CQDXXB重庆大学学报Journal of Chongqing University1000-582X重庆大学学报编辑部中国重庆cqdxxb-42-8-501000-582X(2019)08-050-0910.11835/j.issn.1000-582X.2019.08.006O647.3CO和Cl2在TiO2(110)表面的吸附行为Adsorption of both CO and Cl2 on TiO2(110) surface石胜云SHIShengyun
The first principle calculation based on density functional theory(DFT) is used in this paper to investigate the adsorption behavior of CO and Cl2 on TiO2(110) surface. The behavioral mechanism of the co-adsorption of CO and Cl2 on the TiO2 (110) surface is revealed by the calculation of the adsorption structure, adsorption energy, charge density and density of states (DOS) of the system. The adsorption of both CO and Cl2 on the TiO2(110) surface was mutually reinforcing, and the average adsorption energy was -1.367 4 eV, and Cl2 could be captured by the surface Ti atom, the sd3 orbital hybridization happening on the surface Ti(5c) atom. When the adsorption reaction occurred, a transient electron flow CO→TiO2(110)→Cl was formed on the surface. The DOS showed that the strength of Ti-O bond on (110) surface was weakened, indicating that the presence of CO has a promoting effect on the chlorination of TiO2. Meanwhile, the surface O atoms was activated and the average energy of 1.418 6 eV was released as the dissociation of this O atom with CO from the surface to form CO2 molecules, which destroyed the structure of TiO2(110) and provided a good adsorption site for the next Cl2 molecules.
二氧化钛吸附行为密度泛函理论吸附结构态密度分布rutile TiO2adsorption behaviordensity functional theoryadsorption structuredensity of states国家自然科学基金资助项目51674052国家自然科学基金资助项目91634106重庆市基础研究与前沿技术研究计划项目cstc2018jcyjAX0003国家自然科学基金资助项目(51674052,91634106);重庆市基础研究与前沿技术研究计划项目(cstc2018jcyjAX0003)the National Science Foundation of China51674052the National Science Foundation of China91634106the Chongqing Research Program of Basic Research and Frontier Technologycstc2018jcyjAX0003Supported by the National Science Foundation of China(51674052 and 91634106) and the Chongqing Research Program of Basic Research and Frontier Technology(cstc2018jcyjAX0003)
在本研究中拟基于密度泛函理论,利用CASTEP(Cambridge Sequential Total Energy Package)软件包构造金红石TiO2(110)表面,并对CO和Cl2作用于该表面时所发生的吸附反应进行计算分析,揭示CO和Cl2同时作用于TiO2(110)表面的吸附行为,为进一步探究钛氧化物的加碳氯化催化反应机理过程奠定基础。
Schematic diagram of adsorption structure of CO and Cl2 onto TiO2(110) surface. The upper part is the positive view and the bottom is the top view. The C, O and Cl atoms are in grey, red and green respectively. The red dashed lines represent van der Waals forces while the green dotted lines is used to mark distance without any practical significance
Differential charge density for adsorption of Cl2 and CO on TiO2(110) surface. The isosurface level is 0.000 05e/nm3. The blue and yellow colors indicate the electron accumulation and depletion, respectively.
Mulliken charge analysis for adsorption of Cl2 and CO on TiO2(110) surface*
被吸附对象
原子轨道
qCO/e
qCl2/e
qⅠ/e
ΔqⅠ/e
qⅡ/e
ΔqⅡ/e
qⅢ/e
ΔqⅢ/e
*正的Δq表示失电子,负的Δq表示得电子。对应的C, O和Cl原子在图 3中已标记。* Positive Δq indicates the electron donor and negative Δq indicates the electron acceptor. The C, O and Cl atoms are marked in configurations in Fig. 3.
Partial density of states (PDOS) for O(3c) and Ti(5c) atoms of TiO2(110) surface. The dashed vertical line at energy = 0 eV indicates the Fermi level (Ef).
The energy profiles for reaction pathway of desorption of CO2 from TiO2(110). IS′ refers to a state of free TiO2(110)surface, free CO and Cl2 molecules, IS to a state of adsorption of Cl2 and CO on TiO2(110) surface, TS to a state of transformation of CO2 species into transition state on surface, and FS to a state of formation of CO2
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