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Electrochemical Synthesis of Ammonia: a Review”, J Electrochemical Synthesis of Why Go Ammonia: A Low Pressure, Open Access at ECS Low Temperature Approach* Reach more readers OA for FREE! by Julie N. Renner, Lauren F. Greenlee, ECS offers Author Choice Open You can publish your papers as Access, giving you the opportunity Open Access for FREE if you have Andrew M. Herring, and Katherine E. Ayers to make your papers Open Access an Article Credit. Authors who are bout half of the people on this planet exist because of the Island Act.3 The guano industry eventually fell to more reliable nitrate (OA) – available to any scientist ECS members, who have attended human mastery of nitrogen.1 The earth’s soil and natural salt deposit mining. By the end of the century, scientists had raised (or anyone, for that matter) with an a recent ECS meeting, or who are processes simply could not support seven billion people the alarm about an impending societal problem — the increasingly Internet connection, and increasing coming from subscribing institutions without modern chemistry enabling the production of large demand for nitrogen compounds and the limited supply.4 your pool of potential readers. qualify. Those who cannot claim an reactive nitrogen compounds from stubbornly inert Scientists began attempting to fix atmospheric nitrogen, resulting in Anitrogen gas. All biological processes depend on nitrogen. It is an the industrialization of various processes in the early 1900s. In 1909, Article Credit will be asked to pay essential component of chlorophyll, proteins, and genetic material. Fritz Haber demonstrated the feasibility of his technique, producing Quality publications an $800 Article Processing Charge to A WORD ABOUT For millions of years, plants have relied on natural mineralization, ammonia from nitrogen and hydrogen gas at high temperatures make their papers Open Access – a COPYRIGHT nitrogen fixing bacteria, or animal waste as their source of more and pressures over a catalyst. Carl Bosch transformed this bench- The research published in fee ECS continues to keep low. reactive nitrogen in the soil. Over this past century, however, the scale demonstration into an unprecedented industrial process as our journals (Journal of The 4 When publishing OA the plants we eat have increasingly relied on chemically synthesized an engineer at BASF, resulting in commercial production in 1913.5 Electrochemical Society, ECS copyright remains with fertilizers to keep up with demand. In fact, nearly half of the nitrogen Ultimately known as the Haber-Bosch process, it rose to be the most Keep your copyright 2 Journal of Solid State Science and the author. in our bodies may have originated in a factory — where we have bent economical way to manufacture fertilizer, and remains so today. This Technology, ECS Electrochemistry ECS’s Open Access publishing this inert gas to our own human wills. The story of how we came to process earned both men a Nobel Prize and enabled exponential world 4 The author selects one of “make bread from air” demonstrates how science and engineering can population growth, shown in Fig. 1. Letters, and ECS Solid State agreement with authors does not two Creative Commons (CC) respond to a large societal problem, and impact the entire globe for the Today, the Haber-Bosch process involves the heterogeneous Letters) is truly at the cutting edge require a transfer of copyright: the usage licenses defining coming centuries. reaction of nitrogen (N ) obtained from air, and hydrogen (H ) obtained how the article may 2 2 of our technical arenas, and ECS copyright remains with the author. be used by the general In the mid 1800s, mining of fertilizers became more common as from fossil fuels. The process occurs at high pressure (150–300 atm) publications have continued to focus Authors, however, must choose public. demand increased. Explorers even went searching for guano deposits, and high temperature (400–500 °C) over an iron-based catalyst. It on achieving quality through a what kind of license they want to large quantities of sun-baked avian excrement full of nitrogen and is one of the most impactful developments in human history, but it 4 CC BY license is the phosphorous. This “white gold” became so important agriculturally comes at a price. Converting the highly inert N2 to fertilizer is energy high standard of peer-review. Our grant their readers, and ECS offers most liberal allowing that it was mentioned in U.S. President Millard Fillmore’s 1850 State intensive, and accounts for about ~1% of the world’s annual energy four peer-reviewed titles are among a choice of two Creative Commons for unrestricted reuse of the Union Address, and in 1856 the U.S. Congress passed the Guano consumption.6 In addition, the fossil fuel reforming of natural gas the most highly-regarded in their usage licenses that authors may of content, subject only to the requirement (continued on next page) areas. attach to their work (see sidebar). that the source work is appropriately attributed. Choosing to make your paper Save the