N-K_2Ti_4O_9/UiO-66-NH_2复合材料的协同效应及其光催化降解阳离子型染料（英文）
|
摘要
半导体光催化剂作为一种可再生和可持续降解有机污染物的材料被广泛研究.K_2Ti_4O_9由于无毒、低成本、稳定的物理化学性质和独特的光电性能被应用于光催化反应.但是,K_2Ti_4O_9只能被紫外光所激发(因为其带隙能为3.2–3.4 e V),所以大量工作致力于研究如何降低其带隙能,从而使其可以被太阳光中的可见光激发,扩大其应用范围.其中N元素掺杂K_2Ti_4O_9(N-K_2Ti_4O_9)是最常见的方法之一.单纯的N-K_2Ti_4O_9虽然具有光催化能力,但其吸附容量太小,不能有效地将溶液中的有机物吸附至其表面,因而催化降解有机物效果不显著.UiO-66-NH_2是一种Zr基金属-有机骨架化合物,它对阳离子染料具有良好的吸附性能,且具有一些常规无机半导体光催化材料所没有的性质.本文将UiO-66-NH_2和N-K_2Ti_4O_9经高温焙烧制备了N-K_2Ti_4O_9/UiO-66-NH_2复合材料,发现该复合材料不仅具有UiO-66-NH_2优良的吸附性能,还因为复合提高了其光电性能,从而大大提高了光催化性能,当N-K_2Ti_4O_9/ZrCl_4质量比为3:7时光催化性能最佳.为了考察N-K_2Ti_4O_9/UiO-66-NH_2复合材料的微观形貌、复合结构及光生电子-空穴分离效率,首先通过场发射透射电镜分析N-K_2Ti_4O_9,UiO-66-NH_2和N-K_2Ti_4O_9/UiO-66-NH_2(3:7)复合材料的形貌,然后采用能量散射谱测定复合材料的元素分布,并利用N-K_2Ti_4O_9和UiO-66-NH_2中代表性元素K,Ti和Zr的分布判断复合材料的复合结构,最后运用高分辨电镜观察复合材料中N-K_2Ti_4O_9和UiO-66-NH_2的异质结界面,确定了两者是通过自组装复合在一起,而不是简单的物理混合.X射线衍射结果表明,复合材料具有N-K_2Ti_4O_9和UiO-66-NH_2两者的特征衍射峰,仅在强度和位置上略有变化.这可能是N-K_2Ti_4O_9/UiO-66-NH_2异质结构所致.通过UiO-66-NH_2和N-K_2Ti_4O_9的紫外-可见吸收光谱,用公式计算出它们的带隙能分别是2.645和3.195 e V,与文献结果基本一致.由于光催化剂的光生载流子迁移速率同样影响光催化性能,因此我们在CHI-660D电化学工作站上控制光源反复开关数次,同时记录N-K_2Ti_4O_9,UiO-66-NH_2和N-K_2Ti_4O_9/UiO-66-NH_2(3:7)的光响应电流,发现N-K_2Ti_4O_9/UiO-66-NH_2(3:7)复合材料展现出最高的光响应电流强度,表明其具有最高的光生载流子迁移速率和最低的光生载流子复合速率.可见,N-K_2Ti_4O_9和UiO-66-NH_2复合有利于光生载流子迁移,这可能是由于N-K_2Ti_4O_9/UiO-66-NH_2异质结界面有利于光生载流子在两种材料之间迁移所致.测试了N-K_2Ti_4O_9/UiO-66-NH_2(3:7)复合材料对不同染料的光催化降解性能.结果发现,该材料对阳离子型染料(罗丹明B和亚甲基蓝)的光催化性能远远高于对阴离子型染料(甲基橙和刚果红).这是由于它对阳离子型染料的吸附性能远高于对阴离子型染料,因此N-K_2Ti_4O_9/UiO-66-NH_2复合材料对阳离子型染料具有选择性光催化.
