Effects of Solvents on Adsorption Energies: A General Bond-Additivity Model
Effects of Solvents on Adsorption Energies: A General Bond-Additivity Model
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溶剂对吸附能的影响：一般键加和模型
DOI：
10.1021/acs.jpcc.1c06781
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Singh, Nirala
中科院分区：
文献类型：
--
作者：
Akinola, James;Campbell, Charles T.;Singh, Nirala
虽然基于量子力学的实验研究和计算，关于气体或真空条件下催化反应中间体在固体表面上的吸附能存在大量的知识，但对于液体溶剂存在下的吸附能知之甚少。本文提出了一种基于气相吸附能、溶剂对固体表面的附着能、气相吸附物的溶剂化能来估算液相吸附能的方法。最近开发了一个简单的键加性模型，用于使用溶剂的粘附能和气体吸附能来近似由于液体溶剂的额外存在而导致的吸附能（相对于气相）的变化，但该模型仅限于厚度远小于其横向尺寸（平行于表面）的吸附物。在这里，我们提出了一个简单的推广该模型的有限厚度和一般形状的吸附剂。我们提出了一个模型，通过假设分子与溶剂的各向同性相互作用，将气态分子的实验溶剂化能转化为分子-溶剂粘附能。根据分子的形状、大小和吸附几何形状，这种粘附能使我们能够估计分子被吸附时保留的溶剂化能的比例。与先前的键加性模型一样，溶剂中的吸附能比气相中的吸附能小，其大小大约等于溶剂对表面的粘附能乘以吸附时位移的溶剂分子的表面积。我们还报告了不同溶剂对金属表面分子的预测影响，其中溶剂化能，气相吸附能和溶剂/表面粘附能在文献中可用。
While a vast body of knowledge exists about adsorption energies of catalytic reaction intermediates on solid surfaces in gas or vacuum conditions based on experimental studies and calculations using quantum mechanics, much less is known about adsorption energies in the presence of liquid solvents. We present here a method for estimating adsorption energies in the liquid phase based on the gas-phase adsorption energy, the solvent’s adhesion energy to the solid surface, and the gas-phase adsorbate’s solvation energy. A simple bond-additivity model was recently developed for approximating the change in adsorption energy (relative to gas phase) due to the additional presence of liquid solvents using the solvent’s adhesion energy and the gaseous adsorbate’s solvation energy, but that model was limited to adsorbates whose thickness is much smaller than its lateral dimension (parallel to the surface). Here we present a simple extension of that model to adsorbates of finite thickness and general shape. We propose a model to convert the experimental solvation energy of a gaseous molecule into a molecule–solvent adhesion energy by assuming isotropic interaction of the molecule with the solvent. This adhesion energy allows us to estimate the fraction of this solvation energy that is retained when the molecule is adsorbed, based on the molecule’s shape, size, and adsorption geometry. As in the earlier bond-additivity model, adsorption energies in solvent are lower in magnitude than in the gas phase by an amount approximately equal to the adhesion energy of the solvent to the surface times the surface area of the solvent molecules displaced upon adsorption. We also report the predicted effects of different solvents for molecules on metal surfaces where solvation energies, gas-phase adsorption energies, and solvent/surface adhesion energies are available in the literature.
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