g-C3N4的硫酸铵-尿素混合法制备及其可见光催化性能
Preparation of g-C3N4 by ammonium sulfate-urea mixed method and its visible light photocatalytic performance
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摘要: 以尿素（CON2H4）和不同质量的硫酸铵为前驱体，使用高温煅烧法制备得到产率和可见光催化活性都较高的石墨相氮化碳（g-C3N4）.采用XRD、DRS、SEM和PL等方法对其理化性质进行表征，以罗丹明B（RhB）和苯酚为模拟污染物，考察了g-C3N4在可见光下的催化活性，通过活性物种捕捉实验推测出了RhB的降解机理.结果表明，与只使用尿素相比，硫酸铵和尿素混合作为前驱体制备g-C3N4，不仅产率提高2.2倍，而且也保持了较高的可见光催化活性；其中当硫酸铵的添加量为3.00 g时，制备的g-C3N4对RhB的降解速率最快，在可见光下照射2 h，对RhB的降解率达到97.42%，与单独使用尿素制得的g-C3N4的可见光催化活性基本持平；硫酸铵的添加，使得g-C3N4的制备成本降低了45%；活性物种捕捉实验结果证明硫酸铵的引入改变了g-C3N4对RhB的降解路径.Abstract: Using urea (CON2H4) and ammonium sulfate of different amounts as precursors,graphite phase carbon nitride (g-C3N4) with high yield and visible light catalytic activity was synthesized by high-temperature calcination method. The physical and chemical properties of as-prepared samples were characterized by X-ray diffraction(XRD),UV-Vis diffuse reflectance spectroscopy(UV-Vis DRS),scanning electron microscopy(SEM),and photoluminescence spectroscopy(PL) respectively. The photocatalytic performance of g-C3N4 was evaluated by photocatalytic degradation rates of Rhodamine B (RhB) and phenol aqueous solution under the irradiation of visible light. The degradation mechanism of RhB was proposed according to the test of active species catching. The results showed that,compared with g-C3N4 prepared by urea alone,the g-C3N4 synthesized by employing ammonium sulfate combined with urea as precursors not only increased the yield by 2.2 times but also maintained higher catalytic activity under visible light irradiation. In addition,there was an optimal amount of ammonium sulfate for the g-C3N4 photocatalyst. When the dosage of ammonium sulfate was 3.00 g,the obtained g-C3N4 showed the highest photocatalytic performance, for example,the degradation of RhB reached 97.42% when the irradiation time was 120 min. The photocatalytic performance was basically the same as the visible light photocatalytic activity of g-C3N4 prepared by urea alone. The addition of ammonium sulfate reduced the preparation cost of g-C3N4 by 45%. The results obtained from the test of active species catching proved that the introduction of ammonium sulfate had changed the degradation pathway of RhB when g-C3N4 was used as the catalyst.
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Key words:
- g-C3N4 /
- visible light catalysis /
- ammonium sulfate /
- urea /
- rhodamine B /
- phenol
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[1] FUJISHIMA A,HONDA K.Electrochemical photolysis of water at a semiconductor electrode[J].Nature,1972,238:37-38. [2] DING F,YANG D,TONG Z W,et al.Graphitic carbon nitride-based nanocomposites as visible-light driven photocatalysts for environm-ental purification[J].Environmental Science:Nano,2017,4:1455-1469. [3] DARKWAH W K,AO Y.Mini review on the structure and properties (photocatalysis),and preparation techniques of graphitic carbon nitride nano-based particle,and its applications[J].Nanoscale Research Letters,2018,13(1):388-403. [4] WANG H,ZHANG X D, XIE Y.Recent progress in ultrathin two-dimensional semiconductors for photocatalysis[J].Materials Science and Engineering,2018,130:1-39. [5] FUJISHIMA A,ZHANG X T,TRYKC D A.TiO2 photocatalysis and related surface phenomena[J]. Surface Science Reports,2008,63(12):515-582. [6] LOU X W,WANG Y,YUAN C,et al.Template-Free Synthesis of SnO2 Hollow Nanostructures with High Lithium Storage Capacity[J].Advanced Materials,2006,18(17):2325-2329. [7] TAK Y,HONG S J,LEE J S,et al.Fabrication of ZnO/CdS core/shell nanowire arrays for efficient solar energy conversion[J].Journal of Materials Chemistry,2009,19:5945-5951. [8] WANG X,MAEDA K,THOMAS A,et al.A metal-free polymeric photocatalyst for hydrogen production from water under visible light[J].Nature Materials,2008,8(1):76-80. [9] CAO S W,YU J G.g-C3N4 based photocatalysts for hydrogen generation[J].The journal of physical chemistry letters,2014,5:2101-2107. [10] XU B T,AHMED M B,ZHOU J L,et.al.Graphitic carbon nitride based nanocomposites for the photocatalysis of organic contaminantsunder visible irradiation:Progress,limitations and future directions[J].Science of the Total Environment,2018,633:546-559. [11] 张金水,王博,王心晨.氮化碳聚合物半导体光催化[J].化学进展,2014,26(1):19-29. ZHANG J S,WANG B,WANG X C.Carbon nitride polymeric semiconductor for photocatalysis[J].Progress in Chemistry,2014,26(1):19-29(in Chinese).
