恒定潜能热力学集成,以获得电化学反应的自由能量概况
Hao Cao1, Xinmao Lv1, Shengjie Qian1
1Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
The journal of physical chemistry letters
|January 29, 2024
概括
我们开发了一种模拟电化学反应的新方法,准确地捕捉了潜在诱导的溶解效应和催化剂的能量. 这种方法增强了对固体-液体界面上的电催化过程的理解.
科学领域:
- 计算化学的计算化学
- 电化学 电化学 电化学
- 材料科学 材料科学 材料科学
背景情况:
- 模拟电化学反应需要对固体-液体界面进行准确的建模.
- 目前的方法很难有效地捕捉潜在依赖的溶解效应.
研究的目的:
- 开发一种高效的自由能量采样方法,用于恒定表面电荷密度的电化学反应.
- 准确模拟潜在诱导的溶解效应和电催化反应能量.
主要方法:
- 受到限制的ab initio分子动力学 (cAIMD) 具有完全明确的溶剂层.
- 恒定电位热力学集成 (CPTI) 方法.
- 一个"即时"的程序,用于自动调整表面电荷密度.
主要成果:
- 该CPTI方法成功地预测了单原子催化剂上二氧化碳吸附的潜在依赖的自由能量概况.
- 该方法考虑了静电潜在能量变化和潜在诱导的溶解效应.
- 完成了完整的固体-液体界面和电催化能量的精确模拟.
结论:
- CPTI方法为模拟电化学环境提供了一种高效准确的方法.
- 这种方法可以对电催化反应能量进行可靠的计算.
- 开发的方法是研究潜在依赖的表面现象的重大进展.
相关概念视频
Cell Potential and Free Energy
40.2K
Thermodynamics of a Redox Reaction
Thermodynamics is the branch of physics dealing with the relationship between heat and other forms of energy. In an electrochemical cell, chemical energy is converted into electrical energy.
Thus, a link can be predicted between cell potential, free energy change, and the equilibrium constant for the reaction. Cell potential can also be measured as the oxidant or the reducing strength, and similar acid-base strength measures are reflected in equilibrium...
Thermodynamics is the branch of physics dealing with the relationship between heat and other forms of energy. In an electrochemical cell, chemical energy is converted into electrical energy.
Thus, a link can be predicted between cell potential, free energy change, and the equilibrium constant for the reaction. Cell potential can also be measured as the oxidant or the reducing strength, and similar acid-base strength measures are reflected in equilibrium...
40.2K
Thermodynamic Potentials
836
Thermodynamic potentials are state functions that are extremely useful in analyzing a thermodynamic system. They have dimensions of energy. The four important thermodynamic potentials are internal energy, enthalpy, Helmholtz free energy, and Gibbs free energy. These thermodynamic potentials can be expressed using two of the following variables: pressure, volume, temperature, and entropy. These two variables are expressed as the rate of change of the thermodynamic potential with respect to other...
836
Calculating Standard Free Energy Changes
21.3K
The free energy change for a reaction that occurs under the standard conditions of 1 bar pressure and at 298 K is called the standard free energy change. Since free energy is a state function, its value depends only on the conditions of the initial and final states of the system. A convenient and common approach to the calculation of free energy changes for physical and chemical reactions is by use of widely available compilations of standard state thermodynamic data. One method involves the...
21.3K
Gibbs Free Energy and Thermodynamic Favorability
6.8K
The spontaneity of a process depends upon the temperature of the system. Phase transitions, for example, will proceed spontaneously in one direction or the other depending upon the temperature of the substance in question. Likewise, some chemical reactions can also exhibit temperature-dependent spontaneities. To illustrate this concept, the equation relating free energy change to the enthalpy and entropy changes for the process is considered:
6.8K
Redox Equilibria: Overview
564
A reduction-oxidation reaction is commonly called a redox reaction. In a redox reaction, electrons are transferred from one species to another rather than being shared between or among atoms. The reducing agent or reductant is the species that loses electrons and gets oxidized in the process. The species that gains electrons and gets reduced in the process is the oxidizing agent or oxidant. Redox reactions are represented as two separate equations called half-reactions, where one equation...
564
Thermodynamics: Chemical Potential and Activity
969
The effective concentration of a species in a solution can be expressed precisely in terms of its activity. Activity considers the effect of electrolytes present in the vicinity of the species of interest and depends on the ionic strength of the solution. The activity of a species is expressed as the product of molar concentration and the activity coefficient of the species.
The thermodynamic equilibrium constant is more accurately defined in terms of activity rather than concentration.
The thermodynamic equilibrium constant is more accurately defined in terms of activity rather than concentration.
969


