Raman Spectroscopy Reveals the Multifunctional Role of Interfacial Water in CO-to-C Electroreduction on Cu() Surfaces.

Interfacial water serves as both a proton donor and a competitor for active sites at the copper-catalyst interface in the electrochemical CO reduction reaction (CORR). However, its precise impact on C product selectivity remains debatable. Here, through the utilization of Raman spectroscopy and theoretical calculations, we have discovered that the population of K cation hydrated water (K-HO) rises concurrently with the increase of C yield on atomically flat model Cu() single crystal surfaces.

Revealing the CO Tolerance Mechanism in Acidic Hydrogen Oxidation Reactions on Platinum-Based Catalyst Surfaces.

The presence of trace CO impurity gas in hydrogen fuel can rapidly deactivate platinum-based hydrogen oxidation reaction (HOR) catalysts due to poisoning effects, yet the precise CO tolerance mechanism remains debated. Our designed Au@PtX bifunctional core-shell nanocatalysts exhibit excellent performance of CO tolerance in acidic solution during HOR and possess exceptional Raman spectroscopy enhancement. Through capturing and analyzing in situ Raman spectroscopy evidences on *OH, metal-O species and *CO evolution under 0.

Visualization of Electrooxidation on Palladium Single Crystal Surfaces via In Situ Raman Spectroscopy.

The electrooxidation of catalyst surfaces is across various electrocatalytic reactions, directly impacting their activity, stability and selectivity. Precisely characterizing the electrooxidation on well-defined surfaces is essential to understanding electrocatalytic reactions comprehensively. Herein, we employed in situ Raman spectroscopy to monitor the electrooxidation process of palladium single crystal.

In situ Raman spectroscopy reveals the structure and dissociation of interfacial water.

Understanding the structure and dynamic process of water at the solid-liquid interface is an extremely important topic in surface science, energy science and catalysis. As model catalysts, atomically flat single-crystal electrodes exhibit well-defined surface and electric field properties, and therefore may be used to elucidate the relationship between structure and electrocatalytic activity at the atomic level. Hence, studying interfacial water behaviour on single-crystal surfaces provides a framework for understanding electrocatalysis.

The Difference Se Makes: A Bio-Inspired Dppf-Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance.

Inspired by the metal active sites of [NiFeSe]-hydrogenases, a dppf-supported nickel(II) selenolate complex (dppf=1,1'-bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme-like H evolution turnover frequency (TOF) of 7838 s under an Ar atmosphere, which markedly surpasses the activity of a dppf-supported nickel(II) thiolate analogue with a low TOF of 600 s . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio-inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O and H tolerance.