磷酸盐的添加对甲烷氧化偶联反应镧基催化剂的影响
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摘要
采用柠檬酸法制备了不同含量磷酸盐修饰的镧基催化剂,考察了磷酸盐的添加对镧基催化剂甲烷氧化偶联反应(OCM)活性的影响,并借助X射线衍射(XRD)、O_2-程序升温脱附(O_2-TPD)及X射线光电子能谱(XPS)等手段对催化剂的理化性质进行了表征.结果表明,随着磷酸盐加入量的增大,催化剂样品的粒径逐渐减少,催化剂的物相由La_2O_3向La_3PO_7和LaPO_4逐步转变.当催化剂的物相由La_2O_3和适量的La_3PO_7构成时,催化剂具有较多的表面缺陷位点数和较大的亲电氧物种/晶格氧物种比值,并呈现出良好的OCM反应性能.
A series of La-based catalysts promoted by different contents of PO_4~(3-)was synthesized by the citric acid method and their catalytic performance for oxidative coupling of methane(OCM)was investigated to clarify the effect of PO_4~(3-)on La-based catalyst.With characterizations such as X-ray powder diffraction(XRD),O_2-temperature programmed desorption(O_2-TPD)and X-ray photoelectron spectroscopy(XPS),we studied the physicochemical properties of the catalysts.The results showed that the phases of the catalysts were changed from La_2O_3,La_3PO_7 to La PO_4 along with the decreased size when phosphate added.If the catalyst was composed of two phases(La_2O_3 and right amount of La_3PO_7),it showed better performances in OCM,which corresponded to the more quantities of surface defect sites and the larger ratio of electrophilic oxygen species/lattice oxygen species than other samples.
A series of La-based catalysts promoted by different contents of PO_4~(3-)was synthesized by the citric acid method and their catalytic performance for oxidative coupling of methane(OCM)was investigated to clarify the effect of PO_4~(3-)on La-based catalyst.With characterizations such as X-ray powder diffraction(XRD),O_2-temperature programmed desorption(O_2-TPD)and X-ray photoelectron spectroscopy(XPS),we studied the physicochemical properties of the catalysts.The results showed that the phases of the catalysts were changed from La_2O_3,La_3PO_7 to La PO_4 along with the decreased size when phosphate added.If the catalyst was composed of two phases(La_2O_3 and right amount of La_3PO_7),it showed better performances in OCM,which corresponded to the more quantities of surface defect sites and the larger ratio of electrophilic oxygen species/lattice oxygen species than other samples.
引文
[1]Tang P.,Zhu Q.J.,Wu Z.X.,Ma D.,Energy Environ.Sci.,2014,7(8),2580—2591
[2]Guo Z.,Liu B.,Zhang Q.H.,Deng W.P.,Wang Y.,Yang Y.H.,Chem.Soc.Rev.,2014,43(10),3480.
[3]Song J.,Sun Y.,Ba R.,Huang S.,Zhao Y.,Zhang J.,Sun Y.H.,Zhu Y.,Nanoscale,2015,7(6),2260—2264
[4]Li Z.N.,Hei L.,Wang S.L.,Yi W.Z.,Zou S.H.,Xiao L.P.,Fan J.,ACS Comb.Sci.,2017,19(1),15—24
