Sn-based film electrodeposited on Ag foil for selective electrochemical CO2 reduction to CO.

Electrochemical CO2 reduction (ECR) to valuable chemicals and fuels using renewable energy is a promising way to reduce carbon emission. Herein, Sn-based films were electrodeposited on Ag foil surfaces (Sn/Ag-y) for selective ECR to CO, where y represented the concentration of SnCl2 in the electrodeposition bath. The Sn/Ag-20 electrode achieved a high CO faradaic efficiency of 96.0% with a current density of 69.3 mA cm-2. The enhanced catalytic performance could be attributed to appropriate superficial properties, large electrochemical active surface areas, low charge transfer resistance, efficient stabilization capacity of the CO2˙- intermediates, and suitable combination with electrolytes.

Crystalline CdS/Amorphous Cd(OH)2 Composite for Electrochemical CO2 Reduction to CO in a Wide Potential Window.

Electrochemical CO2 reduction is a promising method for converting atmospheric CO2 into valuable low-carbon chemicals. In this study, a crystalline cadmium sulfide/amorphous cadmium hydroxide composite was successfully deposited on the carbon paper substrate surface by in-situ chemical bath deposition (named as c-CdS/a-Cd(OH)2/CP electrodes) for the efficient electrochemical CO2 reduction to produce CO. The c-CdS/a-Cd(OH)2/CP electrode exhibited high CO Faradaic efficiencies (>90 %) under a wide potential window of 1.0 V, with the highest value reaching ~100 % at the applied potential ranging from -2.16 V to -2.46 V vs. ferrocene/ferrocenium (Fc/Fc+), superior to the crystalline counterpart c-CdS/CP and c-CdS/c-Cd(OH)2@CP electrodes. Meanwhile, the CO partial current density reached up to 154.7 mA cm-2 at -2.76 V vs. Fc/Fc+ on the c-CdS/a-Cd(OH)2/CP electrode. The excellent performance of this electrode was mainly ascribed to its special three-dimensional structure and the introduction of a-Cd(OH)2. These structures could provide more active sites, accelerate the charge transfer, and enhance adsorption of *COOH intermediates, thereby improving the CO selectivity. Moreover, the electrolytes consisting of 1-butyl-3-methylimidazolium tetrafluoroborate and acetonitrile also enhanced the reaction kinetics of electrochemical CO2 reduction to CO.

Electrocatalytic Activity of CO2 Reduction to CO on Cadmium Sulfide Enhanced by Chloride Anion Doping.

The electrocatalytic CO2 reduction (ECR) to produce valuable fuel is a promising process for addressing atmospheric CO2 emissions and energy shortages. In this study, Cl-anion doped cadmium sulfide structures were directly fabricated on a nickel foam surface (Cl/CdS-NF) using an in situ hydrothermal method. The Cl-anion doping could significantly improve ECR activity for CO production in ionic liquid and acetonitrile mixed solution, compared to pristine CdS. The highest Faradaic efficiency of CO is 98.1 % on a Cl/CdS-NF-2 cathode with an excellent current density of 137.0 mA cm-2 at -2.25 V versus ferrocene/ferrocenium (Fc/Fc+ , all potentials are versus Fc/Fc+ in this study). In particular, CO Faradaic efficiencies remained above 80 % in a wide potential range of -2.05 V to -2.45 V and a maximum partial current density (192.6 mA cm-2 ) was achieved at -2.35 V. The Cl/CdS-NF-2, with appropriate Cl anions, displayed abundant active sites and a suitable electronic structure, resulting in outstanding ECR activity. Density functional theory calculations further demonstrated that Cl/CdS is beneficial for increasing the adsorption capacities of *COOH and *H, which can enhance the activity of the ECR toward CO and suppress the hydrogen evolution reaction.

Cd/Cd(OH)2 Nanosheets Enhancing the Electrocatalytic Activity of CO2 Reduction to CO.

Electric-driven conversion of carbon dioxide (CO2 ) to carbon monoxide (CO) under mild reaction conditions offers a promising approach to mitigate the greenhouse effect and the energy crisis. Surface engineering is believed to be one of the prospective methods for enhancing the electrocatalytic activity of CO2 reduction. Herein, hydroxyl (OH) groups were successfully introduced to cadmium nanosheets to form cadmium and cadmium hydroxide nanocomposites (i. e. Cd/Cd(OH)2 nanosheets) via a facile two-step method. The as-prepared Cd/Cd(OH)2 /CP (CP indicates carbon paper) electrode displays excellent electrocatalytic activity for CO2 reduction to produce CO. The Faradaic efficiency of CO reaches 98.3 % and the current density achieves 23.8 mA cm-2 at -2.0 V vs. Ag/Ag+ in a CO2 -saturated 30 wt% 1-butyl-3-methylimidazole hexafluorophosphate ([Bmim]PF6 )-65 wt% acetonitrile (CH3 CN)-5 wt% water (H2 O) electrolyte. And the CO partial current density can reach up to 71.6 mA cm-2 with the CO Faradaic efficiency of more than 85 % at -2.3 V vs. Ag/Ag+ , which stands out against Cd/CP, Cd(OH)2 /CP, and Cd/CdO/CP electrodes. The excellent electrocatalytic performance of the Cd/Cd(OH)2 /CP electrode can be attributed to its unique structural properties, suitable OH groups, perfect interaction with electrolyte, abundant active sites and fast electron transfer rate.

Full-Color Tunable Circularly Polarized Luminescence Induced by the Crystal Defect from the Co-assembly of Chiral Silver(I) Clusters and Dyes.

Four pairs of defective crystals exhibiting full-color emission and circularly polarized luminescence (CPL) with high luminescence dissymmetry factor (glum) values (∼3 × 10-3) were successfully obtained by doping dye molecules into the chiral crystalline metal cluster-based matrixes. The dye molecules function as defect inducers and confer fluorescence on the crystals. Studies reveal that electrostatic interactions provide the main impetus in generating defective crystals, and the restricted effect of chiral space and the weak interactions in defect crystal enable the efficient chiral transfer from the intrinsically chiral host silver(I) clusters to achiral luminescent dopants and finally induce them to emit bright CPL. This defect engineering strategy opens a new way to versatile functions for crystalline cluster-based materials.