镧掺杂石墨烯水凝胶对罗丹明染料的光降解性能
|
摘要
利用石墨烯在一定条件下形成凝胶的特性,采用水热法原位掺杂金属离子(Ag~+、Cu~(2+)、La~(3+))制备了掺杂金属石墨烯基水凝胶(AgGH、CuGH、LaGH)。该水凝胶对染料表现出良好的光降解能力。金属掺杂石墨烯基水凝胶降解罗丹明的速度遵循LaGH>CuGH>AgGH的顺序。光解试验表明,La~(3+)掺杂LaGH的最佳浓度为2 mmol/L。XRD和FTIR表征说明,经过水热反应后,LaGH中出现了镧的氧化物和氢氧化物。该水凝胶循环5次后仍能保持较好的光解染料的能力。淬灭试验表明,光照条件下掺杂金属石墨烯基水凝胶表面产生的空穴和超氧化物是分解染料的主要活性基团。
Based on the aerogel forming property of graphene, metal-doped graphene hydrogel(AgGH,CuGH, LaGH) are prepared by adding metal ions(Ag~+、Cu~(2+)、La~(3+)) in situ using hydrothermal method. The hydrogels feature good photodegradability. The degradation rate to Rhodamine of metal-doped grapheme hydrogel(MGH) follows the sequence of LaGH>CuGH>AgGH. The optimum doping concentration of La~(3+)is 2 mmol/L. XRD and FTIR illustrate that La(OH)_3 and La_2O_3 appeare in LaGH. The hydrogel remains a good photodegradability to decompose dye after 5 cycles. Trapping experiment suggests that h~+ and O·~(2-) are the prominent radical groups.
Based on the aerogel forming property of graphene, metal-doped graphene hydrogel(AgGH,CuGH, LaGH) are prepared by adding metal ions(Ag~+、Cu~(2+)、La~(3+)) in situ using hydrothermal method. The hydrogels feature good photodegradability. The degradation rate to Rhodamine of metal-doped grapheme hydrogel(MGH) follows the sequence of LaGH>CuGH>AgGH. The optimum doping concentration of La~(3+)is 2 mmol/L. XRD and FTIR illustrate that La(OH)_3 and La_2O_3 appeare in LaGH. The hydrogel remains a good photodegradability to decompose dye after 5 cycles. Trapping experiment suggests that h~+ and O·~(2-) are the prominent radical groups.
引文
[1]单国荣,张宁.2018氧化石墨烯复合水凝胶研究进展[J].化工学报,69(2):535-545.
[2]张倩,李可培,张惠云,等.三维石墨烯气凝胶的制备及对罗丹明B的吸附性能[J].印染,2018,44(10):1-7.
[3]何叶丽.纺织品的石墨烯功能整理[J].印染,2018,44(6):48-54.
[4]贾明亮,张克勤.石墨烯在纺织材料基透明电极中的研究进展[J].印染,2013,39(11):50-54.
[5]BAI H,LI C,WANG X L,et al.A pH-sensitive graphene oxide composite hydrogel[J].Chemical Communications,2010,46(14):2376-2378.
[6]HUANG C C,BAI H,LI C,et al.A graphene oxide/hemoglobin composite hydrogelfor enzymatic catalysis in organic solvents[J].Chemical Communications,2011,47(17):4962-4964.
[7]SAHU A,CHOI W,TAE G.A stimuli-sensitive injectable graphene oxide composite hydrogel[J].Chemical Communications,2012,48(47):5820-5822.
[8]张慧娟,翟丹丹,贺洋.石墨烯基水凝胶的研究进展[J].高分子通报,2014,11:45-52.
[9]MENG J K,SUO Y,LI J,et al.Nitrogen-doped graphene aerogels as anode materials for lithium-ion battery:Assembly and electrochemical properties[J].Materials Letters,2015,160:392-396.
[10]SUO Y,ZHAO Q Q,MENG J K,et al.Fabrication and electro chemical properties of 3DFe3O4@graphene aerogel composites as lithium-ion battery anodes[J].Materials Letters,2016,174:36-39.
[11]BAI H,Li C,WANG X L.On the gelation of graphene oxide.Journal of Physical Chemistry[C].2011,115(13):5545-5551.
[12]甄德帅,罗小虎,隋国哲,等.稀土Eu3+掺杂TiO2光催化降解罗丹明B的研究[J].染整技术,2018,40(6):17-28.
[13]GAO Y,ZHANG Y W,ZHOU Y M,et al.Synthesis of ordered mesoporous La2O3-ZrO2composites with encapsulated Pt NPs and the effect of La-dopping on catalytic activity[J]Journal of Colloid and Interface Science,2017,503:178-185.
[14]ZHANG Q L,ZHU J L,YUAN D Q,et al.The First-Principle Calculation of La-doping Effect on Piezoelectricity in Tetragonal KNN Crystal[J].Plasma Science and Technology,2012,14(5):442-444.
[15]陈旭伟,郑旭,王晓峰,等.超高容量氧化石墨烯/碳纳米管气凝胶用于血红蛋白的吸附分离[J].高等学校化学学报,2015,36(8):1498-1504.
[16]黄剑坤,刘会娥,黄扬帆,等.石墨烯气凝胶的制备及其对水中油分的吸附特性[J].化工学报,2016,67(12):5408-5056.
