Tailoring the efficiency of porphyrin molecular frameworks for the electroactivation of molecular N2.

The combination of compositional versatility and topological diversity for the integration of electroactive species into high-porosity molecular architectures is perhaps one of the main appeals of metal-organic frameworks (MOFs) in the field of electrocatalysis. This premise has attracted much interest in recent years, and the results generated have also revealed one of the main limitations of molecular materials in this context: low stability under electrocatalytic conditions. Using zirconium MOFs as a starting point, in this work, we use this stability as a variable to discriminate between the most suitable electrocatalytic reaction and specific topologies within this family. Our results revealed that the PCN-224 family is particularly suitable for the electroreduction of molecular nitrogen for the formation of ammonia with faradaic efficiencies above 30% in the presence of Ni2+ sites, an activity that improves most of the catalysts described. We also introduce the fluorination of porphyrin at the meso position as a good alternative to improve both the activity and stability of this material under electrocatalytic conditions.

Revealing the Intrinsic Restructuring of Bi2O3 Nanoparticles into Bi Nanosheets during Electrochemical CO2 Reduction.

Bismuth is a catalyst material that selectively produces formate during the electrochemical reduction of CO2. While different synthesis strategies have been employed to create electrocatalysts with better performance, the restructuring of bismuth precatalysts during the reaction has also been previously reported. The mechanism behind the change has, however, remained unclear. Here, we show that Bi2O3 nanoparticles supported on Vulcan carbon intrinsically transform into stellated nanosheet aggregates upon exposure to an electrolyte. Liquid cell transmission electron microscopy observations first revealed the gradual restructuring of the nanoparticles into nanosheets in the presence of 0.1 M KHCO3 without an applied potential. Our experiments also associated the restructuring with solubility of bismuth in the electrolyte. While the consequent agglomerates were stable under moderate negative potentials (-0.3 VRHE), they dissolved over time at larger negative potentials (-0.4 and -0.5 VRHE). Operando Raman spectra collected during the reaction showed that under an applied potential, the oxide particles reduced to metallic bismuth, thereby confirming the metal as the working phase for producing formate. These results inform us about the working morphology of these electrocatalysts and their formation and degradation mechanisms.

Electrochemical Reduction of CO2 to Formate on Easily Prepared Carbon-Supported Bi Nanoparticles.

Herein, the electrochemical reduction of CO2 to formate on carbon-supported bismuth nanoparticles is reported. Carbon-supported Bi nanoparticles (about 10 nm in size) were synthesized using a simple, fast and scalable approach performed under room conditions. The so-prepared Bi electrocatalyst was characterized by different physicochemical techniques, including transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction and subsequently air-brushed on a carbon paper to prepare electrodes. These electrodes were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy and also by cyclic voltammetry. Finally, CO2 electroreduction electrolyses were performed at different electrode potentials for 3 h. At the optimal electrode potential (-1.6 V vs AgCl/Ag), the concentration of formate was about 77 mM with a faradaic efficiency of 93 ± 2.5%. A 100% faradaic efficiency was found at a lower potential (-1.5 V vs AgCl/Ag) with a formate concentration of about 55 mM. In terms of stability, we observed that after about 70 h (in 3 h electrolysis experiments at different potentials), the electrode deactivates due to the gradual loss of metal as shown by SEM/EDX analyses of the deactivated electrodes.