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Evaluating Copper-Modified Carbon Composite Nanofiber Electrodes for Electrocatalytic Nitrate Reduction
Ashley Hesterberg Butzlaff1, Abdulsattar H Ghanim2, Yun Young Choi3
1Department of Civil and Environmental Engineering, University of Iowa, Iowa City, Iowa 52242, United States.
Abstract:
The increasing urgency to address nitrate (NO3 -) pollution in water sources has intensified research on electrochemical nitrate reduction, a process capable of transforming NO3 - into valuable ammonia (NH3) by using renewable electricity. Copper (Cu) catalysts can reduce NO3 -, but their activity and selectivity toward NH3 can vary based on their structure, reaction environment, and support material. This study examines the efficacy of Cu-modified carbon nanofiber (CNF) supports, tailored through electrospinning, in enhancing the electrocatalytic reduction of NO3 - to NH3. Three variants of CNF supports were synthesized: pristine CNFs, CNFs integrated with carbon nanotubes (CNF/CNTs), and CNFs embedded with titanium dioxide nanoparticles (CNF/TiO2). Each electrode's physical and electrochemical properties were analyzed before and after Cu electrodeposition. Notably, the CNF/TiO2/Cu composites demonstrated a selectivity exceeding 40% for the conversion of NO3 - to NH3 at neutral pHsignificantly outperforming the CNF/CNT/Cu (<5%) and CNF/Cu (20%) configurations when deposited with equivalent amounts of Cu. The CNF/TiO2/Cu electrode also exhibited consistent and stable performance over the extended experimental duration (|Q| = 70 C), maintaining NH3 selectivity rates of over 50%. Tafel analysis and operando Raman spectroscopy suggest that TiO2 plays an active role in hydrogenating nitrogenous reduction products for enhanced selectivity. This research highlights the importance of electrode-catalyst selection in electrochemical NO3 - reduction and identifies TiO2-containing electrodes as promising solutions in this domain.

