CN108380203A - 一种介孔壁中空核壳球形LaMnO3钙钛矿催化剂及其制备方法 - Google Patents
一种介孔壁中空核壳球形LaMnO3钙钛矿催化剂及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002328 LaMnO3 Inorganic materials 0.000 claims abstract description 20
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
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- 238000005265 energy consumption Methods 0.000 abstract description 4
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- 238000006243 chemical reaction Methods 0.000 description 14
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- 239000011572 manganese Substances 0.000 description 9
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
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- 229910002254 LaCoO3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
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- 241001269238 Data Species 0.000 description 1
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- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种介孔壁中空核壳球形LaMnO3钙钛矿催化剂及其制备方法,特点是该催化剂的球外径为100‑750nm且其介孔壁由ø26×52nm的棒状纳米颗粒构筑而成,LaMnO3钙钛矿催化剂的介孔壁中的介孔平均孔径67.81 nm,孔容0.15 cm3/g,比表面积15.56 m2/g,其制备方法包括利用P123为软模板剂,以水和乙醇为溶剂,以柠檬酸为络合剂,La和Mn为金属源制备介孔壁中空核壳球形LaMnO3前驱体的步骤;将催化剂前驱体置于马弗炉中,在700℃下焙烧5h,得介孔壁中空核壳球形LaMnO3钙钛矿催化剂的步骤,优点是能耗低,收率近100%以及产物形貌可调控,可用于汽车尾气净化。
Description
技术领域
本发明涉及一种LaMnO3钙钛矿催化剂,尤其是涉及一种介孔壁中空核壳球形LaMnO3钙钛矿催化剂及其制备方法。
背景技术
与目前采用的贵金属汽车尾气催化剂相比,非贵金属稀土钙钛矿型复合氧化物ABO3具有资源丰富、成本低廉、结构稳定、易于化学剪裁等优点,在汽车尾气和烟气催化净化领域具有极大的应用前景。多孔中空球形催化剂具有特殊的空间几何结构,具有低密度、高比表面积以及大内部空腔等优点,从而相比于常规块体与实心纳米颗粒具有更好的催化性能。
现有的中空球形钙钛矿的制备方法主要有溶剂热法和模板法以及二者结合。溶剂热法是在密闭容器中高温高压下反应, 是特殊形貌多孔材料最常用的方法。在CN101804353A中,以柠檬酸为络合剂,以硝酸铁和硝酸稀土为原料,在高压釜中170-190℃反应24-72h, 水洗,醇洗,烘干,再于700-900℃焙烧1-3h得系列钙钛矿型稀土铁酸盐多孔空心球,球外径1-5µm,壁厚30-200nm,球壁为由20-80nm的纳米颗粒构筑成的多孔结构,该系列催化剂可高活性高选择性地实现CO还原NO为N2。模板法分为硬模板法和软模板法,前者是利用模板的固定空间结构控制产物形貌,后者则是通过控制反应条件利用软模板剂与原料的相互作用控制产物形貌。G.S.Guo等(G.S.Guo et al.,RSC Advances, 2014, 4,58699-58707)将碳微球分散在金属硝酸盐溶液中,再于高压釜中180℃反应6小时,得前驱体,水洗,醇洗,烘干,在400℃、700℃先后焙烧2h、4h,得空心球型钙钛矿LaCoO3;在300℃和700℃先后焙烧2h和3h,得空心球型钙钛矿LaMnO3。