AgAuPd/meso-Co_3O_4高效甲醇氧化催化剂（英文）
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摘要
甲醇是重要的化工原料和溶剂,也是一种典型的挥发性有机物(VOCs),其排放会对人体和大气环境造成危害.迄今为止,最有效的消除低浓度VOCs的方法是催化氧化.该方法具有VOCs去除效率高、起燃温度低、设备简单且无二次污染等优点.众所周知,负载贵金属催化剂对VOCs氧化显示良好的低温活性,但反应气流中的水分会降低贵金属的催化性能.研究表明,与单一贵金属催化剂相比,贵金属合金催化剂不仅具有高的催化活性,而且还具有良好的水热稳定性.尽管已有文献报道了二元贵金属合金催化剂对VOCs的催化氧化,然而VOCs在三元贵金属合金上催化氧化的研究则较少.本文采用三维有序介孔结构的二氧化硅(KIT-6)硬模板法和聚乙烯醇保护的硼氢化钠还原法制备了0.68 wt%和0.93 wt%Ag_0.51Au_0.65Pd/meso-Co_3O_4三元贵金属合金催化剂以及0.28 wt%Ag/meso-Co_3O_4,0.35 wt%Au/meso-Co_3O_4和0.33 wt%Pd/meso-Co_3O_4单一贵金属催化剂.利用电感耦合等离子体-原子发射光谱(ICP-AES)、X射线衍射(XRD)、透射电子显微镜(TEM)、高角环形暗场-扫描透射电子显微镜(HAADF-STEM)、X射线光电子能谱(XPS)和氢气-程序升温还原技术表征了催化剂的物化性质.催化剂的活性评价在固定床石英微型反应器中进行,反应气组成为0.1%甲醇+氧气+氮气(平衡气),甲醇/氧气摩尔比为1/200,空速约为80000 mL g–1 h–1,利用气相色谱检测反应物和产物的浓度.广角度XRD结果表明具有立方晶相结构.XRD谱中未检测到Ag,Au和Pd的衍射峰,系贵金属负载量低且均匀分散在载体表面所致.贵金属粒径为2.8-4.5 nm.小角度XRD和TEM结果表明具有有序介孔结构.从HAADF-STEM照片可以观察到中的贵金属形成了Ag-Au-Pd合金.BET结果显示,所制得催化剂的比表面积为115-120 m~2/g,孔径为5.7-6.0 nm,孔容为0.15-0.16 cm3/g.XPS结果表明,贵金属与载体之间较强的相互作用使0.68 wt%Ag_(0.75)Au_(1.14)Pd/meso-Co_3O_4具有最低的表面摩尔比,从而使该催化剂表面拥有更多的氧空位,有利于吸附和活化氧气,提高表面吸附氧浓度,从而提高催化活性具有最低的还原温度(即最好的低温还原性),有利于催化活性的提高.因此,高分散的纳米粒子、高的吸附氧浓度、优良的低温还原性以及载体与粒子之间强的相互作用是0.68Ag_(0.75) Au_(1.14)Pd/meso-Co_3O_4具有最高催化活性(当空速为80000 mL g–1 h–1时和)的主要原因.在反应温度为110°C和空速为80000 mL g–1 h–1的条件下,向反应体系中分别引入3.0 vol%水蒸气和5.0 vol%二氧化碳,甲醇转化率分别下降6.0%和7.0%;当切断水和二氧化碳后,甲醇转化率均恢复到在无水和二氧化碳时的数值.因此,水和二氧化碳对该催化剂的失活是可逆的.换句话说,0.68 wt%Ag_(0.75)Au_(1.14)Pd/meso-Co_3O_4具有优良的水热稳定性和抗二氧化碳中毒能力.
