CN113426453A - La0.7Sr0.3Mn(1-x)FexO3的制备及其催化作用 - Google Patents
La0.7Sr0.3Mn(1-x)FexO3的制备及其催化作用 Download PDFInfo
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明提供一种La0.7Sr0.3Mn(1‑x)FexO3的制备及其催化作用,制备了系列掺杂铁的La0.7Sr0.3Mn(1‑x)FexO3(x=0.05,0.10,0.15,0.2)钙钛矿型复合氧化物粉体,所得粉体具有良好的类芬顿‑光催化协同催化作用,其中La0.7Sr0.3Mn0.85Fe0.15O3的催化效果最好,其特征在于:所述的催化剂用于甲基橙、实际染料废水处理中,获得了很好的催化降解作用。由于La0.7Sr0.3Mn(1‑x)FexO3(x=0.05,0.10,0.15,0.2)具有光催化和类芬顿作用,且其明显的协同催化作用使其在废水处理领域可望有广阔的应用前景。
Description
技术领域
本发明涉及催化材料技术领域,特别是系列具有类芬顿-光催化作用的催化剂La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)及其制备方法与应用。
背景技术
工业废水处理后所排放的COD几乎是所有工业污染排放水的管控指标。随着工业持续的发展,各种有机溶剂及化学合成有机物被大量使用,也因此严重的污染了自然环境,因此如何有效去除这些污染物是现今废水处理技术的一大课题。
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。Fenton法具有对环境友善,占地空间小,操作弹性大,氧化能力强等优点,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,且由于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。
光催化氧化技术是一种新型高级氧化技术,已逐渐成为生物难降解废水处理的热点。光催化剂的材料众多,钙钛矿型氧化物光催化剂禁带宽度较窄,太阳光利用率高,尤其在可见光区具有较好的响应,且由于周期表中大部分元素都能形成钙钛矿结构的氧化物,故可通过负载、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-χSrχMnO3 (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La0.7Sr 0.3MnO3的磁性最好,对其进行掺杂后所得粉体不仅增加了光催化性能,也可以在外加磁场下实现简单分离。更为重要的是实验过程中发现其与过氧化氢结合具有类芬顿催化作用,且能与光催化形成协同催化,所以这种同时具有磁性、类芬顿作用的太阳光活性的催化剂具有更高的催化作用,在降解有机污染物方面具有广阔的应用前景。
人们将紫外光、可见光及除了Fe2+外其它催化剂引入Fenton(芬顿)体系,如热稳定性好的钙钛矿氧化物替代芬顿反应中的Fe2+,由此形成的类芬顿-光催化协同体系可显著增强Fenton(芬顿)试剂和光催化剂对有机物的氧化降解能力,减少Fenton(芬顿)试剂的用量,且与光催化协同作用,在降低处理成本的同时,大大提高了系统的催化降解有机物的作用。
目前,用作类芬顿及光催化剂的钙钛矿复合氧化物已有研究。本发明制备了系列La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)复合氧化物,实验结果表明:全部具有明显的类芬顿-光催化协同作用,其中La0.7Sr0.3Mn0.85Fe0.15O3的类芬顿-光催化剂的效果最好,在外界磁场的作用下易于回收,可重复利用,能在太阳光下催化过氧化氢产生羟基自由基,结合光催化产生的光生空穴和光生电子,可大大提高其降解有机污染物的能力,形成的类芬顿-光催化协同催化体系是一个具有广阔应用前景的多功能催化剂。
发明内容
本发明的目的是提供系列钙钛矿型类芬顿-光催化剂La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)的制备方法,选择光催化效果最好的La0.7Sr0.3Mn0.85Fe0.15O3探讨其对甲基橙及染料废水的类芬顿-光催化的协同降解作用。
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及掺杂不同量的硝酸铁,使其摩尔比nLa(CH3COO)3·5H2O:nSr(CH3COO)2:nMn(CH3COO)2·4H2O:nFe(NO3)3·9H2O=0.7:0.3:(1- x):x,将称量的全部反应物溶解在是其3-7倍质量的去离子水中,待固体完全溶解后,将该溶液放在60-90 ℃的温度下水解,等透明溶液变成糊状时冷却到室温,加入浸没湖状物量的无水乙醇,浸泡并搅拌20-30分钟,放入30-50℃真空干燥箱干燥,随后放入逐渐升温至800-1000℃马弗炉中,煅烧2-6 h,冷却研磨得到系列黑色粉体产物La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)。
本发明还探索了系列掺铁La0 La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)对生物难降解废水如甲基橙及染料废水的光催化-类芬顿协同催化降解作用。结果表明:所合成的系列掺铁La0 La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)复合氧化物,全部具有良好的类芬顿性能、且是太阳光活性的光催化剂,其中La0.7Sr0.3Mn0.85Fe0.15O3是效果最好的具有磁性、太阳光驱动的类芬顿-光催化剂,且其光催化与类芬顿作用能产生明显的协同催化效果。在太阳光下,可将模拟甲基橙废水、公司里实际产生的染料废水进行达标处理,且这种多功能材料易在外加磁场下实现简单分离,易再生和且能重复使用多次,故在实际废水处理中可望得到广泛应用。
