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Abstract Electrosynthesis, a viable path to decarbonize the chemical industry, has been harnessed to generate valuable chemicals under ambient conditions. Here, we present a membrane-free flow electrolyzer for paired electrocatalytic upcycling of nitrate (NO₃⁻) and chloride (Cl⁻) to ammonia (NH₃) and chlorine (Cl₂) gases by utilizing waste streams as substitutes for traditional electrolytes. The electrolyzer concurrently couples electrosynthesis and gaseous-product separation, which minimizes the undesired redox reaction between NH₃and Cl₂and thus prevents products loss. Using a three-stacked-modules electrolyzer system, we efficiently processed a reverse osmosis retentate waste stream. This yielded high concentrations of (NH₄)₂SO₄(83.8 mM) and NaClO (243.4 mM) at an electrical cost of 7.1 kWh per kilogram of solid products, while residual NH₃/NH₄⁺(0.3 mM), NO₂⁻(0.2 mM), and Cl₂/HClO/ClO⁻(0.1 mM) pollutants in the waste stream could meet the wastewater discharge regulations for nitrogen- and chlorine-species. This study underscores the value of pairing appropriate half-reactions, utilizing waste streams to replace traditional electrolytes, and merging product synthesis with separation to refine electrosynthesis platforms. 

Carbon dioxide (CO2) can be converted into valuable organic chemicals using light irradiation and photocatalysis. Today, light-energy loss, poor conversion efficiency, and low quantum efficiency (QE) hamper application of photocatalytic CO2 reduction. To overcome these drawbacks, we developed an efficient photocatalytic reactor platform for producing formic acid (HCOOH) by coating iron-based metal-organic framework (Fe-MOF) onto side-emitting polymeric optical fiber (POFs) and using hollow-fiber membranes (HFMs) to deliver bubble-free CO2. The photocatalyst, Fe-MoF with amine-group (−NH2) decoration, provided exceptional dissolved inorganic carbon (DIC) absorption. The dual-fiber system gave a CO2-to-HCOOH conversion rate of 116 ± 1.2 mM h-1 g-1, which is ≥18-fold higher than rates in photocatalytic slurry systems. The 12% QE obtained using the POF was 18-fold greater than the QE obtained by a photocatalytic slurry. The conversion efficiency and product selectivity of CO2-to-HCOOH were up to 22% and 99%, respectively. Due to the dual efficiencies of bubble-free CO2 delivery and the high QE achieved using the POF platform, the dual-fiber system had energy consumption of only 0.60 ± 0.05 kWh mole-1, 3000-fold better than photocatalysis using slurry-based systems. This innovative dual-fiber design enables efficient CO2 valorization without use of platinum group metals or rare earth elements. 

Quaternary ammonium compounds (QAC, e.g., cetyltrimethylammonium bromide, (CTAB)) are widely used as surfactants and disinfectants. QAC already are commonly found in wastewaters, and their concentration could increase, since QAC are recommended to inactivate the SARS-CoV-2 (COVID-19) virus. Exposure of bacteria to QAC can lead to proliferation of antibiotic resistance genes (ARG). In particular, O2-based membrane biofilm reactors (O2-MBfRs) achieved excellent CTAB biodegradation, but ARG increased in their biofilms. Here, we applied meta-transcriptomic analyses to assess the impacts of CTAB exposure and operating conditions on microbial community's composition and ARG expression in the O2-MBfRs. Two opportunistic pathogens, Pseudomonas aeruginosa and Stenotrophomonas maltophilia, dominated the microbial communities and were associated with the presence of ARG. Operating conditions that imposed stress on the biofilms, i.e., limited supplies of O2 and nitrogen or a high loading of CTAB, led to large increases in ARG expression, particularly for genes conferring antibiotic-target protection. Important within the efflux pumps was the Resistance-Nodulation-Division (RND) family, which may have been active in exporting CTAB from cells. Oxidative stress appeared to be the key factor that triggered ARG proliferation by selecting intrinsically resistant species and accentuating the expression of ARG. Our findings suggest that means to mitigate the spread of ARG, such as shown here in a O2-based membrane biofilm reactor, need to consider the impacts of stressors, including QAC exposure and stressful operating conditions.