N-K_2Ti_4O_9/UiO-66-NH_2 composites synthesized by a facile solvothermal method have a core-shell structure with UiO-66-NH_2 forming the shell around a N-K_2Ti_4O_9 core.Their photocatalytic activities in the degradation of dyes under visible light irradiation were investigated.The N-K_2Ti_4O_9/UiO-66-NH_2 composites exhibited higher photocatalytic activity than the pure components.This synergistic effect was due to the high adsorption capacity of UiO-66-NH_2 and that the two components together induced an enhanced separation efficiency of photogenerated electron-hole pairs.The mass ratio of N-K_2Ti_4O_9 to ZrCl_4 of 3:7 in the composite exhibited the highest photocatalytic activity.Due to the electrostatic attraction between the negatively charged backbone of UiO-66-NH_2with the positively charged groups of cationic dyes,the composites were more photocatalytically active for cationic dyes than for anionic dyes.
N-K_2Ti_4O_9/UiO-66-NH_2 composites synthesized by a facile solvothermal method have a core-shell structure with UiO-66-NH_2 forming the shell around a N-K_2Ti_4O_9 core.Their photocatalytic activities in the degradation of dyes under visible light irradiation were investigated.The N-K_2Ti_4O_9/UiO-66-NH_2 composites exhibited higher photocatalytic activity than the pure components.This synergistic effect was due to the high adsorption capacity of UiO-66-NH_2 and that the two components together induced an enhanced separation efficiency of photogenerated electron-hole pairs.The mass ratio of N-K_2Ti_4O_9 to ZrCl_4 of 3:7 in the composite exhibited the highest photocatalytic activity.Due to the electrostatic attraction between the negatively charged backbone of UiO-66-NH_2with the positively charged groups of cationic dyes,the composites were more photocatalytically active for cationic dyes than for anionic dyes.
引文
[1]A.S.Bhatt,P.L.Sakaria,M.Vasudevan,R.R.Pawar,N.Sudheesh,H.C.Bajaj,H.M.Mody,RSC Adv.,2012,2,8663-8671.
[2]H.Chen,J.Zhao,Adsorption,2009,15,381-389.
[3]V.K.Gupta,B.Gupta,A.Rastogi,S.Agarwal,A.Nayak,J.Hazard.Mater.,2011,186,891-901.
[4]A.Dolbecq,P.Mialane,B.Keita,L.Nadjo,J.Mater.Chem.,2012,22,24509-24521.
[5]A.Kubacka,M.Fernández‐García,G.Colón,Chem.Rev.,2012,112,1555-1614.
[6]W.Q.Fan,Q.H.Zhang,Y.Wang,Phys.Chem.Chem.Phys.,2013,15,2632-2649.
[7]Y.Hosogi,H.Kato,A.Kudo,J.Phys.Chem.C,2008,112,17678-17682.
[8]J.C.Cao,A.L.Wang,H.B.Yin,L.Q.Shen,M.Ren,S.Q.Han,Y.T.Shen,L.B.Yu,T.S.Jiang,Ind.Eng.Chem.Res.,2010,49,9128-9134.
[9]W.Q.Cui,S.S.Ma,L.Liu,J.S.Hu,Y.H.Liang,J.G.McE voy,Appl.Surf.Sci.,2013,271,171-181.
[10]J.S.Wang,H.Li,H.Y.Li,S.Yin,T.Sato,Solid State Sci.,2009,11,988-993.
[11]P.Romero‐Go?mez,S.Hamad,J.C.Gonza?lez,A.Barranco,J.P.Es‐pino?s,J.Cotrino,A.R.Gonza?lez‐Elipe,J.Phys.Chem.C,2010,114,22546-22557.
[12]Y.J.Hwang,A.Boukai,P.D.Yang,Nano Lett.,2009,9,410-415.
[13]G.Q.Song,Z.Q.Wang,L.Wang,G.R.Li,M.J.Huang,F.X.Yin,Chin.J.Catal.,2014,35,185-195.
[14]G.Férey,Chem.Soc.Rev.,2008,37,191-214.
[15]H.L.Li,M.Eddaoudi,M.O'Keeffe,M.Yaghi,Nature,1999,402,276-279.
[16]Y.S.Li,W.S.Yang,Chin.J.Catal.,2015,36,692-697.
[17]S.Kitagawa,R.Kitaura,S.I.Noro,Angew.Chem.Int.Ed.,2004,43,2334-2375.
[18]S.Hasegawa,S.Horike,R.Matsuda,S.Furukawa,K.Mochizuki,Y.Kinoshita,S.Kitagawa,J.Am.Chem.Soc.,2007,129,2607-2614.
