RESUMEN
The electrocatalytic reduction of carbon dioxide (CO2RR) into value-added fuels is a promising initiative to overcome the adverse effects of CO2 on climate change. Most electrocatalysts studied, however, overlook the harmful mining practices used to extract these catalysts in pursuit of achieving high-performance. Repurposing scrap metals to use as alternative electrocatalysts would thus hold high privilege even at the compromise of high performance. In this work, we demonstrated the repurposing of scrap brass alloys with different Zn content for the conversion of CO2 into carbon monoxide and formate. The scrap alloys were activated towards CO2RR via simple annealing in air and made more selective towards CO production through galvanic replacement with Ag. Upon galvanic replacement with Ag, the scrap brass-based electrocatalysts showed enhanced current density for CO production with better selectivity towards the formation of CO. The density functional theory (DFT) calculations were used to elucidate the potential mechanism and selectivity of the scrap brass catalysts towards CO2RR. The d-band center in the different brass samples with different Zn content was elucidated.
RESUMEN
The electrochemical conversion of carbon dioxide (CO2) to high-value chemicals is an attractive approach to create an artificial carbon cycle. Tuning the activity and product selectivity while maintaining long-term stability, however, remains a significant challenge. Here, we study a series of Au-Pb bimetallic electrocatalysts with different Au/Pb interfaces, generating carbon monoxide (CO), formic acid (HCOOH), and methane (CH4) as CO2 reduction products. The formation of CH4 is significant because it has only been observed on very few Cu-free electrodes. The maximum CH4 formation rate of 0.33 mA cm-2 was achieved when the most Au/Pb interfaces were present. In situ Raman spectroelectrochemical studies confirmed the stability of the Pb native substoichiometric oxide under the reduction conditions on the Au-Pb catalyst, which seems to be a major contributor to CH4 formation. Density functional theory simulations showed that without Au, the reaction would get stuck on the COOH intermediate, and without O, the reaction would not evolve further than the CHOH intermediate. In addition, they confirmed that the Au/Pb bimetallic interface (together with the subsurface oxygen in the model) possesses a moderate binding strength for the key intermediates, which is indeed necessary for the CH4 pathway. Overall, this study demonstrates how bimetallic nanoparticles can be employed to overcome scaling relations in the CO2 reduction reaction.
RESUMEN
CuO nanostructures (NSs) of different morphologies were prepared, applied as catalysts for the pyrolysis of sugarcane bagasse (PSCB), and applied for thermally-conductive nanofluids. Both size and shape of the prepared NSs ranged from 5 to 1000 nm, and from nanodots (NDs) to spindle nano-aggregates (NAs), respectively. The catalytic activity of these NSs towards the PSCB was followed up by thermogravimetric analysis (TGA), where they increased the percentage of total weight loss, and lowered the decomposition temperatures of PSCB. The Coats-Redfern kinetic model showed a decline in activation energy by 57 and 9-43 kJ mol-1 for NDs and NAs, respectively. Colloidal dispersions of CuO NDs and NAs in monoethylene glycol (MEG) were prepared with volume fractions ([Formula: see text]) of 0.01-0.04%, where thermal conductivity improved with increasing [Formula: see text]. At all values of [Formula: see text], the best enhancements were exerted by NDs. The nature of assembly impacted the catalyzed PSCB and the thermal conductivity of MEG. This behavior depends to a large extent on the NAs that expose a different fraction of crystal facets of different reactivities and surface areas, not on the constituent nanorods (NRs).