The meso-Co_3O_4 and Agx Auy Pd/meso-Co_3O_4 catalysts were prepared using the KIT-6-templating and polyvinyl alcohol-protected NaBH4 reduction methods, respectively. Various techniques were used to characterize physicochemical properties of these materials. Catalytic performance of the samples was evaluated for methanol combustion. The cubically crystallized Co_3O_4 support displayed a three-dimensionally ordered mesoporous structure. The supported noble metal nanoparticles(NPs) possessed a surface area of 115-125 m~2/g, with the noble NPs(average size = 2.8-4.5 nm) being uniformly dispersed on the surface of meso-Co_3O_4. Among all of the samples, 0.68 wt% Ag_(0.75) Au_(1.14) Pd/meso-Co_3O_4 showed the highest catalytic activity(T_(50%) = 100 °C and T_(90%) = 112 °C at a space velocity of 80000 m L(g~(–1) h~(–1)). The partial deactivation of the 0.68 wt% Ag_(0.75) Au_(1.14) Pd/meso-Co_3O_4 sample due to water vapor or carbon dioxide introduction was reversible. It is concluded that the good catalytic performance of 0.68 wt% Ag_(0.75) Au_(1.14 )Pd/meso-Co_3O_4 was associated with its highly dispersed Ag_(0.75) Au_(1.14) Pd alloy NPs, high adsorbed oxygen species concentration, good low-temperature reducibility, and strong interaction between Ag_(0.75) Au_(1.14) Pd alloy NPs and meso-Co_3O_4.
The meso-Co_3O_4 and Agx Auy Pd/meso-Co_3O_4 catalysts were prepared using the KIT-6-templating and polyvinyl alcohol-protected NaBH4 reduction methods, respectively. Various techniques were used to characterize physicochemical properties of these materials. Catalytic performance of the samples was evaluated for methanol combustion. The cubically crystallized Co_3O_4 support displayed a three-dimensionally ordered mesoporous structure. The supported noble metal nanoparticles(NPs) possessed a surface area of 115-125 m~2/g, with the noble NPs(average size = 2.8-4.5 nm) being uniformly dispersed on the surface of meso-Co_3O_4. Among all of the samples, 0.68 wt% Ag_(0.75) Au_(1.14) Pd/meso-Co_3O_4 showed the highest catalytic activity(T_(50%) = 100 °C and T_(90%) = 112 °C at a space velocity of 80000 m L(g~(–1) h~(–1)). The partial deactivation of the 0.68 wt% Ag_(0.75) Au_(1.14) Pd/meso-Co_3O_4 sample due to water vapor or carbon dioxide introduction was reversible. It is concluded that the good catalytic performance of 0.68 wt% Ag_(0.75) Au_(1.14 )Pd/meso-Co_3O_4 was associated with its highly dispersed Ag_(0.75) Au_(1.14) Pd alloy NPs, high adsorbed oxygen species concentration, good low-temperature reducibility, and strong interaction between Ag_(0.75) Au_(1.14) Pd alloy NPs and meso-Co_3O_4.
引文
[1]L.A.Calzada,S.E.Collins,C.W.Han,V.Ortalan,R.Zanella,Appl.Catal.B,2017,207,79-92.
[2]N.G.Patel,P.D.Patel,V.S.Vaishnav,Sens.Actuat.B,2003,96,180-189.
[3]A.Mirzaei,S.G.Leonardi,G.Neri,Ceram.Int.,2016,42,15119-15141.
[4]W.L.Wang,Q.J.Meng,Y.H.Xue,X.L.Weng,P.F.Sun,Z.B.Wu,J.Catal.,2018,366,213-222.
[5]S.C.Kim,W.G.Shim,Appl.Catal.B,2009,92,429-436.
[6]F.J.Maldonado-Hódar,C.Moreno-Castilla,A.F.Pérez-Cadenas,Appl.Catal.B,2004,54,217-224.
[7]A.M.Sica,J.H.Z.D.Santos,I.M.Baibich,C.E.Gigola,J.Mol.Catal.A,1999,137,287-295.
[8]K.Persson,L.D.Pfefferle,W.Schwartz,A.Ersson,S.G.Jaras,Appl.Catal.B,2007,74,242-250.
[9]J.Q.Jiao,Y.C.Wei,Y.L.Zhao,Z.Zhao,A.J.Duan,J.Liu,Y.Y.Pang,J.M.Li,G.Y.Jiang,Y.J.Wang,Appl.Catal.B,2017,209,228-239.
[10]Y.C.Wei,X.X.Wu,Y.L.Zhao,L.Wang,Z.Zhao,X.T.Huang,J.Liu,J.M.Li,Appl.Catal.B,2018,236,445-457.
[11]J.Xiong,Q.Q.Wu,X.L.Mei,J.Liu,Y.C.Wei,Z.Zhao,D.Wu,J.M.Li,ACS Catal.,2018,8,7915-7930.
