g-C3N4 Nanosheet Supported CuO Nanocomposites for the Electrochemical Carbon Dioxide Reduction Reaction.

We have prepared CuO-derived electrocatalysts on a graphitic carbon nitride (g-C3N4) nanosheet support for the electrochemical carbon dioxide reduction reaction (CO2RR). Highly monodisperse CuO nanocrystals made by a modified colloidal synthesis method serve as the precatalysts. We use a two-stage thermal treatment to address the active site blockage issues caused by the residual C18 capping agents. The results show that the thermal treatment effectively removed the capping agents and increased the electrochemical surface area. During the process, the residual oleylamine molecules incompletely reduced CuO to a Cu2O/Cu mixed phase in the first stage of thermal treatment, and the following treatment in forming gas at 200 °C completed the reduction to metallic Cu. The CuO-derived electrocatalysts show different selectivities over CH4 and C2H4, and this might be due to the synergistic effects of Cu-g-C3N4 catalyst-support interaction, varied particle sizes, dominant surface facets, and catalyst ensemble. The two-stage thermal treatment enables sufficient capping agent removal, catalyst phase control, and CO2RR product selection, and with precise controls of the experimental parameters, we believe that this will help to design and fabricate g-C3N4-supported catalyst systems with narrower product distribution.

Shape-programmed nanofabrication: understanding the reactivity of dichalcogenide precursors.

Dialkyl and diaryl dichalcogenides are highly versatile and modular precursors for the synthesis of colloidal chalcogenide nanocrystals. We have used a series of commercially available dichalcogenide precursors to unveil the molecular basis for the outcome of nanocrystal preparations, more specifically, how precursor molecular structure and reactivity affect the final shape and size of II-VI semiconductor nanocrystals. Dichalcogenide precursors used were diallyl, dibenzyl, di-tert-butyl, diisopropyl, diethyl, dimethyl, and diphenyl disulfides and diethyl, dimethyl, and diphenyl diselenides. We find that the presence of two distinctively reactive C-E and E-E bonds makes the chemistry of these precursors much richer and interesting than that of other conventional precursors such as the more common phosphine chalcogenides. Computational studies (DFT) reveal that the dissociation energy of carbon-chalcogen (C-E) bonds in dichalcogenide precursors (R-E-E-R, E=S or Se) increases in the order (R): diallyl