Yan Yiming, Zeng Fuping, Wang Long, Wang Xiangyu, Zhu Kexin, Yao Qiang, Tang Ju
State Key Laboratory of Power Grid Environmental Protection, School of Electrical Engineering and Automation, Wuhan University, Wuhan, 430072, China.
State Grid Chongqing Electric Power Company, Institute of Electric Power Science, Chongqing, 401123, China.
J Mol Model. 2023 Oct 25;29(11):350. doi: 10.1007/s00894-023-05737-8.
SF gas has a strong greenhouse effect, and how to treat SF in an environmentally friendly way has been a hot topic of current research. In this paper, the adsorption behavior of SF on the surface of Pd-doped hydroxyl-terminated modified TiCT (i.e., TiC(OH)) was investigated based on the density functional theory using two-dimensional MXene as the catalyst. The structures of different Pd-doped TiC(OH) were analyzed and the most structurally stable doped structures were selected as the basis for subsequent calculations. A large number of adsorption configurations were constructed and geometrically optimized, and the adsorption energy, charge transfer, differential charge density, and density of states of the systems were calculated in order to analyze the gas-solid interactions and find the surface active sites; compared with the adsorption performance of undoped TiC(OH) on SF, it was found that Pd doping played a less inhibitory role in the adsorption of SF on the TiC(OH) surface. The results of this study can provide theoretical support for the use of Pd-doped TiC(OH) as a catalyst for the degradation of SF.
In this paper, simulations of SF adsorption on TiCT surfaces are based on density functional theory and are carried out in the Dmol module of Material Studio. To better describe the non-uniform electron density of the actual system, the PBE functional in the generalized gradient approximation (GGA) was chosen for the optimization of the structure of the gas-solid interface system and the calculation of the relevant electronic properties, combined with the Grimme dispersion correction in the DFT-D dispersion correction for the electron exchange correlation term. Because both Pd and Ti are transition metal elements, the mode-conserving pseudopotential DNP basis set containing relativistic effects was chosen for the electronic wave function expansion. In this paper, an all-electron model is used for the inner core treatment of gas molecules and a density generalized semi-nuclear pseudopotential DSSP is used for the solid surface treatment.
六氟化硫（SF）具有很强的温室效应，如何以环境友好的方式处理SF一直是当前研究的热点话题。本文基于密度泛函理论，以二维MXene为催化剂，研究了SF在掺钯羟基封端改性TiCT（即TiC(OH)）表面的吸附行为。分析了不同掺钯TiC(OH)的结构，选择结构最稳定的掺杂结构作为后续计算的基础。构建了大量吸附构型并进行几何优化，计算了体系的吸附能、电荷转移、差分电荷密度和态密度，以分析气固相互作用并找到表面活性位点；与未掺杂的TiC(OH)对SF的吸附性能相比，发现钯掺杂对SF在TiC(OH)表面的吸附起到的抑制作用较小。本研究结果可为使用掺钯TiC(OH)作为降解SF的催化剂提供理论支持。
本文中，SF在TiCT表面吸附的模拟基于密度泛函理论，在Material Studio的Dmol模块中进行。为了更好地描述实际体系的非均匀电子密度，选择广义梯度近似（GGA）中的PBE泛函来优化气固界面体系的结构并计算相关电子性质，并结合DFT-D色散校正中的Grimme色散校正来处理电子交换相关项。由于钯和钛都是过渡金属元素，选择包含相对论效应的模守恒赝势DNP基组来展开电子波函数。本文中，对气体分子的内芯处理采用全电子模型，对固体表面处理采用密度广义半核赝势DSSP。
