Au/g-C_3N_4复合微粒的制备及光催化还原对硝基苯酚
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摘要
为了解决光生电子-空穴因分离难而对g-C_3N_4光催化活性造成影响的问题,采用原位法制备了Au/g-C_3N_4复合微粒,利用TEM,SEM,XRD,XPS和FTIR等测试方法对复合微粒的形貌、微观结构和组成进行表征,通过UV-vis DRS,PL和EIS等方法分析了复合微粒的光电性能,并以对硝基苯酚还原反应为模型,考察了Au/g-C_3N_4复合微粒的可见光催化性能。结果表明:g-C_3N_4为片层堆积结构的六方相晶体,片层间的纳米金为面心立方晶型;纳米金的引入显著提高了g-C_3N_4基体对可见光的吸收及其光生电子-空穴对的分离效率;当金含量为0.5%(质量分数)、氯金酸钠与柠檬酸钠物质的量比为1∶3时,光催化剂的活性最高。所制备的复合催化剂可见光响应性强,催化活性较纯g-C_3N_4明显提高,为合成g-C_3N_4基高效光催化剂提供了理论依据。
In order to solve the problem of photo-generated electron-hole separation which affects g-C_3N_4 photocatalytic activity,Au/g-C_3N_4 composite particles are in situ prepared.The morphology,microstructure and composition of as-prepared Au/g-C_3N_4 composite particles were characterized by TEM,SEM,XRD,XPS and FTIR,the photoelectric property of the composite particles is also characterized by UV-vis DRS,PL and EIS,and the catalytic activities were examined using the reduction of 4-NP as a model reaction.The results show that the laminated g-C_3N_4 is hexagonal crystal,while the gold nanoparticles dispersing between the lamella of the g-C_3N_4 are face-centered cubic crystallites.The visible-light absorption and electron-hole separation efficiency of g-C_3N_4 matrix are improved by the introduction of gold nanoparticles.When the mass fraction of Au is 0.5%,the amount of substance ratio of sodium chloroaurate and sodium citrate is 1∶3,the Au/g-C_3N_4 composite demonstrates the best photocatalytic activity.The composite catalyst has strong visible light responsiveness and significantlyhigher catalytic activity than pure g-C_3N_4,which provides a theoretical basis for the synthesis of g-C_3N_4 photocatalyst with high photocatalytic activity.
In order to solve the problem of photo-generated electron-hole separation which affects g-C_3N_4 photocatalytic activity,Au/g-C_3N_4 composite particles are in situ prepared.The morphology,microstructure and composition of as-prepared Au/g-C_3N_4 composite particles were characterized by TEM,SEM,XRD,XPS and FTIR,the photoelectric property of the composite particles is also characterized by UV-vis DRS,PL and EIS,and the catalytic activities were examined using the reduction of 4-NP as a model reaction.The results show that the laminated g-C_3N_4 is hexagonal crystal,while the gold nanoparticles dispersing between the lamella of the g-C_3N_4 are face-centered cubic crystallites.The visible-light absorption and electron-hole separation efficiency of g-C_3N_4 matrix are improved by the introduction of gold nanoparticles.When the mass fraction of Au is 0.5%,the amount of substance ratio of sodium chloroaurate and sodium citrate is 1∶3,the Au/g-C_3N_4 composite demonstrates the best photocatalytic activity.The composite catalyst has strong visible light responsiveness and significantlyhigher catalytic activity than pure g-C_3N_4,which provides a theoretical basis for the synthesis of g-C_3N_4 photocatalyst with high photocatalytic activity.
引文
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[2]IVANOV A S,MILLER E,BOLDYREV A I,et al.Pseudo jahn-teller origin of buckling distortions in two-dimensional triazine-based graphitic carbon nitride(g-C3N4)sheets[J].The Journal of Physical Chemistry C,2015,119(21):12008-12015.
[3]孙志明,李雪,马建宁,等.类石墨氮化碳/伊利石复合材料的制备及其可见光催化性能[J].复合材料学报,2018,35(6):1558-1565.SUN Zhiming,LI Xue,MA Jianning,et al.Preparation and visible light catalytic properties of g-C3N4/illite composite[J].Acta Meteriae Compositae Sinica,2018,35(6):1558-1565.
[4]SUN Shanfu,SUN Mingxuan,FANG Yalin,et al.One-step in situ calcination synthesis of g-C3N4/N-TiO2hybrids with enhanced photoactivity[J].RSC Advances,2016,6(16):13063-13071.
[5]KONG H J,WON D H,KIM J,et al.Sulfur-doped g-C3N4/BiVO4composite photocatalyst for water oxidation under visible light[J].Chemistry of Materials,2016,28(5):1318-1324.