[12] DONG G P,ZHANG Y H,PAN Q W,et al.A fantastic graphitic carbon nitride (g-C3N4) material:Electronic structure, photocatalytic and photoelectronic properties[J].Journal of Photochemistry and Photobiology C:Photochemistry Reviews,2014,20:33-50. [13] WEN J Q,XIE J,CHEN X B,et al.A review on g-C3N4-based photocatalysts[J].Applied Surface Science.2017,391:72-123. [14] CAO S W,LOW J X,YU J G,et al.Polymeric photocatalysts based on graphitic carbon nitride[J].Advanced Materials,2015,27(13):2150-2176. [15] 刘宗梅,李玲艳,朱诗月,等.不同前驱体制备g-C3N4光催化性能及稳定性[J].应用化工,2018,47(3):421-424 ,433. LIU Z M,LI L Y,ZHU S Y,et al.Photocatalytic activity and stability of g-C3N4 synthesized by different precursors[J].2018,47(3):421-424,433(in Chinese).
[16] FAN D,WANG, Z Y,SUN Y J,et al.Engineering the nanoarchitecture and texture of polymeric carbon nitride semiconductor for enhanced visible light photocatalytic activity[J].Journal of Colloid and Interface Science,2013,401:70-79. [17] ZHANG L N,WANG H,SHEN W Z,et al.Controlled synthesis of graphitic carbon nitride and its catalytic properties in Knoevenagel condensations[J]. Journal of Catalysis, 2016,344:293-302. [18] SHI L,LIANG L,WANG F X,et al.Higher yield urea-derived polymeric graphitic carbon nitride with mesoporous structure and superior visible-light-responsive activity[J].ACS Sustainable Chemistry & Engineering,2015,3(12):3412-3419. [19] 王悦,蒋权,尚介坤,许杰,李永昕.介孔氮化碳材料合成的研究进展[J].物理化学学报,2016,32(8):1913-1928. WANG Y,JIANG Q,SHANG J K,et al.Advances in the synthesis of mesoporous carbon nitride materials[J].Acta Physico-Chimica Sinica, 2016,32(8):1913-1928(in Chinese).
[20] 任学昌,马学琴,任晓亮,等.TiO2/PANI/Fe3O4的低温水热法制备及其光催化活性与磁回收性能[J].环境化学,2013,32(11):2149-2155. REN X C,MA X Q,REN X L,et al.Preparation of TiO2/PANI/Fe3O4 by low temperature hydrothermal method and its photocatalytic activity and magnetic recovery characteristic[J]. Environmental Chemistry, 2013,32(11):2149-2155(in Chinese).
[21] 国家环境保护总局水和废水监测分析方法编委会.水和废水监测分析方法[M].四版.北京:中国环境科学出版社,2002:460-462. State Environmental Protection Administration SEPA.Monitoring and analytical method of water and wastewater[M].4th Edition.Beijing:Environmental and Scientific Press of China,2002 :460-462(in Chinese).
[22] 李佩东.高活性g-C3N4的共聚合制备及可见光催化净化NO的性能增强[D].重庆:重庆工商大学,2017. LI P D.Copolymerization Preparation of g-C3N4 with enhanced visible light photocatalytic NO[D].Chongqing:Chongqing Technology and Business University,2017 (in Chinese).