[19]N.L.Rosi,J.Eckert,M.Eddaoudi,D.T.Vodak,J.Kim,M.O’Keeffe,O.M.Yaghi,Science,2003,300,1127-1129.
[20]M.Eddaoudi,J.Kim,N.Rosi,D.Vodak,J.Wachter,M.?Keeffe,O.M.Yaghi,Science,2002,295,469-472.
[21]M.Latroche,S.Surblé,C.Serre,C.Mellot‐Draznieks,P.L.Llewellyn,J.H.Lee,J.S.Chang,S.H.Jhung,G.Férey,Angew.Chem.Int.Ed.,2006,45,8227-8231.
[22]P.Horcajada,C.Serre,M.Vallet‐Regí,M.Sebban,F.Taulelle,G.Férey,Angew.Chem.Int.Ed,2006,45,5974-5978.
[23]C.G.Silva,I.Luz,F.X.Llabrés i Xamena,A.Corma,H.García,Chem.‐Eur.J.,2010,16,11133-11138.
[24]L.J.Shen,W.M.Wu,R.W.Liang,R.Lin,L.Wu,Nanoscale,2013,19,9374-9382.
[25]Q.H.Zhang,W.G.Fan,L.Gao,Appl.Catal.B,2007,76,168-173.
[26]M.A.Aramendía,V.Borau,J.C.Colmenares,A.Marinas,J.M.Mari‐nas,J.A.Navío,F.J.Urbano,Appl.Catal.B,2008,80,88-97.
[27]M.H.Zhou,J.G.Yu,S.W.Liu,P.C.Zhai,L.Jiang,J.Hazard.Mater.,2008,154,1141-1148.
[28]M.R.Allen,A.Thibert,E.M.Sabio,N.D.Browning,D.S.Larsen,F.E.Osterloh,Chem.Mater.,2010,22,1220-1228.
[29]D.Mitoraj,H.Kisch,Angew.Chem.Int.Ed.,2008,47,9975-9978.
[30]C.D.Wagner,W.M.Riggs,L.E.Davis,J.F.Moulder,G.E.Muilen‐berg,Hand Book of X‐Ray Photoelectron Spectroscopy,Per‐kin‐Elmer,Eden Prairie,MN,1979.
[31]R.L.Arechederra,K.Artyushkova,P.Atanassov,S.D.Minteer,ACSAppl.Mater.Interfaces,2010,2,3295-3302.
[32]Y.Mosqueda,E.Pérez‐Cappe,J.Arana,E.Longo,A.Ries,M.Cilense,P.A.P.Nascentec,P.Arandad,E.Ruiz‐Hitzky,J.Solid State Chem.,2006,179,308-314.
[33]Q.Chen,Q.Q.He,M.M.Lv,Y.L.Xu,H.B.Yang,X.T.Liu,F.Y.Wei,Appl.Surf.Sci.,2015,327,77-85.
[34]V.K.Gupta,A.Mittal,L.Krishnan,V.Gajbe,Sep.Purif.Technol.,2004,40,87-96.
[35]X.G.Zhao,J.G.Huang,B.Wang,Q.Bi,L.L.Dong,X.J.Liu,Appl.Surf.Sci.,2014,292,576-582.
[36]Y.S.Ho,G.McK ay,Process Biochem.,1999,34,451-465.
[37]D.Kavitha,C.Namasivayam,Bioresource Technol.,2007,98,14-21.
[38]P.Xiong,Q.Chen,M.Y.He,X.Q.Sun,X.Wang,J.Mater.Chem.,2012,22,17485-17493.
[39]P.Xiong,L.J.Wang,X.Q.Sun,B.H.Xu,X.Wang,Ind.Eng.Chem.Res.,2013,52,10105-10113.
[40]Q.Chen,Q.Q.He,M.M.Lv,X.T.Liu,J.Wang,J.P.Lv,Appl.Surf.Sci.,2014,311,230-238.
[41]X.B.Chen,L.Liu,P.Y.Yu,S.S.Mao,Science,2011,331,746-750.
[42]A.J.Bard,R.Parsons,J.Jordan,Standard Potentials in Aqueous Solution,Marcel Dekker,New York,1985.
