Cr掺杂Cu_2O的光催化性质的第一性原理研究
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摘要
采用第一性原理计算的方法,研究了不同浓度及不同位置Cr掺杂Cu_2O体系的缺陷形成能、电子结构和可见光区域的光催化性质及产生机理。结果表明,本征Cu_2O显示半导体特性,在可见光区域吸收很弱;不同浓度、不同位置的Cr掺杂体系均是稳定的,显示金属特性。与本征Cu_2O相比,随着Cr掺杂浓度的增大,体系在可见光范围内的吸收峰均有不同程度的增强,并且两个Cr原子近邻掺杂时可见光区域的吸收系数最大,光催化效率最强。态密度分析发现,Cr掺杂体系在可见光范围的吸收主要由Cr 3d态电子的带内跃迁产生;不同掺杂浓度和结构构型主要影响材料在长波长段的物理性质,而对短波长段的性质影响很小。因此,通过增大Cr掺杂浓度及调控掺杂位置可以提高Cu_2O在可见光区域的光催化效率,推动Cu_2O在光催化方面的发展。
It was found in recent years that inorganic semiconductor materials exhibited excellent photocatalytic performance and had broad application prospects in environmental treatment and energy conversion;in this aspect,Cu_2O semiconductor has attracted extensive attention owing its superior adsorption capacity for oxygen and high photo absorption coefficient.Considering that doping in Cu_2O could improve its photocatalytic efficiency in the visible region,in this work,the formation energy,electronic structure,and photocatalytic properties of Cu_2O doped with different concentrations of Cr were investigated by first-principle calculation.The results indicate that intrinsic Cu_2O shows semiconductor properties and the absorption of visible-light is weak;after doping with different concentrations of Cr and in different positions,the Cr-doped Cu_2O system are all stable and show metallic characteristics.Compared with intrinsic Cu_2O,the absorption peaks of Cr-doped Cu_2O in the visible-light range are enhanced.When two Cr atoms are doped in the nearest neighbor configuration,the absorption coefficient in the visible-light region is the largest,with the strongest photocatalytic efficiency.The density of states shows that the visible-light absorption of Cr-doped Cu_2O systems is mainly induced by the intraband transition of electrons in Cr 3d states.The doping concentration and configuration influence mainly the physical properties of Cu_2O in the long wavelength range,but have little effect in the short wavelength range.Therefore,an increase in the doping concentration of Cr dopants and a change in the configuration can improve its photocatalytic efficiency in the visible region,and then promote the progress of Cu_2O application in photocatalysis.
It was found in recent years that inorganic semiconductor materials exhibited excellent photocatalytic performance and had broad application prospects in environmental treatment and energy conversion;in this aspect,Cu_2O semiconductor has attracted extensive attention owing its superior adsorption capacity for oxygen and high photo absorption coefficient.Considering that doping in Cu_2O could improve its photocatalytic efficiency in the visible region,in this work,the formation energy,electronic structure,and photocatalytic properties of Cu_2O doped with different concentrations of Cr were investigated by first-principle calculation.The results indicate that intrinsic Cu_2O shows semiconductor properties and the absorption of visible-light is weak;after doping with different concentrations of Cr and in different positions,the Cr-doped Cu_2O system are all stable and show metallic characteristics.Compared with intrinsic Cu_2O,the absorption peaks of Cr-doped Cu_2O in the visible-light range are enhanced.When two Cr atoms are doped in the nearest neighbor configuration,the absorption coefficient in the visible-light region is the largest,with the strongest photocatalytic efficiency.The density of states shows that the visible-light absorption of Cr-doped Cu_2O systems is mainly induced by the intraband transition of electrons in Cr 3d states.The doping concentration and configuration influence mainly the physical properties of Cu_2O in the long wavelength range,but have little effect in the short wavelength range.Therefore,an increase in the doping concentration of Cr dopants and a change in the configuration can improve its photocatalytic efficiency in the visible region,and then promote the progress of Cu_2O application in photocatalysis.
引文
[1]SU J,LIN Z,CHEN G.Ultrasmall graphitic carbon nitride quantum dots decorated self-organized TiO2nanotube arrays with highly efficient photoelectrochemical activity[J].Appl Catal B:Environ,2016,186:127-135.
