还原氧化石墨烯/磷酸银光催化剂制备及其对卡马西平的降解
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摘要
为进一步增强Ag_3PO_4的催化应用性能,采用水热还原法制备还原氧化石墨烯/磷酸银(rGO/Ag3PO4)复合光催化剂并对其进行表征;考察了氧化石墨烯(GO)掺量、溶液pH、光源对其光催化降解卡马西平效果的影响;通过对催化降解过程中活性物种的确定,初步推断其降解机理。结果表明,复合改性有助于提高Ag_3PO_4颗粒分散性,增强其光响应能力和光催化活性。当GO掺量为0.7%,初始pH为5～9时,全波段辐射处理初始浓度200μg·L~(-1),卡马西平在6 min内基本可实现对其完全降解。催化降解过程中光生空穴是主要的活性物质,其与羟基自由基、水合电子共同作用实现卡马西平的降解。
To further enhance the photocatalytic performance of Ag_3PO_4, a composite photocatalyst of reduced graphene oxide/silver phosphate(rGO/Ag_3PO_4) was prepared by the hydrothermal reduction method and characterized.The effects of graphene oxide(GO) addition, solution pH and light source on carbamazepine photo-degradation were studied. And its degradation mechanism was preliminarily proposed on the basis of the photocatalytic active species identification. The results showed that the composite modification could not only improve the dispersibility of Ag_3PO_4 particles, but also strengthen their photoresponse and catalytic activity. For the rGO/Ag_3PO_4 with 0.7% GO doping, carbamazepine could be completed degraded after 6 min photocatalysis with fullwave radiation at the initial carbamazepine concentration of 200 μg·L~(-1) and pH of 5～9. During the process of photodegradation, photogenerated cavities were identified as be the main active substance, which combined with hydroxyl radicals and hydrated electrons to degrade carbamazepine.
To further enhance the photocatalytic performance of Ag_3PO_4, a composite photocatalyst of reduced graphene oxide/silver phosphate(rGO/Ag_3PO_4) was prepared by the hydrothermal reduction method and characterized.The effects of graphene oxide(GO) addition, solution pH and light source on carbamazepine photo-degradation were studied. And its degradation mechanism was preliminarily proposed on the basis of the photocatalytic active species identification. The results showed that the composite modification could not only improve the dispersibility of Ag_3PO_4 particles, but also strengthen their photoresponse and catalytic activity. For the rGO/Ag_3PO_4 with 0.7% GO doping, carbamazepine could be completed degraded after 6 min photocatalysis with fullwave radiation at the initial carbamazepine concentration of 200 μg·L~(-1) and pH of 5～9. During the process of photodegradation, photogenerated cavities were identified as be the main active substance, which combined with hydroxyl radicals and hydrated electrons to degrade carbamazepine.
引文
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[2] EBELE A J, ABOU-ELWAFA ABDALLAH M, HARRAD S. Pharmaceuticals and personal care products(PPCPs)in the freshwater aquatic environment[J]. Emerging Contaminants, 2017, 3(1):1-16.
[3] YANG L, HE J T, SU S H, et al. Occurrence, distribution, and attenuation of pharmaceuticals and personal care products in the riverside groundwater of the Beiyun River of Beijing, China[J]. Environmental Science&Pollution Research International, 2017, 24(18):1-14.
[4] NA L, WEI J X, DONG X L, et al. Concentrations distribution and ecological risk assessment of pharmaceuticals and personal care products in Taihu Lake[J]. China Environmental Science, 2017, 37(9):3515-3522.
[5] WANG J, WANG S. Removal of pharmaceuticals and personal care products(PPCPs)from wastewater:A review[J]. Journal of Environmental Management, 2016, 182:620-640.
[6] BOHDZIEWICZ J, KUDLEK E, DUDZIAK M. Influence of the catalyst type(TiO2 and ZnO)on the photocatalytic oxidation of pharmaceuticals in the aquatic environment[J]. Desalination&Water Treatment, 2016, 57(3):1552-1563.
[7] LIANG R, LUO S, JING F, et al. A simple strategy for fabrication of Pd@MIL-100(Fe)nanocomposite as a visible-light-driven photocatalyst for the treatment of pharmaceuticals and personal care products(PPCPs)[J]. Applied Catalysis B:Environmental, 2015, 176-177(3):240-248.
[8] FRONTISTIS Z, DROSOU C, TYROVOLA K, et al. Experimental and modeling studies of the degradation of estrogen hormones in aqueous TiO2 suspensions under simulated solar radiation[J]. Industrial&Engineering Chemistry Research, 2017,51:16552-16563.
