title: Influence of NO and (NO)2adsorption on the properties of Fe-N4 porphyrin-like graphene sheets.
abstract: Detection of NO in biological systems and removing or reducing NO for environment protection is paramount. Herein, we investigate the influence of NO and (NO)2adsorption on the properties of Fe-N4 porphyrin-like graphene (G-Fe-N4) sheets using periodic DFT calculations with the dispersion correction. The results show that NO can be converted into N2O through adsorbed (NO)2with a total energy barrier of 0.92 eV. The adsorption of N2O and of two NO on O/G-Fe-N4 sheets can proceed through (N2)gas+ (O2)adsand (N2O)gas+ (O2)ads, respectively. Both paths have a rate-determining step with a high (∼1.80 eV) energy barrier. Nevertheless, the formation of (O2)adson the G-Fe-N4 can be regarded as an oxygen reduction reaction (ORR) precursor. Detailed analyses of the electronic properties of the various systems involved in this reaction reveal the increased spin filter characteristics for some structures. Hence, the obtained spin filter parameters of the NO@G-Fe-N4 and (NO)2@G-Fe-N4 structures are 72.53% and 47.96%, respectively. Also, it is found that the adsorption of NO gas molecules induces different energy antiresonant dips not found in G-Fe-N4, which are induced by quasi-bound states related to the adsorbate and Fe-N4 defect.
authors.affiliation: Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan 45137-66731, Iran. nazari@iasbs.ac.ir.
authors.forename: Elham
authors.initials: E
authors.lastname: Ashori
authors.affiliation: Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan 45137-66731, Iran. nazari@iasbs.ac.ir and Center of Climate Change and Global Warming, Institute for Advanced Studies in Basic Sciences, Zanjan 45137-66731, Iran.
authors.forename: Fariba
authors.initials: F
authors.lastname: Nazari
authors.affiliation: Departament de Ciència de Materials i Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/Martí i Franquès 1, 08028 Barcelona, Spain. francesc.illas@ub.edu.
authors.forename: Francesc
authors.identifier: http://orcid.org/0000-0003-2104-6123
authors.initials: F
authors.lastname: Illas