[2]LI C,CHEN G,SUN J,RAO J,HAN Z,HU Y,XING W,ZHANG C.Doping effect of phosphate in Bi2WO6,and universal improved photocatalytic activity for removing various pollutants in water[J].Appl Catal B:Environ,2016,188:39-47.
[3]LOU S,JIA X,WANG Y,ZHOU S.Template-assisted in-situ synthesis of porous AgBr/Ag composite microspheres as highly efficient visiblelight photocatalyst[J].Appl Catal B:Environ,2015,176:586-593.
[4]HE Y R,YAN F F,YU H Q,YUAN S J,TONG Z H,SHENG G P.Hydrogen production in a light-driven photoelectrochemical cell[J].Appl Energy,2014,113(1):164-168.
[5]OSTERLOH F E.Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting[J].Chem Soc Rev,2013,42(6):2294-2320.
[6]高鑫,刘祥萱,王煊军,朱左明.改性Cu2O光催化剂的研究进展[J].材料工程,2016,44(1):120-128.(GAO Xin,LIU Xiang-xuan,WANG Xuan-jun,ZHU Zuo-ming.Progress in research on modified Cu2O photocatalyst[J].J M ater Eng,2016,44(1):120-128.)
[7]JIANG D,XUE J,WU L,ZHOU W,ZHANG Y,LI X.Photocatalytic performance enhancement of CuO/Cu2O heterostructures for photodegradation of organic dyes:Effects of CuO morphology[J].Appl Catal B:Environ,2017,211:199-204.
[8]PANG H,GAO F,LU Q.Glycine-assisted double-solvothermal approach for various cuprous oxide structures with good catalytic activities[J].CrystEngCommun,2010,12(2):406-412.
[9]DAS K,SHARMA S N,KUMAR M,DE S K.Luminescence properties of the solvothermally synthesized blue light emitting Mn doped Cu2Onanoparticles[J].J Appl Phys,2010,107(2):433-147.
[10]LU Y M,CHEN C Y,MING H L.Effect of hydrogen plasma treatment on the electrical properties of sputtered N-doped cuprous oxide films[J].Thin Solid Films,2005,480(1-3):482-485.
[11]唐爱东,胡莉琴,王朵.Cu2O的室温液相法合成及光催化性能[J].功能材料,2011,42(11):2034-2037.(TANG Ai-dong,HU Li-qin,WANG Duo.Photo-catalytic property of Cu2O prepared by roomtemperature liquid phase redox method[J].JFunct M ater,2011,42(11):2034-2037.)
[12]LI L,CHENG Y,WANG W,REN S,YANG Y,LUO X,LIU H.Effects of copper and oxygen vacancies on the ferromagnetism of Mn-and Co-doped Cu2O[J].Solid State Commun,2011,151(21):1583-1587.
[13]ZHENG Z,HUANG B,WANG Z,GUO M,QIN X,ZHANG X,WANG P,DAI Y.Crystal faces of Cu2O and their stabilities in photocatalytic reaction[J].J Phys Chem C,2009,113(32):462-470.
[14]LEAH ISSEROFF B,CARTER E A.First-principles predictions of the structure,stability,and photocatalytic potential of Cu2O surfaces[J].J Phys Chem B,2013,117(49):15750-60.
[15]GAI Y,LI J,LI S S,XIA J B,WEI S H.Design of narrow-gap TiO2:A passivated codoping approach for enhanced photoelectrochemical activity[J].Phys Rev Lett,2009,102(3):036402.
[16]BALACHANDRAN S,SWAMINATHAN M.Facile fabrication of heterostructured Bi2O3-ZnO photocatalyst and its enhanced photocatalytic activity[J].J Phys Chem C,2013,116(50):26306-26312.
[17]WANG Z,HUANG B,DAI Y,QIN X,ZANG X,WANG P,LIU H,YU J.Highly photocatalytic ZnO/In2O3heteronanostructures synthesized by a coprecipitation method[J].J Phys Chem C,2009,113(11):4612-4617.
