Electrochemically converting nitrate, a widespread water pollutant, back to valuable ammonia is a green and delocalized route for ammonia synthesis, and can be an appealing and supplementary alternative to the Haber-Bosch process. However, as there are other nitrate reduction pathways present, selectively guiding the reaction pathway towards ammonia is currently challenged by the lack of efficient catalysts. Here we report a selective and active nitrate reduction to ammonia on Fe single atom catalyst, with a maximal ammonia Faradaic efficiency of ~ 75% and a yield rate of up to ~ 20,000 μg h−1 mgcat.−1 (0.46 mmol h−1 cm−2). Our Fe single atom catalyst can effectively prevent the N-N coupling step required for N2 due to the lack of neighboring metal sites, promoting ammonia product selectivity. Density functional theory calculations reveal the reaction mechanisms and the potential limiting steps for nitrate reduction on atomically dispersed Fe sites.
As renewable electricity prices continue to decline, interest grows in alternative routes for the synthesis of sustainable fuels and chemicals, including ammonia. Considering demand for fertilizers, as well as its future potential as a dispatchable energy vector, sustainable synthesis of ammonia is being explored as an alternative to the capital- and carbon-intensive fossil-fuel-driven Haber–Bosch process. Here we assess stages along a transition to the sustainable synthesis of ammonia, looking at economic feasibility and climate impacts compared to the incumbent Haber–Bosch without and with CO2 capture. This analysis enables us to suggest technological thresholds for sustainable synthesis of ammonia to become economically and environmentally favourable. When driven by renewable energy sources, the water electrolyzer (near $400 per kW) coupled Haber–Bosch process will reach cost parity near 2.5 cents per kWh electricity. In the case of direct electrochemical ammonia synthesis, achieving cost-parity using the same 2.5 cents per kWh electricity will rely on achieving major advances in performance: an electrolysis full-cell energy efficiency exceeding 40% at a current density of 0.5 A cm−2. Once this operating performance is reached, electrically-powered ammonia synthesis will bring climate benefits when coupled with low-carbon electricity (<180 gCO2e per kWh), achievable when over half of today's U.S. electricity generation is supplied by renewable energy sources. We conclude with a forward-looking perspective on the key challenges and opportunities for sustainable ammonia synthesis routes to be competitive with the incumbent Haber–Bosch process in the future.
Due to their ability to differentiate into cell types from all the three germ layers and their potential unlimited capacity for expansion, embryonic stem cells have tremendous potential to treat diseases and injuries. Spontaneous differentiation of human embryonic stem cells (hESCs) is influenced by the size of the differentiating embryoid bodies (EBs). To further understand the dynamics between nutrient mass transfer, EB size, and stem cell differentiation, a transient mass diffusion model of a single hESC EB was constructed. The results revealed that the oxygen concentration at the centers of large EBs (400-µm radius) was 50% lower when compared to that in smaller EBs (200-µm radius). In addition, the concentration profile of cytokines within an EB depended strongly on their depletion rate, with higher depletion rates resulting in cytokine concentrations that varied significantly throughout the EB. A comparison of the results of our model with published experimental data reveals a close correlation between the fraction of cells that differentiate to a given lineage and the fraction of cells exposed to different oxygen or cytokine concentrations. This, along with other data from the literature, suggests that diffusive mass transfer influences the differentiation of hESCs within EBs by controlling the spatial distribution of soluble factors. This has important implications for research involving the differentiation of embryonic stem cells in EBs, as well as for bioprocess design and the development of robust differentiation protocols where mass transfer could be altered to control the cell differentiation trajectory.