Adsorption of Acetonitrile, Benzene, and Benzonitrile on Pt(111): Single Crystal Adsorption Calorimetry and Density Functional Theory

Abstract

Single crystal adsorption calorimetry on Pt(111) surfaces allows us to study the influence of different functional groups on heats of adsorption. At zero coverage we find 103, 194, and 325 kJ/mol for acetonitrile, benzene, and benzonitrile, respectively. This leads to the idea of summing up the heats of adsorption of acetonitrile and benzene, assuming that the total heat of adsorption of benzonitrile is due to the combined effect of isolated functional groups. This idea is discussed in light of the recent literature regarding nitrile adsorption on metal surfaces and further investigated theoretically by density functional theory. In order to figure out the importance of dispersive effects on the heats of adsorption, van der Waals corrected calculations are performed considering different binding modes and surface reconstructions.

Interfacial Electron Transfer and Ion Solvation in the Solid Electrolyte Interphase

“…In fact, electrode charge polarization is strongly sensitive to rare fluctuations in the solvent structure. 42,53 however, that the effect also appears in the other electrolytes for which such direct lithium- (Fig. 7E), it is seen that rare ion-solvation fluctuations do indeed occur for the PEO, P(2EO-MO), and G4 electrolytes, which give rise to this strongly non-Gaussian interfacial behavior.…”

Interfacial Electron Transfer and Ion Solvation in the Solid Electrolyte Interphase

“…However, we reduce the LJ interactions between the platinum and electrolyte atoms by half throughout this study, such that ij = 0.5 √ i j to approximately match the adsorption energy of acetonitrile on platinum. 53 Finally, to avoid rare, unphysical penetration of the lithium ions into the anode layers during the simulations, we employ the additional short-ranged repulsive potential…”

“…In fact, electrode charge polarization is strongly sensitive to rare fluctuations in the solvent structure. 42,53 Fig. 7 displays the distribution of induced charge per atom of the anode, where P (q) = δ(q − A j (t)) with the index j running for all atoms of the anode.…”

Friends or strangers? Attempts at reactivating buyer–supplier relationships

“…It also works for studies of the role of polycyclic aromatic hydrocarbons in interstellar H 2 formation [130], of electric-field driven reactions [131], and of mechanochemical cocrystal formation [132]. Use of vdW-DF-cx is also helping the understanding of the crossover from physisorption to weak chemisorption in molecular adhesion [11,[133][134][135][136][137][138][139][140][141][142][143][144][145], of catalysis [146][147][148], of hydrogen tunneling [149], of magnetic coupling between adsorbates [150], and of charge transfer and electron transport in and through molecular adsorbates [151][152][153]. It is therefore worth exploring why (spin) vdW-DF-cx works well.…”