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- 2017
原位反应制备ZnS/还原氧化石墨烯复合材料及其光催化性能
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Abstract:
以氧化石墨烯和ZnAc2为反应前驱物，采用二甲基亚砜（DMSO）作为硫源和反应溶剂，通过一步溶剂热法原位制备出负载ZnS的还原氧化石墨烯（RGO）复合材料（ZnS/RGO）。采用SEM、XRD、激光拉曼（Raman）和荧光光谱对样品的微观形貌和化学结构进行表征。结果显示：原位反应制备的ZnS/RGO复合材料是由呈圆球状并均匀负载的纳米ZnS和6~7层RGO层状结构组成；在模拟紫外光照射下，对甲基橙污染物的光催化结果表明，ZnS/RGO复合材料的降解效率明显高于纯ZnS；同时，在多次循环催化过程中，ZnS/RGO复合材料的光催化效率仍基本保持不变，表明原位反应使ZnS与RGO结合增强。荧光光谱结果表明，ZnS/RGO复合材料光催化效率增强的主要原因在于ZnS中光生电子通过RGO得到有效的分离，进而延长了电子-空穴的复合效率。 ZnS decotrated onto reduced graphene oxide(RGO) composite (ZnS/RGO) had been synthesized through one-step in-situ solvothermal reaction using ZnAc2 and graphene oxide as reaction precursor and dimethyl sulfoxide (DMSO) as a source of sulfur and reaction solvent. SEM、XRD、Raman and fluorescence spectroscopy had been used to characterize microtopography and chemical structure of ZnS and ZnS/RGO. The results show that the ZnS/RGO composite synthesized through in-situ reaction consists of uniformly decorated spherical ZnS particles and 6-7 layer-structured RGO sheets. Under the simulated ultraviolet irradiation, the photocatalytic results for methyl orange pollutants show that the degradation ratio of ZnS/RGO hybrid is remarkly higher than that of pure ZnS. During the recycling degradation process photocatalytic efficiency of ZnS/RGO remain stable, which demonstrates in-situ reaction enhance the interaction between ZnS and RGO. Fluorescence spectroscopy result shows enchanced photocatalytic degradation efficiency of ZnS/RGO hybrid is mainly attributed to in-situ incorporation of ZnS with RGO sheets, which can efficiently transfer the excited photoelectrons from ZnS to conjugated graphene structures, and further enlarges recombination efficiency of photogenergated electron-hole. 河南省科技攻关项目（172102310478）；许昌市科技攻关项目（2016-8）；河南省科技创新人才计划（174100510014）
| [1] | FUJISHIMA A, HONDA K. Electrochemical photolysis of water at a semiconductor electrode[J]. Nature, 1972, 238(5358):37-38. |
| [2] | PAUL S, CHETRI P, CHOUDURY A. Effect of manganese doping on the optical property and photocatalytic activity of nano-crystalline titania:Experimental and theoretical investigation[J]. Journal of Alloys & Compounds, 2014, 583:578-586. |
| [3] | WANG H L, ZHANG L S, CHEN Z G, et al. Semiconductor heterojunction photocatalysts:Design, construction, and photocatalytic performances[J]. Chemical Society Reviews, 2014, 43(15):5234-5244. |
| [4] | ZHAO D, YANG X, CHEN C, et al. Enhanced photocatalytic degradation of methylene blue on multiwalled carbon nanotubes-TiO2[J]. Journal of Colloid and Interface Science, 2013, 398(19):234-239. |
| [5] | ZHAO Y, ZHAO D, CHEN C, et al. Enhanced photo-reduction and removal of Cr(VI) on reduced graphene oxide decorated with TiO2 nanoparticles[J]. Journal of Colloid and Interface Science, 2013, 405(9):211-217. |
| [6] | LI J, CHEN C L, ZHANG R, et al. Reductive immobilization of Re (V Ⅱ) by graphene modified nanoscale zero-valent iron particles using a plasma technique[J]. China Science Chemistry, 2016, 59(1):150-158. |
