g-C_3N_4负载Keggin型Fe单晶取代杂多酸盐对催化性能的影响
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摘要
应用乙醚萃取法制备了Fe单晶取代的Keggin型磷钨酸盐(PW_(11)Fe),并成功负载于石墨相氮化碳(g-C_3N_4),制备了不同掺杂量的复合催化剂。采用FTIR,XRD,XPS,UV-Vis,EIS,PL对催化剂进行表征。结果表明:PW_(11)Fe的掺杂有效地调控了g-C_3N_4的能级结构。并且能够有效降低光生电子空穴的复合几率,拓宽了光的响应范围,其中当掺杂量为15%(0. 15CN)时表征结果最佳。以罗丹明B(Rh B)为反应探针,在500 W氙灯(配420 nm滤光片)照射下考察催化剂的反应活性及稳定性。结果表明:负载PW_(11)Fe后显著提高了g-C_3N_4对于反应底物的吸附性能以及反应活性。0. 15CN表现出最佳的反应活性,光照90 min降解率达到100%,反应速率常数为0. 042 66 min~(-1),是纯g-C_3N_4的21. 9倍。当循环使用4次后,催化活性几乎不变。
Fe substituted heteropoly acid potassium with Keggin type( PW_(11) Fe) was synthesized by extraction method with ether and loading on g-C_3N_4 to composite catalysts with different amounts. The structure of catalysts was characterized by FTIR spectroscopy,XRD,XPS,UV-Vis,EIS and PL. The results indicate that the band gap of g-C_3N_4 is effectively controlled by doping of PW_(11) Fe. In addition,it reduces the recombination probability of the photogenerated electrons and holes,and broadens the response range of light. Among them,when the doping amount was 15%( 0. 15 CN),the best result was obtained. The catalytic activity and stability of the catalysts were tested in the photocatalytic degradation of RhB under xenon lamp with 420 nm filter. The results show that doping of PW_(11) Fe can significantly improve the adsorption performance and reactivity of g-C_3N_4. The best reactivity occurs at 0. 15 CN,and the degradation rate reaches 100% after 90 min illumination. The reaction rate constant of 0. 15 CN was 0. 042 66 min~(-1),which is 21. 9 times that of pure g-C_3N_4. The catalytic activity is almost unchanged after using 4 times.
Fe substituted heteropoly acid potassium with Keggin type( PW_(11) Fe) was synthesized by extraction method with ether and loading on g-C_3N_4 to composite catalysts with different amounts. The structure of catalysts was characterized by FTIR spectroscopy,XRD,XPS,UV-Vis,EIS and PL. The results indicate that the band gap of g-C_3N_4 is effectively controlled by doping of PW_(11) Fe. In addition,it reduces the recombination probability of the photogenerated electrons and holes,and broadens the response range of light. Among them,when the doping amount was 15%( 0. 15 CN),the best result was obtained. The catalytic activity and stability of the catalysts were tested in the photocatalytic degradation of RhB under xenon lamp with 420 nm filter. The results show that doping of PW_(11) Fe can significantly improve the adsorption performance and reactivity of g-C_3N_4. The best reactivity occurs at 0. 15 CN,and the degradation rate reaches 100% after 90 min illumination. The reaction rate constant of 0. 15 CN was 0. 042 66 min~(-1),which is 21. 9 times that of pure g-C_3N_4. The catalytic activity is almost unchanged after using 4 times.
引文
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[18]王辉,裴彦博,胡绍争,等.能级可调的钾离子掺杂石墨相氮化碳的可控制备及其“双渠道”光催化合成双氧水性能研究[J].高等学校化学学报,2018,39(7):1503-1510.
[19]ZHANG Xiaodong,XIE Xiao,WANG Hui,et al.Enhanced photoresponsive ultrathin graphitic-phase C3N4nanosheets for bioimaging[J].Journal of the American Chemical Society,2013,135(1):18.
[2]YU Yongzhi,WANG Chengcheng,LUO Linghong,et al.An environment-friendly route to synthesize pyramid-like g-C3N4arrays for efficient degradation of rhodamine B under visible-light irradiation[J].Chemical Engineering Journal,2018(334):1869-1877.
