Thermodynamics electrocrystallization

Sometimes, semiconductivity depends on the type of a structural phase that arises from synthesis. Thus, in the case of (TCNQ) Cu the semiconducting phase is thermodynamically disfavored. To prepare this semiconductor, Harris et al. (2005) proposed to perform the reduction of TCNQ in acetonitrile at glass-carbon, gold, or platinum electrode in the presence of Cu. This allows the electrocrystallization of sparingly soluble TCNQCu semiconducting phase to occur by a nucleation... 

In the previous sections, PEVD thermodynamic equilibrium relationships were discussed in connection with electrocrystallization phenomena occurring in PEVD processes for applications in sensors and fuel... 

For oxide electrocrystallization, the last condition is the most strenuous, sine many oxides are insulating non-stoichiometric compounds, however, are sufficient conductive. When two (or more) substances are codeposited, certain specific feature of the crystallization can be expressed for both cathodic and anodic processes on th basis of the thermodynamics of binary (or more complex) systems. If stabl multicomponent phases exist, then it is their deposition (not the deposition of mixture of simpler products) that preferentially proceeds in a certain potential regioi In such cases, intermetallic compounds are deposited in cathodic processes, and th deposition of mixed oxides takes place in anodic processes. These products ca represent both chemical compounds and solid solutions. 

Improved understanding of the mechanism, energetics, and structure of the bonding of water to surfaces is needed. Such information is a key to fundamental clarification of the interfacial structure at solid-liquid surfaces. Poor understanding of the thermodynamics of polymer adsorption at interfaces is impeding scientific progress on corrosion inhibition, colloidal stability, alteration of membrane selectivity, and electrocrystallization additives. 

Zhao C, MacFarlane DR, Bond AM (2009) Modified thermodynamics in ionic liquids for controlled electrocrystallization of nanocubes, nanowires, and crystalline thin films of silver-tetracyanoquinodimethane. JAm Chem Soc 131(44) 16195-16205... 

Apart from the purely thermodynamic analysis, the description of the electrocrystallization phenomena requires special consideration of the kinetics of nucleus formation [i-v]. Accounting for the discrete character of the clusters size alteration at small dimensions the atomistic nucleation theory shows that the supersaturation dependence of the stationary nucleation rate Jo is a broken straight line (Figure 2) representing the intervals of A p within which different clusters play the role of critical nuclei. Thus, [A//, A/l"] is the supersaturation interval within which the -atomic cluster is the critical nucleus formed with a maximal thermodynamic work AG (nc). 

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