Beyond fossil fuel–driven nitrogen transformations

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Science  25 May 2018:
Vol. 360, Issue 6391, eaar6611
DOI: 10.1126/science.aar6611

Transforming nitrogen without carbon

How much carbon does it take to make nitric acid? The counterintuitive answer nowadays is quite a lot. Nitric acid is manufactured by ammonia oxidation, and all the hydrogen to make ammonia via the Haber-Bosch process comes from methane. That's without even accounting for the fossil fuels burned to power the process. Chen et al. review research prospects for more sustainable routes to nitrogen commodity chemicals, considering developments in enzymatic, homogeneous, and heterogeneous catalysis, as well as electrochemical, photochemical, and plasma-based approaches.

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Structured Abstract


The invention of the Haber-Bosch (H-B) process in the early 1900s to produce ammonia industrially from nitrogen and hydrogen revolutionized the manufacture of fertilizer and led to fundamental changes in the way food is produced. Its impact is underscored by the fact that about 50% of the nitrogen atoms in humans today originate from this single industrial process. In the century after the H-B process was invented, the chemistry of carbon moved to center stage, resulting in remarkable discoveries and a vast array of products including plastics and pharmaceuticals. In contrast, little has changed in industrial nitrogen chemistry. This scenario reflects both the inherent efficiency of the H-B process and the particular challenge of breaking the strong dinitrogen bond. Nonetheless, the reliance of the H-B process on fossil fuels and its associated high CO2 emissions have spurred recent interest in finding more sustainable and environmentally benign alternatives. Nitrogen in its more oxidized forms is also industrially, biologically, and environmentally important, and synergies in new combinations of oxidative and reductive transformations across the nitrogen cycle could lead to improved efficiencies.


Major effort has been devoted to developing alternative and environmentally friendly processes that would allow NH3 production at distributed sources under more benign conditions, rather than through the large-scale centralized H-B process. Hydrocarbons (particularly methane) and water are the only two sources of hydrogen atoms that can sustain long-term, large-scale NH3 production. The use of water as the hydrogen source for NH3 production requires substantially more energy than using methane, but it is also more environmentally benign, does not contribute to the accumulation of greenhouse gases, and does not compete for valuable and limited hydrocarbon resources. Microbes living in all major ecosystems are able to reduce N2 to NH3 by using the enzyme nitrogenase. A deeper understanding of this enzyme could lead to more efficient catalysts for nitrogen reduction under ambient conditions. Model molecular catalysts have been designed that mimic some of the functions of the active site of nitrogenase. Some modest success has also been achieved in designing electrocatalysts for dinitrogen reduction. Electrochemistry avoids the expense and environmental damage of steam reforming of methane (which accounts for most of the cost of the H-B process), and it may provide a means for distributed production of ammonia. On the oxidative side, nitric acid is the principal commodity chemical containing oxidized nitrogen. Nearly all nitric acid is manufactured by oxidation of NH3 through the Ostwald process, but a more direct reaction of N2 with O2 might be practically feasible through further development of nonthermal plasma technology. Heterogeneous NH3 oxidation with O2 is at the heart of the Ostwald process and is practiced in a variety of environmental protection applications as well. Precious metals remain the workhorse catalysts, and opportunities therefore exist to develop lower-cost materials with equivalent or better activity and selectivity. Nitrogen oxides are also environmentally hazardous pollutants generated by industrial and transportation activities, and extensive research has gone into developing and applying reduction catalysts. Three-way catalytic converters are operating on hundreds of millions of vehicles worldwide. However, increasingly stringent emissions regulations, coupled with the low exhaust temperatures of high-efficiency engines, present challenges for future combustion emissions control. Bacterial denitrification is the natural analog of this chemistry and another source of study and inspiration for catalyst design.


Demands for greater energy efficiency, smaller-scale and more flexible processes, and environmental protection provide growing impetus for expanding the scope of nitrogen chemistry. Nitrogenase, as well as nitrifying and denitrifying enzymes, will eventually be understood in sufficient detail that robust molecular catalytic mimics will emerge. Electrochemical and photochemical methods also demand more study. Other intriguing areas of research that have provided tantalizing results include chemical looping and plasma-driven processes. The grand challenge in the field of nitrogen chemistry is the development of catalysts and processes that provide simple, low-energy routes to the manipulation of the redox states of nitrogen.

Possible routes for nitrogen transformations that eliminate or minimize the need for fossil fuels.

A more thorough understanding of nitrogenase may lead to more efficient homogeneous catalysts for reduction of N2 to NH3. Coupling of theory and experiment will lead to more effective and stable heterogeneous and electrocatalysts. Innovative energy sources, such as plasmas, which involve nonequilibrium chemistry, may lead to new nitrogen conversion mechanisms.



Nitrogen is fundamental to all of life and many industrial processes. The interchange of nitrogen oxidation states in the industrial production of ammonia, nitric acid, and other commodity chemicals is largely powered by fossil fuels. A key goal of contemporary research in the field of nitrogen chemistry is to minimize the use of fossil fuels by developing more efficient heterogeneous, homogeneous, photo-, and electrocatalytic processes or by adapting the enzymatic processes underlying the natural nitrogen cycle. These approaches, as well as the challenges involved, are discussed in this Review.

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