Nonaqueous Solvent Adsorption on Transition Metal Surfaces with Density Functional Theory: Interaction of N,N-Dimethylformamide (DMF), Tetrahydrofuran (THF), and Dimethyl Sulfoxide (DMSO) with Ag, Cu, Pt, Rh, and Re Surfaces

Abstract

Interfaces between solvents and transition metals play a critical role in many catalytic and electrochemical systems. In this work, we use density functional theory (DFT) to study the interactions between several common nonaqueous solvents and a number of transition metal surfaces. We investigate trends in binding energies among the metals, and the influence of specific surface sites and facets. We examine the electrostatic field dependence of the most stable binding configurations, and shed light on experimentally observed field-dependent or potential-dependent adsorption structures. We demonstrate that the reorientation of DMSO on noble metal surfaces can occur with only a relatively small change in the surface dipole moment; this result is simultaneously consistent with experimental evidence for field-dependent reorientation and measurements of surprisingly low differential capacitance of DMSO on noble metals. These results contribute to understanding competitive adsorption effects in catalysis, and also have implications for fundamental surface properties such as the surface structure, solvated work function, and potential of zero charge.

Interactions of CO2 Anion Radicals with Electrolyte Environments from First-Principles Simulations

“…Similar qualitative trends in CO 2 RR were also reported by Berto et al and Shi et al, where voltammetric experiments in the presence of NBu 4 + electrolytes have shown larger current density values for CO 2 RR in highly polar DMF and MeCN, as compared to low polarity THF. Here, DMSO has the largest standard deviation (Figure ), which was also found to exhibit the largest deviation from trends due to coordination via the sulfur atom (as opposed to via the oxygen atom in water and THF) in a study of aprotic solvent (THF, DMF, and DMSO) adsorption on metal surfaces by Nørskov and co-workers . In aprotic solvents and NBu 4 + salts, tailoring the lifetime of the CO 2 – will likely depend on solvent, due to the stabilizing influence of more polar solvents.…”

“…Here, DMSO has the largest standard deviation ( Figure 3 ), which was also found to exhibit the largest deviation from trends due to coordination via the sulfur atom (as opposed to via the oxygen atom in water and THF) in a study of aprotic solvent (THF, DMF, and DMSO) adsorption on metal surfaces by Nørskov and co-workers. 61 In aprotic solvents and NBu 4 + salts, tailoring the lifetime of the CO 2 – will likely depend on solvent, due to the stabilizing influence of more polar solvents.…”

Surfactant-Free Colloidal Syntheses of Precious Metal Nanoparticles for Improved Catalysts

“…However, the synthesis suffers from some limitations. DMF can interact relatively strongly with metal surfaces . DMF itself is a relatively non-ecofriendly solvent with a high boiling point.…”

CO2 Electroreduction in Organic Aprotic Solvents: A Mini Review

“…e electrondonor capability of the aprotic solvent also determines the adsorption of organic molecules on the cathode surface [55][56][57]. Reactions ( 13) and ( 15) take place on the latter, the course of which depends on the adsorption-desorption of CO 2 and CO molecules, CO 2 radicals, and CO 3 (2) Influence of CO 2 Solubility.…”