[12]Z.W.Wang,Y.X.Liu,T.Yang,J.G.Deng,S.H.Xie,H.X.Dai,Chin.J.Catal.,2017,38,207-216.
[13]S.H.Xie,J.G.Deng,S.M.Zang,H.G.Yang,G.S.Guo,H.Arandiyan,H.X.Dai,J.Catal.,2015,322,38-48.
[14]Y.Y.Guo,S.Zhang,J.Zhu,L.Q.Su,X.M.Xie,Z.Li,Appl.Surf.Sci.,2017,416,358-364.
[15]S.H.Xie,Y.X.Liu,J.G.Deng,S.M.Zang,Z.H.Zhang,H.Arandiyan,H.X.Dai,Environ.Sci.Technol.,2017,51,2271-2279.
[16]H.J.Sedjame,C.Fontaine,G.Lafaye,J.Barbier Jr.,Appl.Catal.B,2014,144,233-242.
[17]B.Rivas,J.I.Gutierrez-Ortiz,R.Lopez-Fonseca,J.R.Gonzalez-Velasco,Appl.Catal.A,2006,314,54-63.
[18]K.Okumura,T.Kobayashi,H.Tanaka,M.Niwa,Appl.Catal.B,2003,44,325-331.
[19]Y.Ren,Z.Ma,P.G.Bruce,Chem.Soc.Rev.,2012,41,4909-4927.
[20]D.Gu,F.Schüth,Chem.Soc.Rev.,2014,43,313-344.
[21]Y.F.Wang,C.B.Zhang,F.D.Liu,H.He,Appl.Catal.B,2013,142-143,72-79.
[22]X.M.Zhang,Y.Q.Deng,P.F.Tian,H.H.Shang,J.Xu,Y.F.Han,Appl.Catal.B,2016,191,179-191.
[23]B.Y.Bai,J.H.Li,J.M.Hao,Appl.Catal.B,2015,164,241-250.
[24]Q.Liu,L.C.Wang,M.Chen,Y.Cao,H.Y.He,K.N.Fan,J.Catal.,2009,263,104-113.
[25]Z.X.Wu,J.G.Deng,Y.X.Liu,S.H.Xie,Y.Jiang,X.T.Zhao,J.Yang,H.Arandiyan,G.S.Guo,H.X.Dai,J.Catal.,2015,332,13-24.
[26]Y.X.Liu,H.X.Dai,J.G.Deng,S.H.Xie,H.G.Yang,W.Tan,W.Han,Y.Jiang,G.S.Guo,J.Catal.,2014,309,408-418.
[27]Z.X.Wu,J.G.Deng,S.H.Xie,H.G.Yang,X.T.Zhao,K.F.Zhang,H.X.Lin,H.X.Dai,G.S.Guo,Microporous Mesoporous Mater.,2016,224,311-322.
[28]P.Xu,Z.X.Wu,J.G.Deng,Y.X.Liu,S.H.Xie,G.S.Guo,H.X.Dai,Chin.J.Catal.,2017,38,92-105.
[29]Y.S.Xia,H.X.Dai,H.Y.Jiang,J.G.Deng,H.He,C.T.Au,Environ.Sci.Technol.,2009,43,8355-8360.
[30]Y.S.Xia,H.X.Dai,L.Zhang,J.G.Deng,H.He,C.T.Au,Appl.Catal.B,2010,100,229-237.
[31]F.Kleitz,S.H.Choi,R.Ryoo,Chem.Commun.,2003,2136-2137.
[32]X.C.Zhang,J.Wang,L.C.Xuan,Z.B.Zhu,Q.J.Pan,K.Y.Shi,G.Zhang,J.Alloys Compd.,2018,768,190-197.
[33]S.Dubey,J.Kumar,A.Kumar,Y.C.Sharma,Adv.Powder Technol.,2018,29,2583-2590.
[34]S.R.Naik,A.V.Salker,S.M.Yusuf,S.S.Meena,J.Alloys Compd.,2013,566,54-61.
[35]C.V.Schenck,J.G.Dillard,J.W.Murray,J.Colloid Interface Sci.,1983,95,398-409.
