Surface strain and linear thermodynamic‐kinetic relation are interesting topics in catalysis. Development of low temperature methanol catalysts of high activity and selectivity is of particularly importance for conversion of CO2 to methanol. In the present paper CO2 hydrogenation to methanol on Znx@TiO2(110) (x = 0‐2) was explored using density functional calculations and microkinetic simulations. The reaction mechanisms on the three model systems were determined and it is shown that Zn2@TiO2(110) is the most active. The most favorable pathway on Zn2@TiO2(110) is identified and CO2 + H to HCOO is found to be the rate‐controlling step. It is demonstrated that there is a linear relation (named AEB relation) between the adsorption energies of the initial states and the barriers for the controlling step on the 18 systems studied. Calculations on strained surfaces show that the AEB relation exists within ±1% strain. Sr2@TiO2(110) and ‐1% strained CaZn and ZnCu doped TiO2(110) are potential good low temperature catalysts and deserve experimental testing.

中文翻译：

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金属掺杂 TiO2(110) 上 CO2 加氢生成 CH3OH：机理、应变效应和新的热力学动力学关系

表面应变和线性热力学-动力学关系是催化领域有趣的话题。开发高活性和选择性的低温甲醇催化剂对于二氧化碳转化为甲醇尤为重要。本文利用密度泛函计算和微动力学模拟探讨了 Znx@TiO2(110) (x = 0-2) 上 CO2 加氢生成甲醇的过程。确定了三个模型体系的反应机理，结果表明 Zn2@TiO2(110) 是最活跃的。确定了 Zn2@TiO2(110) 上最有利的途径，并且发现 CO2 + H 生成 HCOO 是速率控制步骤。结果表明，在所研究的 18 个系统中，初始态吸附能与控制步骤势垒之间存在线性关系（称为 AEB 关系）。对应变表面的计算表明，AEB 关系存在于 ±1% 应变范围内。 Sr2@TiO2(110)和‐1%应变CaZn和ZnCu掺杂TiO2(110)是潜在的良好低温催化剂，值得进行实验测试。