Amine-based synthesis of Fe3C nanomaterials: mechanism and impact of synthetic conditions

Iron-based catalysts are a preferred variant of metal catalysts due to the high abundance of iron on earth. Iron carbide has been investigated in recent times as an electrochemical catalyst due to its potential as a great ORR catalyst. Using a unique amine-metal complex anion composite (AMAC) method, iron carbide/nitride nanoparticles (Fe3C and Fe3−x N) were synthesized through varying several reaction parameters. While the synthesis is generally quite robust and can easily afford phase pure Fe3C, it now has been shown that the particle size, morphology, excess carbon, and amount of nitrogen in the resulting nanomaterials can readily be tuned. In addition, it was discovered that Fe2N can be synthesized as an intermediate by stopping the reaction at a lower heating temperature. These nanomaterials were tested for their electrochemical activity in oxygen evolution reactions (OER).

A Water-Soluble Sodium Pectate Complex with Copper as an Electrochemical Catalyst for Carbon Dioxide Reduction

A selective noble-metal-free molecular catalyst has emerged as a fruitful approach in the quest for designing efficient and stable catalytic materials for CO2 reduction. In this work, we report that a sodium pectate complex of copper (PG-NaCu) proved to be highly active in the electrocatalytic conversion of CO2 to CH4 in water. Stability and selectivity of conversion of CO2 to CH4 as a product at a glassy carbon electrode were discovered. The copper complex PG-NaCu was synthesized and characterized by physicochemical methods. The electrochemical CO2 reduction reaction (CO2RR) proceeds at −1.5 V vs. Ag/AgCl at ~10 mA/cm2 current densities in the presence of the catalyst. The current density decreases by less than 20% within 12 h of electrolysis (the main decrease occurs in the first 3 h of electrolysis in the presence of CO2). This copper pectate complex (PG-NaCu) combines the advantages of heterogeneous and homogeneous catalysts, the stability of heterogeneous solid materials and the performance (high activity and selectivity) of molecular catalysts.

Proton Exchange Membrane Fuel Cells (PEMFCs): Advances and Challenges

The study of the electrochemical catalyst conversion of renewable electricity and carbon oxides into chemical fuels attracts a great deal of attention by different researchers. The main role of this process is in mitigating the worldwide energy crisis through a closed technological carbon cycle, where chemical fuels, such as hydrogen, are stored and reconverted to electricity via electrochemical reaction processes in fuel cells. The scientific community focuses its efforts on the development of high-performance polymeric membranes together with nanomaterials with high catalytic activity and stability in order to reduce the platinum group metal applied as a cathode to build stacks of proton exchange membrane fuel cells (PEMFCs) to work at low and moderate temperatures. The design of new conductive membranes and nanoparticles (NPs) whose morphology directly affects their catalytic properties is of utmost importance. Nanoparticle morphologies, like cubes, octahedrons, icosahedrons, bipyramids, plates, and polyhedrons, among others, are widely studied for catalysis applications. The recent progress around the high catalytic activity has focused on the stabilizing agents and their potential impact on nanomaterial synthesis to induce changes in the morphology of NPs.

Fabrication of Soft-Oxometalates {Mo132} Clusters With Novel Azobenzene Surfactants: Size Control by Micelles and Light

Soft-oxometalates (SOMs) are colloid suspensions of superstructured assemblies of polyoxometalates (POMs) and are found to be very effective photo-catalysts in a number of chemical reactions. The stabilization of SOMs generally requires legends or stabilizers, e.g., polymers and surfactants. In this paper, a light responsive azobenzene surfactant, C10AZOC2N3, was developed and used to stable {Mo132} SOMs. Various techniques such as Dynamic light scattering, TEM, UV-Vis spectra and cyclic voltammetry were employed to characterize the experimental results. The outstanding structure-directing effect of surfactant self-assembly micelles in solution on inorganic counter-anions was demonstrated. Different amount of cyclohexane was solubilized into C10AZOC2N3 micelles to successfully control the size of {Mo132} SOMs cluster. Furthermore, the clusters exposed to UV light for a certain time can be served as a second trigger to control the size of SOMs due to the trans-cis conformation transition of surfactant molecules. The redox potentials of C10AZOC2N3-{Mo132} SOMs were investigated as the cluster size varied. Interestingly, the redox potential of {Mo132} was not affected by the cluster size, indicating that the presence of surfactant did not change the main function of {Mo132} as an electrochemical catalyst, but merely assisted in the size control of SOM aggregation.

Bayesian data analysis reveals no preference for cardinal Tafel slopes in CO2 reduction electrocatalysis

The Tafel slope is a key parameter often quoted to characterize the efficacy of an electrochemical catalyst. In this paper, we develop a Bayesian data analysis approach to estimate the Tafel slope from experimentally-measured current-voltage data. Our approach obviates the human intervention required by current literature practice for Tafel estimation, and provides robust, distributional uncertainty estimates. Using synthetic data, we illustrate how data insufficiency can unknowingly influence current fitting approaches, and how our approach allays these concerns. We apply our approach to conduct a comprehensive re-analysis of data from the CO2 reduction literature. This analysis reveals no systematic preference for Tafel slopes to cluster around certain "cardinal values” (e.g. 60 or 120 mV/decade). We hypothesize several plausible physical explanations for this observation, and discuss the implications of our finding for mechanistic analysis in electrochemical kinetic investigations.

Carbon Nanotube Supported Amorphous MoS2 via Microwave Heating Synthesis for Enhanced Performance of Hydrogen Evolution Reaction

Amorphous molybdenum disulfide (MoS2) is a promising electrochemical catalyst for hydrogen evolution reaction (HER) due to more active sites exposed on the surface compared to its crystalline counterpart. In this study, a novel fast three-minute one-pot method is proposed to prepare the single-wall carbon nanotube- (SWCNT-) supported amorphous MoS2 via a microwave heating process. Compared to traditional hydro- or solvent thermal methods to prepare MoS2 which usually consume more than 10 hours, it is more promising for fast production. An overpotential at 10 mA/cm2 of amorphous MoS2@SWCNT is 178 mV, which is 99 mV and 22 mV lower than crystalline MoS2@SWCNT and pure amorphous MoS2, respectively. After running 1000 cycles of polarization, ~2% increase in overpotential is observed, indicating its good stability. The enhanced performance results from the beneficial combination of the SWCNT substrate and the amorphous microstructures. The introduction of SWCNT increases catalyst conductivity and prevents MoS2 aggregation. The amorphous microstructures of MoS2 prepared by a microwave heating method lead to more Mo edges or active sites exposed.