[18]VAIANO V,MATARANGOLO M,SACCO O,SANNINO D.Photocatalytic treatment of aqueous solutions at high dye concentration using praseodymium-doped ZnO catalysts[J].Appl Catal B:Environ,2017,209:621-630.
[19]JIANG Z Q,YAO G,AN X Y,FU Y J,GAO L H,WU W D,WANG X M.Electronic and optical properties of Au-doped Cu2O:A first principles investigation[J].Chin Phys B,2014,23(5):470-477.
[20]ZHANG L,JING D,GUO L,YAO X.In situ photochemical synthesis of Zn-doped Cu2O hollow microcubes for high efficient photocatalytic H2production[J].Acs Sustainable Chem Eng,2014,2(6):1446-1452.
[21]彭健,任荣康,李健宁,张明举,牛猛,马蕾,闫小兵,郑树凯.Cl掺杂Cu2O的第一性原理计算[J].微纳电子技术,2017,(3):157-161.(PENG Jian,REN Rong-kang,LI Jian-ning,ZHANG Ming-ju,NIU Meng,MA Lei,YAN Xiao-bing,ZHENG Shu-kai.First principles calculation of Cl doped Cu2O[J].M icronanoelectronic Technol,2017,(3):157-161.)
[22]SEGALL M D,LINDAN P J D,PROBERT M J,PICKARD C J,HASNIP P J,CLARK S J,PAYNE M C.First-principles simulation:ideas,illustrations and the CASTEP code[J].J Phys Condens M atter,2002,14(11):2717-2744.
[23]VANDERBILT D.Soft self-consistent pseudopotentials in a generalized eigenvalue formalism[J].Phys Rev B:Condens Matter,1990,41(11):7892-7895.
[24]PERDEW J P,BURKE K,ERNZERHOF M.Generalized gradient approximation made simple[J].Phys Rev Lett,1996,77(18):3865-3868.
[25]ZHAO R,HASKELL W B,TAN V Y F.Stochastic L-BFGS:Improved convergence rates and practical acceleration strategies[J].IEEETrans Signal Process,2018,66(5):1155-1169.
[26]KATAYAMA J,ITO K,MATSUOKA M,TAMAKI J.Performance of Cu2O/ZnO solar cell prepared by two-step electrodeposition[J].JAppl Electrochem,2004,34(7):687-692.
[27]濮春英,李洪婧,唐鑫,张庆瑜.N掺杂Cu2O薄膜的光学性质及第一性原理分析[J].物理学报,2012,61(4):380-385.(PU Chun-ying,LI Hong-jing,TANG Xin,ZHANG Qing-yu.Opyical properties of N-doped Cu2O films and relevant analysis with firstprinciples calculations(in Chinese)[J].Acta Phys Sin,2012,61(4):380-385.)
[28]陈婷,庞军,何红,彭赟,吴楠,徐建,杜成旭,庞星星,毋志民,崔玉亭.Mn掺杂LiMgP新型稀磁半导体的光电性质[J].科学通报,2017,62(35):4169-4178.(CHEN Ting,PANG Jun,HE Hong,PENG Yun,WU Nan,XU Jian,DU Cheng-xu,PANG Xing-xing,WU Zhi-min,CUI Yu-ting.Photoelectric properties of Mn-doped LiMgP new diluted magnetic semiconductor(in Chinese)[J].Chin Sci Bull,2017,62(35):4169-4178.)
[29]ALEJANDRO M R,MORENO M G,TAKEUCHI N.First principles calculations of the electronic properties of bulk Cu2O,clean and doped with Ag,Ni,and Zn[J].Solid State Sci,2003,5(2):291-295.
[30]XIA S,LIU L,KONG Y,DIAO Y.A DFT study on NEA GaN photocathode with an ultrathin n-type Si-doped GaN cap layer[J].Chem Phys Lett,2016,663:90-96.
[31]SAHA S,SINHA T P,MOOKERJEE A.Electronic structure,chemical bonding,and optical properties of paraelectric BaTiO3[J].Phys Rev B,2000,62(13):699-702.
[32]LI L,WANG W,LIU H,LIU X,SONG Q,REN S.First principles calculations of electronic band structure and optical properties of Crdoped ZnO[J].J Phys Chem C,2009,113(19):8460-8464.
