RESUMO
Density functional theory was used to investigate the effects of doping alkaline earth metal atoms (beryllium, magnesium, calcium and strontium) on graphene. Electron transfer from the dopant atom to the graphene substrate was observed and was further probed by a combined electron localization function/non-covalent interaction (ELF/NCI) approach. This approach demonstrates that predominantly ionic bonding occurs between the alkaline earth dopants and the substrate, with beryllium doping having a variant characteristic as a consequence of electronegativity equalization attributed to its lower atomic number relative to carbon. The ionic bonding induces spin-polarized electronic structures and lower workfunctions for Mg-, Ca-, and Sr-doped graphene systems as compared to the pristine graphene. However, due to its variant bonding characteristic, Be-doped graphene exhibits non-spin-polarized p-type semiconductor behavior, which is consistent with previous works, and an increase in workfunction relative to pristine graphene. Dirac half-metal-like behavior was predicted for magnesium doped graphene while calcium doped and strontium doped graphene were predicted to have bipolar magnetic semiconductor behavior. These changes in the electronic and magnetic properties of alkaline earth doped graphene may be of importance for spintronic and other electronic device applications.
RESUMO
Traditional understanding of electrocatalytic reactions generally focuses on either covalent interactions between adsorbates and the reaction interface (i.e., electrical double layer, EDL) or electrostatic interactions between electrolyte ions. Here, our work provides valuable insights into interfacial structure and ionic interactions during alkaline oxygen evolution reaction (OER). The importance of inner-sphere OH- adsorption is demonstrated as the IrOx activity in 4.0 M KOH is 6.5 times higher than that in 0.1 M KOH. Adding NaNO3 as a supporting electrolyte, which is found to be inert for long-term stability, complicates the electrocatalytic reaction in a half cell. The nonspecially adsorbed Na+ in the outer compact interfacial layer is suggested to form a stronger noncovalent interaction with OH- through hydrogen bond than adsorbed K+, leading to the decrease of interfacial OH- mobility. This hypothesis highlights the importance of outer-sphere adsorption for the OER, which is generally recognized as a pure inner-sphere process. Meanwhile, based on our experimental observations, the pseudocapacitive behavior of solid-state redox might be more reliable in quantifying active sites for OER than that measured from the conventional EDL charging capacitive process. The interfacial oxygen transport is observed to improve with increasing electrolyte conductivity, ascribing to the increased accessible active sites. The durability results in a liquid alkaline electrolyzer which shows that adding NaNO3 into KOH solution leads to additional degradation of OER activity and long-term stability. These findings provide an improved understanding of the mechanistic details and structural motifs required for efficient and robust electrocatalysis.