[5]Sollier B.M.,Gómez L.E.,Boix A.V.,MiróE.E.,Appl.Cataly.A:Gen.,2017,532,65—76
[6]Wang Z.L.,Chen L.,Luo X.,Zou G.J.,Gao R.X.,Chou L.J.,Wang X.L.,J.Mol.Catal.,2013,27(2),152—158
[7]Elkins T.W.,Roberts S.J.,Hagelin-Weaver H.E.,Appl.Catal.A:Gen.,2016,528,175—190
[8]Hou Y.H.,Lin Y.L.,Li Q.,Weng W.Z.,Xia W.S.,Wan H.L.,Chem Cat Chem,2013,5(12),3725—3735
[9]Lin X.Z.,Li G.C.,Huang C.J.,Weng W.Z.,Wan H.L.,Chinese Chem.Lett.,2013,24(9),789—792(林晓张,李广超,黄传敬,翁维正,万惠霖.中国化学快报,2013,24(9),789—792)
[10]Trotu爧I.T.,Teodorescu C.M.,Prvulescu V.I.,Marcu I.C.,Chem Cat Chem,2013,5(3),757—765
[11]Hou Y.H.,Han W.C.,Xia W.S.,Wan H.L.,ACS Catal.,2015,5(3),1663—1674
[12]Yang Y.L.,Dong L.Y.,Xia W.S.,Wan H.L.,Chem.J.Chinese Universities,2016,37(12),2206—2214(杨艳玲,董玲玉,夏文生,万惠霖.高等学校化学学报,2016,37(12),2206—2214)
[13]Bernal S.,Botana F.J.,Garcia R.,Rodiguez-Izquierdo J.M.,Reactivity of Soliak,1987,4,23—40
[14]Farrukh M.A.,Imran F.,Ali S.,Khaleeq-Ur-Rahman M.,Naqvi I.I.,Russ.J.Appl.Chem.,2015,88(9),1523—1527
[15]Djerdj I.,Garnweitner G.,Su D.S.,Niederberger M.,J.Solid State Chem.,2007,180(7),2154—2165
[16]Méndez M.,Carvajal J.J.,Cesteros Y.,AguilóM.,Díaz F.,Giguère A.,Drouin D.,Martínez-Ferrero E.,Salagre P.,Formentín P.,Optical Materials,2010,32(12),1686—1692
[17]Loitongbam R.S.,Singh N.S.,Singh W.R.,S.,Ningthoujam R.,J.Lumin.,2013,134,14—23
[18]Lien D.T.,Huong D.T.M.,Le V.V.,Long N.N.,J.Lumin.,2015,161,389—394
[19]Macalik L.,Tomaszewski P.E.,Matraszek A.,SzczygieI.,Solarz P.,Godlewska P.,Sobczyk M.,Hanuza J.,J.Alloys Compd.,2011,509(27),7458—7465
[20]Guo X.H.,Mao C.C.,Zhang J.,Huang J.,Wang W.N.,Deng Y.H.,Wang Y.Y.,Cao Y.,Huang W.X.,Yu S.H.,Small,2012,8(10),1515—1520
[21]LüS.,Zhang J.,J.Nanosci.Nanotechnol.,2008,8(3),1410—1413
[22]Zhang H.B.,Lin G.D.,Wan H.L.,Liu Y.D.,Weng W.Z.,Cai J.X.,Shen Y.F.,Tsai K.R.,Catal.Lett.,2001,73(2),141—147
[23]Peil K.P.,Jr J.G.G.,Marcelin G.,J.Catal.,1991,131(1),143—155
[24]Wang J.X.,Lunsford J.H.,Research Gate,1986,90(17),3890—3891
[25]Ferreira V.J.,Tavares P.,Figueiredo J.L.,Faria J.L.,Catal.Commun.,2013,42(23),50—53
[26]Peng X.D.,Richards D.A.,Stair P.C.,J.Catal.,1990,121(1),99—109
[27]Huang P.,Zhao Y.,Zhang J.,Zhu Y.,Sun Y.H.,Nanoscale,2013,5(22),10844—10848
[28]Rodriguez J.A.,Hrbek J.,Kuhn M.,Sham T.K.,J.Phys.Chem.,1993,97(18),4737—4744
[29]Zhang X.,He D.,Zhang Q.,Xu B.,Zhu Q.,Top.Catal.,2005,32(3),215—223
[2]Guo Z.,Liu B.,Zhang Q.H.,Deng W.P.,Wang Y.,Yang Y.H.,Chem.Soc.Rev.,2014,43(10),3480.
