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  1. Abstract

    The conversion of waste CO2to value‐added chemicals through electrochemical reduction is a promising technology for mitigating climate change while simultaneously providing economic opportunities. The use of non‐aqueous solvents like methanol allows for higher CO2availability and novel products. In this work, the electrochemistry of CO2reduction in acidic methanol catholyte at a Pb working electrode was investigated while using a separate aqueous anolyte to promote a sustainable water oxidation half‐reaction. The selectivity among methyl formate (a product unique to reduction of CO2in methanol), formic acid, and formate was critically dependent on the catholyte pH, with higher pH conditions leading to formate and low pH favoring methyl formate. The potential dependence of the product distribution in acidic catholyte was also investigated, with a faradaic efficiency for methyl formate as high as 75 % measured at −2.0 V vs. Ag/AgCl.

     
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  2. Free, publicly-accessible full text available September 1, 2024
  3. Increasing fossil fuel demands and growing concerns of global climate change have stimulated interest in the development of electrocatalysts to produce H 2 as an alternative zero-emission fuel from the electrolysis of water via hydrogen evolution reaction (HER). Precious or non-precious catalysts are typically loaded on high surface area carbon materials, and these supports play a critical role in both thermodynamics and kinetics of the HER. In this paper, we evaluate the electrocatalytic activity of a molecular hydrogen evolving catalyst, diacetyl-bis(4-methyl)-3-thiosemicarbazone Ni( ii ) (Ni-ATSM), on three different carbon surfaces: glassy carbon, carbon paste and pencil graphite. The overpotential for each modified electrode was benchmarked at a current density of −10 mA cm −2 . Carbon paste electrodes showed highest overpotentials (495 mV) compared to the other electrode surfaces. Polished pencil and glassy carbon modified electrodes performed similarly ( η = 395 mV for GCE and η = 400 mV for pencil). Pencil electrodes etched in acetone overnight prior to Ni-ATSM deposition produced lowest overpotentials ( η = 354 mV). Etching results in an increase in electroactive surface area and substantial decrease in the charge transfer resistance of the graphitic interface from 275 Ω to 50 Ω, verified using electrochemical impedance spectroscopy (EIS). Our studies demonstrate pencil graphite may serve as versatile, disposable, cost effective, and reproducible electrode surface for the evaluation of heterogeneous HER catalysts. Moreover, pencils can be easily cut with table saw to generate new surface for easy characterization of the surface such as electrochemistry, imaging and spectroscopy. 
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