CO_(2)在二氧化钛(101)表面上转换为HCOOH和CO机制的第一性原理研究  

The First-principle Study on the Mechanism of CO_(2)Conversion to HCOOH and CO on TiO_(2)(101)Surface

作　　者：郭浩 杨蕊 郎秀峰[2] 安娜[1] 贾鹏飞 GUO Hao;YANG Rui;LANG Xiufeng;An Na;JIA Pengfei(College of Urban Construction,Hebei Normal University of Science&Technology;College of Physical Science and Technology,Hebei Normal University of Science&Technology,Qinghuangdao Hebei,066004,China)

机构地区：[1]河北科技师范学院城市建设学院,河北秦皇岛066004 [2]河北科技师范学院物理科学与技术学院,河北秦皇岛066004

出　　处：《河北科技师范学院学报》2024年第4期1-6,共6页Journal of Hebei Normal University of Science & Technology

基　　金：国家自然科学基金青年项目(项目编号:12202134);河北省自然科学基金面上项目(项目编号:A2024407001);河北省高等学校科学技术研究青年拔尖人才项目(项目编号:BJK2024032)。

摘　　要：光催化还原CO_(2)生成一些可燃物是有效缓解全球变暖的一种方式。二氧化钛(TiO_(2))是最有前景且化学稳定性良好的半导体材料之一,它也是优良的CO_(2)还原剂。基于此,本次研究运用第一性原理计算对锐钛矿TiO_(2)(101)表面上CO_(2)催化还原为HCOOH和CO的热力学能和动力学势垒进行了系统研究。结果表明,TiO_(2)(101)表面上CO_(2)催化还原为CO的路径具有更低的热力学能垒。通过计算中间产物COOH和HCOO的态密度和差分电荷密度,表明较稳定的COOH吸附结构是导致CO更容易生成的重要原因。运用过渡态理论计算出锐钛矿TiO_(2)(101)表面上CO_(2)还原为CO的决速步势垒为2.12 eV,低于CO_(2)转化为HCOOH决速步势垒(2.27 eV),证实了相比于产物HCOOH,TiO_(2)(101)表面上的CO_(2)能更快地转化为CO。上述研究结果有助于进一步认识锐钛矿TiO_(2)(101)表面上CO_(2)光催化还原机制。It is an effective way to mitigate global warming with CO_(2)reduction and combustibles production.Titanium dioxide(TiO_(2))is one of the most common,promising,and chemically stable semiconductor materials,and it is also an excellent CO_(2)reducer.The thermodynamic energies and kinetic barriers for the catalytic reduction of CO_(2)to HCOOH and CO on the anatase TiO_(2)(101)surface were systematically studied with first-principle calculation.The results showed that the pathway of the photocatalytic reduction of CO_(2)to CO on the TiO_(2)(101)surface had a lower energy barrier.Stable COOH adsorption structure could easily generate CO by calculating the density of states and differential charge density of the intermediate products COOH and HCOO.The rate-determining step barrier for the reduction of CO_(2)to CO on the anatase TiO_(2)(101)surface was 2.12 eV with the transition state theory,which was lower than that for the conversion of CO_(2)to HCOOH(2.27 eV).The result confirmed that CO_(2)could be converted to CO faster than to HCOOH on the TiO_(2)(101)surface.These findings significantly enhanced the understanding of the photocatalytic reduction mechanism of CO_(2)on the anatase TiO_(2)(101)surface.

关 键 词：二氧化钛 CO_(2)还原 密度泛函理论 热力学能 动力学势垒 

分 类 号：O64[理学—物理化学]