Probing Cation Effects on *CO Intermediates from Electroreduction of CO2 through Operando Raman Spectroscopy.

Cations in an electrolyte modulate microenvironments near the catalyst surface and affect product distribution from an electrochemical CO2 reduction reaction, and thus, their interaction with intermediate states has been tried to be probed. Herein, we directly observed the cation effect on *CO intermediates on the Cu(OH)2-derived catalyst in real time through operando surface-enhanced Raman spectroscopy at high overpotentials (-1.0 VRHE). Atop *CO peaks are composed of low-frequency binding *CO (*COLFB) and high-frequency binding *CO (*COHFB) because of their adsorption sites. These two *CO intermediates are found to have different sensitivities to the cation-induced field, and each *CO is proposed to be suitably stabilized for efficient C-C coupling. The proportions between *COHFB and *COLFB are dependent on the type of alkali cations, and the increases in the *COHFB ratio have a high correlation with selective C2H4 production under K+ and Cs+, indicating that *COHFB is the dominant and fast active species. In addition, as the hydrated cation size decreases, *COLFB is more sensitively red-shifted than *COHFB, which promotes C-C coupling and suppresses C1 products. Through time-resolved operando measurements, dynamic changes between the two *CO species are observed, showing the rapid initial adsorption of *COHFB and subsequently reaching a steady ratio between *COLFB and *COHFB.

Nanocluster Surface Microenvironment Modulates Electrocatalytic CO2 Reduction.

The catalytic activity and product selectivity of the electrochemical CO2 reduction reaction (eCO2RR) depend strongly on the local microenvironment of mass diffusion at the nanostructured catalyst and electrolyte interface. Achieving a molecular-level understanding of the electrocatalytic reaction requires the development of tunable metal-ligand interfacial structures with atomic precision, which is highly challenging. Here, the synthesis and molecular structure of a 25-atom silver nanocluster interfaced with an organic shell comprising 18 thiolate ligands are presented. The locally induced hydrophobicity by bulky alkyl functionality near the surface of the Ag25 cluster dramatically enhances the eCO2RR activity (CO Faradaic efficiency, FECO: 90.3%) with higher CO partial current density (jCO) in an H-cell compared to Ag25 cluster (FECO: 66.6%) with confined hydrophilicity, which modulates surface interactions with water and CO2. Remarkably, the hydrophobic Ag25 cluster exhibits jCO as high as -240 mA cm-2 with FECO >90% at -3.4 V cell potential in a gas-fed membrane electrode assembly device. Furthermore, this cluster demonstrates stable eCO2RR over 120 h. Operando surface-enhanced infrared absorption spectroscopy and theoretical simulations reveal how the ligands alter the neighboring water structure and *CO intermediates, impacting the intrinsic eCO2RR activity, which provides atomistic mechanistic insights into the crucial role of confined hydrophobicity.

Nickel decorated manganese oxynitride over graphene nanosheets as highly efficient visible light driven photocatalysts for acetylsalicylic acid degradation.

In this work, we prepared nanocomposites of nickel-decorated manganese oxynitride on graphene nanosheets and demonstrated them as photocatalysts for degradation of acetylsalicylic acid (ASA). The catalyst exhibited a high degradation efficiency over ASA under visible light irradiation and an excellent structural stability after multiple uses. Compared to manganese oxide (MnO) and manganese oxynitride (MnON) nanoparticles, larger specific surface area and smaller band gap were observed for the nanocomposite accounting for the enhanced photocatalytic efficiency. Besides the compositional effect of the catalyst, we also examined the influence of various experimental parameters on the degradation of ASA such as initial concentration, catalyst dose, initial pH and additives. The best performance was obtained for the nanocomposite when the catalyst dose was 10 mg/mL and the initial pH 3. Detection of intermediates during photocatalysis showed that ASA undergoes hydroxylation, demethylation, aromatization, ring opening, and finally complete mineralization into CO2 and H2O by reactive species. For practical applications as a photocatalyst, cytotoxicity of the nanocomposite was also evaluated, which revealed its insignificant impact on the cell viability. These results suggest the nanocomposite of nickel-decorated manganese oxynitride on graphene nanosheets as a promising photocatalyst for the remediation of ASA-contaminated water.