An ionicity rationale to design solid phase metal nitride reactants for solar ammonia production

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dc.contributor.author Michalsky, Ronald
dc.contributor.author Pfromm, Peter H.
dc.date.accessioned 2012-11-21T19:28:29Z
dc.date.available 2012-11-21T19:28:29Z
dc.date.issued 2012-10-17
dc.identifier.uri http://hdl.handle.net/2097/14978
dc.description.abstract Ammonia is an important fertilizer component and could be used as a convenient hydrogen carrier. This work studies a solar thermochemical reaction cycle that separates the reductive N[subscript 2] cleavage from the hydrogenation of nitrogen ions to NH[subscript 3] without using electricity or fossil fuel. The hydrolysis of binary metal nitrides of magnesium, aluminum, calcium, chromium, manganese, zinc, or molybdenum at 0.1 MPa and 200-1000°C recovered up to 100 mol% of the lattice nitrogen with up to 69.9 mol% as NH[subscript 3] liberated at rates of up to 1.45 x 10ˉ³ mol NH[subscript 3] (mol metal)ˉ¹ sˉ¹ for ionic nitrides. These rates and recoveries are encouraging when extrapolated to a full scale process. However, nitrides with lower ionicity are attractive due to simplified reduction conditions to recycle the oxidized reactant after NH[subscript 3] formation. For these materials diffusion in the solid limits the rate of NH3 liberation. The nitride ionicity (9.96-68.83% relative to an ideal ionic solid) was found to correlate with the diffusion constants (6.56 x 10[superscript -14] to 4.05 x 10[superscript -7] cm² sˉ¹) suggesting that the reduction of H[subscript 2]O over nitrides yielding NH[subscript 3] is governed by the activity of the lattice nitrogen or ion vacancies, respectively. The ionicity appears to be a useful rationale when developing an atomic-scale understanding of the solid-state reaction mechanism and when designing prospectively optimized ternary nitrides for producing NH[subscript 3] more sustainably and at mild conditions compared to the Haber Bosch process. en_US
dc.language.iso en_US en_US
dc.relation.uri http://doi.org/10.1021/jp307382r en_US
dc.rights This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s). en_US
dc.rights.uri https://rightsstatements.org/page/InC/1.0/
dc.subject Solar radiation en_US
dc.subject Heterogeneous catalysis en_US
dc.subject Transition metal nitride en_US
dc.subject Transition metal oxide en_US
dc.subject Nitrogen diffusion en_US
dc.subject Mulliken population analysis en_US
dc.title An ionicity rationale to design solid phase metal nitride reactants for solar ammonia production en_US
dc.type Text en_US
dc.date.published 2012 en_US
dc.citation.doi 10.1021/jp307382r en_US
dc.citation.epage 23251 en_US
dc.citation.issue 44 en_US
dc.citation.jtitle Journal of Physical Chemistry C en_US
dc.citation.spage 23243 en_US
dc.citation.volume 116 en_US
dc.contributor.authoreid pfromm en_US
dc.description.version Article (author version)


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This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s). Except where otherwise noted, the use of this item is bound by the following: This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).

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