| [7] | ZHAO D, SHENG G, CHEN C, et al. Enhanced photocatalytic degradation of methylene blue under visible irradiation on graphene@TiO2 dyade structure[J]. Applied Catalysis B:Environmental, 2012, 111-112(2):303-308. |
| [8] | SUBRAHMANYAM K S, VIVEKCHAND S R C, GOVINDARAJ A, et al. A study of graphenes prepared by different methods:Characterization, properties and solubilization[J]. Journal of Materials Chemistry, 2008, 18(13):1517-1523. |
| [9] | 李鑫, 余长林, 樊启哲, 等. 溶剂热制备球状ZnS纳米光催化剂及其光催化性能[M]. 有色金属科学与工程, 2012, 03(3):21-26. LI X, YU C L, FAN Q Z, et al. Solvothermal preparation spherical ZnS nano-photocatalyst and its photocatalytic activity[M]. Jiangxi Nonferrous Metals, 2012, 03(3):21-26 (in Chinese). |
| [10] | CHEN F J, CAO Y L, JIA D Z. Facile synthesis of ZnS nano-particles and their excellent photocatalytic performance[J]. Ceramics International, 2015, 41(5):6645-6652. |
| [11] | NETHRAVATHIA C, NISHAA T, RAVISHANKARB N, et al. Graphene nanocrystalline metal sulphide composites produced by a one-pot reaction starting from graphite oxide[J]. Carbon, 2009, 47(8):2054-2059. |
| [12] | ZHANG H, LV X J, LI Y M, et al. P25-graphene composite as a high performance photocatalyst[J]. ACS Nano, 2010, 4(1):380-386. |
| [13] | BAO C L, ZHU G X, SHEN M Q, et al. Carbon-coated zinc sulfide nano-clusters:Synthesis, photothermal conversion and adsorption properties[J]. Journal of Colloid and Interface Science, 2014, 436:63-69. |
| [14] | 任芳, 朱光明, 任鹏刚. 纳米石墨烯复合材料的制备及应用研究进展[J]. 复合材料学报, 2014, 31(2):263-272. REN F, ZHU G M, REN P G. The latest advances in preparation and application of nano graphene composites[J]. Acta Materiae Compositae Sinica, 2014, 31(2):263-272 (in Chinese). |
| [15] | CHEN F J, CAO Y L, JIA D Z. A room-temperature solid-state route for the synthesis of graphene oxide-metal sulfide composites with excellent photocatalytic activity[J]. Crystal Engineering Communications, 2013, 15(15):4747-4754. |
| [16] | LIU Y, HU Y, ZHOU M J, et al. Microwave-assisted non-aqueous route to deposit well-dispersed ZnO nanocrystals on reduced graphene oxide sheets with improved photoactivity for the decolorization of dyes under visible light[J]. Applied Catalysis B:Environmental, 2012, 125(33):425-431. |
| [17] | DENZLER D, OLSCHEWSKI M, SATTLER K. Luminescence studies of localized gap states in colloidal ZnS nanocrystals[J]. Journal of Applied Physics, 1998, 84(5):2841-2845. |
| [18] | LIN D D, WU H, ZHANG R, et al. Preparation of ZnS nanofibers via electrospinning[J]. Journal of the American Ceramic Society, 2007, 90(11):3664-3666. |
| [19] | CHEN F J, CAO Y L, JIA D Z, et al. Solid-state synthesis of ZnS/graphene nanocomposites with enhanced photocatalytic activity[J]. Dyes and Pigments, 2015, 120:8-14. |
| [20] | HUO Y N, XIE Z L, WANG X D, et al. Methyl orange removal by combined visible-light photocatalysis and membrane distillation[J]. Dyes and Pigments, 2013, 98(1):106-112. |
| [21] | HU H T, WANG X B, LIU F M, et al. Rapid microwave-assisted synthesis of graphene nanosheets-zinc sulfide nanocomposites:Optical and photocatalytic properties[J]. Synthetic Metals, 2011, 161(5):404-410. |
