Nitrate electroreduction reaction (NO₃RR) to ammonia (NH₃) still faces fundamental and technological challenges. While Cu-based catalysts have been widely explored, their activity and stability relationship are still not fully understood. Here, we systematically monitored the dynamic alterations in the chemical and morphological characteristics of Cu₂O nanocubes (NCs) during NO₃RR in an alkaline electrolyte. In 1 h of electrolysis from -0.10 to -0.60 V vs RHE, the electrocatalyst achieved the maximum NH₃ faradaic efficiency (FE) and yield rate at -0.3 V (94% and 149 μmol h^-1 cm^-2, respectively). Similar efficiency could be found at a lower overpotential (-0.20 V vs RHE) in long-term electrolysis. At -0.20 V vs RHE, the catalyst FE increased from 73% in the first 2 h to ∼90% in 10 h of electrolysis. Electron microscopy revealed the loss of the cubic shape with the formation of sintered domains. In situ Raman, X-ray diffraction (XRD), and in situ Cu K-edge X-ray absorption near-edge spectroscopy (XANES) indicated the reduction of Cu₂O to oxide-derived Cu⁰ (OD-Cu). Nevertheless, a remaining Cu₂O phase was noticed after 1 h of electrolysis at -0.3 V vs RHE. This observation indicates that the activity and selectivity of the initially well-defined Cu₂O NCs are not solely dependent on the initial structure. Instead, it underscores the emergence of an OD-Cu-rich surface, evolving from near-surface to underlying layers over time and playing a crucial role in the reaction pathways. By employing online differential electrochemical mass spectrometry (DEMS) and in situ Fourier transform infrared spectroscopy (FTIR), we experimentally probed the presence of key intermediates (NO and NH₂OH) and byproducts of NO₃RR (N₂ and N₂H _x ) for NH₃ formation. These results show a complex relationship between activity and stability of the nanostructured Cu₂O oxide catalyst for NO₃RR.

Obtaining CO and H₂ from electrochemical CO₂ reduction (CO₂RR) offers a viable alternative to reduce CO₂ emissions and produce chemicals and fuels. Herein, we report a simple strategy for obtaining polycrystalline copper deposited on oxidized graphite felt (Cu-OGF) and its performance on the selective conversion of CO₂ and H₂O to CO and H₂. For the electrode obtaining, graphite felt (GF) was first oxidized (OGF) in order to make the substrate hydrophilic and then copper particles were electrochemically deposited onto OGF. The pH of deposition was investigated, and the CO₂RR activity was assessed for the prepared electrodes at each pH (2.0, 4.0, 6.0, 8.0, and 10.0). It was found that pH 2.0 was the most promising for CO₂RR due to the presence of hexagonal copper microparticles. Fourier transform infrared analysis of the produced gases showed that this is a low-cost catalyst capable of reducing CO₂ and H₂O to CO and H₂, with Faradaic efficiencies between 0.50 and 5.21% for CO and 50.87 to 98.30% for H₂, depending on the experimental conditions. Hence, it is possible for this gas mixture to be used as a fuel gas or to be enriched with CO for use in Fischer-Tropsch processes.

Gelatin (GE), amino-functionalized polyphenolic tannin derivative (TN), and graphene oxide (GO) were associated to yield thermo- and pH-responsive hydrogels for the first time. Durable hydrogel assemblies for drug delivery purposes were developed using the photosensitizer methylene blue (MB) as a drug model. The cooling GE/TN blends provide brittle physical assemblies. To overcome this disadvantage, different GO contents (between 0.31% and 1.02% wt/wt) were added to the GE/TN blend at 89.7/10.3 wt/wt. FTIR and RAMAN spectroscopy analyses characterized the materials, indicating GO presence in the hydrogels. Incorporation studies revealed a total MB (0.50 mg/mL) incorporation into the GE/TN-GO hydrogel matrices. Additionally, the proposed systems present a mechanical behavior similar to gel. The GO presence in the hydrogel matrices increased the elastic modulus from 516 to 1650 Pa. SEM revealed that hydrogels containing MB present higher porosity with interconnected pores. Dissolution and swelling degree studies revealed less stability of the GE/TN-GO-MB hydrogels in SGF medium (pH 1.2) than SIF (pH 6.8). The degradation increased in SIF with the GO content, making the polymeric matrices more hydrophilic. MB release studies revealed a process controlled by Fickian diffusion. Our results point out the pH-responsible behavior of mechanically reinforced GE/TN-GO-MB hydrogels for drug delivery systems purposes.