The structures and thermodynamic stability of copper(II) chloride surfaces

被引：12

作者：

Altarawneh, Mohammednoor ^{[1
]}

Jiang, Zhong-Tao ^{[1
]}

Dlugogorski, Bogdan Z. ^{[1
]}

机构：

[1] Murdoch Univ, Sch Engn & Informat Technol, Perth, WA, Australia

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2014年 / 16卷 / 44期

基金：

澳大利亚研究理事会;

关键词：

DENSITY-FUNCTIONAL THEORY; DEACON PROCESS; ADSORPTION; CHLORINATION; DIFFRACTION; CU(111); DIOXINS; CU(100); SYSTEM;

D O I：

10.1039/c4cp03558e

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Using density functional theory calculations of periodic slabs, within the generalised gradient approximation, this study provides optimised structures for all plausible terminations of copper(II) chloride surfaces along the three low-index orientations. The ab initio atomistic thermodynamic approach serves to construct a thermodynamic stability diagram for CuCl2 configurations as a function of the chemical potential of chlorine (Delta mu(Cl)(T,P)). We observe a shift in thermodynamic stability ordering at around Delta mu(Cl)(T,P) = -1.0 eV between a copper-chlorine terminated (001) surface (i.e., (001)CuCl) and a (001) chlorine-covered surface (i.e., (001)Cl). This conclusion accords with experimental observations that report CuCl-bulk like structures, acting as a prerequisite for the formation of CuCl2-bulk like arrangements in the course of copper chlorination. Profound stabilities and optimised structures of (001)CuCl and (001)Cl configurations are discussed within the context of the functionality of CuCl2 as the chief chlorination and condensation catalyst of aromatic pollutants under conditions relevant to their formation in thermal systems, i.e. 400-1000 K, a total operating pressure of 1.0 atm and P-cl2 = 10(- 6)-10(-4) atm (1.0-100.0 ppm).

引用

页码：24209 / 24215

页数：7

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