[3]曲晓钰,胡绍争,李萍.等.镍掺杂石墨相氮化碳的熔盐辅助微波法制备及光催化固氮性能[J].高等学校化学学报,2017,38(12):2280-2288.
[4]WANG Cheng,HU Liya,WANG Meiyin,et al.Vanadium supported on graphitic carbon nitride as a heterogeneous catalyst for the direct oxidation of benzene to phenol[J].Chinese Journal of Catalysis,2016(37):2003-2008.
[5]GUO Yuan,CHU Sunnan,YAN Sshengli,et al.Developing a polymeric semiconductor photocatalyst with visible light response[J].Chemical Communications,2010,46(39):7325-7327.
[6]美春,王月林,徐玲,等.Worm-like分子筛负载磷钨酸催化剂的制备及光降解甲基橙的性能研究[J].环境污染与防治,2014,12:27-30.
[7]乌英嘎,白丽梅,刘思晗,等.Keggin型杂多酸Si Mo12-xVx(x=1,3,5)光催化甲基橙脱色性能研究[J].化学研究与应用,2017,29(1):123-126.
[8]金瑞瑞,游继光,张倩,等.Fe掺杂g-C3N4的制备及其可见光催化性能[J].物理化报,2014,30(9):1706-1712.
[9]YUAN Bo,WEI Jiangxia,HU Tianjiao,et al.Simple synthesis of g-C3N4/r GO hybrid catalyst for the photocatalytic degradation of rhodamine B[J].Chinese Journal of catalysis,2015(36):1009-1016.
[10]毛丽萍,玉轶聪,史妍,等.Keggin型Sn单取代的杂多酸盐催化合成环己酮[J].精细化工,2017,34(3):300-306.
[11]曲晓钰,胡绍争,李萍,等.镍掺杂石墨相氮化碳的熔盐辅助微波法制备及光催化固氮性能[J].高等学校化学学报,2017,38(12):2280-2288.
[12]ZENG Zhenxing,LI Kexin,WEI Kai,et al.Fabrication of highly dispersed platinum-deposited porous g-C3N4by a simple in situ photoreduction strategy and their excellent visible light photocatalytic activity toward aqueous 4-fluorophenol degradation[J].Chinese Journal of Catalysis,2017(38):29-38.
[13]LIU Jing,LEI Jiandu,HE Jing,et al.Hydroprocessing of jatropha oil for production of green diesel over non-sulfided ni-PTA/Al2O3catalyst[J].Scientific Reports,2015,5:11327-11340.
[14]WANG Xinchen,MAEDA K,THOMAS A,et al.Ametal-free polymeric photocatalyst for hydrogen production from water under visible light[J].Nat,Mater,2009,8(12):890-899.
[15]ZENG Zhenxing,LI Kexin,WEI Kai,et al.Fabrication of porous g-C3N4and supported porous g-C3N4by a simple precursor pretreatment strategy and their efficient visible-light photocatalytic activity[J].Chinese Journal of Catalysis,2017(38):498-508.
[16]ZHANG Guigang,ZHANG Jinshui,ZHANG Mingwen,et al.Polycondensation of thiourea into carbon nitride semiconductorw as visible light photocatalysts[J].Journal of Materials Chemistry,2012,22(16):8083-8091.
[17]XU Yuanguo,XU Hui,WANG Lei,et al.The CNTmodified white C3N4composite photocatalyst with enhanced visible-light response photoactivity[J].Dalton Trans,2013,42(41):7604-7613.
[18]王辉,裴彦博,胡绍争,等.能级可调的钾离子掺杂石墨相氮化碳的可控制备及其“双渠道”光催化合成双氧水性能研究[J].高等学校化学学报,2018,39(7):1503-1510.
[19]ZHANG Xiaodong,XIE Xiao,WANG Hui,et al.Enhanced photoresponsive ultrathin graphitic-phase C3N4nanosheets for bioimaging[J].Journal of the American Chemical Society,2013,135(1):18.