[43]Z.G.Xiong,X.S.Zhao,J.Am.Chem.Soc.,2012,134,5754-5757.
[44]M.A.Butler,J.Appl.Phys.,1977,48,1914-1920.
[45]A.J.Bard,L.R.Faulkner,Electrochemical Methods Fundamentals and Applications,John Wiley&Sons,New York,1980.
[46]T.X.Wu,G.M.Liu,J.C.Zhao,H.Hidaka,N.Serpone,J.Phys.Chem.B,1998,102,5845-5851.
[47]L.Mohapatra,K.Parida,M.Satpathy,J.Phys.Chem.C,2012,116,13063-13070.
[48]B.Yuan,J.X.Wei,T.J.Hu,H.B.Yao,Z.H.Jiang,Z.W.Fang,Z.Y.Chu,Chin.J.Catal.,2015,36,1009-1016.
[2]H.Chen,J.Zhao,Adsorption,2009,15,381-389.
[3]V.K.Gupta,B.Gupta,A.Rastogi,S.Agarwal,A.Nayak,J.Hazard.Mater.,2011,186,891-901.
[4]A.Dolbecq,P.Mialane,B.Keita,L.Nadjo,J.Mater.Chem.,2012,22,24509-24521.
[5]A.Kubacka,M.Fernández‐García,G.Colón,Chem.Rev.,2012,112,1555-1614.
[6]W.Q.Fan,Q.H.Zhang,Y.Wang,Phys.Chem.Chem.Phys.,2013,15,2632-2649.
[7]Y.Hosogi,H.Kato,A.Kudo,J.Phys.Chem.C,2008,112,17678-17682.
[8]J.C.Cao,A.L.Wang,H.B.Yin,L.Q.Shen,M.Ren,S.Q.Han,Y.T.Shen,L.B.Yu,T.S.Jiang,Ind.Eng.Chem.Res.,2010,49,9128-9134.
[9]W.Q.Cui,S.S.Ma,L.Liu,J.S.Hu,Y.H.Liang,J.G.McE voy,Appl.Surf.Sci.,2013,271,171-181.
[10]J.S.Wang,H.Li,H.Y.Li,S.Yin,T.Sato,Solid State Sci.,2009,11,988-993.
[11]P.Romero‐Go?mez,S.Hamad,J.C.Gonza?lez,A.Barranco,J.P.Es‐pino?s,J.Cotrino,A.R.Gonza?lez‐Elipe,J.Phys.Chem.C,2010,114,22546-22557.
[12]Y.J.Hwang,A.Boukai,P.D.Yang,Nano Lett.,2009,9,410-415.
[13]G.Q.Song,Z.Q.Wang,L.Wang,G.R.Li,M.J.Huang,F.X.Yin,Chin.J.Catal.,2014,35,185-195.
[14]G.Férey,Chem.Soc.Rev.,2008,37,191-214.
[15]H.L.Li,M.Eddaoudi,M.O'Keeffe,M.Yaghi,Nature,1999,402,276-279.
[16]Y.S.Li,W.S.Yang,Chin.J.Catal.,2015,36,692-697.
[17]S.Kitagawa,R.Kitaura,S.I.Noro,Angew.Chem.Int.Ed.,2004,43,2334-2375.
[18]S.Hasegawa,S.Horike,R.Matsuda,S.Furukawa,K.Mochizuki,Y.Kinoshita,S.Kitagawa,J.Am.Chem.Soc.,2007,129,2607-2614.
[19]N.L.Rosi,J.Eckert,M.Eddaoudi,D.T.Vodak,J.Kim,M.O’Keeffe,O.M.Yaghi,Science,2003,300,1127-1129.
[20]M.Eddaoudi,J.Kim,N.Rosi,D.Vodak,J.Wachter,M.?Keeffe,O.M.Yaghi,Science,2002,295,469-472.
[21]M.Latroche,S.Surblé,C.Serre,C.Mellot‐Draznieks,P.L.Llewellyn,J.H.Lee,J.S.Chang,S.H.Jhung,G.Férey,Angew.Chem.Int.Ed.,2006,45,8227-8231.
[22]P.Horcajada,C.Serre,M.Vallet‐Regí,M.Sebban,F.Taulelle,G.Férey,Angew.Chem.Int.Ed,2006,45,5974-5978.