[36]G.J.Zhang,Y.E.Wang,X.Wang,Y.Chen,Y.M.Zhou,Y.W.Tang,L.D.Lu,J.C.Bao,T.H.Lu,Appl.Catal.B,2011,102,614-619.
[37]G.Corro,E.Vidal,S.Cebada,U.Pal,F.Banuelos,D.Vargas,E.Guilleminot,Appl.Catal.B,2017,216,1-10.
[38]X.She,M.Flytzani-Stephanopoulos,J.Catal.,2006,237,79-93.
[39]A.K.Sinha,K.Suzuki,M.Takahara,H.Azuma,T.Nonaka,K.Fukumoto,Angew.Chem.Int.Ed.,2007,46,2891-2894.
[40]K.R.Priolkar,P.Bera,P.R.Sarode,M.S.Hegde,S.Emura,R.Kumashiro,N.P.Lalla,Chem.Mater.,2002,14,2120-2128.
[41]H.Gabasch,K.Hayek,B.Klo1tzer,W.Unterberger,E.Kleimenov,D.Teschner,S.Zafeiratos,M.Halvecker,A.Knop-Gericke,R.Schlolg,B.Aszalos-Kiss,D.Zemlyanov,J.Phys.Chem.C,2007,111,7957-7962.
[42]A.R.Belambe,R.Oukaci,J.G.Goodwin Jr.,J.Catal.,1997,166,8-15.
[43]B.Solsona,T.E.Davies,T.Garcia,I.Vazquez,A.Dejoz,S.H.Taylor,Appl.Catal.B,2008,84,176-184.
[44]K.D.Chen,S.B.Xie,A.T.Bell,E.Iglesia,J.Catal.,2001,198,232-242.
[45]H.X.Dai,A.T.Bell,E.Iglesia,J.Catal.,2004,221,491-499.
[46]Y.S.Xia,H.X.Dai,H.Y.Jiang,L.Zhang,J.G.Deng,Y.X.Liu,J.Hazard.Mater.,2011,186,84-91.
[47]Y.S.Xia,H.X.Dai,H.Y.Jiang,L.Zhang,Catal.Commun.,2010,11,1171-1175.
[48]Y.X.Liu,H.X.Dai,J.G.Deng,Y.C.Du,X.W.Li,Z.X.Zhao,Y.Wang,B.Z.Gao,H.G.Yang,Appl.Catal.B,2013,140-141,493-505.
[49]N.Shimoda,S.Umehara,M.Kasahara,T.Hongoa,A.Yamazaki,S.Satokaw,Appl.Catal.A,2015,507,56-64.
[50]Y.J.Luo,Y.H.Xiao,G.H.Cai,Y.Zheng,K.M.Wei,Fuel,2012,93,533-538.
[51]S.H.Xie,H.X.Dai,J.G.Deng,Y.X.Liu,H.G.Yang,Y.Jiang,W.Tan,A.S.Ao,G.S.Guo,Nanoscale,2013,5,11207-11219.
[52]S.H.Xie,Y.X.Liu,J.G.Deng,X.T.Zhao,J.Yang,K.F.Zhang,Z.Han,H.Arandiyan,H.X.Dai,Appl.Catal.B,2017,206,221-232.
[53]X.Y.Li,Y.X.Liu,J.G.Deng,S.H.Xie,X.T.Zhao,Y.Zhang,K.F.Zhang,H.Arandiyan,G.S.Guo,H.X.Dai,Appl.Surf.Sci.,2017,403,590-600.
[2]N.G.Patel,P.D.Patel,V.S.Vaishnav,Sens.Actuat.B,2003,96,180-189.
[3]A.Mirzaei,S.G.Leonardi,G.Neri,Ceram.Int.,2016,42,15119-15141.
[4]W.L.Wang,Q.J.Meng,Y.H.Xue,X.L.Weng,P.F.Sun,Z.B.Wu,J.Catal.,2018,366,213-222.
[5]S.C.Kim,W.G.Shim,Appl.Catal.B,2009,92,429-436.
[6]F.J.Maldonado-Hódar,C.Moreno-Castilla,A.F.Pérez-Cadenas,Appl.Catal.B,2004,54,217-224.
[7]A.M.Sica,J.H.Z.D.Santos,I.M.Baibich,C.E.Gigola,J.Mol.Catal.A,1999,137,287-295.
