RESUMEN
The electrochemical carbon dioxide reduction (CO2RR) on Cu-based catalysts is a promising strategy to store renewable electricity and produce valuable C2+ chemicals. We investigate the CO2RR on Cu-Ag nanostructures that have been electrodeposited in a green choline chloride and urea deep eutectic solvent (DES). We determine the electrochemically active surface area (ECSA) using lead underpotential deposition (UPD) to investigate the CO2RR intrinsic activity and selectivity. We show that the addition of Ag on electrodeposited Cu primarily suppresses the production of hydrogen and methane. While the production of carbon monoxide slightly increases, the partial current of the total C2+ products does not considerably increase. Despite that the production rate of C2+ is similar on Cu and Cu-Ag, the addition of Ag enhances the formation of alcohols and oxygenates over ethylene. We highlight the potential of metal electrodeposition from DES as a sustainable strategy to develop bimetallic Cu-based nanocatalysts for CO2RR.
RESUMEN
Electrocatalytic reactions are sensitive to the catalyst surface structure. Therefore, finding methods to determine active surface sites with different geometry is essential to address the structure-electrocatalytic performance relationships. In this work, we propose a simple methodology to tune and quantify the surface structure on copper catalysts. We tailor the distribution and ratio of facets on copper by electrochemically oxidizing and reducing the surface in chloride-rich aqueous solutions. We then address the formation of new facets with voltammetric lead (Pb) underpotential deposition (UPD). We first record the voltammetric lead UPD on different single facets, which have intense peaks at different potential values. We use this data to decouple each facet peak-contribution in the lead (Pb) UPD curves of the tailored and multifaceted copper surfaces and determine the geometry of the active sites. We combine experiments with density functional theory (DFT) calculations to assess the ligand effect of chloride anions on the copper facet distribution during the surface oxidation/electrodeposition treatment. Our experiments and Wulff constructions suggest that chloride preferentially adsorbs on the (310) facet, reducing the number of (111) sites and inducing the growth of (310) or n(100) × (110) domains. Our work provides a tool to correlate active sites with copper geometries, which is needed to assess the structure-performance relationships in electrocatalysis. We also demonstrate an easy method for selectively tailoring the facet distribution of copper, which is essential to design a well-defined nanostructured catalyst.
RESUMEN
Heating mediated by iron oxide nanoparticles subjected to near infrared irradiation has recently gained lots of interest. The high optical loss values reported in combination with the optical technologies already existing in current clinical practices, have made optical heating mediated by iron oxide nanoparticles an attractive choice for treating internal or skin tumors. However, the identification of the relevant parameters and the influence of methodologies for quantifying the optical losses released by iron oxide nanoparticles are not fully clear. Here, we report on a systematic study of different intrinsic (size, shape, crystallinity, and iron oxidation state) and extrinsic (aggregation, concentration, intracellular environment and irradiation conditions) parameters involved in the photothermal conversion of iron oxide nanoparticles under near infrared irradiation. We have probed the temperature increments to determine the specific loss power of iron oxide nanoparticles with different sizes and shapes dispersed in colloidal suspensions or inside live breast cancer cells. Our results underline the relevance of crystal surface defects, aggregation, concentration, magnetite abundance, excitation wavelength and density power on the modulation of the photothermal conversion. Contrary to plasmonic or magnetic losses, no significant influence of nanoparticle size nor shape was observed on the optical losses released by the studied iron oxide nanoparticles. Interestingly, no significant differences of measured temperature increments and specific loss power values were either observed when nanoparticles were inside live cells or in colloidal dispersion. Our findings highlight the advantages of optical heat losses released by iron oxide nanoparticles for therapeutic applications.