fabrication of bilayer Pd-Pt nanocages with sub-nanometer thin shells for enhanced hydrogen evolution reaction

The hydrogen evolution reaction (HER),which generates molecular hydrogen through the electrochemical reduction of water,is an important clean-energy technology.Platinum (Pt) is an ideal material for HER electrocatalysts in terms of low overpotential and fast kinetics.An effective method to improve the atom utilization efficiency of Pt is to fabricate Pt-based core-shell or nanocage structures with ultra-thin walls.This paper describes the construction of bilayer palladium (Pd)-Pt alloy nanocages catalyst with enhanced HER catalytic activity.The nanocages were fabricated by etching away the Pd templates of multishelled nanocubes composed of alternate shells of Pd and Pt with well-defined (100) facets.The bilayer Pd-Pt nanocages with sub-nanometer shells have a high dispersion of the active atoms on the outside and inside surfaces of outer layer and inner layer,respectively.Moreover,the Pd-Pt alloy lowers the overpotential for HER and speeds up the reaction rate of HER due to the synergies between Pd and Pt.The rational design of bilayer nanocages provided a novel route for boosting the atom utilization efficiency of Pt catalysts.

Theory assisted design of N-doped tin oxides for enhanced electrochemical CO2 activation and reduction

Clearly understanding the structure-function relationship and rational design of efficient CO2 electrocatalysts are still the challenges.This article describes the molecular origin of high selectivity of formic acid on N-doped SnO2 nanoparticles,which obtained via thermal treatment of g-C3N4 and SnCl2·2H2O precursor.Combined with density functional theory(DFT)calculations,we discover that N-doping effectively introduces oxygen vacancies and increases the charge density of Sn sites,which plays a positive role in CO2 activation.In addition,N-doping further regulates the adsorption energy of^*OCHO,^*COOH,^*H and promotes HCOOH generation.Benefited from above modulation,the obtained N-doped SnO2 catalysts with oxygen vacancies(Ov-N-SnO2)exhibit faradaic efficiency of 93% for C1 formation,88% for HCOOH production and well-suppression of H2 evolution over a wide range of potentials.

Effect of bicarbonate on CO_(2) electroreduction over cathode catalysts

CO_(2) electroreduction (CO_(2) ER) using renewable energy is ideal for mitigating the greenhouse effect and closing the carbon cycle. Bicarbonate (HCO_(3)−) is most commonly employed as the electrolyte anion because it is known to facilitate CO_(2) ER. However, its dynamics in the electric double layer remains obscure and requires more in-depth investigation. Herein, we investigate the refined reduction process of bicarbonate by employing in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy. By comparing the product distributions in Ar-saturated KCl and KHCO_(3) electrolytes, we confirmed CO production from HCO_(3)^(−) in the absence of an external CO_(2) source. Notably, in contrast to an electric compulsion, negatively charged HCO_(3)− anions were found to accumulate near the electrode surface. A reduction mechanism of HCO3− is proposed in that HCO3− is not adsorbed over a catalyst, but may be enriched near the electrode surface and converted to CO_(2) and react over Au and Cu electrodes. The dependence of the CO_(2) ER activity on the local HCO3− concentration was subsequently discovered, which was in turn dependent on the bulk HCO3− concentration and cathodic potential. In particular, the local HCO3− concentration was limited by the cathodic potential, leading to a plateau in the CO_(2) ER activity. The proposed mechanism provides insights into the interaction between the catalyst and the electrolyte in CO_(2) ER.