World 4 CC BY-NC-ND license is Open Access within these journals more similar to the makes no difference to the quality Next time you submit a paper, current usage rights processes we uphold at ECS— why not make it Open Access? under the transfer of Electrochemistry and solid state copyright agreement: selection criteria and peer review it limits use to non- remain exactly the same. The science research is helping scientists commercial use (NC), difference is in who can see your and researchers across the globe and restricts others solve problems facing our modern from creating derivative content. Papers not published as works(ND). Open Access can only be read by world, and the more people who can those from a subscribing institution access your work, the faster those or those who are willing to pay a fee problems may be solved. If you to access it. Make your work more have any questions about our Open accessible by making it OA. Access program, please visit www. electrochem.org/oa or email us at [email protected]. FIG. 1. Historical estimates of world population (source: U.S. Census Bureau), and the exponential population growth occurring shortly after fertilizer mining and manufacturing practices began to increase. Find out more at *Contribution of NIST, an agency of the U.S. government; not subject www.electrochem.org/oa to copyright in the United States. The Electrochemical Society Interface • Summer 2015 • www.electrochem.org 51 Renner, et al. (continued from previous page) emissions would be eliminated from the production step, and further reduction of emissions would be realized through the reduced need to hydrogen results in substantial carbon dioxide (CO2) emissions. for ammonia transport. Since electrochemical technology based According to the U.S. Greenhouse Gas Inventory, total CO2 emissions on flow cells is highly scalable, products could support a range of from ammonia production were 10.2 million metric tons of CO2 small to mid-sized farms, or could be designed on a larger scale to equivalents in 2013, accounting for ~3% of the world’s greenhouse distribute ammonia locally for multiple farms. As megawatt (MW)- gas emissions.7 Additional emissions are incurred because of the need scale electrolysis systems are already becoming a reality at companies to transport the ammonia from a large centralized plant. The extreme such as Proton OnSite, localized ammonia production at relevant conditions and pre- and post-processing steps combined with the low scales is not hard to envision. There is also a natural synergy in using equilibrium conversion (~15%), which requires gas-recycling, makes distributed wind power for fertilizer production. In the U.S. Plains these facilities highly capital intensive. These centralized plants are and Upper Midwest, excess wind production capacity, transmission installed at a cost of more than $1 billion per plant, inhibitive for some limitations, and high regional demand for N-fertilizers combine to countries that need fertilizer. As fossil fuels dwindle, and concerns create excellent economic drivers for this technology. Additionally, rise over increasing greenhouse gas emissions, more sustainable and there are many other industrial uses for ammonia besides agricultural economical ammonia production methods will be required to support fertilizers. Ammonia is used to synthesize a variety of chemicals growing world demand for fertilizer. including urea, nitric acid and pharmaceutical compounds. It is also important in emissions capture as well as refrigeration, and could be The Electrochemical used in a fuel cell for electricity generation. This flexibility in use makes ammonia an attractive renewable energy storage option. Production of Ammonia Despite these potential advantages, only a few major studies have been conducted on electrochemical ammonia generation One alternative approach to solve the ammonia problem is to use devices to date. Some groups are leveraging oxide conductors13,15-17 electricity to drive the ammonia production reaction, decreasing the for electrochemical production of ammonia, and others are using 8-10 need for high pressure and heat, and reducing energy demand. The proton conductors. Proton exchange membrane (PEM) materials are concept of using electricity to drive nitrogen reactions and fertilizer well established and have been recently incorporated into a number production is not new. As early as 1901, Bradley and Lovejoy were of ammonia synthesis devices.18-23 In addition, the Energy and attempting to pass electrical sparks though the air to make nitric acid Environmental Research Center (EERC) in Grand Forks North Dakota 11 on a commercial scale. However, the electricity costs proved to has also some highly relevant work in this area, with demonstration be too high and their process was abandoned. Today, methods exist of large reductions in energy usage by using an integrated acid-based to more efficiently utilize the energy input for an electrochemical electrochemical-thermal ammonia production process that operates at process.
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