LaCoO3球外径100 nm-300 nm,球壁15nm- 35 nm。LaMnO3球外径200nm,球壁20nm,为2-3多壳层结构,比表面积42.6 m2g-1,平均孔径75.4nm, 孔容0.153cm2/g, 对甲烷燃烧催化活性好。在CN201010289455.1中,采用PMMA为硬模板,聚乙二醇作为添加剂,以六水硝酸镧和硝酸锰为金属源,甲醇为溶剂,浸渍,干燥,750℃焙烧4h,得LaMnO3空心球,球外径25-50nm。软模板法常用高分子表面活性剂作模板剂,P123是具有ABA型三嵌段高分子非离子型表面活性剂,其形成的胶团结构稳定,通过调节溶液浓度、温度、添加剂,在水溶液中可形成不同尺寸和形状的稳定胶团或囊泡,与无机金属离子或其络合物形成配位键或氢键,可合成不同形貌的无机多孔材料,其中,文献中以P123为模板制备空心球材料多为简单金属氧化物(TiO2,CeO2)或氟化物(BaF2)或非金属氧化物(SiO2)(CN200910218009.9;B.Mazinani et al.,Ceramics International,2017,43,11786-11791),且多采用溶剂热法。用P123制备多孔球形钙钛矿催化剂的研究很少。P.Gao等(P.Gao et al.,Chinese Journal of Catalysis,2013,34,1811-1815;P.Gao etal.,Mater Lett,2013,92:17;CN103357396A)以P123为模板,以柠檬酸、尿素为添加剂,以水-乙醇-乙二醇为溶剂,在高压反应釜中100℃反应 48 h,水洗,醇洗,烘干,在600℃焙烧4h, 得系列钙钛矿型LaFexMn1-xO3,La1-xSrxMnO3,LaMnO3纳米空心球,球外径40-150nm, 壁厚10-20nm,比表面积30-40m2g-1,该系列催化剂比传统柠檬酸法制得的催化剂对木质素、苯酚等有机物的氧化或对过氧化氢的分解具有更高的催化活性。但是上述文献中的研究均采用溶剂热法或硬膜板法或软模板-溶剂热联合法,溶剂热法,能耗高,产率低。硬模板法制备钙钛矿,形貌调控空间小,且采用浸渍吸附法时,产率低。
发明内容
本发明所要解决的技术问题是提供一种能耗低,收率近100%以及产物形貌可调控的介孔壁中空核壳球形LaMnO3钙钛矿催化剂及其制备方法。
本发明解决上述技术问题所采用的技术方案为一种介孔壁中空核壳球形LaMnO3钙钛矿催化剂,所述的LaMnO3钙钛矿催化剂的球外径为100-750nm且其介孔壁由ø26×52nm的棒状纳米颗粒构筑而成,LaMnO3钙钛矿催化剂的介孔壁中的介孔平均孔径67.81 nm,孔容0.15 cm3/g,比表面积15.56 m2/g。
所述的LaMnO3钙钛矿催化剂的球外径为290-310 nm时,壁厚65-97 nm,核径52-65nm。
上述介孔壁中空核壳球形LaMnO3钙钛矿催化剂的制备方法,包括以下步骤:
(1)介孔壁中空核壳球形LaMnO3前驱体的制备
A.称取0.01molLa(NO3)3•6H2O、0.01mol Mn(NO3)2和0.02mol柠檬酸后,溶于73.33-110mL水中,搅拌至完全溶解,得第一溶液;
B.按总金属硝酸盐与P123的摩尔比为(60-70):1的比例,称取(2.8571×10-4)-(3.3333×10-4)mol的P123溶于去由离子水和乙醇按体积比1:2组成的20-30mL混合溶液中,搅拌至完全溶解,得第二溶液;
C.将第二溶液逐滴加入到第一溶液中,在15-35℃下封闭搅拌10h,得第三溶液;
D.将第三溶液置于鼓风干燥箱中,于40℃恒温蒸发至凝胶,所得凝胶在鼓风干燥箱中150℃充分干燥4h,得催化剂前驱体;
(2)介孔壁中空核壳球形LaMnO3的制备
将步骤(1)得到的催化剂前驱体置于马弗炉中,以2℃/min的速率升温,在700℃下,焙烧5h,得介孔壁中空核壳球形LaMnO3钙钛矿催化剂。
上述介孔壁中空核壳球形LaMnO3钙钛矿催化剂在汽车尾气净化方面的应用。
