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This study reports the accuracy and applications of an attenuated total reflectance–surface-enhanced infrared absorption spectroscopy (ATR–SEIRAS) technique to indirectly measure the interfacial pH of the electrolyte within 10 nm of the electrocatalyst surface. This technique can be used in situ to study aqueous electrochemical reactions with a calibration range from pH 1–13, time resolution down to 4 s, and an average 95% confidence interval of 14% that varies depending on the pH region (acidic, neutral, or basic). The method is applied here to electrochemical nitrate reduction at a copper cathode to demonstrate its capabilities, but is broadly applicable to any aqueous electrochemical reaction (such as hydrogen evolution, carbon dioxide reduction, or oxygen evolution) and the electrocatalyst may be any SEIRAS-active thin film (e.g., silver, gold, or copper). The time-resolved results show a dramatic increase in the interfacial pH from pH 2–7 in the first minute of operation during both constant current and pulsed current experiments where the bulk pH is unchanged. Attempts to control the pH polarization at the surface by altering the electrochemical operating conditions—lowering the current or increasing the pulse frequency—showed no significant change, demonstrating the challenge of controlling the interfacial pH.

 

Ammonia is an essential compound to modern society, underpinning fertilizer production and chemical manufacturing. Global ammonia demand currently exceeds 150 million tons a year and is projected to increase over 2% annually. Over 96% of ammonia is currently generated through the Haber-Bosch (HB) process, in which steam-reformed hydrogen reacts with nitrogen under reaction conditions that consume 1–2% of global energy and contribute 1.2–1.4% of anthropogenic CO2 emissions every year. In an environmental context, ammonia is a form of reactive nitrogen. Large amounts of reactive nitrogen, such as HB ammonia, accumulate in the biosphere because 80% of wastewater globally is discharged without treatment. The resulting skew in the global nitrogen cycle leads to imbalanced ecosystems and threatens water quality. Conventional water treatment removes reactive nitrogen by converting it to N2 (biological nitrification–denitrification); at HB facilities, the N2 is then cycled back to produce ammonia. Directly valorizing reactive nitrogen in waste streams would shortcut the use of N2 as an intermediate in water remediation and ammonia production, allowing savings in energy, emissions, and costs. Indeed, treating nitrogen as a resource to recover rather than simply a pollutant to remove aligns with the US National Academy of Engineering’s call to manage the nitrogen cycle, a challenge central to chemical manufacturing and ecosystem protection. 

Removal of pharmaceuticals in source-separated urine is an important step toward gaining acceptance of urine-derived fertilizers among important stakeholders such as consumers, farmers, and regulatory agencies. Advanced oxidation processes (AOPs) have been studied for the removal of pharmaceuticals in various complex matrices, including treated wastewaters. A complexity associated with AOP methods that rely primarily on hydroxyl radicals as the oxidizing agents is that they readily lose effectiveness in the presence of scavengers. Here, we investigated the potential for capturing the synergistic effects of producing multiple oxidative chemical species simultaneously in a plasma reactor to oxidize six pharmaceuticals (acetaminophen, atenolol, 17α-ethynyl estradiol, ibuprofen, naproxen, and sulfamethoxazole) in source-separated urine being processed into a fertilizer. The results show that the plasma reactor produced hydroxyl radicals as the primary oxidizing agent and the effects of other oxidizing species were minimal. Plasma experienced scavenging in both fresh and hydrolyzed urine; furthermore, it oxidized pharmaceuticals at similar rates across both matrices. Additionally, the negative impacts of electrical discharge formation stemming from increased solution conductivity appeared to plateau. The energy required per order of magnitude of pharmaceutical transformed was up to 2 orders of magnitude higher for plasma than for a traditional UV/H 2 O 2 reactor and depended upon the matrix. Despite scavenging and energy concerns, plasma can oxidize pharmaceuticals in fresh and hydrolyzed urine and is worthy of further development for on-site or building-scale applications where the value of convenience, simplicity, and performance offsets energy efficiency concerns.