[8]K.Persson,L.D.Pfefferle,W.Schwartz,A.Ersson,S.G.Jaras,Appl.Catal.B,2007,74,242-250.
[9]J.Q.Jiao,Y.C.Wei,Y.L.Zhao,Z.Zhao,A.J.Duan,J.Liu,Y.Y.Pang,J.M.Li,G.Y.Jiang,Y.J.Wang,Appl.Catal.B,2017,209,228-239.
[10]Y.C.Wei,X.X.Wu,Y.L.Zhao,L.Wang,Z.Zhao,X.T.Huang,J.Liu,J.M.Li,Appl.Catal.B,2018,236,445-457.
[11]J.Xiong,Q.Q.Wu,X.L.Mei,J.Liu,Y.C.Wei,Z.Zhao,D.Wu,J.M.Li,ACS Catal.,2018,8,7915-7930.
[12]Z.W.Wang,Y.X.Liu,T.Yang,J.G.Deng,S.H.Xie,H.X.Dai,Chin.J.Catal.,2017,38,207-216.
[13]S.H.Xie,J.G.Deng,S.M.Zang,H.G.Yang,G.S.Guo,H.Arandiyan,H.X.Dai,J.Catal.,2015,322,38-48.
[14]Y.Y.Guo,S.Zhang,J.Zhu,L.Q.Su,X.M.Xie,Z.Li,Appl.Surf.Sci.,2017,416,358-364.
[15]S.H.Xie,Y.X.Liu,J.G.Deng,S.M.Zang,Z.H.Zhang,H.Arandiyan,H.X.Dai,Environ.Sci.Technol.,2017,51,2271-2279.
[16]H.J.Sedjame,C.Fontaine,G.Lafaye,J.Barbier Jr.,Appl.Catal.B,2014,144,233-242.
[17]B.Rivas,J.I.Gutierrez-Ortiz,R.Lopez-Fonseca,J.R.Gonzalez-Velasco,Appl.Catal.A,2006,314,54-63.
[18]K.Okumura,T.Kobayashi,H.Tanaka,M.Niwa,Appl.Catal.B,2003,44,325-331.
[19]Y.Ren,Z.Ma,P.G.Bruce,Chem.Soc.Rev.,2012,41,4909-4927.
[20]D.Gu,F.Schüth,Chem.Soc.Rev.,2014,43,313-344.
[21]Y.F.Wang,C.B.Zhang,F.D.Liu,H.He,Appl.Catal.B,2013,142-143,72-79.
[22]X.M.Zhang,Y.Q.Deng,P.F.Tian,H.H.Shang,J.Xu,Y.F.Han,Appl.Catal.B,2016,191,179-191.
[23]B.Y.Bai,J.H.Li,J.M.Hao,Appl.Catal.B,2015,164,241-250.
[24]Q.Liu,L.C.Wang,M.Chen,Y.Cao,H.Y.He,K.N.Fan,J.Catal.,2009,263,104-113.
[25]Z.X.Wu,J.G.Deng,Y.X.Liu,S.H.Xie,Y.Jiang,X.T.Zhao,J.Yang,H.Arandiyan,G.S.Guo,H.X.Dai,J.Catal.,2015,332,13-24.
[26]Y.X.Liu,H.X.Dai,J.G.Deng,S.H.Xie,H.G.Yang,W.Tan,W.Han,Y.Jiang,G.S.Guo,J.Catal.,2014,309,408-418.
[27]Z.X.Wu,J.G.Deng,S.H.Xie,H.G.Yang,X.T.Zhao,K.F.Zhang,H.X.Lin,H.X.Dai,G.S.Guo,Microporous Mesoporous Mater.,2016,224,311-322.
[28]P.Xu,Z.X.Wu,J.G.Deng,Y.X.Liu,S.H.Xie,G.S.Guo,H.X.Dai,Chin.J.Catal.,2017,38,92-105.
[29]Y.S.Xia,H.X.Dai,H.Y.Jiang,J.G.Deng,H.He,C.T.Au,Environ.Sci.Technol.,2009,43,8355-8360.
[30]Y.S.Xia,H.X.Dai,L.Zhang,J.G.Deng,H.He,C.T.Au,Appl.Catal.B,2010,100,229-237.