[2]LI C,CHEN G,SUN J,RAO J,HAN Z,HU Y,XING W,ZHANG C.Doping effect of phosphate in Bi2WO6,and universal improved photocatalytic activity for removing various pollutants in water[J].Appl Catal B:Environ,2016,188:39-47.
[3]LOU S,JIA X,WANG Y,ZHOU S.Template-assisted in-situ synthesis of porous AgBr/Ag composite microspheres as highly efficient visiblelight photocatalyst[J].Appl Catal B:Environ,2015,176:586-593.
[4]HE Y R,YAN F F,YU H Q,YUAN S J,TONG Z H,SHENG G P.Hydrogen production in a light-driven photoelectrochemical cell[J].Appl Energy,2014,113(1):164-168.
[5]OSTERLOH F E.Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting[J].Chem Soc Rev,2013,42(6):2294-2320.
[6]高鑫,刘祥萱,王煊军,朱左明.改性Cu2O光催化剂的研究进展[J].材料工程,2016,44(1):120-128.(GAO Xin,LIU Xiang-xuan,WANG Xuan-jun,ZHU Zuo-ming.Progress in research on modified Cu2O photocatalyst[J].J M ater Eng,2016,44(1):120-128.)
[7]JIANG D,XUE J,WU L,ZHOU W,ZHANG Y,LI X.Photocatalytic performance enhancement of CuO/Cu2O heterostructures for photodegradation of organic dyes:Effects of CuO morphology[J].Appl Catal B:Environ,2017,211:199-204.
[8]PANG H,GAO F,LU Q.Glycine-assisted double-solvothermal approach for various cuprous oxide structures with good catalytic activities[J].CrystEngCommun,2010,12(2):406-412.
[9]DAS K,SHARMA S N,KUMAR M,DE S K.Luminescence properties of the solvothermally synthesized blue light emitting Mn doped Cu2Onanoparticles[J].J Appl Phys,2010,107(2):433-147.
[10]LU Y M,CHEN C Y,MING H L.Effect of hydrogen plasma treatment on the electrical properties of sputtered N-doped cuprous oxide films[J].Thin Solid Films,2005,480(1-3):482-485.
[11]唐爱东,胡莉琴,王朵.Cu2O的室温液相法合成及光催化性能[J].功能材料,2011,42(11):2034-2037.(TANG Ai-dong,HU Li-qin,WANG Duo.Photo-catalytic property of Cu2O prepared by roomtemperature liquid phase redox method[J].JFunct M ater,2011,42(11):2034-2037.)
[12]LI L,CHENG Y,WANG W,REN S,YANG Y,LUO X,LIU H.Effects of copper and oxygen vacancies on the ferromagnetism of Mn-and Co-doped Cu2O[J].Solid State Commun,2011,151(21):1583-1587.
[13]ZHENG Z,HUANG B,WANG Z,GUO M,QIN X,ZHANG X,WANG P,DAI Y.Crystal faces of Cu2O and their stabilities in photocatalytic reaction[J].J Phys Chem C,2009,113(32):462-470.
[14]LEAH ISSEROFF B,CARTER E A.First-principles predictions of the structure,stability,and photocatalytic potential of Cu2O surfaces[J].J Phys Chem B,2013,117(49):15750-60.
[15]GAI Y,LI J,LI S S,XIA J B,WEI S H.Design of narrow-gap TiO2:A passivated codoping approach for enhanced photoelectrochemical activity[J].Phys Rev Lett,2009,102(3):036402.
[16]BALACHANDRAN S,SWAMINATHAN M.Facile fabrication of heterostructured Bi2O3-ZnO photocatalyst and its enhanced photocatalytic activity[J].J Phys Chem C,2013,116(50):26306-26312.
[17]WANG Z,HUANG B,DAI Y,QIN X,ZANG X,WANG P,LIU H,YU J.Highly photocatalytic ZnO/In2O3heteronanostructures synthesized by a coprecipitation method[J].J Phys Chem C,2009,113(11):4612-4617.
