Bi与rGO共修饰SnO_2光催化高效降解TCH和染料研究
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摘要
通过简单水热法制备新型铋金属(Bi)与还原氧化石墨烯(r GO)共修饰SnO_2三元光催化剂,并采用多种手段对其进行表征。以亚甲基蓝(MB)和四环素(TCH)为目标污染物,考察三元材料对污染物的光催化降解性能。结果表明,在可见光条件下,复合光催化材料对四环素去除率为94. 1%(60 min),对亚甲基蓝去除率为75. 5%(120 min),降解效果显著好于纯SnO_2与二元催化剂Bi-SnO_2。光致发光光谱(PL)、瞬态光电流响应和电化学阻抗谱(EIS)结果表明,复合材料中电子转移及分离效率的提升显著提高了自由基的产生及光催化效率。阐述了铋金属、还原氧化石墨烯和二氧化锡中间的协同效应,并基于自由基掩蔽试验和电子自旋共振谱(ESR)提出了光催化机制。
The given paper intends to make an investigation of the SPR effect of bismuth and that of the reduced graphene oxide on the photocatalysis. For the research purpose,we have worked out and prepared a novel ternary photocatalyst via the simple hydrothermal procedure of the bismuth and the reduced graphene oxide co-doped SnO_2. Furthermore,we have also done a series of photocatalytic degradation experiments under the visible light to find the effects of bismuth and the reduced graphene oxide on the photocatalysis. The as-prepared nanocomposites have demonstrated the superior visible light photocatalytic activity for the tetracycline hydrochloride( short for TCH) degradation with a removal efficiency of 94. 1% for 60 min and methylene blue degradation with 75. 5% removal for 120 min. The paper has also examined and presented the impact of the bismuth proportion and the reduced graphene oxide on the degradation of methylene blue and tetracycline by comparing the removal efficiency under the photocatalysts with the different amounts of bismuth and the reduced graphene oxide. The likely reasons may account for the experiment results and the relevant references,which help to improve the photocatalytic activity to some extent. Nevertheless,excessive contents of bismuth and reduced graphene oxide turn to be disadvantageous to the use of light and transfer of charge/electron.The pollutants removal efficiencies in terms of G_(0. 15)Bi_(20)SnO_2 also prove to be much higher than those of SnO_2,G_(0. 15)SnO_2 and Bi_(20)SnO_2. The excellent behavior of G_(0. 15)Bi_(20)SnO_2 should be ascribed to the enhancement of the electronic transfer and separation.Besides,the synergistic effect among the bismuth,the reduced graphene oxide and SnO_2 and the mechanism the paper has proposed in detail should be behaving based on the degradation pathway analysis,whereas the quenching experiment has been also proven of great significance with the electron spin resonance( short for ESR) spectra. The results of the above said study have thus demonstrated that the prepared plasmonic photocatalyst doped with bismuth and reduced graphene oxide has been verified to be a promising one for degrading pollutants. In addition,it has also presented the degradation pathway of the methylene blue and tetracycline through mass spectrometer. Thus,this paper proves to be successful in proposing reasons accounting for the apparent difference on degradation of the antibiotic elements and dye.
The given paper intends to make an investigation of the SPR effect of bismuth and that of the reduced graphene oxide on the photocatalysis. For the research purpose,we have worked out and prepared a novel ternary photocatalyst via the simple hydrothermal procedure of the bismuth and the reduced graphene oxide co-doped SnO_2. Furthermore,we have also done a series of photocatalytic degradation experiments under the visible light to find the effects of bismuth and the reduced graphene oxide on the photocatalysis. The as-prepared nanocomposites have demonstrated the superior visible light photocatalytic activity for the tetracycline hydrochloride( short for TCH) degradation with a removal efficiency of 94. 1% for 60 min and methylene blue degradation with 75. 5% removal for 120 min. The paper has also examined and presented the impact of the bismuth proportion and the reduced graphene oxide on the degradation of methylene blue and tetracycline by comparing the removal efficiency under the photocatalysts with the different amounts of bismuth and the reduced graphene oxide. The likely reasons may account for the experiment results and the relevant references,which help to improve the photocatalytic activity to some extent. Nevertheless,excessive contents of bismuth and reduced graphene oxide turn to be disadvantageous to the use of light and transfer of charge/electron.The pollutants removal efficiencies in terms of G_(0. 15)Bi_(20)SnO_2 also prove to be much higher than those of SnO_2,G_(0. 15)SnO_2 and Bi_(20)SnO_2. The excellent behavior of G_(0. 15)Bi_(20)SnO_2 should be ascribed to the enhancement of the electronic transfer and separation.Besides,the synergistic effect among the bismuth,the reduced graphene oxide and SnO_2 and the mechanism the paper has proposed in detail should be behaving based on the degradation pathway analysis,whereas the quenching experiment has been also proven of great significance with the electron spin resonance( short for ESR) spectra. The results of the above said study have thus demonstrated that the prepared plasmonic photocatalyst doped with bismuth and reduced graphene oxide has been verified to be a promising one for degrading pollutants. In addition,it has also presented the degradation pathway of the methylene blue and tetracycline through mass spectrometer. Thus,this paper proves to be successful in proposing reasons accounting for the apparent difference on degradation of the antibiotic elements and dye.
