Photofixation of N2 to NH3/NOx
Carl Erik Lie Foss a, Svein Sunde a, Truls Norby b, Prangya Parimita Sahoo  b, Wen Xing c, Jonathan Polfus c, Mathieu Grandcolas c
a Norwegian University of Science and Technology (NTNU), Insitutt for materialteknologi, Trondheim, 7491, Norway
b University of Oslo (UiO), Forskningsparken,Oslo,0349, Norway
c SINTEF Materials and Chemistry, Forskningsveien 1a,Oslo,0314, Norway
Materials for Sustainable Development Conference (MATSUS)
Proceedings of September Meeting 2016 (NFM16)
Berlin, Germany, 2016 September 5th - 13th
Organizers: Marin Alexe, Enrique Cánovas, Celso de Mello Donega, Ivan Infante, Thomas Kirchartz, Maksym Kovalenko, Federico Rosei, Lukas Schmidt-Mende, Laurens Siebbeles, Peter Strasser, Teodor K Todorov, Roel van de Krol and Ulrike Woggon
Poster, Carl Erik Lie Foss, 077
Publication date: 14th June 2016

Ammonia NH3 is a major and essential chemical for industrial and agricultural applications, and a precursor for almost all nitrogen-containing products. About 80% of the total ammonia produced globally is utilized for the production of fertilizers via oxidation to NOx and nitrates. Today, the hydrogen and energy required comes mostly from natural gas, which renders the technology unsustainable and with large climate gas emissions. Fixation of dinitrogen is extremely challenging as the N≡N triple bond is very strong and difficult to activate due to the absence of a permanent dipole. In general, the reduction of nitrogen is difficult without a catalyst and require intensive energy inputs. The long-established ammonia synthesis method is the Haber-Bosch process, in which nitrogen and hydrogen react on a catalyst such as ruthenium and iron at high temperature (450-500°C) and high pressure (150-300 bar). The Haber–Bosch synthesis of ammonia is carried out on a large scale, and about 2 % of all energy consumed by mankind is utilized in this process. The process also releases hundreds of millions of tons of carbon dioxide to the atmosphere. It is desirable to have less energy demanding alternatives for capturing nitrogen and converting to ammonia. The most challenging step remains the scission of the strong N≡N bond (bond energy = 945 kJmol-1), for which we explore the use of artificial hard UV radiation (UV B, 315-280 nm and UV C, 280-100 nm, corresponding to 4.4-12.4 eV in energy).Previous studies (Schrauzer 1977) has shown that N2 can be converted to ammonia by using sunlight and TiO2 as photocatalyst however only very small amounts are detected.In the current project we aim to produce ammonia (or NOx) from N2 in air by utilizing sunlight (hard UV) and photocatalysts with optimized band edges and a large band gap. First we reproduce previous studies with TiO2 -demonstrating that N2, phototcatalyst and sunlight are all necessary components to produce ammonia. Then we aim to improve the production of ammonia by careful selection of phototcatalysts that fulfil the desired criterias. Several large band-gap materials has been screened as potential candidates for photofixation. Among these our main result show that Fe-doped SrTiO3 produce NOx (which can later be reduced to ammonia) at almost twice the rate of literature values (and our own reproduction) for TiO2



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