A model for sequential first-order phase transitions occurring in the underpotential deposition of metals

An Oxalate Method for Measuring the Surface Area of Nickel Electrodes

“…66,67 For sufficiently strong lateral interactions, voltammetric sweeps may induce a rapid phase transformation at the surface. 63,67 In general, electron transfer involving more than a monolayer or occurring on multiple crystal faces does not give rise to a single sharp peak. Moreover, such sharp peaks generally correspond to a quick transition from very low (θ ≈ 0) to very high (θ ≈ 1) surface coverage, rather than electron transfer involving only part of the surface layer.…”

Underpotential deposition of Cu on Au(111) in sulfate-containing electrolytes: A theoretical and experimental study

“…Our lattice-gas model for the UPD of Cu on Au(111) in sulfate-containing electrolyte is a refinement of the HB model [12,13,[21][22][23][24][25][26]. It is based on the assumption that the sulfate coordinates the triangular Au(111) surface (STM indicates that the (1×23) reconstruction observed by LEED (see Sec.…”

“…In the theoretical part of the study we formulate a full, two-component lattice-gas model with effective, lateral interactions out to fourth-nearest neighbors. This is a generalization of the HB model [12,13,[21][22][23][24][25][26]. Using group-theoretical ground-state calculations at zero temperature [27][28][29] and Monte Carlo (MC) simulations at room temperature [30][31][32], we estimate the model parameters (the effective, lateral interactions and electrovalences) so as to obtain overall agreement with the available experimental data, including both our own and those of other groups.…”

“…The first detailed, statistical-mechanical lattice-gas model for a UPD system was introduced by Huckaby and Blum (HB), who considered the electrosorption of copper (Cu) onto the (111) plane of gold [Au(111)] in the presence of sulfate [12,13,[21][22][23][24][25][26]. This system also has been intensively studied by a number of experimental techniques (see Sec.…”

“…It was already suggested in Refs. [7,8,11] that the CV current peaks separate ordered and disordered adsorbate structures, and it was later pointed out that the peaks themselves should correspond to phase transitions in the adsorbed layer [1,12,13]. The UPD phenomenon is of fundamental interest as an aspect of the detailed, microscopic structure of electrode-electrolyte interfaces, which is presently the focus of vigorous research [14].…”