CN113101944A - 掺钴La0.7Sr0.3MnO3催化剂及其制备方法与应用 - Google Patents
掺钴La0.7Sr0.3MnO3催化剂及其制备方法与应用 Download PDFInfo
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
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Abstract
本发明涉及催化材料技术领域，合成了系列掺杂钴的La0.7Sr0.3Mn1‑χCoχO3(χ=0、0.01、0.05、0.1、0.15)类芬顿‑光催化剂，其中La0.7Sr0.3Mn0.95Co0.05O3的催化效果最好；La0.7Sr0.3Mn0.95Co0.05O3催化剂是一个具有太阳光活性的光催化剂，且与过氧化氢组合具有类芬顿作用，且两者具有明显的协同催化效果，太阳光下协同降解模拟甲基橙废水效果明显。本发明制备方法原料易得，方法简单。
Description
技术领域
本发明涉及催化材料技术领域，特别是一种具有类芬顿和光催化作用的掺杂钴元素La0.7Sr0.3Mn O3的制备方法及其应用。
背景技术
Fenton氧化法是应用双氧水(H2O2)与亚铁(Fe2+)反应产生氢氧自由基将废水中有机物污染物氧化成小分子或直接矿化成二氧化碳和水的一种高级氧化处理技术,具有氧化能力强、操作简单等优点。但传统Fenton法缺点是H2O2价格昂贵，利用率低，反应pH值低，且不易运输。由于Fe2+为催化剂,使H2O2产生成•OH及OH-，同时伴随着大量Fe(OH)3污泥，成为其应用中的一大缺点。
人们将紫外光、可见光及除Fe( Ⅱ) 以外，Fe( Ⅲ)、含铁矿物以及其他一些过渡金属如Co、Cd、Cu、Ag、Mn、Ni 等引入Fenton(芬顿)体系，可以加速或者替代Fe( Ⅱ)对H2O2起催化作用的一类反应，称为类芬顿氧化法。
钙钛矿型氧化物光催化剂是太阳光活性的光催化剂，可通过负载、掺杂及构建p-n异质结光催化剂来提高其光催化性能。已有研究表明：钙钛矿氧化物La1-χSrχMnO 3 (0＜χ≤0.5)具有超顺磁性的特点，对其掺杂可以改变其磁性、光催化活性等。其中La0.7S 0.3MnO3的磁性最好，对其进行掺杂均可以有效提高光催化剂性能。利用其磁性可通过外加磁场进行简单分离,避免了悬浮催化剂难以分离的弊端。本发明制备了系列掺钴La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)及系列催化剂，其中La0.7Sr0.3Mn0.95Co0.05O3不但是太阳光活性的光催化剂，与过氧化氢结合具有明显的类芬顿作用，且两者具有协同催化效果，催化剂具有磁性的特征，在外界磁场的作用下易于回收，可重复利用。
发明内容
本发明的目的是提供系列类芬顿-光催化剂La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)的制备方法，以模拟甲基橙废水为降解对象，太阳光下，系列掺钴类芬顿-光催化剂起到明显的协同催化作用，可高效的降解甲基橙模拟染料废水。
本发明实现过程如下：
按照计量比准确称量反应物醋酸镧La(CH3COO)3·5H2O、醋酸锶Sr(CH3COO)2、醋酸锰Mn(CH3COO)2·4H2O及醋酸钴Co(CH3COO)2•4H2O，使其摩尔比为nLa(CH3COO)3·5H2O:nSr(CH3COO)2:nMn(CH3COO)2·4H2O:nCo(CH3COO)2•4H2O =0.7:0.3:（1-χ）: χ，将称量的全部反应物溶解在使其质量4-6倍的去离子水中，待固体完全溶解后，将该溶液放在70-80℃的温度下搅拌并水解，等成糊状时冷却到室温，加入无水乙醇浸泡并搅拌，放入30-50 ℃真空干燥箱干燥后，放入逐渐升温至800-900℃马弗炉中，煅烧2-3 h，冷却研磨得到黑色粉体产物La0.7Sr0.3Mn(1-χ)CoχO3（χ=0、0.01、0.05、0.1、0.15)；