[3]Song J.,Sun Y.,Ba R.,Huang S.,Zhao Y.,Zhang J.,Sun Y.H.,Zhu Y.,Nanoscale,2015,7(6),2260—2264
[4]Li Z.N.,Hei L.,Wang S.L.,Yi W.Z.,Zou S.H.,Xiao L.P.,Fan J.,ACS Comb.Sci.,2017,19(1),15—24
[5]Sollier B.M.,Gómez L.E.,Boix A.V.,MiróE.E.,Appl.Cataly.A:Gen.,2017,532,65—76
[6]Wang Z.L.,Chen L.,Luo X.,Zou G.J.,Gao R.X.,Chou L.J.,Wang X.L.,J.Mol.Catal.,2013,27(2),152—158
[7]Elkins T.W.,Roberts S.J.,Hagelin-Weaver H.E.,Appl.Catal.A:Gen.,2016,528,175—190
[8]Hou Y.H.,Lin Y.L.,Li Q.,Weng W.Z.,Xia W.S.,Wan H.L.,Chem Cat Chem,2013,5(12),3725—3735
[9]Lin X.Z.,Li G.C.,Huang C.J.,Weng W.Z.,Wan H.L.,Chinese Chem.Lett.,2013,24(9),789—792(林晓张,李广超,黄传敬,翁维正,万惠霖.中国化学快报,2013,24(9),789—792)
[10]Trotu爧I.T.,Teodorescu C.M.,Prvulescu V.I.,Marcu I.C.,Chem Cat Chem,2013,5(3),757—765
[11]Hou Y.H.,Han W.C.,Xia W.S.,Wan H.L.,ACS Catal.,2015,5(3),1663—1674
[12]Yang Y.L.,Dong L.Y.,Xia W.S.,Wan H.L.,Chem.J.Chinese Universities,2016,37(12),2206—2214(杨艳玲,董玲玉,夏文生,万惠霖.高等学校化学学报,2016,37(12),2206—2214)
[13]Bernal S.,Botana F.J.,Garcia R.,Rodiguez-Izquierdo J.M.,Reactivity of Soliak,1987,4,23—40
[14]Farrukh M.A.,Imran F.,Ali S.,Khaleeq-Ur-Rahman M.,Naqvi I.I.,Russ.J.Appl.Chem.,2015,88(9),1523—1527
[15]Djerdj I.,Garnweitner G.,Su D.S.,Niederberger M.,J.Solid State Chem.,2007,180(7),2154—2165
[16]Méndez M.,Carvajal J.J.,Cesteros Y.,AguilóM.,Díaz F.,Giguère A.,Drouin D.,Martínez-Ferrero E.,Salagre P.,Formentín P.,Optical Materials,2010,32(12),1686—1692
[17]Loitongbam R.S.,Singh N.S.,Singh W.R.,S.,Ningthoujam R.,J.Lumin.,2013,134,14—23
[18]Lien D.T.,Huong D.T.M.,Le V.V.,Long N.N.,J.Lumin.,2015,161,389—394
[19]Macalik L.,Tomaszewski P.E.,Matraszek A.,SzczygieI.,Solarz P.,Godlewska P.,Sobczyk M.,Hanuza J.,J.Alloys Compd.,2011,509(27),7458—7465
[20]Guo X.H.,Mao C.C.,Zhang J.,Huang J.,Wang W.N.,Deng Y.H.,Wang Y.Y.,Cao Y.,Huang W.X.,Yu S.H.,Small,2012,8(10),1515—1520
[21]LüS.,Zhang J.,J.Nanosci.Nanotechnol.,2008,8(3),1410—1413
[22]Zhang H.B.,Lin G.D.,Wan H.L.,Liu Y.D.,Weng W.Z.,Cai J.X.,Shen Y.F.,Tsai K.R.,Catal.Lett.,2001,73(2),141—147
[23]Peil K.P.,Jr J.G.G.,Marcelin G.,J.Catal.,1991,131(1),143—155
[24]Wang J.X.,Lunsford J.H.,Research Gate,1986,90(17),3890—3891
[25]Ferreira V.J.,Tavares P.,Figueiredo J.L.,Faria J.L.,Catal.Commun.,2013,42(23),50—53
[26]Peng X.D.,Richards D.A.,Stair P.C.,J.Catal.,1990,121(1),99—109
[27]Huang P.,Zhao Y.,Zhang J.,Zhu Y.,Sun Y.H.,Nanoscale,2013,5(22),10844—10848
[28]Rodriguez J.A.,Hrbek J.,Kuhn M.,Sham T.K.,J.Phys.Chem.,1993,97(18),4737—4744
[29]Zhang X.,He D.,Zhang Q.,Xu B.,Zhu Q.,Top.Catal.,2005,32(3),215—223