[18]VAIANO V,MATARANGOLO M,SACCO O,SANNINO D.Photocatalytic treatment of aqueous solutions at high dye concentration using praseodymium-doped ZnO catalysts[J].Appl Catal B:Environ,2017,209:621-630.
[19]JIANG Z Q,YAO G,AN X Y,FU Y J,GAO L H,WU W D,WANG X M.Electronic and optical properties of Au-doped Cu2O:A first principles investigation[J].Chin Phys B,2014,23(5):470-477.
[20]ZHANG L,JING D,GUO L,YAO X.In situ photochemical synthesis of Zn-doped Cu2O hollow microcubes for high efficient photocatalytic H2production[J].Acs Sustainable Chem Eng,2014,2(6):1446-1452.
[21]彭健,任荣康,李健宁,张明举,牛猛,马蕾,闫小兵,郑树凯.Cl掺杂Cu2O的第一性原理计算[J].微纳电子技术,2017,(3):157-161.(PENG Jian,REN Rong-kang,LI Jian-ning,ZHANG Ming-ju,NIU Meng,MA Lei,YAN Xiao-bing,ZHENG Shu-kai.First principles calculation of Cl doped Cu2O[J].M icronanoelectronic Technol,2017,(3):157-161.)
[22]SEGALL M D,LINDAN P J D,PROBERT M J,PICKARD C J,HASNIP P J,CLARK S J,PAYNE M C.First-principles simulation:ideas,illustrations and the CASTEP code[J].J Phys Condens M atter,2002,14(11):2717-2744.
[23]VANDERBILT D.Soft self-consistent pseudopotentials in a generalized eigenvalue formalism[J].Phys Rev B:Condens Matter,1990,41(11):7892-7895.
[24]PERDEW J P,BURKE K,ERNZERHOF M.Generalized gradient approximation made simple[J].Phys Rev Lett,1996,77(18):3865-3868.
[25]ZHAO R,HASKELL W B,TAN V Y F.Stochastic L-BFGS:Improved convergence rates and practical acceleration strategies[J].IEEETrans Signal Process,2018,66(5):1155-1169.
[26]KATAYAMA J,ITO K,MATSUOKA M,TAMAKI J.Performance of Cu2O/ZnO solar cell prepared by two-step electrodeposition[J].JAppl Electrochem,2004,34(7):687-692.
[27]濮春英,李洪婧,唐鑫,张庆瑜.N掺杂Cu2O薄膜的光学性质及第一性原理分析[J].物理学报,2012,61(4):380-385.(PU Chun-ying,LI Hong-jing,TANG Xin,ZHANG Qing-yu.Opyical properties of N-doped Cu2O films and relevant analysis with firstprinciples calculations(in Chinese)[J].Acta Phys Sin,2012,61(4):380-385.)
[28]陈婷,庞军,何红,彭赟,吴楠,徐建,杜成旭,庞星星,毋志民,崔玉亭.Mn掺杂LiMgP新型稀磁半导体的光电性质[J].科学通报,2017,62(35):4169-4178.(CHEN Ting,PANG Jun,HE Hong,PENG Yun,WU Nan,XU Jian,DU Cheng-xu,PANG Xing-xing,WU Zhi-min,CUI Yu-ting.Photoelectric properties of Mn-doped LiMgP new diluted magnetic semiconductor(in Chinese)[J].Chin Sci Bull,2017,62(35):4169-4178.)
[29]ALEJANDRO M R,MORENO M G,TAKEUCHI N.First principles calculations of the electronic properties of bulk Cu2O,clean and doped with Ag,Ni,and Zn[J].Solid State Sci,2003,5(2):291-295.
[30]XIA S,LIU L,KONG Y,DIAO Y.A DFT study on NEA GaN photocathode with an ultrathin n-type Si-doped GaN cap layer[J].Chem Phys Lett,2016,663:90-96.
[31]SAHA S,SINHA T P,MOOKERJEE A.Electronic structure,chemical bonding,and optical properties of paraelectric BaTiO3[J].Phys Rev B,2000,62(13):699-702.
[32]LI L,WANG W,LIU H,LIU X,SONG Q,REN S.First principles calculations of electronic band structure and optical properties of Crdoped ZnO[J].J Phys Chem C,2009,113(19):8460-8464.