RESUMEN
Alloys with bimetallic electron modulation effect are promising catalysts for the electrooxidation of urea. However, the side reaction oxygen evolution reaction (OER) originating from the competitive adsorption of OH- and urea severely limited the urea oxidation reaction (UOR) activity on the alloy catalysts. This work successfully constructs the defect-rich NiCo alloy with lattice strain (PMo-NiCo/NF) by rapid pyrolysis and co-doping. By taking advantage of the compressive strain, the d-band center of NiCo is shifted downward, inhibiting OH- from adsorbing on the NiCo site and avoiding the detrimental OER. Meanwhile, the oxygenophilic P/Mo tailored specific adsorption sites to adsorb OH- preferentially, which further released the NiCo sites to ensure the enriched adsorption of urea, thus improving the UOR efficiency. As a result, PMo-NiCo/NF only requires 1.27 V and -57 mV to drive a current density of ±10 mA cm-2 for UOR and hydrogen evolution reaction (HER), respectively. With the guidance of this work, reactant competing adsorption sites could be tailored for effective electrocatalytic performance.
RESUMEN
Adsorption on activated carbon is a common process to remove pharmaceuticals in wastewater treatment. Activated carbon adsorption is usually applied to wastewater with a low content of biological degradable organics, i.e. after biological treatment. Especially low molecular weight (LMW) compounds are known to compete with pharmaceuticals for adsorption sites. The goal of this study was to test the hypothesis that biological treatment is necessary for efficient pharmaceutical removal. Source-separated urine after anaerobic storage (anaerobically stored urine) and after aerobic biological removal of organics without nitrification (organics-depleted urine) were used in this study. In anaerobically stored urine 60% of the organic compounds were LMW organics, of which about 40% were acetate and propionate. 74% of the DOC and 100% of acetate and propionate were removed during aerobic biological treatment. To investigate the effect of the organic compounds on pharmaceutical removal, sorption experiments with 19 spiked pharmaceuticals and one artificial sweetener were conducted with powdered activated carbon. Ethanol, another LMW organic, was included in the study, as it is regularly used for pharmaceutical spiking thereby strongly increasing the DOC content. The experiments showed that the adsorption of the pharmaceuticals and the sweetener were hardly affected by the easily biodegradable LMW organics or ethanol. Therefore, it was concluded that biological pre-treatment is not necessary for efficient pharmaceutical adsorption. Since acetate, propionate and ethanol contribute substantially to the DOC content but do not absorb UV light, the latter is recommended as indicator for pharmaceutical removal in solutions with high contents of biodegradable LMW organics.