本发明具有以下的优点及效果:
1.La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)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-x)FexO3(x=0.05,0.10,0.15,0.2)是同时具有类芬顿-光催化作用,且光催化与类芬顿作用可起协同作用,其催化作用大大提高;
3.La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)具有磁性的特征,可在外磁场作用下实现简单分离,避免了没有磁性的悬浮催化剂难以分离的弊端。
由于在系列类芬顿-光催化剂 La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)中,La0.7Sr0.3Mn0.85Fe0.15O3表现了最好的催化活性。以下以La0.7Sr0.3Mn0.85Fe0.15O3为例,说明其结构特征及催化性能。
附图说明
图1 La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.85Fe0.15O3 的XRD图;
图2 La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.85Fe0.15O3 紫外可见漫反射图;
图3La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.85Fe0.15O3 磁滞回线图;
图4 La0.7Sr0.3Mn0.85Fe0.15O3类芬顿-光催化协同降解模拟甲基橙废水。
具体实施方式
本发明以La0.7Sr0.3Mn0.85Fe0.15O3的制备和催化性能的探讨为实施例,但实施中所述的粉体制备方法及实施的条件和结果对发明的内容和权利不构成限制。
一、La0.7Sr0.3Mn0.85Fe0.15O3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及硝酸铁Fe(NO3)3·9H2O, 摩尔比nLa(CH3COO)3·5H2O:nSr(CH3COO)2:nMn(CH3COO)2·4H2O:nFe(NO3)3·9H2O=0.7:0.3:0.85:0.15, 将所称量的反应物溶解在其5倍质量比的去离子水中,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,加入能浸没湖状物量的无水乙醇,浸泡并搅拌25分钟,放入40℃真空干燥箱中干燥后,放入逐渐升温至800℃马弗炉中,煅烧3 h,冷却研磨得到La0.7Sr0.3Mn0.85Fe0.15O3。
二、La0.7Sr0.3MnO3与La0.7Sr0.3Mn0.85Fe0.15O3的表征
为了了解所合成的催化剂La0.7Sr0.3Mn0.85Fe0.15O3结构特征,以未掺杂的La0.7Sr0.3MnO3做对比进行表征与分析。
2.1、La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.85Fe0.15O3的XRD图 :由图1可见:La0.7Sr0.3MnO3样品分别在2θ值分别为23.1°, 32.7°,40.3°, 46.9°, 58.3°, 68.2°, 78.1°处形成了特征峰,对应于(012), (110), (202), (024), (214), (220), (128)晶面,与JCPDS No.00–051–0409 (a = b = 0.54nm, c = 1.33nm,α=β=90°, γ=120°) 一致,由此可以看出La0.7Sr0.3MnO3成功合成。另外,La0.7Sr0.3Mn0.85Fe0.15O3 的XRD峰位与峰型与La0.7Sr0.3MnO3基本相同,表明掺铁并不改变氧化物的钙钛矿型结构。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 a = b = 0.51nm, c = 1.33nm, α=β=90°, γ= 120°,空间群R-3C。
2.2、La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.85Fe0.15O3的紫外可见漫反射光谱:由图2可知:La0.7Sr0.3MnO3与La0.7Sr0.3Mn0.85Fe0.15O3在200-800nm都具有明显的吸光度,且掺杂后催化剂的吸光度更强,这说明与不掺杂的La0.7Sr0.3MnO3光催化剂相比,La0.7Sr0.3Mn0.85Fe0.15O3具有更强的光催化活性,且La0.7Sr0.3Mn0.85Fe0.15O3在200-800 nm 间有明显吸收,说明La0.7Sr0.3Mn0.85Fe0.15O3 是一个太阳光活性的光催化剂。
2.3、La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.85Fe0.15O3磁滞回线图。由图3的磁滞回线可知:La0.7Sr0.3MnO3 和La0.7Sr0.3Mn0.85Fe0.15O3都有近超顺磁特点, La0.7Sr0.3Mn0.85Fe0.15O3虽然磁性比未掺杂的La0.7Sr0.3MnO3的磁性降低,但其仍有高的饱和磁16.8emu/g,完全可以被外加磁场进行分离。
三、La0.7Sr0.3Mn0.85Fe0.15O3的类芬顿与光催化的协同催化作用
3.1 以模拟甲基橙废水为研究对象
以30 mg/L的模拟甲基橙(MO)为降解目标对象,当La0.7Sr0.3Mn0.85Fe0.15O3用量
0.06-0.3g/L、当甲基橙溶液的pH值为4.0-7.0时、H2O2浓度为6-14mmol/L,草酸(实验表明:对类芬顿作用起增强作用)浓度为0.25-1.25mmol/L,催化剂具有类芬顿和光催化作用,且两者产生明显的协同作用。
