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  1. This work reports a combined experimental and computational study of the activation of an otherwise catalytically inactive cobalt complex, [Co(TIM)Br2]+, for aqueous nitrite reduction. The presence of phosphate buffer leads to efficient electrocatalysis, with rapid reduction to ammonium occurring close to the thermodynamic potential and with high Faradaic efficiency. At neutral pH, increasing buffer concentrations increase catalytic current while simultaneously decreasing overpotential, although high concentrations have an inhibitory effect. Controlled potential electrolysis and rotating ring-disk electrode experiments indicate that ammonium is directly produced from nitrite by [Co(TIM)Br2]+, along with hydroxylamine. Mechanistic investigations implicate a vital role for the phosphate buffer,more »specifically as a proton shuttle, although high buffer concentrations inhibit catalysis. These results indicate a role for buffer in the design of electrocatalysts for nitrogen oxide conversion.« less
    Free, publicly-accessible full text available August 10, 2023
  2. The cobalt pyridinophane complex [Co( H N4)Cl 2 ] + ( H N4 = 3,7-diaza-1,5(2,6)-dipyridinacyclooctaphane) is converted under catalytic conditions to an electrode-adsorbed species. Aqueous Co 2+ solutions similarly deposit a species under these conditions. Surface characterization reveals the formation of Co nanoparticles. These nanoparticles are active in the electrocatalytic redution of aqueous nitrate.
    Free, publicly-accessible full text available March 21, 2023
  3. Free, publicly-accessible full text available November 9, 2022
  4. Over the past century, the global concentration of environmental nitrate has increased significantly from human activity, which has resulted in the contamination of drinking water and aquatic hypoxia around the world, so the development of effective nitrate-reducing agents is urgent. This work compares three potential macrocycle-based nitrate reduction electrocatalysts: [Co(DIM)] 3+ , [Co(cyclam)] 3+ and [Co(TIM)] 3+ . Although all three complexes have similar structures, only [Co(DIM)] 3+ has been experimentally determined to be an active electrocatalyst for selective nitrate reduction to produce ammonia in water. While [Co(cyclam)] 3+ can reduce aqueous nitrate to ammonia and hydroxylamine at heavy metalmore »electrodes, [Co(TIM)] 3+ is inactive for the reduction of nitrate. As an initial step to understanding what structural and electronic properties are important for efficient electrocatalysts for nitrate reduction, density functional theory (DFT) was employed to investigate the electronic structure of the three Co complexes, with the reduction potentials calibrated to experimental results. Moreover, DFT was employed to explore four different reaction mechanisms for the first steps of nitrate reduction. The calculated reaction barriers reveal how a combination of electron transfer in a redox non-innocent complex, substrate binding, and intramolecular hydrogen bonding dictates the activity of Co-based catalysts toward nitrate reduction.« less
  5. Free, publicly-accessible full text available October 27, 2022