[31]F.Kleitz,S.H.Choi,R.Ryoo,Chem.Commun.,2003,2136-2137.
[32]X.C.Zhang,J.Wang,L.C.Xuan,Z.B.Zhu,Q.J.Pan,K.Y.Shi,G.Zhang,J.Alloys Compd.,2018,768,190-197.
[33]S.Dubey,J.Kumar,A.Kumar,Y.C.Sharma,Adv.Powder Technol.,2018,29,2583-2590.
[34]S.R.Naik,A.V.Salker,S.M.Yusuf,S.S.Meena,J.Alloys Compd.,2013,566,54-61.
[35]C.V.Schenck,J.G.Dillard,J.W.Murray,J.Colloid Interface Sci.,1983,95,398-409.
[36]G.J.Zhang,Y.E.Wang,X.Wang,Y.Chen,Y.M.Zhou,Y.W.Tang,L.D.Lu,J.C.Bao,T.H.Lu,Appl.Catal.B,2011,102,614-619.
[37]G.Corro,E.Vidal,S.Cebada,U.Pal,F.Banuelos,D.Vargas,E.Guilleminot,Appl.Catal.B,2017,216,1-10.
[38]X.She,M.Flytzani-Stephanopoulos,J.Catal.,2006,237,79-93.
[39]A.K.Sinha,K.Suzuki,M.Takahara,H.Azuma,T.Nonaka,K.Fukumoto,Angew.Chem.Int.Ed.,2007,46,2891-2894.
[40]K.R.Priolkar,P.Bera,P.R.Sarode,M.S.Hegde,S.Emura,R.Kumashiro,N.P.Lalla,Chem.Mater.,2002,14,2120-2128.
[41]H.Gabasch,K.Hayek,B.Klo1tzer,W.Unterberger,E.Kleimenov,D.Teschner,S.Zafeiratos,M.Halvecker,A.Knop-Gericke,R.Schlolg,B.Aszalos-Kiss,D.Zemlyanov,J.Phys.Chem.C,2007,111,7957-7962.
[42]A.R.Belambe,R.Oukaci,J.G.Goodwin Jr.,J.Catal.,1997,166,8-15.
[43]B.Solsona,T.E.Davies,T.Garcia,I.Vazquez,A.Dejoz,S.H.Taylor,Appl.Catal.B,2008,84,176-184.
[44]K.D.Chen,S.B.Xie,A.T.Bell,E.Iglesia,J.Catal.,2001,198,232-242.
[45]H.X.Dai,A.T.Bell,E.Iglesia,J.Catal.,2004,221,491-499.
[46]Y.S.Xia,H.X.Dai,H.Y.Jiang,L.Zhang,J.G.Deng,Y.X.Liu,J.Hazard.Mater.,2011,186,84-91.
[47]Y.S.Xia,H.X.Dai,H.Y.Jiang,L.Zhang,Catal.Commun.,2010,11,1171-1175.
[48]Y.X.Liu,H.X.Dai,J.G.Deng,Y.C.Du,X.W.Li,Z.X.Zhao,Y.Wang,B.Z.Gao,H.G.Yang,Appl.Catal.B,2013,140-141,493-505.
[49]N.Shimoda,S.Umehara,M.Kasahara,T.Hongoa,A.Yamazaki,S.Satokaw,Appl.Catal.A,2015,507,56-64.
[50]Y.J.Luo,Y.H.Xiao,G.H.Cai,Y.Zheng,K.M.Wei,Fuel,2012,93,533-538.
[51]S.H.Xie,H.X.Dai,J.G.Deng,Y.X.Liu,H.G.Yang,Y.Jiang,W.Tan,A.S.Ao,G.S.Guo,Nanoscale,2013,5,11207-11219.
[52]S.H.Xie,Y.X.Liu,J.G.Deng,X.T.Zhao,J.Yang,K.F.Zhang,Z.Han,H.Arandiyan,H.X.Dai,Appl.Catal.B,2017,206,221-232.
[53]X.Y.Li,Y.X.Liu,J.G.Deng,S.H.Xie,X.T.Zhao,Y.Zhang,K.F.Zhang,H.Arandiyan,G.S.Guo,H.X.Dai,Appl.Surf.Sci.,2017,403,590-600.