[6]FU Songsheng,HUANG Ting,JIA Bingquan,et al.Reduction of nitrophenols to aminophenols under concerted catalysis by Au/g-C3N4contact system[J].Applied Catalysis B:Environmental,2017,202:430-437.
[7]TSUKAMOTO D,SHIRAISHI Y,SUGANO Y,et al.Gold nanoparticles located at the interface of anatase/rutile TiO2particles as active plasmonic photocatalysts for aerobic oxidation[J].Journal of America Chemistry Society,2012,134(14):6309-6315.
[8]PRASHANT K J,HUANG X H,IVAN H E,et al.Noble metals on the nanoscale:Optical and photothermal properties and some applications in imaging,sensing,biology,and medicine[J].Accounts of Chemical Research,2008,41(12):1578-1586.
[9]XUE J J,MA S S,ZHOU Y M,et al.Facile photochemical synthesis of Au/Pt/g-C3N4with plasmon-enhanced photocatalytic activity for antibiotic degradation[J].ACS Applied Materials&Interfaces,2015,7(18):9630-9637.
[10]MO Zhao,XU Hui,CHEN Zhigang,et al.Gold/monolayer graphitic carbon nitride plasmonic photocatalyst for ultrafast electron transfer in solar-to-hydrogen energy conversion[J].Chinese Journal of Catalysis,2018(39):760-770.
[11]FANG Wei,DENG Yaocheng,TAN Lin,et al.Synthesis of Pd/Au bimetallic nanoparticle-loaded ultrathin graphitic carbon nitride nanosheets for highly efficient catalytic reduction of p-nitrophenol[J].Journal of Colloid and Interface Science,2017,490:834-843.
[12]SAMANTA S,MARTHA S,PARIDA K.Facile synthesis of Au/g-C3N4nanocomposites:An inorganic/organic hybrid plasmonic photocatalyst with enhanced hydrogen gas evolution under visible-light irradiation[J].Chem Cat Chem,2014,6(5):1453-1462.
[13]WANG Desong,SUN Haitao,LUO Qingzhi,et al.An efficient visible-light photocatalyst prepared fromg-C3N4and polyvinyl chloride[J].Applied Catalysis B:Environmental,2014,156(5):323-330.
[14]JIANG Jing,YU Jiaguo,CAO Shaowen.Au/PtO nanoparticle-modified g-C3N4for plasmon-enhanced photocatalytic hydrogen evolution under visible light[J].Journal of Colloid and Interface Science,2016,461:56-63.
[15]WANG Xiu,TAN Fatang,WANG Wei,et al.Anchoring of silver nanoparticles on graphitic carbon nitride sheets for the synergistic catalytic reduction of 4-nitrophenol[J].Chemosphere,2017,172:147-154.
[16]ONG W J,PUTRI L K,TAN L L,et al.Heterostructured AgX/g-C3N4(X=Cl and Br)nanocomposites via a sonication-assisted deposition-precipitation approach:Emerging role of halide ions in the synergistic photocatalytic reduction of carbon dioxide[J].Applied Catalysis B:Environmental,2016,180:530-543.
[17]ANTHONY M T,SEAH M P.Energy calibration of electron spectrometers 1-An absolute,traceable energy calibration and the provision of atomic reference line energies[J].Surface&Interface Analysis,2010,6(3):95-106.
[18]TURNER N H,SINGLE A M.Determination of peak positions and areas from wide-scan XPS spectra[J].Surface&Interface Analysis,2010,15(3):215-222.
[19]GAO Hanwei,LIU Chong,JEONG H E,et al.Plasmon-enhanced photocatalytic activity of iron oxide on gold nanopillars[J].Acs Nano,2012,6(1):234-240.
[20]LUO Qingzhi,YANG Xiaolian,WANG Desong,et al.Facile preparation of well-dispersed ZnO/cyclized polyacrylonitrile nanocomposites with highly enhanced visible-light photocatalytic activity[J].Applied Catalysis B:Environmental,2017,204:304-315.
[21]HE Yiming,ZHANG Lihong,TENG Botao,et al.New application of Zscheme Ag3PO4/g-C3N4composite inconverting CO2to fuel[J].Environmental Science&Technology,2015,49(1):649-656.
[22]WUNDER S,POLZER F,LU Y,et al.Kinetic analysis of catalytic reduction of 4-nitrophenol by metallic nanoparticles immobilized in spherical polyelectrolyte brushes[J].The Journal of Physical Chemistry C,2010,114(19):8814-8820.
[23]WANG Yaning,ZHANG Ying,ZHANG Wenshu,et al.A SERS substrate of mesoporous g-C3N4embedded with in situ grown gold nanoparticles for sensitive detection of 6-thioguanine[J].Sensors and Actuators B:Chemical,2018,260:400-407.