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二氧化钛纳米颗粒作为一种光催化剂,目前已经得到了广泛的应用,但是对于光催化反应的理解,尤其是在原子水平上,还明显不足,如TiO2纳米颗粒的几何结构与光催化反应活性的构效关系。本文主要介绍了我们课题组在TiO2裂解水的一些理论研究进展。通过周期性密度泛函以及周期性连续介质模型的理论计算,我们研究了水析氧反应(OER)的机理,得出了反应的决速步骤是失去第一个质子的过程,同时研究了不同纳米颗粒对该决速步骤的影响。研究指出,TiO2纳米颗粒的热力学平衡构型在1—30nm内会受到其颗粒尺寸的显著影响;尖的TiO2纳米颗粒比扁的颗粒具有更高的OER反应活性。综合以上两个因素,最终导致了光催化反应的形态依赖性。
Titanium dioxide nanoparticles as a photocatalyst have been widely used at present, but understanding of the photocatalytic reaction, especially at the atomic level, is still obviously insufficient, such as the structure of the TiO2 nanoparticles and the structure of the photocatalytic reactivity Effective relationship. This paper mainly introduces the progress of some theoretical research on TiO2 water splitting in our group. Through the periodic density functional theory and the theoretical calculation of periodic continuous medium model, we study the mechanism of oxygen evolution reaction (OER), and find out that the rate-determining step of the reaction is the process of losing the first proton. At the same time, Effect of nanoparticles on this rate-fixing step. The study indicates that the thermodynamic equilibrium configuration of TiO2 nanoparticles is significantly affected by their particle size in the range of 1-30 nm. Sharp TiO2 nanoparticles have higher OER reactivity than the flat particles. The combination of the above two factors eventually led to the morphological dependence of the photocatalytic reaction.