[17]邓晓梅,文豪,张楚虹,等.2016.三维多孔还原氧化石墨烯气凝胶的制备及其在锂离子电池中的应用[J].合成化学,24(4):302-307.
[18]姚超,马江权,林西平,等.纳米氧化镧的制备[J].高校化学工程学报,2003,17(6):685-688.
[19]JBELIR,BOUKHACHEM A,BENJEMAA I,et al.An enhancement of photoluminescence property of Ag doped La2O3thin films at room temperature[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2017,184(5):71-81.
[20]HE Y L,LI J H,LI L F,et al.Gamma-rayirradiation-inducedreductionandself-assemblyof grapheme oxide into three-dimension algraphene aerogel[J].Materials Letters,2016,177:76-79.
[21]MUHAMMAD A,TAUSEEF A,MUHAMMAD A K,et al.Structural and optical properties of La2O3:Ho3+and La(OH)3:Ho3+crystalline particles[J].Materials Today:Proceedings,2017,4:4900-4905.
[22]CHEN Y,LI H,MA Q,et al.A novel electrospun approach for highly-dispersed carambola-like SnO2/C composite microparticles with superior photocatalytic performance[J].Materials Letters,2017,202:17-20.
[2]张倩,李可培,张惠云,等.三维石墨烯气凝胶的制备及对罗丹明B的吸附性能[J].印染,2018,44(10):1-7.
[3]何叶丽.纺织品的石墨烯功能整理[J].印染,2018,44(6):48-54.
[4]贾明亮,张克勤.石墨烯在纺织材料基透明电极中的研究进展[J].印染,2013,39(11):50-54.
[5]BAI H,LI C,WANG X L,et al.A pH-sensitive graphene oxide composite hydrogel[J].Chemical Communications,2010,46(14):2376-2378.
[6]HUANG C C,BAI H,LI C,et al.A graphene oxide/hemoglobin composite hydrogelfor enzymatic catalysis in organic solvents[J].Chemical Communications,2011,47(17):4962-4964.
[7]SAHU A,CHOI W,TAE G.A stimuli-sensitive injectable graphene oxide composite hydrogel[J].Chemical Communications,2012,48(47):5820-5822.
[8]张慧娟,翟丹丹,贺洋.石墨烯基水凝胶的研究进展[J].高分子通报,2014,11:45-52.
[9]MENG J K,SUO Y,LI J,et al.Nitrogen-doped graphene aerogels as anode materials for lithium-ion battery:Assembly and electrochemical properties[J].Materials Letters,2015,160:392-396.
[10]SUO Y,ZHAO Q Q,MENG J K,et al.Fabrication and electro chemical properties of 3DFe3O4@graphene aerogel composites as lithium-ion battery anodes[J].Materials Letters,2016,174:36-39.
[11]BAI H,Li C,WANG X L.On the gelation of graphene oxide.Journal of Physical Chemistry[C].2011,115(13):5545-5551.
[12]甄德帅,罗小虎,隋国哲,等.稀土Eu3+掺杂TiO2光催化降解罗丹明B的研究[J].染整技术,2018,40(6):17-28.
[13]GAO Y,ZHANG Y W,ZHOU Y M,et al.Synthesis of ordered mesoporous La2O3-ZrO2composites with encapsulated Pt NPs and the effect of La-dopping on catalytic activity[J]Journal of Colloid and Interface Science,2017,503:178-185.
[14]ZHANG Q L,ZHU J L,YUAN D Q,et al.The First-Principle Calculation of La-doping Effect on Piezoelectricity in Tetragonal KNN Crystal[J].Plasma Science and Technology,2012,14(5):442-444.
[15]陈旭伟,郑旭,王晓峰,等.超高容量氧化石墨烯/碳纳米管气凝胶用于血红蛋白的吸附分离[J].高等学校化学学报,2015,36(8):1498-1504.
[16]黄剑坤,刘会娥,黄扬帆,等.石墨烯气凝胶的制备及其对水中油分的吸附特性[J].化工学报,2016,67(12):5408-5056.
[17]邓晓梅,文豪,张楚虹,等.2016.三维多孔还原氧化石墨烯气凝胶的制备及其在锂离子电池中的应用[J].合成化学,24(4):302-307.
[18]姚超,马江权,林西平,等.纳米氧化镧的制备[J].高校化学工程学报,2003,17(6):685-688.
[19]JBELIR,BOUKHACHEM A,BENJEMAA I,et al.An enhancement of photoluminescence property of Ag doped La2O3thin films at room temperature[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2017,184(5):71-81.
[20]HE Y L,LI J H,LI L F,et al.Gamma-rayirradiation-inducedreductionandself-assemblyof grapheme oxide into three-dimension algraphene aerogel[J].Materials Letters,2016,177:76-79.
[21]MUHAMMAD A,TAUSEEF A,MUHAMMAD A K,et al.Structural and optical properties of La2O3:Ho3+and La(OH)3:Ho3+crystalline particles[J].Materials Today:Proceedings,2017,4:4900-4905.
[22]CHEN Y,LI H,MA Q,et al.A novel electrospun approach for highly-dispersed carambola-like SnO2/C composite microparticles with superior photocatalytic performance[J].Materials Letters,2017,202:17-20.