引文
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[15] DONG X A,ZHANG W,SUN Y,et al. Visible-lightinduced charge transfer pathway and photocatalysis mechanism on Bi semimetal@defective Bi OBr hierarchical microspheres[J]. Journal of Catalysis,2018,357:41-50.
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[19] ZHUANG S,XU X,FENG B,et al. Photogenerated carriers transfer in dye-graphene-SnO2composites for highly efficient visible-light photocatalysis[J]. ACS Applied Materials&Interfaces,2014,6(1):613-621.
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[21] SU D,WANG C,AHN H,et al. Octahedral tin dioxide nanocrystals as high capacity anode materials for Na-ion batteries[J]. Physical Chemistry Chemical Physics,2013,15(30):12543-12550.
[22] ZHANG H,Lü X,LI Y,et al. P25-graphene composite as a high performance photocatalyst[J]. ACS Nano,2010,4(1):380-386.
[23] WEI Q,WANG Y,QIN H,et al. Construction of r GO wrapping octahedral Ag-Cu2O heterostructure for enhanced visible light photocatalytic activity[J]. Applied Catalysis B:Environmental,2018,227:132-144.
[24] LIU J,LI Y,LI Z,et al. In situ growing of Bi/Bi2O2CO3on Bi2WO6nanosheets for improved photocatalytic performance[J]. Catalysis Today,2018,314:2-9.
[25] WANG H,DOU K,TEOH W Y,et al. Engineering of facets,band structure,and gas-sensing properties of hierarchical Sn2+-doped Sn O2nanostructures[J]. Advanced Functional Materials, 2013, 23(38):4847-4853.
[26] WU S,FU G,LV W,et al. A single-step hydrothermal route to 3D hierarchical Cu2O/Cu O/r GO nanosheets as high-performance anode of lithium-ion batteries[J].Small,2018,14(5):1702667.
[27] BABU B,KADAM A N,RAVIKUMAR R V S S N,et al. Enhanced visible light photocatalytic activity of Cudoped Sn O2quantum dots by solution combustion synthesis[J]. Journal of Alloys and Compounds,2017,703:330-336.
[28] BEGUM S,AHMARUZZAMAN M. CTAB and SDS assisted facile fabrication of Sn O2nanoparticles for effective degradation of carbamazepine from aqueous phase:a systematic and comparative study of their degradation performance[J]. Water Research,2018,129:470-485.
[29] HAN X,JIN M,XIE S,et al. Synthesis of tin dioxide octahedral nanoparticles with exposed high-energy{221}facets and enhanced gas-sensing properties[J]. Angewandte Chemie,2009,48(48):9180-9183.
[30] WENG S,CHEN B,XIE L,et al. Facile in situ synthesis of a Bi/Bi OCl nanocomposite with high photocatalytic activity[J]. Journal of Materials Chemistry A,2013,1(9):3068-3075.
[31] TANG D,ZHANG G. Ultrasonic-assistant fabrication of cocoon-like Ag/AgFeO2nanocatalyst with excellent plasmon enhanced visible-light photocatalytic activity[J]. Ultrasonics Sonochemistry,2017,37:208-215.
[32] GNASER H,SAVINA M R,CALAWAY W F,et al.Photocatalytic degradation of methylene blue on nanocrystalline Ti O2:surface mass spectrometry of reaction intermediates[J]. International Journal of Mass Spectrometry,2005,245(1/2/3):61-67.
[33] WANG B,DONG B,XU M,et al. Degradation of methylene blue using doublechamber dielectric barrier discharge reactor under different carrier gases[J].Chemical Engineering Science,2017,168:90-100.
[34] HAMSCHER G,SCZESNY S,HOPER H,et al. Determination of persistent tetracycline residues in soil fertilized with liquid manure by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518.
[35] YANG Y,ZENG Z,ZHANG C,et al. Construction of iodine vacancy-rich Bi OI/Ag@Ag I Z-scheme heterojunction photocatalysts for visible-light-driven tetracycline degradation:transformation pathways and mechanism insight[J]. Chemical Engineering Journal,2018,349:808-821.
[36] PAN S,ZHOU R,NIU H,et al. Hierarchical Sn O2hollow sub-microspheres for panchromatic Pb S quantum dotsensitized solar cells[J]. Journal of Alloys and Compounds,2017,709:187-196.
