Ashori Elham, Nazari Fariba, Illas Francesc
Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan 45137-66731, Iran.
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.
Phys Chem Chem Phys. 2017 Jan 25;19(4):3201-3213. doi: 10.1039/c6cp07898b.
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) adsorption 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 NO through adsorbed (NO) with a total energy barrier of 0.92 eV. The adsorption of NO and of two NO on O/G-Fe-N4 sheets can proceed through (N) + (O) and (NO) + (O), respectively. Both paths have a rate-determining step with a high (∼1.80 eV) energy barrier. Nevertheless, the formation of (O) on 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)@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.
检测生物系统中的一氧化氮以及为保护环境去除或减少一氧化氮至关重要。在此，我们使用带有色散校正的周期性密度泛函理论计算，研究一氧化氮和（一氧化氮）吸附对类卟啉铁 - N4石墨烯（G - Fe - N4）片层性质的影响。结果表明，一氧化氮可通过吸附的（一氧化氮）转化为亚硝酸盐，总能量势垒为0.92电子伏特。一氧化氮和两个一氧化氮在O/G - Fe - N4片层上的吸附可分别通过（氮） + （氧）和（一氧化氮） + （氧）进行。两条路径都有一个速率决定步骤，具有较高（约1.80电子伏特）的能量势垒。然而，G - Fe - N4上（氧）的形成可被视为氧还原反应（ORR）的前驱体。对该反应中涉及的各种体系电子性质的详细分析揭示了某些结构的自旋过滤特性增强。因此，得到的NO@G - Fe - N4和（NO）@G - Fe - N4结构的自旋过滤参数分别为72.53%和47.96%。此外，发现一氧化氮气体分子的吸附会诱导出G - Fe - N4中未发现的不同能量反共振凹陷，这些凹陷是由与吸附质和Fe - N4缺陷相关的准束缚态引起的。