[23]C.G.Silva,I.Luz,F.X.Llabrés i Xamena,A.Corma,H.García,Chem.‐Eur.J.,2010,16,11133-11138.
[24]L.J.Shen,W.M.Wu,R.W.Liang,R.Lin,L.Wu,Nanoscale,2013,19,9374-9382.
[25]Q.H.Zhang,W.G.Fan,L.Gao,Appl.Catal.B,2007,76,168-173.
[26]M.A.Aramendía,V.Borau,J.C.Colmenares,A.Marinas,J.M.Mari‐nas,J.A.Navío,F.J.Urbano,Appl.Catal.B,2008,80,88-97.
[27]M.H.Zhou,J.G.Yu,S.W.Liu,P.C.Zhai,L.Jiang,J.Hazard.Mater.,2008,154,1141-1148.
[28]M.R.Allen,A.Thibert,E.M.Sabio,N.D.Browning,D.S.Larsen,F.E.Osterloh,Chem.Mater.,2010,22,1220-1228.
[29]D.Mitoraj,H.Kisch,Angew.Chem.Int.Ed.,2008,47,9975-9978.
[30]C.D.Wagner,W.M.Riggs,L.E.Davis,J.F.Moulder,G.E.Muilen‐berg,Hand Book of X‐Ray Photoelectron Spectroscopy,Per‐kin‐Elmer,Eden Prairie,MN,1979.
[31]R.L.Arechederra,K.Artyushkova,P.Atanassov,S.D.Minteer,ACSAppl.Mater.Interfaces,2010,2,3295-3302.
[32]Y.Mosqueda,E.Pérez‐Cappe,J.Arana,E.Longo,A.Ries,M.Cilense,P.A.P.Nascentec,P.Arandad,E.Ruiz‐Hitzky,J.Solid State Chem.,2006,179,308-314.
[33]Q.Chen,Q.Q.He,M.M.Lv,Y.L.Xu,H.B.Yang,X.T.Liu,F.Y.Wei,Appl.Surf.Sci.,2015,327,77-85.
[34]V.K.Gupta,A.Mittal,L.Krishnan,V.Gajbe,Sep.Purif.Technol.,2004,40,87-96.
[35]X.G.Zhao,J.G.Huang,B.Wang,Q.Bi,L.L.Dong,X.J.Liu,Appl.Surf.Sci.,2014,292,576-582.
[36]Y.S.Ho,G.McK ay,Process Biochem.,1999,34,451-465.
[37]D.Kavitha,C.Namasivayam,Bioresource Technol.,2007,98,14-21.
[38]P.Xiong,Q.Chen,M.Y.He,X.Q.Sun,X.Wang,J.Mater.Chem.,2012,22,17485-17493.
[39]P.Xiong,L.J.Wang,X.Q.Sun,B.H.Xu,X.Wang,Ind.Eng.Chem.Res.,2013,52,10105-10113.
[40]Q.Chen,Q.Q.He,M.M.Lv,X.T.Liu,J.Wang,J.P.Lv,Appl.Surf.Sci.,2014,311,230-238.
[41]X.B.Chen,L.Liu,P.Y.Yu,S.S.Mao,Science,2011,331,746-750.
[42]A.J.Bard,R.Parsons,J.Jordan,Standard Potentials in Aqueous Solution,Marcel Dekker,New York,1985.
[43]Z.G.Xiong,X.S.Zhao,J.Am.Chem.Soc.,2012,134,5754-5757.
[44]M.A.Butler,J.Appl.Phys.,1977,48,1914-1920.
[45]A.J.Bard,L.R.Faulkner,Electrochemical Methods Fundamentals and Applications,John Wiley&Sons,New York,1980.
[46]T.X.Wu,G.M.Liu,J.C.Zhao,H.Hidaka,N.Serpone,J.Phys.Chem.B,1998,102,5845-5851.
[47]L.Mohapatra,K.Parida,M.Satpathy,J.Phys.Chem.C,2012,116,13063-13070.
[48]B.Yuan,J.X.Wei,T.J.Hu,H.B.Yao,Z.H.Jiang,Z.W.Fang,Z.Y.Chu,Chin.J.Catal.,2015,36,1009-1016.