与现有技术相比,本发明的优点在于:本发明一种介孔壁中空核壳球形LaMnO3钙钛矿催化剂及其制备方法,利用P123为软模板剂,以水和乙醇为溶剂,以柠檬酸为络合剂,通过成胶、烘干、焙烧,制备了具有介孔壁中空核壳球形LaMnO3钙钛矿汽车尾气催化剂,前驱体成胶在常压低温下形成,而非高温高压水热法,该方法能耗低,操作简单易行,原料廉价易得,金属利用率100%,催化剂形貌可控。该催化剂对汽车尾气中的NO+CO同时具有较高的催化转化活性,对CO的催化转化温度为T50%=259℃、T90% =311℃、T100%=329℃;对NO的催化转化温度为T50% =279℃、T90%=344℃、T100% =405℃。该催化剂在汽车尾气净化领域具有良好的应用前景。
附图说明
图1为样品1-4的XRD图;
图2为样品1-4的SEM图;扫描电镜(a)样品1;(b)样品2;(c)样品3;(d)样品4;
图3为样品4的TEM图;
图4为样品4的氮气吸附-脱附等温线图;
图5为样品4的孔径分布曲线图;
图6为样品1-4对CO的催化转化率图;
图7为样品1-4对NO的催化转化率图。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
一、具体实施例
实施例1
称取4.3301g(0.01mol)La(NO3)3•6H2O,3.5790g的50wt%Mn(NO3)2溶液(其中Mn(NO3)2的用量为1.7895g,即0.01mol)和3.8426g(0.02mol)柠檬酸溶于110mL水中,得第一溶液;按照总金属硝酸盐与P123的摩尔比为60:1的比例,称量1.9333g(3.3333×10-4mol)P123溶于由10mL去离子水和20mL无水乙醇组成的混合溶液中,得第二溶液;将第二溶液逐滴加入到第一溶液中,在25℃下封闭搅拌10h,配成P123摩尔分数为2.381mmol/L的第三溶液;将第三溶液置于鼓风干燥箱中40℃恒温蒸发至凝胶状态,然后升温至150℃干燥4h,得催化剂前驱体;将所制备的催化剂前驱体置于马弗炉中,在700℃下焙烧5h,最后得介孔壁中空核壳球形LaMnO3钙钛矿催化剂,命名为样品1。
实施例2
称取4.3301g(0.01mol)La(NO3)3•6H2O,3.5790g的50wt%Mn(NO3)2溶液(其中Mn(NO3)2的用量为1.7895g,即0.01mol)和3.8426g(0.02mol)柠檬酸溶于110mL水中,得第一溶液;按照总金属硝酸盐与P123摩尔比为65:1的比例,称量1.7846g(3.0769×10-4mol)P123溶于由10mL去离子水和20mL无水乙醇组合的混合溶液中,得第二溶液,将第二溶液逐滴加入到第一溶液中,在35℃下封闭搅拌10h,配成P123摩尔分数为2.198mmol/L 的第三溶液;将第三溶液置于鼓风干燥箱中40℃恒温至凝胶状态,然后升温至150℃干燥4h,得催化剂前驱体;将所制备的催化剂前驱体置于马弗炉中,在700℃下焙烧5h,最后得介孔壁中空核壳球形LaMnO3钙钛矿催化剂,命名为样品2。
实施例3
称取4.3301g(0.01mol)La(NO3)3•6H2O,3.5790g的50wt%Mn(NO3)2溶液(其中Mn(NO3)2的用量为1.7895g,即0.01mol)和3.8426g(0.02mol)柠檬酸溶于82.5mL水中,得第一溶液;按照总金属硝酸盐与P123摩尔比为70:1的比例,称量1.6571g(2.8571×10-4mol)P123溶于由7.5mL去离子水和15mL无水乙醇组成的混合溶液中,得第二溶液;并将第二溶液逐滴加入到第一溶液中,在30℃下搅拌10h,配成P123摩尔分数为2.721mmol/L的第三溶液,将第三溶液置于鼓风干燥箱中40℃恒温蒸发至凝胶状态,然后升温至150℃充分干燥4h,得到催化剂前驱体;将所制备的催化剂前驱体置于马弗炉中,在700℃下焙烧5h,最后得介孔壁中空核壳球形LaMnO3钙钛矿催化剂,命名为样品3。
实施例4
称取4.3301g(0.01mol)La(NO3)3•6H2O,3.5790g的50wt%Mn(NO3)2溶液(其中Mn(NO3)2的用量为1.7895g,即0.01mol)和3.8426g(0.02mol)柠檬酸溶于73.33mL水中,得第一溶液;按照总金属盐:P123摩尔比为70:1的比例,称量1.6571g(2.8571×10-4mol)P123溶于由6.66mL去离子水和13.34mL无水乙醇组成的混合溶液中,得第二溶液,将第二溶液逐滴加入到第一溶液中,在30℃下封闭搅拌10h,配成P123摩尔分数为3.061mmol/L的第三溶液;将第三溶液置于鼓风干燥箱中40℃恒温蒸发至凝胶状态,然后升温至150℃干燥4h,得到催化剂前驱体;将所制备的催化剂前驱体置于马弗炉中,在700℃下焙烧5h,最后得介孔壁中空核壳球形LaMnO3钙钛矿催化剂,命名为样品4。
