Laboratoire Matériaux Divisés Interfaces Réactivité Electrochimie, UMR 7246, Aix-Marseille Université et CNRS, Avenue de l'Escadrille Normandie-Niemen, 13397, Marseille Cedex, France.
J Mol Model. 2012 Nov;18(11):4819-30. doi: 10.1007/s00894-012-1486-0. Epub 2012 Jun 16.
A theoretical investigation of the adsorption of CO₂ onto ZrO₂ is presented. Various cluster models were used to mimic different basic and acidic sites on the surface. The method used was the density functional theory with the generalized gradient approximation and including Grimme's empirical model in order to properly describe the weak interactions that may occur between the adsorbate and the surface. We found that the adsorption at sites exhibiting two adjacent unsaturated zirconium atoms led to either the exothermic dissociation of CO₂ or to a strongly physisorbed state. By contrast, on a single unsaturated zirconium, CO₂ was adsorbed in an apical manner. In this case, the molecule is highly polarized and the adsorption energy amounts to -64.6 kJ mol⁻¹. Finally, the weakest adsorption of CO₂ occurred on the basic OH sites on the surface.
本文对 CO₂在 ZrO₂上的吸附进行了理论研究。使用了各种团簇模型来模拟表面上不同的碱性和酸性位。所使用的方法是密度泛函理论与广义梯度近似相结合，并包括 Grimme 的经验模型，以便正确描述吸附物与表面之间可能发生的弱相互作用。我们发现，在具有两个相邻不饱和锆原子的位上的吸附导致 CO₂的放热离解或强物理吸附状态。相比之下，在单个不饱和锆原子上，CO₂以顶端方式吸附。在这种情况下，分子被高度极化，吸附能达到-64.6 kJ mol⁻¹。最后，CO₂在表面上的碱性 OH 位上的吸附最弱。
