用密度泛函理论研究汞在CeO_2(111)表面的吸附
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摘要
采用密度泛函理论计算了Hg、HgCl、HgCl_2在CeO_2(111)表面的吸附构型、吸附能和态密度。结果表明,Hg在CeO_2(111)表面属于弱化学吸附。HgCl与CeO_2(111)表面为强化学吸附,是反应的重要中间体。HgCl_2在CeO_2(111)表面是物理吸附,易发生解离,脱除。氯对于汞的吸附和氧化产生较强的影响,这与实验结果相一致。基于计算结果,得到汞在CeO_2(111)表面的反应机理。
Using density functional theory (DFT),the adsorption configuration,adsorption energies and density of states for Hg,HgCl,HgCl_2 on CeO_2(111) surface were calculated.The calculated results show that the adsorption of Hg and HgCl on CeO_2(111) surface are mainly chemisorption.The adsorption energy of HgCl on CeO_2(111) surface is stronger than that of Hg,which indicates that the HgCl-surface is an important reaction intermediate.HgCl_2 adsorption on CeO_2(111) surface is physisorption,such that it is easy to remove from the CeO_2(111) surface.The chlorine species has a strong effect on the mercury adsorption and oxidation,which is consistent with the available experimental results.Based on the calculation results,the reaction mechanism of mercury on CeO_2(111) surface is proposed.
Using density functional theory (DFT),the adsorption configuration,adsorption energies and density of states for Hg,HgCl,HgCl_2 on CeO_2(111) surface were calculated.The calculated results show that the adsorption of Hg and HgCl on CeO_2(111) surface are mainly chemisorption.The adsorption energy of HgCl on CeO_2(111) surface is stronger than that of Hg,which indicates that the HgCl-surface is an important reaction intermediate.HgCl_2 adsorption on CeO_2(111) surface is physisorption,such that it is easy to remove from the CeO_2(111) surface.The chlorine species has a strong effect on the mercury adsorption and oxidation,which is consistent with the available experimental results.Based on the calculation results,the reaction mechanism of mercury on CeO_2(111) surface is proposed.
引文
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[3]Xu W,Wang H,Zhu T,Kuang J,Jing P.Mercury Removal from Coal Combustion Flue Gas by Modified Fly Ash[J].J Environ Sci.,2013,25(2):393~398.
[4]黄永健,周蓉生,张成江,汪云亮.大气环境中汞污染的研究进展[J].物探与化探,2002,26(4):296~298.
[5]Ye Wu,Shuxiao Wang,David G.Streets,et al.Trends in Anthropogenic Mercury Emissions in China from 1995to 2003[J].Environmental Science&Technology,2006,40(17):5312~5318.
[6]Xiaoyu Wen,Caiting Li,Xiaopeng Fan,et al.Experimental Study of Gaseous Elemental Mercury Removal with CeO2/gammaAl2O3[J].Energy&Fuels,2011,25(7):2939~2944.
[7]Jianrong Li,Jinsheng Chen,et al.Fe-Mn-Ce/ceramic Powder Composite Catalyst for Highly Volatile Elemental Mercury Removal in Simulated Coal-fired Flue Gas[J].Journal of Industrial and Engineering Chemistry,2015,25(25):352~358.
[8]雷艳丽,黄华伟,等.第一原理研究Zr元素对UO2结构与力学性能的影响[J].材料科学与工程学报,2014,32(1):126~129.
[9]李文明,吴一,刘晨吉,郑树凯,闫小兵.Cd-O共掺杂ZnTe第一性原理计算[J].材料科学与工程学报,2015,33(3):405~409.
[10]陈佰树,胡飞,吴坤,高智勇.基于第一性原理研究Heusler合金Fe2CuCa的结构和性能[J].材料科学与工程学报,2015,33(2):168~172.
[11]Wenchao Ji,Zhemin Shen,Maohong Fan,et al.Adsorption Mechanism of Elemental Mercury(Hg0)on the Surface of MnCl2(110)Studied by Density Functional Theory[J].Chemical Engineering Journal,2016,283(1):58~64.
[12]Bingkai Zhang,Jing Liu,Yingju Yang,Ming Chang.Oxidation Mechanism of Elemental Mercury by HCl over MnO2 Catalyst:Insights from First Principles[J].Chemical Engineering Journal,2015,280:354~362.
[13]Shujuan Sun,Dongsheng Zhang,Chunyu Li,et al.Density Functional Theory Study of Mercury Adsorption and Oxidation on CuO(111)Surface[J].Chemical Engineering Journal,2014,258(15):128~135.
[14]Wenpo Shan,Fudong Liu,Hhong He,XiaoyanShi,Changbin Zhang.An Environmentally-benign CeO2-TiO2 Catalyst for the Selective Catalytic Reduction of NOx with NH3in Simulated Diesel Exhaust[J].Catal Today,2012,184(1):160~165.
[15]王钲源,张红艳,潘飞,等.PANI/CeO2/WC复合材料的制备及性能[J].材料科学与工程学报,2015,33(4):564~569.
[16]张红艳,黄惠,郭忠诚,赖耀斌,付仁春.水热法制备杂化型CeO2/WC复合材料的电化学性能及表面结[J].材料科学与工程学报,2015,33(2):197~202.
[17]闫志国,周小渊,徐艳萍,宣爱国,吴元欣.CeO2掺杂Mn的密度泛函理论[J].武汉工程大学学报,2011,33(4):7~12.
[18]Yine Xie,Caiting Li,et al.Experimental Study on Hg0Removal from Flue Gas over Columnar MnOx-CeO2/activated Coke[J].Applied Surface Science,2015,333(1):59~67.
[19]Xunan Zhang,Caiting Li,et al.Simultaneous Removal of Elemental Mercury and NO from Flue Gas by V2O5-CeO2/TiO2Catalysts[J].Applied Surface Science,2015,347:392~400.
[20]Nolan Michael,Grigoleit Sonja,Sayl Dean C.,et al.Density Functional Theory Studies of the Structure and Electronic Structure of Pure and Defective Low Index Surfaces of Ceria[J].Surface Science,2005,576(1/3):217~229.