本发明探索了系列掺钴La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)对生物难降解废水如甲基橙染料废水的类芬顿-光催化协同催化降解作用。结果表明：所合成的系列掺钴La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)全部在pH =3-6之间具有明显的光催化和类芬顿作用，且两者能发生明显的协同催化用，其中La0.7Sr0.3Mn0.95Co0.05O3是效果最好的具有磁性的太阳光驱动的类芬顿-光催化剂。在太阳光下，La0.7Sr0.3Mn0.95Co0.05O3可将模拟甲基橙废水降解处理完全，且这种多功能材料易在外加磁场下实现简单分离，能再生和重复使用，故可在实际废水处理中得到广泛应用。
本发明具有以下的优点及效果：
1.La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)是具有太阳光活性的光催化剂，所以可以充分利用太阳光，降低废水处理成本。
2.La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)是同时具有类芬顿-光催化作用，且光催化与类芬顿作用可协同催化有机废水的降解，其催化作用大大提高。
3.La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)具有磁性的特征，可在外加磁场下实现简单分离，避免没有磁性的悬浮催化剂难以分离的弊端。
附图说明
图1 La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.95Co0.05O3的XRD图；
图2 La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.95Co0.05O3紫外可见漫反射图；
图3La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.95Co0.05O3磁滞回线图；
图4 La0.7Sr0.3Mn0.95Co0.05O3类芬顿-光催化协同降解模拟甲基橙染料废水。
具体实施方式
本发明主要以La0.7Sr0.3Mn0.95Co0.05O3为例，说明所合成的系列La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)粉体具有类芬顿-光催化性能。通过以下实施例说明其协同催化作用，但实施中所述条件和结果对发明的内容和权利不构成限制。
一、La0.7Sr0.3Mn0.95Co0.05O3的制备：
按照计量比准确称量反应物醋酸镧La(CH3COO)3·5H2O、醋酸锶Sr(CH3COO)2、醋酸锰Mn(CH3COO)2·4H2O及醋酸钴Co(CH3COO)2·4H2O，使其 nLa(CH3COO)3·5H2O:nSr(CH3COO)2:nMn(CH3COO)2·4H2O:nCo(CH3COO)2·4H2O=0.7:0.3:0.95:0.05。所称量的反应物溶解在使其5倍质量比去离子水中，待固体完全溶解后，将该溶液放在80 ℃的温度下水解，等透明溶液变成糊状时冷却到室温，加入淹没湖状物量的无水乙醇，浸泡并搅拌25分钟，放入40℃真空干燥箱干燥后，放入逐渐升温至800℃马弗炉中，煅烧2 h，冷却研磨得到La0.7Sr0.3Mn0.95Co0.05O3。
二、La0.7Sr0.3MnO3与La0.7Sr0.3Mn0.95Co0.05O3的表征
为了了解掺杂钴催化剂La0.7Sr0.3Mn0.95Co0.05O3的结构特征和性能，以未掺杂的La0.7Sr0.3MnO3做对比进行表征。
La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.95Co0.05O3的XRD图：由图1可见： La0.7Sr0.3MnO3样品分别在2θ值为23.1°，32.7°，40.3°，46.8°，58.1°，68.3°，78.2°处具有明显的特征峰，对应La0.7Sr0.3MnO3的(012)、(110)、(202)、(024)、(030)、(220)、(128)晶面，与JCPDS No. 51-0409 (a = b = 0.549 nm, c = 1.332 nm, α = β = 90°, γ = 120°)卡片图谱峰一致。掺钴的La0.7Sr0.3Mn0.95Co0.05O3样品的衍射峰与La0.7Sr0.3MnO3几乎保持不变，根据Rietveld精修方法原理，采用精修软件Fullprof来确定合成样品的晶胞参数为 a = b = 0.551 nm,c = 1.336 nm，空间群R-3c。钴氧化物的衍射峰没有出现，可能是由于钴的掺杂量过低或者掺杂的钴进入La0.7Sr0.3MnO3样品的晶格中，说明掺钴没有改变其钙钛矿结构。
