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1. Advanced Reactor Design for Ammonia Production from Electrochemical Nitrogen and Nitrate Reduction

   Yifu Chen, Wenzhen Li (November 2021, AIChE 2021 Annual Conference)

   Motivated by the increasing demand for flexible and sustainable routes of ammonia (NH3) production, the electrochemical nitrogen (N2) and nitrate reduction reaction (NRR and NO3RR) have attracted intense research interest in the past few years1,2. Compared to the centralized Haber-Bosch process that operates at elevated temperature and pressure, the electrochemical pathway features mild operating conditions but high input energy density, allowing for distributed and on-site generation of NH3 with water as the proton source, thereby reducing the transportation and storage costs of NH3 and H23. Besides N2 which is highly abundant in the atmosphere, nitrate-N exists widely in agricultural and industrial wastewaters, and its presence has raised severe concerns due to its known impacts on the environment and human health4,5. In this regard, NO3RR provides a promising strategy of simultaneously removing the harmful nitrate-N and generating NH3 as a useful product from those wastewater streams. While research activities on both NRR and NO3RR are blooming with substantial progress in the field of electrocatalysis, some major challenges remain unnoticed or unresolved so far. Due to the wide existence of reactive N-containing species in laboratory environments, the source of NH3 in NRR measurements is sometimes elusive and requires rigorous examination by control experiments with costly 15N26,7. On the other hand, while the electro-reduction of nitrate is much more facile, additional costs arising from the enrichment and purification of nitrate in contaminated waste resources have challenged the practical feasibility of NO3RR both technically and economically2. In this talk, we will present our latest research progress as part of the solutions to these challenges in state-of-the-art NRR and NO3RR studies, from the perspective of reactor design. By taking advantage of the prior developments in 15N2 control experiments, here we suggest an improved 15N2 circulation system that is effective and affordable for NRR research, allowing for more accurate and economized quantitative assessment of NH3 origins, so that false positives and subtle catalytic activities can be identified more reliably. For NO3RR, we developed a compact reactor system for rapid and efficient electrochemical conversion of nitrate to NH3 from real nitrate-containing waste sources, accompanied by the concurrent separation and enrichment of the produced NH3 in a trapping solution to yield pure ammonium compounds. Our work highlights the importance of advanced reactor design in N-related electrochemistry research, which will facilitate the transformation of the current N-centric chemical industries towards a sustainable future. 

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2. Reports from the Frontier: Electrifying Chemical Transformations and Separations to Valorize Wastewater Nitrogen

   https://doi.org/10.1149/2.F04232IF  

   Liu, Matthew; Tarpeh, William (June 2023, The Electrochemical Society Interface)

   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. 

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3. Unbiased solar H2 production with current density up to 23 mA cm2 by Swiss-cheese black Si coupled with wastewater bioanode

   Lu, L.; Vakki, W.; Aguiar, A. J.; Xiao, C.X.; Hurst, K.; Fairchild, M.; Chen, X.; Yang, F.; Gu, J.* (January 2019, Energy & environmental science)

   Unbiased photoelectrochemical hydrogen production with high efficiency and durability is highly desired for solar energy storage. Here, we report a microbial photoelectrochemical (MPEC) system that demonstrated superior performance when equipped with bioanodes and black silicon photocathode with a unique ‘‘Swiss-cheese’’ interface. The MPEC utilizes the chemical energy embedded in wastewater organics to boost solar H2 production, which overcomes barriers on anode H2O oxidation. Without any bias, the MPEC generates a record photocurrent (up to 23 mA cm2) and retains prolonged stability for over 90 hours with high Faradaic efficiency (96–99%). The calculated turnover number for MoSx catalyst during a 90 h period is 495 471 with an average frequency of 1.53 s1 . The system replaced pure water on the anode with actual wastewater and achieved waste organic removal up to 16 kg COD m2 photocathode per day. Cost credits from concurrent wastewater treatment and low-cost design make photoelectrochemical H2 production practical for the first time 

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4. Green ammonia from air, water, and renewable electricity: Energy costs using natural gas reforming, solid oxide electrolysis, liquid water electrolysis, chemical looping, or a Haber–Bosch loop

   https://doi.org/10.1063/5.0101709  

   Pfromm, Peter H.; Aframehr, Wrya (September 2022, Journal of Renewable and Sustainable Energy)

   The purpose of this work is to quantitatively compare the energy cost of design alternatives for a process to produce ammonia (NH3) from air, water, and renewable electricity. It is assumed that a Haber–Bosch (H–B) synthesis loop is available to produce 1000 metric tons (tonnes) of renewable NH3 per day. The overall energy costs per tonne of NH3 will then be estimated at U.S.$195, 197, 158, and 179 per tonne of NH3 when H2 is supplied by (i) natural gas reforming (reference), (ii) liquid phase electrolysis, (iii) solid oxide electrolysis (SOE) of water only, and (iv) simultaneous SOE of water and air. A renewable electricity price of U.S.$0.02 per kWh electric, and U.S.$6 per 10^6 BTU for natural gas is assumed. SOE provides some energy cost advantage but incurs the inherent risk of an emerging process. The last consideration is replacement of the H–B loop with atmospheric pressure chemical looping for ammonia synthesis (CLAS) combined with SOE for water electrolysis, and separately oxygen removal from air to provide N2, with energy costs of U.S.$153 per tonne of NH3. Overall, the most significant findings are (i) the energy costs are not substantially different for the alternatives investigated here and (ii) the direct SOE of a mixture of steam and air, followed by a H.–B. synthesis loop, or SOE to provide H2 and N2 separately, followed by CLAS may be attractive for small scale production, modular systems, remote locations, or stranded electricity resources with the primary motivation being process simplification rather than significantly lower energy cost. 

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5. Sustainable waste-nitrogen upcycling enabled by low-concentration nitrate electrodialysis and high-performance ammonia electrosynthesis

   https://doi.org/10.1039/D3EY00058C  

   Chen, Yifu; Ammari-Azar, Pouya; Liu, Hengzhou; Lee, Jungkuk; Xi, Yu; Castellano, Michael J.; Gu, Shuang; Li, Wenzhen (March 2023, EES Catalysis)

   Reactive nitrogen (Nr) is an essential nutrient to life on earth, but its mismanagement in waste has emerged as a major problem in water pollution to our ecosystems, causing severe eutrophication and health concerns. Sustainably recovering Nr [such as nitrate (NO3−)–N] and converting it into ammonia (NH3) could mitigate the environmental impacts of Nr, while reducing the NH3 demand from the carbon-intensive Haber–Bosch process. In this work, high-performance NO3−-to-NH3 conversion was achieved in a scalable, versatile, and cost-effective membrane-free alkaline electrolyzer (MFAEL): a remarkable NH3partial current density of 4.22 ± 0.25 A cm−2 with a faradaic efficiency of 84.5 ± 4.9%. The unique configuration of MFAEL allows for the continuous production of pure NH3-based chemicals (NH3 solution and solid NH4HCO3) without the need for additional separation procedures. A comprehensive techno-economic analysis (TEA) revealed the economic competitiveness of upcycling waste N from dilute sources by combining NO3− reduction in MFAEL and a low-energy cost electrodialysis process for efficient NO3− concentration. In addition, pairing NO3− reduction with the oxidation of organic Nr compounds in MFAEL enables the convergent transformation of N–O and C–N bonds into NH3 as the sole N-containing product. Such an electricity-driven process offers an economically viable solution to the growing trend of regional and seasonal Nr buildup and increasing demand for sustainable NH3 with a reduced carbon footprint. 

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