采用基于密度泛函理论的第一性原理方法研究了本征石墨烯、Pt掺杂石墨烯在不同吸附位点和方向上对氰化氢(HCN)的吸附作用。计算、分析了本征石墨烯和Pt掺杂石墨烯的几何结构,以及吸附单个HCN分子后的吸附能、吸附高度和态密度的变化。研究发现,本征石墨烯吸附时,C—C键长由1.42Å变为1.416～1.430Å;垂直吸附相较于平行吸附,吸附能提高。Pt掺杂后,石墨烯的几何结构改变明显,C—Pt键长由1.42Å增加至1.838～1.839Å,对HCN的吸附性能显著提高,吸附能增大,吸附距离减小,最佳吸附位点为H位。Pt掺杂石墨烯与本征石墨烯相比,掺杂后的石墨烯与HCN分子之间的电子态密度杂化效果增强,表明Pt掺杂石墨烯提高了对HCN分子的吸附作用。
The adsorption of hydrogen cyanide (HCN) on intrinsic graphene and Pt-doped graphene at different adsorption sites and directions was studied using first-principles method based on density functional theory.The geometric structures of intrinsic graphene and Pt-doped graphene,as well as the changes in the adsorption energy,adsorption height,and density of states after adsorbing a single HCN molecule,were calculated and analyzed.The study found that when intrinsic graphene adsorbed,the C—C bond length changed from 1.42Å to a range of 1.416-1.430Å,and the adsorption energy increased for vertical adsorption compared to parallel adsorption.After Pt-doping,the geometric structure of graphene changed significantly,and the C—Pt bond length increased from 1.42Å to a range of 1.838-1.839Å.The adsorption performance of HCN was significantly improved,with an increase in adsorption energy and a decrease in adsorption distance,and the optimal adsorption site was the H site.Compared with intrinsic graphene,the hybridization effect of the electronic density of states between Pt-doped graphene and HCN molecules was enhanced,indicating that Pt-doped graphene improved the adsorption of HCN molecules.
[1] 伊志豪,孙杰,李吉刚,等.气相中氰化氢消除研究进展[J].精细化工,2021,38(1):62-70.
[2] 曾洪亮.石墨烯制备方法的研究进展[J].炭素技术,2021,40(5):8-13.
[3] 黄毅,陈永胜.石墨烯的功能化及其相关应用[J].中国科学,2009,39(9):887-896.
[4] Dai J,Yuan J,Giannozzi P.Gas adsorption on graphene doped with B,N,Al,and S:a theoretical study[J].Applied Physics Letters,2009,95(23):232105.
[5] Chi M,Zhao Y P.Adsorption of formaldehyde molecule on the intrinsic and Al-doped graphene:a first principle study[J].Computational Materials Science,2009,46(4):1085-1090.
[6] Zhou Q,Yuan L,Yang X,et al.DFT study of formaldehyde adsorption on vacancy defected graphene doped with B,N,and S[J].Chemical Physics,2014,440:80-86.
[7] Jia X,Zhang H,Zhang Z,et al.Effect of doping and vacancy defects on the adsorption of CO on graphene[J].Materials Chemistry and Physics,2020,249:123114.
[8] Wang W,Zhang Y,Shen C,et al.Adsorption of CO molecules on doped graphene:a first-principles study[J].Aip Advances,2016,6(2):025317.
[9] 覃礼.本征石墨烯和Al掺杂石墨烯吸附H2S分子的密度泛函理论研究[D].太原:太原理工大学,2017.
[10] 何沛,杨文娟,杨晨,等.石墨烯对苯酚的吸附性能及机理研究[J].化工新型材料,2022,50(7):193-198,203.
[11] Ni J,Quintana M,Song S.Adsorption of small gas molecules on transition metal (Fe,Ni and Co,Cu) doped graphene:a systematic DFT study[J].Physica E:Low-dimensional Systems and Nanostructures,2020,116:113768.
[12] 郭惠霞,闫任翔,席晓华.Pt掺杂氧化石墨烯在酸性介质中催化氧还原反应DFT研究[J].分子催化,2018,32(5):471-480.
[13] 孙建平,缪应蒙,曹相春.基于密度泛函理论研究掺杂Pd石墨烯吸附O2及CO[J].物理学报,2013,62(3):265-272.
[14] Vanderbilt D.Soft self-consistentpseudopotentials ina generalized eigenvalue formalism[J].Phys Rev B,1990,41:7892.
[15] 王琳琳.掺杂石墨烯吸附H2、CO的第一性原理研究[D].南京:南京邮电大学,2020.
[16] 唐珊,姜丽,刘佳鑫,等.甲醛在本征和金掺杂石墨烯表面的吸附:第一性原理研究[J].贵州师范大学学报(自然科学版),2022,40(6):95-101.
[17] 向鑫,刘浪,把静文.B、N、S掺杂石墨烯表面质子吸附的第一性原理研究[J].原子与分子物理学报,2023,40(3):85-90.
[18] 苗一凡.掺杂石墨烯吸附甲醛与一氧化碳气体的第一性原理研究[D].成都:电子科技大学,2019.
[19] 张炎,安立宝,范青青,等.空位缺陷及B掺杂石墨烯吸附CO2+的第一性原理研究[J].中国有色金属学报,2022,32(1):139-147.
[20] 曲研.石墨烯内聚能的密度泛函理论研究[J].应用物理,2021,11(1):8.
[21] 段良平.石墨烯吸附甲醛第一性原理计算及传感器应用研究[D].杭州:浙江大学,2018.
基金资助
国家自然科学基金(51301144);云南省农业基础研究联合专项(202301BD070001-012)
PDF