2.2 La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.95Co0.05O3的紫外可见漫反射光谱：由图2可知：La0.7Sr0.3MnO3与La0.7Sr0.3Mn0.95Co0.05O3在200-800nm都具有明显的吸光度，且掺杂后催化剂吸光度尤其在可见光区域更强，这说明与不掺杂的La0.7Sr0.3MnO3光催化剂相比，La0.7Sr0.3Mn0.95Co0.05O3具有更强的光催化活性，且La0.7Sr0.3Mn0.95Co0.05O3在200-800 nm 间有明显吸收，说明La0.7Sr0.3Mn0.95Co0.05O3是一个太阳光活性的光催化剂。
2.3 La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.95Co0.05O3磁滞回线图：由图3的磁滞回线可知：La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.95Co0.05O3都有近超顺磁特点， La0.7Sr0.3Mn0.95Co0.05O3虽然磁性比未掺杂的La0.7Sr0.3MnO3的磁性降低，但其饱和磁为18.7 emu/g，完全可以被外加磁场进行分离。
三、La0.7Sr0.3Mn0.95Co0.05O3 的类芬顿与光催化的协同催化作用
以30mg/L甲基橙（MO）溶液20.0ml为降解对象。太阳光下，太原5月，选择晴天，早上8:30至下午4:00进行光催化实验，平均光照强度95klux。进行以下三个实验，1）太阳光下，甲基橙废水中只加入催化剂的光催化实验；2）黑暗处，甲基橙废水中加入催化剂、过氧化氢及草酸类芬顿实验，实验结果表明：草酸对催化剂的类芬顿作用有增强作用。3）太阳光下，甲基橙废水中加入催化剂、过氧化氢及草酸。设定甲基橙废水溶液的pH=4，La0.7Sr0.3Mn0.95Co0.05O3催化剂浓度0.2g/L，草酸浓度0.75mmol/L，8mmol/L H2O2，催化时间为2h。所有实验在黑暗处搅拌30min达到吸附平衡后分别进行。结果如图4所示。甲基橙的COD（244 mg/L）经过光催化后降解率为18%；类芬顿作用后降解为50%；太阳光下，两者共同作用后，甲基橙的COD降解率为80%。显然太阳光下，类芬顿与光催化共同作用后对COD 的降解大于类芬顿与光催化降解之和，说明La0.7Sr0.3Mn0.95Co0.05O3的光催化与类芬顿作用存在协同效果，是一个具有磁性和太阳光活性的类芬顿-光催化剂。
Claims (2)
1.掺钴La0.7Sr0.3MnO3催化剂制备方法,其特征杂在于:包括以下步骤：
按照计量比准确称量反应物醋酸镧La(CH3COO)3·5H2O、醋酸锶Sr(CH3COO)2、醋酸锰Mn(CH3COO)2·4H2O及醋酸钴Co(CH3COO)2•4H2O，使其摩尔比为nLa(CH3COO)3·5H2O:nSr(CH3COO)2:nMn(CH3COO)2·4H2O:nCo(CH3COO)2•4H2O =0.7:0.3:（1-χ）: χ， 将称量的全部反应物溶解在使其质量4-6倍的去离子水中，待固体完全溶解后，将该溶液放在70-80℃的温度下搅拌并水解，等成糊状时冷却到室温，加入无水乙醇浸泡并搅拌，放入30-50 ℃真空干燥箱干燥后，放入逐渐升温至800-900℃马弗炉中，煅烧2-3 h，冷却研磨得到黑色粉体产物La0.7Sr0.3Mn(1-χ)CoχO3（χ=0、0.01、0.05、0.1、0.15)。
2.权利要求1所述的系列掺杂钴的La0.7Sr0.3Mn(1-χ)CoχO3 （χ=0、0.01、0.05、0.1、0.15)是多功能催化剂，其特征在于：催化剂不但是一个具有太阳光活性的光催化剂，而且能与过氧化氢结合产生类芬顿催化作用，且两者具有明显的协同催化效果；太阳光下协同催化降解模拟甲基橙废水的效果显著。
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