[9] MIRZAEI A, CHEN Z, HAGHIGHAT F, et al. Removal of pharmaceuticals and endocrine disrupting compounds from water by zinc oxide-based photocatalytic degradation:A review[J]. Sustainable Cities and Society, 2016, 27:407-418.
[10] PAN D, JIAO J, LI Z, et al. Efficient separation of electron-hole pairs in graphene quantum dots by TiO2 heterojunctions for dye degradation[J]. ACS Sustainable Chemistry&Engineering, 2015, 8(9):191-197.
[11] KUVAREGA A T, KRAUSE R W M, MAMBA B B. Nitrogen/palladium-codoped TiO2 for efficient visible light photocatalytic dye degradation[J]. Journal of Physical Chemistry C, 2016, 115(45):22110-22120.
[12] SUNITA K, SANDEEP K, ASHOK K G. Comparative study of TiO2/CuS core/shell and composite nanostructures for efficient visible-light photocatalysis[J]. ACS Sustainable Chemistry&Engineering, 2016, 4(3):1487-1499.
[13] FRONTISTIS Z, ANTONOPOULOU M, PETALA A, et al. Photodegradation of ethyl paraben using simulated solar radiation and Ag3PO4photocatalyst[J]. Journal of Hazardous Materials, 2017, 323:478-488.
[14] CHEN W, NIU X, WANG J. A photocatalyst of graphene oxide(GO)/Ag3PO4 with excellent photocatalytic activity over decabromodiphenyl ether(BDE-209)under visible light irradiation[J]. Journal of Photochemistry&Photobiology A:Chemistry,2017, 356:304-311.
[15] WANG P Q, CHEN T, YU B, et al. Tollens-assisted preparation of Ag3PO4/GO photocatalyst with enhanced photocatalytic activity and stability[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 62:267-274.
[16] 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.
[17]余长林,魏龙福,李家德,等. GO/Ag3PO4复合光催化剂的制备、表征及光催化性能[J].物理化学学报, 2015, 31(10):1932-1938.
[18] MIAO X, YUE X, SHEN X P, et al. Nitrogen-doped carbon dots modified Ag3PO4/GO photocatalyst with excellent visiblelight-driven photocatalytic performance and mechanism insight[J]. Catalysis Science&Technology, 2018, 8:632-641.
[19] GUEX L G, SACCHI B, PEUVOT K F, et al. Experimental review:Chemical reduction of grapheneoxide(GO)to reduced graphene oxide(rGO)by aqueous chemistry[J]. Nanoscale, 2017, 9(27):9562-9571.
[20] LIANG Q, SHI Y, MA W, et al. Enhanced photocatalytic activity and structural stability by hybridizing Ag3PO4 nanospheres with graphene oxide sheets[J]. Physical Chemistry Chemical Physics, 2012,14(45):15657-15665.
[21] LIU J, REN H, JIAO Q J, et al. The influence of GO/RGO on the thermal decomposition of HNIW[J]. Integrated Ferroelectrics, 2014, 152(1):127-136.
[22]翁程杰,史叶勋,何大方,等.水热法制备还原氧化石墨烯及其导电性调控[J].化工学报, 2018, 69(7):3263-3269.
[23] YANG X, CUI H, LI Y, et al. Fabrication of Ag3PO4-graphene composites with highly efficient andstable visible light photocatalytic performance[J]. ACS Catalysis, 2013, 3(3):363-369.
[24]徐国梅.以腰果酚型液态苯并噁嗪为基体的氧化石墨烯复合材料及含磷和钼阻燃材料的研究[D].合肥:合肥工业大学, 2016.
[25] FAN X, SHAO J, LI Z, et al. Facile synthesis of rGO/Ag3PO4 by enhanced photocatalytic degradation of an organic dye using a microwave-assisted method[J]. New Journal of Chemistry, 2016, 40(2):1330-1335.
[26]孙梅香,刘会应,刘松,等.光电-Fenton体系中羟基自由基生成影响因素分析[J].环境工程学报, 2017, 11(6):3391-3398.
[27]曾小龙. TiO2光催化光生电子反应机理研究[D].广州:暨南大学, 2013.
[28] GAO X, PENG W, TANG G, et al. Highly efficient and visible-light-driven BiOCl for photocatalytic degradation of carbamazepine[J]. Journal of Alloys&Compounds, 2018, 757:455-465.
[29] JIAN X, LEI L, GUO C, et al. Photocatalytic degradation of carbamazepine by tailored BiPO4:Efficiency, intermediates and pathway[J]. Applied Catalysis B:Environmental, 2013, 130(6):285-292.