[23] 刘科伟,陈天朗.硫酸铵的热分解[J].化学研究与应用,2002(6):737-738,765. LIU K W,CHEN T L.Studies on the thermal decomposition of ammonium sulfate[J].Chemical Research and Application, 2002(6):737-738,765(in Chinese).
[24] LIU J H,ZHANG T K,WANG Z C,et al.Simple pyrolysis of urea into graphitic carbon nitride with recyclable adsorption and photoc-atalytic activity[J].Journal of Materials Chemistry,2011,21:14398-14401. [25] 梁庆华.石墨相氮化碳的结构调控及增强光催化性能研究[D].北京:清华大学,2016. LIANG Q H.Structural tuning of graphitic carbon nitrides with highly improved photocatalytic performance[D].Beijing:Tsinghua University,2016(in Chinese). [26] FU T J,WANG X,ZHENG H Y,et al.Effect of Cu location and dispersion on carbon sphere supported Cu catalysts for oxidative carbonylation of methanol to dimethyl carbonate[J].Carbon,2017,115:363-374. [27] CHEN A B,YU Y F,LV H J,et al.Thin-walled, mesoporous and nitrogen-doped hollow carbon spheres using ionic liquids as precursors[J].Journal of Materials Chemistry A,2013,1:1045-1047 [28] YU H J,SHI R,ZHAO Y X,et al.Alkali-assisted synthesis of nitrogen deficient graphitic carbon nitride with tunable band structures for efficient visible-light-driven hydrogen evolution[J].Advanced Materials,2017,29(16):1605148. [29] WONG M S,HSU S W,RAO K,et al.Influence of crystallinity and carbon content on visible light photocatalysis of carbon doped titania thin films[J].Journal of Molecular Catalysis A:Chemical,2008,279(1):20-26. [30] XU C K,KILLMEYER R,GRAY M M,et al.Photocatalytic effect of carbonmodified n-TiO2 nanoparticles under visible light illumination[J].Applied Catalysis B:Environmental,2006,64(3-4):312-317. [31] CUI L F,SONG J L,MCGUIRE A F,et al.Constructing highly uniform onion-ring-like graphitic carbon nitride for efficient visible-light-driven photocatalytic hydrogen evolution[J].ACS Nano,2018,12(6):5551-5558. [32] 范芸珠,曹发海.硫酸铵热分解反应动力学研究[J].高校化学工程学报,2011,25(2):341-346. FAN Y Z,CAO F H.Thermal decomposition kinetics of ammonium sulfate[J].Journal of Chemical Engineering of Chinese Universities, 2011,25(2):341-346(in Chinese).
[33] KONG L,JIANG Z,LAI H H,et al.Unusual reactivity of visible-light-responsive AgBr-BiOBr heterojunction photocatalysts[J].Journal of Catalysis,2012,293:116-125. [34] MOUSAVI M, HABIBI-YANGJEH A,ABITORABI M.Fabrication of novel magnetically separable nano-composites using graphitic carbon nitride, silver phosphate and silver chloride and their applications in photocatalytic removal of different pollutants using visiblelight irradiation[J].Journal of Colloid and Interface Science,2016,480:218-231. [35] YUAN Q,CHEN L,XIONG M,et al.Cu2O/BiVO4 heterostructures:Synthesis and application in simultaneous photocatalytic oxidation of organic dyes and reduction of Cr(Ⅵ) under visible light[J].Chemical Engineering Journal,2014,255:394-402. [36] KIM J,LEE C W,CHOI W.Platinized WO3 as an environmental photocatalyst that generates oh radicals under visible light[J].Environ. Sci. Technol,2010,44:6849-6854. [37] ZENG J,LI J Z,ZHONG J B,et al.Improved sun light photocatalytic activity of α-Fe2O3 prepared with the assistance of CTAB[J].Materials Letters,2015,160:526-528. [38] LIU Y,YUAN X Z,WANG H,et al.Solvothermal synthesis of graphene/BiOCl0.75Br0.25 microspheres with excellent visible-light photoca-talytic activity[J].RSC Advances,2015,5:33696-33704. -
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