[37] DONG F,LI Q,SUN Y,et al. Noble metal-like behavior of plasmonic Bi particles as a cocatalyst deposited on(Bi O)2CO3microspheres for efficient visible light photocatalysis[J]. ACS Catalysis, 2014, 4(12):4341-4350.
[38] ZHANG X,LUO D,ZHANG W,et al. Inhibition of hydrogen and oxygen recombination over amide-functionalized graphene and the enhancement of photocatalytic hydrogen generation in dye-sensitized AF-RGO/Pt photocatalyst dispersion[J]. Applied Catalysis B:Environmental,2018,232:371-383.
[2] BHATTACHARJEE A,AHMARUZZAMAN M,DEVI T B,et al. Photodegradation of methyl violet 6B and methylene blue using tin-oxide nanoparticles(synthesized via a green route)[J]. Journal of Photochemistry and Photobiology A:Chemistry,2016,325:116-124.
[3] WANG P,YAP P S,LIM T T. C-N-S tridoped Ti O2for photocatalytic degradation of tetracycline under visiblelight irradiation[J]. Applied Catalysis A:General,2011,399(1/2):252-261.
[4] REYES C,FERN NDEZ J,FREER J,et al. Degradation and inactivation of tetracycline by Ti O2photocatalysis[J].Journal of Photochemistry and Photobiology A:Chemistry,2006,184(1/2):141-146.
[5] FUJISHIMA A,HONDA K. Electrochemical photolysis of water at a semiconductor electrode[J]. Nature,1972,238(5358):37-38.
[6] LYASHENKO L V,GOROKHOVAT-SKII Y B. Photocatalytic oxidation of carbon monoxide on metal oxides[J].Theoretical and Experimental Chemistry,1975,10(2):138-142.
[7] DAS S,JAYARAMAN V. Sn O2:a comprehensive review on structures and gas sensors[J]. Progress in Materials Science,2014,66:112-255.
[8] DENG Y,TANG L,FENG C,et al. Construction of plasmonic Ag and nitrogen-doped graphene quantum dots codecorated ultrathin graphitic carbon nitride nanosheet composites with enhanced photocatalytic activity:fullspectrum response ability and mechanism insight[J].ACS Applied Materials&Interfaces, 2017, 9(49):42816-42828.
[9] SHENG Q,QIAO X,ZHENG J. The hybrid of gold nanoparticles and 3D flower-like MnO2nanostructure with enhanced activity for detection of hydrogen peroxide[J].Electroanalysis,2018,30(1):137-145.
[10] ZHAO Z,ZHANG W,Lü X,et al. Noble metal-free Bi nanoparticles supported on Ti O2with plasmon-enhanced visible light photocatalytic air purification[J]. Environmental Science:Nano,2016,3(6):1306-1317.
[11] MEI Ping(梅平),ZHANG Manzheng(张曼征). A study on polymer-supported bimetallic catalystⅢ. the support effect and the interactions between two metals of Pt-Bi/P catalyst[J]. Journal of Jianghan Petroleum Institute(江汉石油学院学报), 1989, 11(1):114-118.
[12] DONG F,XIONG T,SUN Y,et al. A semimetal bismuth element as a direct plasmonic photocatalyst[J].Chemical Communications, 2014, 50(72):10386-10389.
[13] YU Y,CAO C,LIU H,et al. A Bi/Bi OCl heterojunction photocatalyst with enhanced electron-hole separation and excellent visible light photodegrading activity[J].Journal Mater Chem A,2014,2(6):1677-1681.
[14] TOUDERT J,SERNA R,JIME NEZ Má. Exploring the optical potential of nano-bismuth:tunable surface plasmon resonances in the near ultraviolet-to-near infrared range[J]. The Journal of Physical Chemistry C,2012,116(38):20530-20539.
[15] DONG X A,ZHANG W,SUN Y,et al. Visible-lightinduced charge transfer pathway and photocatalysis mechanism on Bi semimetal@defective Bi OBr hierarchical microspheres[J]. Journal of Catalysis,2018,357:41-50.
[16] LI F,JIANG X,ZHAO J,et al. Graphene oxide:a promising nanomaterial for energy and environmental applications[J]. Nano Energy,2015,16:488-515.
[17] NOVOSELOV K S,GEIM A K,MOROZOV S V,et al.Electric field effect in atomically thin carbon films[J].Science,2004,306(5696):666-669.
[18] LI X,YU J,WAGEH S,et al. Graphene in photocatalysis:a review[J]. Small,2016,12(48):6640-6696.
[19] ZHUANG S,XU X,FENG B,et al. Photogenerated carriers transfer in dye-graphene-SnO2composites for highly efficient visible-light photocatalysis[J]. ACS Applied Materials&Interfaces,2014,6(1):613-621.