二、结果分析
图1为样品1-4的XRD图,由图1可知样品1-4均为纯钙钛矿型晶相结构。
图2为样品1-4的SEM图;扫描电镜(a)样品1;(b)样品2;(c)样品3;(d)样品4。由图2可知,LaMnO3为纳米颗粒构筑的介孔壁球状结构,其中,构筑介孔壁的纳米颗粒为棒状ø26×52nm(指棒状纳米颗粒横截面直径为26nm,长度为52nm)。样品1球状规整,球壁孔洞较小,外径200-700nm,其中较多的球径为300-400nm,但少部分纳米颗粒未组装成球;样品2纳米颗粒构筑的球壁具有较大的孔,纳米颗粒结合疏松,部分球体球壁缺失,球外径150-700nm,其中较多的球径为300-400nm;样品3球间共壁或联结紧密,球体形成不完全,但球壁孔也较大,球外径150-750nm,其中较多的球径为500-600nm;样品4球体更完整,分散最好,球壁孔洞较小,球外径100-750nm,其中较多的球径为300-500nm。
图3为样品4的TEM图,由图3可知,LaMnO3形成了中空核壳球形结构,球外径为290-310 nm时,壁厚65-97 nm,核径为52-65 nm。
图4为样品4的氮气吸附-脱附等温线图;图5为样品4的孔径分布曲线图;表1为样品4的BET测试数据,图4说明催化剂具有介孔结构,图5表明样品具有介孔大孔多级孔结构,介孔有利于吸附,大孔有利于传质,从而有利于催化活性的提高。
图6为样品1-4对CO的催化转化率图,图7为样品1-4对NO的催化转化率图。介孔壁中空核壳球形LaMnO3对NO+CO催化活性的测试方法如下:称取0.75 g催化剂装入反应管中,置于催化剂评价装置(天津先权,WFSM-3060)中。以反应空速为20000 mL·g-1·h-1,通入NO和CO(浓度均为1200ppm,N2作为平衡气)气体,以2 ℃/min的升温速率,对催化剂进行25-475 ℃下的催化活性测试,出口CO和NO的浓度采用Gasboard-3000(武汉四方光电科技有限公司)在线红外烟气分析仪进行检测,然后再进行其转化率的计算。由图6和图7可知,对于NO+CO的催化氧化还原,样品3在所有的样品中表现出最好的催化活性,对CO的催化转化温度为T50%=259℃、T90% =311℃、T100%=329℃;对NO的催化转化温度为T50% =279℃、T90%=344℃、T100% =405℃。
上述说明并非对本发明的限制,本发明也并不限于上述举例。本技术领域的普通技术人员在本发明的实质范围内,作出的变化、改型、添加或替换,也应属于本发明的保护范围。
Claims (4)
1.一种介孔壁中空核壳球形LaMnO3钙钛矿催化剂,其特征在于:所述的LaMnO3钙钛矿催化剂的球外径为100-750nm且其介孔壁由ø26×52nm的棒状纳米颗粒构筑而成,LaMnO3钙钛矿催化剂的介孔壁中的介孔平均孔径67.81 nm,孔容0.15 cm3/g,比表面积15.56 m2/g。
2.根据权利要求1所述的一种介孔壁中空核壳球形LaMnO3钙钛矿催化剂,其特征在于:所述的LaMnO3钙钛矿催化剂的球外径为290-310 nm时,壁厚65-97 nm,核径52-65 nm。
3.一种权利要求1或2所述的介孔壁中空核壳球形LaMnO3钙钛矿催化剂的制备方法,其特征在于包括以下步骤:
(1)介孔壁中空核壳球形LaMnO3前驱体的制备
A.称取0.01molLa(NO3)3•6H2O、0.01mol Mn(NO3)2和0.02mol柠檬酸后,溶于73.33-110mL水中,搅拌至完全溶解,得第一溶液;
B.按总金属硝酸盐与P123的摩尔比为(60-70):1的比例,称取(2.8571×10-4)-(3.3333×10-4)mol的P123溶于去由离子水和乙醇按体积比1:2组成的20-30mL混合溶液中,搅拌至完全溶解,得第二溶液;
C.将第二溶液逐滴加入到第一溶液中,在15-35℃下封闭搅拌10h,得第三溶液;
D.将第三溶液置于鼓风干燥箱中,于40℃恒温蒸发至凝胶,所得凝胶在鼓风干燥箱中150℃充分干燥4h,得催化剂前驱体;
(2)介孔壁中空核壳球形LaMnO3的制备
将步骤(1)得到的催化剂前驱体置于马弗炉中,以2℃/min的速率升温,在700℃下,焙烧5h,得介孔壁中空核壳球形LaMnO3钙钛矿催化剂。
4.一种权利要求1-3中任一项所述的介孔壁中空核壳球形LaMnO3钙钛矿催化剂在汽车尾气净化方面的应用。
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