Cyanide-modified Pt(111) : structure, stability and hydrogen adsorption

A.C. acknowledges the support of the DGI (Spanish Ministry of Science and Innovation) through Project CTQ2009-07017. W.S. acknowledges financial support by the Deutsche Forschungsgemeinschaft under Schm 344/40-1, Schm 344/34-1.2 and FOR 1376. W.S. and P.Q. thank DFG-CONICET International Cooperation and CONICET for continued support. E.P.M.L. and M.Z.-M. wish to acknowledge CONICET PIP: 112-200801-000983, Secyt UNC, Program BID (PICT 2006N 946), and PME: 2006-01581 for financial support. P.Q. acknowledges PICT 0737-2008. A generous grant of computing time from the Baden-Wuerttemberg grid is gratefully acknowledged. M.E.-E. acknowledges an FPI fellowship from the Spanish Ministry of Science and Innovation and an accommodation grant at the Residencia de Estudiantes from the Madrid City Council.Peer reviewedPostprin

The role of an interface in stabilizing reaction intermediates for hydrogen evolution in aprotic electrolytes

By combining idealized experiments with realistic quantum mechanical simulations of an interface, we investigate electro-reduction reactions of HF, water and methanesulfonic acid (MSA) on the single crystal (111) facets of Au, Pt, Ir and Cu in organic aprotic electrolytes, 1 M LiPF(6) in EC/EMC 3:7W (LP57), the aprotic electrolyte commonly used in Li-ion batteries, 1 M LiClO(4) in EC/EMC 3:7W and 0.2 M TBAPF(6) in 3 : 7 EC/EMC. In our previous work, we have established that LiF formation, accompanied by H(2) evolution, is caused by a reduction of HF impurities and requires the presence of Li at the interface, which catalyzes the HF dissociation. In the present paper, we find that the measured potential of the electrochemical response for these reduction reactions correlates with the work function of the electrode surfaces and that the work function determines the potential for Li(+) adsorption. The reaction path is investigated further by electrochemical simulations suggesting that the overpotential of the reaction is related to stabilizing the active structure of the interface having adsorbed Li(+). Li(+) is needed to facilitate the dissociation of HF which is the source of protons. Further experiments on other proton sources, water and methanesulfonic acid, show that if the hydrogen evolution involves negatively charged intermediates, F(−) or HO(−), a cation at the interface can stabilize them and facilitate the reaction kinetics. When the proton source is already significantly dissociated (in the case of a strong acid), there is no negatively charged intermediate and thus the hydrogen evolution can proceed at much lower overpotentials. This reveals a situation where the overpotential for electrocatalysis is related to stabilizing the active structure of the interface, facilitating the reaction rather than providing the reaction energy

Determination of Specific Electrocatalytic Sites in the Oxidation of Small Molecules on Crystalline Metal Surfaces

The identification of active sites in electrocatalytic reactions is part of the elucidation of mechanisms of catalyzed reactions on solid surfaces. However, this is not an easy task, even for apparently simple reactions, as we sometimes think the oxidation of adsorbed CO is. For surfaces consisting of non-equivalent sites, the recognition of specific active sites must consider the influence that facets, as is the steps/defect on the surface of the catalyst, cause in its neighbors; one has to consider the electrochemical environment under which the “active sites” lie on the surface, meaning that defects/steps on the surface do not partake in chemistry by themselves. In this paper, we outline the recent efforts in understanding the close relationships between site-specific and the overall rate and/or selectivity of electrocatalytic reactions. We analyze hydrogen adsorption/desorption, and electro-oxidation of CO, methanol, and ammonia. The classical topic of asymmetric electrocatalysis on kinked surfaces is also addressed for glucose electro-oxidation. The article takes into account selected existing data combined with our original works.M.J.S.F. is grateful to PNPD/CAPES (Brazil). J.M.F. thanks the MCINN (FEDER, Spain) project-CTQ-2016-76221-P

The Role of Interface in Stabilizing Reaction Intermediates for Hydrogen Evolution in Aprotic Li-Ion Battery Electrolyte

p { margin-bottom: 0.1in; direction: ltr; color: rgb(0, 0, 10); line-height: 120%; text-align: left; }p.western { font-size: 12pt; }p.cjk { font-size: 12pt; }a:link { color: rgb(5, 99, 193); } By combining idealized experiments with realistic quantum mechanical simulations of the interface, we investigate electro-reduction reactions of HF and water impurities on the single crystal (111) facets of Au, Pt, Ir and Cu in an organic aprotic electrolyte, 1M LiPF6 in EC/EMC 3:7w (LP57), which are common reactions happening during the formation of the SEI on graphite. In our previous work, we have established that the LiF formation, accompanied with H2 evolution, is caused by a reduction of HF impurities and requires the presence of Li at the interface, which catalyzes the HF dissociation. In the present paper, we find that the measured potential of the electrochemical response for these reduction reactions correlates with the work function of the electrode surfaces and that the work function determines the potential for Li+ adsorption. The reaction path is investigated further by electrochemical simulations suggesting that the overpotential of the reaction is related to stabilizing the active structure of the interface having Li+ adsorbed. The Li+ is needed to facilitate the dissociation of HF which is the source of proton. Further experiments on the other proton sources, water and methanesulfonic acid, show that if the hydrogen evolution involves negatively charged intermediates, F- or HO-, a cation at the interface can stabilize them and facilitate the reaction kinetics. When the proton source is already significantly dissociated (in the case of a strong acid), there is no negatively charged intermediate and thus the hydrogen evolution can proceed at much lower overpotentials. This reveals a situation where the overpotential for electrocatalysis is related to stabilizing the active structure of the interface, facilitating the reaction rather than providing the reaction energy. This has implications for the SEI layer formation in Li-ion batteries and for reduction reactions in alkaline environment as well as for design principles for better electrodes.</p