图4是在太原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太阳光下光催化作用;2)黑暗处,甲基橙废水中加入催化剂、过氧化氢及草酸的类芬顿催化作用; 3)太阳光下,甲基橙废水中加入催化剂、过氧化氢及草酸。上述三个实验中,设定La0.7Sr0.3Mn0.85Fe0.15O3用量0.1g/L、甲基橙溶液的pH值为4.0时、H2O2浓度为12mmol/L,草酸浓度为1.0mmol/L,结果如图4所示:La0.7Sr0.3Mn0.85Fe0.15O3 具有类芬顿和光催化作用,且产生明显的协同催化作用,进行2小时太阳光照射后,在λ=464 nm 下,甲基橙去色率达到94%,COD 从131mg/L 降解为 24mg/L,降解率82%, 显然大于类芬顿对COD 的降解(42%)与光催化对COD 降解(25%)之和,说明La0.7Sr0.3Mn0.85Fe0.15O3具有类芬顿和光催化作用,且两者可起到明显的协同催化作用。
对实际染料废水的催化降解作用
太原5月,选择晴天,早上8:30至下午4:00进行催化降解来自某染料厂的染料废水(COD为749mg/L)的降解实验,La0.7Sr0.3Mn0.85Fe0.15O3 为催化剂,当废水pH为1.5,La0.7Sr0.3Mn0.85Fe0.15O3 3.9g/L, H2O2浓度为95.6mmol/L, 草酸浓度为1.95mmol/L,黑暗条件下搅拌吸附半小时,太阳光下照射3小时后,催化剂回收重复使用,调节催化体系的H2O2浓度为95.6mmol/L,草酸浓度为1.95mmol/L后,太阳光下照射3小时后,最后测得COD为120mg/L,达到纺织染整工业水污染排放标准(GB 4287-2012)的间接排放标准。
Claims (2)
1.La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)的制备方法,其特征在于,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及硝酸铁Fe(NO3)3·9H2O,使其摩尔比nLa(CH3COO)3·5H2O:nSr(CH3COO)2:nMn(CH3COO)2·4H2O:nFe(NO3)3·9H2O=0.7:0.3:(1- x):x,
将称量的全部反应物溶解在是其3-7倍质量的去离子水中,待固体完全溶解后,将该溶液放在60-90 ℃的温度下水解,等透明溶液变成糊状时冷却到室温,加入浸没湖状物量的无水乙醇,浸泡并搅拌20-30分钟,放入30-50℃真空干燥箱干燥,随后放入逐渐升温至800-1000℃马弗炉中,煅烧2-6 h,冷却研磨得到系列黑色粉体产物La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)。
2.权利要求1所述的系列掺杂铁的La0.7Sr0.3Mn(1-x)FexO3(x=0.05,0.10,0.15,0.2)多功能催化剂的应用,所有粉体表现出较好的类芬顿和光催化两种催化作用,且两者具有明显的协同催化性能,其中La0.7Sr0.3Mn0.85Fe0.15O3的效果最好,其特征在于:它们不但是太阳光活性的光催化剂,且与过氧化氢结合还有明显的类芬顿作用,由于两者具有明显的协同催化作用,将其用于甲基橙、染料废水的处理中催化效果显著。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101584987A (zh) * | 2009-06-24 | 2009-11-25 | 中北大学 | 磁性光催化剂制备及用于吸附和光催化降解染料废水 |
CN103263943A (zh) * | 2013-05-14 | 2013-08-28 | 中南民族大学 | 一种LaFeO3/SBA-15的制备方法及应用 |
CN109126816A (zh) * | 2018-09-20 | 2019-01-04 | 哈尔滨工业大学 | 有序介孔钙钛矿催化剂的制备方法及应用 |
CN111659412A (zh) * | 2020-07-08 | 2020-09-15 | 中北大学 | La0.7Sr0.3MnO3/α-Fe2O3制备及其光催化作用 |
-
2021
- 2021-04-12 CN CN202110386199.6A patent/CN113426453A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101584987A (zh) * | 2009-06-24 | 2009-11-25 | 中北大学 | 磁性光催化剂制备及用于吸附和光催化降解染料废水 |
CN103263943A (zh) * | 2013-05-14 | 2013-08-28 | 中南民族大学 | 一种LaFeO3/SBA-15的制备方法及应用 |
CN109126816A (zh) * | 2018-09-20 | 2019-01-04 | 哈尔滨工业大学 | 有序介孔钙钛矿催化剂的制备方法及应用 |
CN111659412A (zh) * | 2020-07-08 | 2020-09-15 | 中北大学 | La0.7Sr0.3MnO3/α-Fe2O3制备及其光催化作用 |
Non-Patent Citations (3)
Title |
---|
XUE-FANG CAO ET.AL: ""Synthesis, characterization and catalytic performance of magnetic La0.7Sr0.3MnO3/a-Fe2O3 with p–n heterojunction structure"", 《J MATER SCI》 * |
王绍增等: ""La0.7Sr0.3Mn(1-x)FexO3稀土钙钛矿催化剂 NOx储存性能研究"", 《中国稀土学报》 * |
钱睿昕: "钙钛矿型化合物LaMnO_3的搀杂及其对染料分子光催化降解性能", 《科技展望》 * |
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