Elucidation of Critical Catalyst Layer Phenomena toward High Production Rates for the Electrochemical Conversion of CO to Ethylene.

This work utilizes EIS to elucidate the impact of catalyst-ionomer interactions and cathode hydroxide ion transport resistance (RCL,OH-) on cell voltage and product selectivity for the electrochemical conversion of CO to ethylene. When using the same Cu catalyst and a Nafion ionomer, varying ink dispersion and electrode deposition methods results in a change of 2 orders of magnitude for RCL,OH- and ca. a 25% change in electrode porosity. Decreasing RCL,OH- results in improved ethylene Faradaic efficiency (FE), up to ∼57%, decrease in hydrogen FE, by ∼36%, and reduction in cell voltage by up to 1 V at 700 mA/cm2. Through the optimization of electrode fabrication conditions, we achieve a maximum of 48% ethylene with >90% FE for non-hydrogen products in a 25 cm2 membrane electrode assembly at 700 mA/cm2 and <3 V. Additionally, the implications of optimizing RCL,OH- is translated to other material requirements, such as anode porosity. We find that the best performing electrodes use ink dispersion and deposition techniques that project well into roll-to-roll processes, demonstrating the scalability of the optimized process.

Investigation of Electrolyte-Dependent Carbonate Formation on Gas Diffusion Electrodes for CO2 Electrolysis.

The electrochemical reduction of CO2 (ECO2R) is a promising method for reducing CO2 emissions and producing carbon-neutral fuels if long-term durability of electrodes can be achieved by identifying and addressing electrode degradation mechanisms. This work investigates the degradation of gas diffusion electrodes (GDEs) in a flowing, alkaline CO2 electrolyzer via the formation of carbonate deposits on the GDE surface. These carbonate deposits were found to impede electrode performance after only 6 h of operation at current densities ranging from -50 to -200 mA cm-2. The rate of carbonate deposit formation on the GDE surface was determined to increase with increasing electrolyte molarity and became more prevalent in K+-containing as opposed to Cs+-containing electrolytes. Electrolyte composition and concentration also had significant effects on the morphology, distribution, and surface coverage of the carbonate deposits. For example, carbonates formed in K+-containing electrolytes formed concentrated deposit regions of varying morphology on the GDE surface, while those formed in Cs+-containing electrolytes appeared as small crystals, well dispersed across the electrode surface. Both deposits occluding the catalyst layer surface and those found within the microporous layer and carbon fiber substrate of the electrode were found to diminish performance in ECO2R, leading to rapid loss of CO production after ∼50% of the catalyst layer surface was occluded. Additionally, carbonate deposits reduced GDE hydrophobicity, leading to increased flooding and internal deposits within the GDE substrate. Electrolyte engineering-based solutions are suggested for improved GDE durability in future work.

Modeling Equilibrium Binding at Quantum Dot Surfaces Using Cyclic Voltammetry.

Cyclic voltammetry is demonstrated as a useful method to model equilibrium binding between quantum dots and redox active small molecules. Specifically, the interaction of a library of ferrocene derivatives with CdSe quantum dots is examined. For the strongly interacting systems, ferrocene carboxylic acid (FcCOOH) and ferrocene hexanethiol (Fc-hexSH), the binding equilibria can be quantitatively deduced by modeling the cyclic voltammetry data. This modeling allows extraction of the diffusion coefficients, equilibrium constants associated with both the reduced and oxidized species, and forward and reverse rates associated with binding for both the reduced and oxidized species. Taken together these data give direct insight into the binding of small molecules to quantum-dot surfaces as a function of oxidation state, critical information for the design of quantum dots as photoredox catalysts and charge transfer mediators.

Improved HER Catalysis through Facile, Aqueous Electrochemical Activation of Nanoscale WSe2.

In the search for nonprecious metal catalysts for the hydrogen evolution reaction (HER), transition metal dichalcogenides (TMDCs) have been proposed as promising candidates. Here, we present a facile method for significantly decreasing the overpotential required for catalyzing the HER with colloidally synthesized WSe2. Solution phase deposition of 2H WSe2 nanoflowers (NFs) onto carbon fiber electrodes results in low catalytic activity in 0.5 M H2SO4 with an overpotential at -10 mA/cm2 of greater than 600 mV. However, two postdeposition electrode processing steps significantly reduce the overpotential. First, a room-temperature treatment of the prepared electrodes with a dilute solution of the alkylating agent Meerwein's salt ([Et3O][BF4]) results in a reduction in overpotential by approximately 130 mV at -10 mA/cm2. Second, we observe a decrease in overpotential of approximately 200-300 mV when the TMDC electrode is exposed to H+, Li+, Na+, or K+ ions under a reducing potential. The combined effect of ligand removal and electrochemical activation results in an improvement in overpotential by as much as 400 mV. Notably, the Li+ activated WSe2 NF deposited carbon fiber electrode requires an overpotential of only 243 mV to generate a current density of -10 mA/cm2. Measurement of changes in the material work function and charge transfer resistance ultimately provide rationale for the catalytic improvement.

A doubly deprotonated diimine dioximate metalloligand as a synthon for multimetallic complex assembly.

An electrocatalytically active cobalt diimine monoxime monoximate complex was deprotonated by 1-methylimidazole affording a doubly deprotonated complex that serves as a versatile precursor for synthesis of a variety of multimetallic complexes with Co-Zn, -Cd, -Mn and -Ru coordination. These complexes were studied using a combination of spectroscopic, analytical and electrochemical techniques, revealing the electronic and structural parameters unique to this new class of compounds. The ability of these complexes to catalyze proton reduction was also investigated. These complexes are homogeneous electrocatalysts for the hydrogen evolution reaction through reduction of [NEt3H][BPh4] in CH3CN, however decompose under extended electrolysis conditions.

A four coordinate parent imide via a titanium nitridyl.

Treatment of d(1) [(nacnac)TiCl(Ntol(2))] with NaN(3) results in NaCl formation and N(2) ejection to yield the first four coordinate, parent imide [(nacnac)Ti=NH(Ntol(2))] (nacnac(-)=[ArNC(CH(3))](2)CH, Ar = 2,6-iPr(2)C(6)H(3), tol = 4-CH(3)C(6)H(4)).