[20] ZHANG J,YU J,JARONIEC M,et al. Noble metalfree reduced graphene oxide-ZnxCd1-xS nanocomposite with enhanced solar photocatalytic H2-production performance[J]. Nano Letters,2012,12(9):4584-4589.
[21] SU D,WANG C,AHN H,et al. Octahedral tin dioxide nanocrystals as high capacity anode materials for Na-ion batteries[J]. Physical Chemistry Chemical Physics,2013,15(30):12543-12550.
[22] ZHANG H,Lü X,LI Y,et al. P25-graphene composite as a high performance photocatalyst[J]. ACS Nano,2010,4(1):380-386.
[23] WEI Q,WANG Y,QIN H,et al. Construction of r GO wrapping octahedral Ag-Cu2O heterostructure for enhanced visible light photocatalytic activity[J]. Applied Catalysis B:Environmental,2018,227:132-144.
[24] LIU J,LI Y,LI Z,et al. In situ growing of Bi/Bi2O2CO3on Bi2WO6nanosheets for improved photocatalytic performance[J]. Catalysis Today,2018,314:2-9.
[25] WANG H,DOU K,TEOH W Y,et al. Engineering of facets,band structure,and gas-sensing properties of hierarchical Sn2+-doped Sn O2nanostructures[J]. Advanced Functional Materials, 2013, 23(38):4847-4853.
[26] WU S,FU G,LV W,et al. A single-step hydrothermal route to 3D hierarchical Cu2O/Cu O/r GO nanosheets as high-performance anode of lithium-ion batteries[J].Small,2018,14(5):1702667.
[27] BABU B,KADAM A N,RAVIKUMAR R V S S N,et al. Enhanced visible light photocatalytic activity of Cudoped Sn O2quantum dots by solution combustion synthesis[J]. Journal of Alloys and Compounds,2017,703:330-336.
[28] BEGUM S,AHMARUZZAMAN M. CTAB and SDS assisted facile fabrication of Sn O2nanoparticles for effective degradation of carbamazepine from aqueous phase:a systematic and comparative study of their degradation performance[J]. Water Research,2018,129:470-485.
[29] HAN X,JIN M,XIE S,et al. Synthesis of tin dioxide octahedral nanoparticles with exposed high-energy{221}facets and enhanced gas-sensing properties[J]. Angewandte Chemie,2009,48(48):9180-9183.
[30] WENG S,CHEN B,XIE L,et al. Facile in situ synthesis of a Bi/Bi OCl nanocomposite with high photocatalytic activity[J]. Journal of Materials Chemistry A,2013,1(9):3068-3075.
[31] TANG D,ZHANG G. Ultrasonic-assistant fabrication of cocoon-like Ag/AgFeO2nanocatalyst with excellent plasmon enhanced visible-light photocatalytic activity[J]. Ultrasonics Sonochemistry,2017,37:208-215.
[32] GNASER H,SAVINA M R,CALAWAY W F,et al.Photocatalytic degradation of methylene blue on nanocrystalline Ti O2:surface mass spectrometry of reaction intermediates[J]. International Journal of Mass Spectrometry,2005,245(1/2/3):61-67.
[33] WANG B,DONG B,XU M,et al. Degradation of methylene blue using doublechamber dielectric barrier discharge reactor under different carrier gases[J].Chemical Engineering Science,2017,168:90-100.
[34] HAMSCHER G,SCZESNY S,HOPER H,et al. Determination of persistent tetracycline residues in soil fertilized with liquid manure by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518.
[35] YANG Y,ZENG Z,ZHANG C,et al. Construction of iodine vacancy-rich Bi OI/Ag@Ag I Z-scheme heterojunction photocatalysts for visible-light-driven tetracycline degradation:transformation pathways and mechanism insight[J]. Chemical Engineering Journal,2018,349:808-821.
[36] PAN S,ZHOU R,NIU H,et al. Hierarchical Sn O2hollow sub-microspheres for panchromatic Pb S quantum dotsensitized solar cells[J]. Journal of Alloys and Compounds,2017,709:187-196.
[37] DONG F,LI Q,SUN Y,et al. Noble metal-like behavior of plasmonic Bi particles as a cocatalyst deposited on(Bi O)2CO3microspheres for efficient visible light photocatalysis[J]. ACS Catalysis, 2014, 4(12):4341-4350.
[38] ZHANG X,LUO D,ZHANG W,et al. Inhibition of hydrogen and oxygen recombination over amide-functionalized graphene and the enhancement of photocatalytic hydrogen generation in dye-sensitized AF-RGO/Pt photocatalyst dispersion[J]. Applied Catalysis B:Environmental,2018,232:371-383.
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