Temperature promotes selectivity during electrochemical CO2 reduction on NiO:SnO2 nanofibers.

Electrolyzers operate over a range of temperatures; hence, it is crucial to design electrocatalysts that do not compromise the product distribution unless temperature can promote selectivity. This work reports a synthetic approach based on electrospinning to produce NiO:SnO2 nanofibers (NFs) for selectively reducing CO2 to formate above room temperature. The NFs comprise compact but disjoined NiO and SnO2 nanocrystals identified with STEM. The results are attributed to the segregation of NiO and SnO2 confirmed with XRD. The NFs are evaluated for the CO2 reduction reaction (CO2RR) over various temperatures (25, 30, 35, and 40 °C). The highest faradaic efficiencies to formate (FEHCOO- ) are reached by NiO:SnO2 NFs containing 50% of NiO and 50% SnO2 (NiOSnO50NF), and 25% of NiO and 75% SnO2 (NiOSnO75NF), at an electroreduction temperature of 40 °C. At 40 °C, product distribution is assessed with in situ differential electrochemical mass spectrometry (DEMS), recognizing methane and other species, like formate, hydrogen, and carbon monoxide, identified in an electrochemical flow cell. XPS and EELS unveiled the FEHCOO- variations due to a synergistic effect between Ni and Sn. DFT-based calculations reveal the superior thermodynamic stability of Ni-containing SnO2 systems towards CO2RR over the pure oxide systems. Furthermore, computational surface Pourbaix diagrams showed that the presence of Ni as a surface dopant increases the reduction of the SnO2 surface and enables the production of formate. Our results highlight the synergy between NiO and SnO2, which can promote the electroreduction of CO2 at temperatures above room temperature.

Characterization of NaTaO3 synthesized by ultrasonic method.

NaTaO(3) perovskite-like materials were synthesized using sodium acetate and tantalum ethoxide as precursors in an ultrasonic bath at room temperature. The pristine sample was thermally treated at 600 °C and characterized using XRD, N(2) physisorption, DRS, SEM and TEM techniques. The structural characterization by X-ray powder diffraction revealed that the crystallization of the NaTaO(3) phase prepared at 600 °C showed agglomerates sizes in the micrometric scale, as confirmed by scanning electron microscopy (SEM). On the other hand, well-defined NaTaO(3) particles in the nanometric scale were determined using TEM. It was found that, for the treated sample, the band gap and BET area was 3.8 eV and 9.5m(2) g(-1), respectively. The annealed perovskite, deposited onto ITO glass, presented an important variation in the open circuit potential transient during UV light irradiation in neutral solution, compared with its counterpart prepared by solid-state method. These intrinsic properties, given by the preparation route, might be appropriate for increase its photocatalytic activity.

Electrochemical behavior of nitrogen gas species adsorbed onto boron-doped diamond (BDD) electrodes.

The adsorption of nitrogen species, in neutral electrolyte solutions, onto boron-doped diamond (BDD) electrode surfaces from dissolved NO2, NO, and N2O gases was induced at 0 V/SCE. Modified BDD electrode surfaces showed a different electrochemical response toward the hydrogen evolution reaction than did a nonmodified electrode surface in electrolyte base solution. The formation of molecular hydrogen and nitrogen gaseous species was confirmed by the online differential electrochemical mass spectrometry (DEMS) technique. Among the three nitrogen oxides gases, NO2 substantially modifies the electrolyte via hydrolysis leading to the formation of NO3- and its adsorption on the BDD electrode surface. The BDD/(NO3-) interface was the only N2O and N2 species generating system.