CN108607572A - 三维多孔钙钛矿-纤维素碳凝胶复合催化剂及其制备和应用 - Google Patents
三维多孔钙钛矿-纤维素碳凝胶复合催化剂及其制备和应用 Download PDFInfo
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
本发明涉及三维多孔钙钛矿‑纤维素碳凝胶复合催化剂及其制备和应用,所述催化剂为LaFe0.5M0.5O3‑CA,其中M为Cu、Mn、Ni或Co,以PMMA模板,以纤维素凝胶为载体,将La(NO3)3、Fe(NO3)3以及金属M的硝酸盐溶于甲醇、聚乙二醇和去离子水混合溶剂,加入模板剂PMMA,搅拌干燥后与溶解了羧甲基纤维素、丙烯酰胺、过硫酸铵和N‑N'亚甲基双丙烯酰胺的去离子水混合,水浴干燥高温煅烧后制得,该复合催化剂主要用于降解有机废水。与现有技术相比,本发明可直接通过钙钛矿B位元素化合价转化而在催化剂表面原位产生各种活性氧物种,结合纤维素碳凝胶的吸附和电子传递能力,在微波的协同作用下实现有机物的降解。
Description
技术领域
本发明涉及一种催化剂,尤其是涉及一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂及其制备和应用。
背景技术
随着城市工业化的快速发展,由此产生的工业有机污染物已经严重影响了水生态环境,该如何治理这些污染物就得到了国内外学者的广泛关注。
对有机类废水的处理,传统方法包括活性炭吸附、絮凝、离子交换等物理方法以及活性污泥等生物处理方法和化学反应方法。近年来,一种新型降解污染物的方法——高级氧化法在废水治理中得到了广泛应用。微波诱导催化是高级氧化法的一种,其是在常温常压或者低温低压条件下引入具有吸波性质的催化剂,利用微波对催化剂选择性地加热,使其形成活跃的“热点”和活性中心,溶液中的有机物接触到这些活性位点时即可发生化学反应,最终被降解为CO2和H2O。另一方面,微波诱导可产生高温活性氧化物质(如羟基自由基等),利用·OH的强氧化性诱发一系列自由基链反应,可直接将污染物降解为小分子物质或者彻底矿化。微波诱导催化具有反应速率快、降解效率高且对设备环境要求低等优点。
目前微波诱导催化剂主要包括活性炭、过渡金属氧化物、纳米金属材料和双阳离子有机膨润土等,然而其普遍存在热稳定性差、催化剂活性成分易流失导致催化效率下降等问题,使得上述催化剂难以重复使用,在一定程度上限制了其实际应用。钙钛矿型氧化物(ABO3)具有氧化还原性能好、高温稳定性优良、氧移动性能好以及成本低等特点,被研究者认为具有潜在发展前景的催化剂之一。其具有立方对称性,A位主要是稀土元素或碱土元素,B位为过渡金属元素,并且可通过取代A、B位上的阳离子以对钙钛矿的物理化学性质进行调控(如产生氧空位),从而调控其催化性能。然而,传统的钙钛矿催化剂大多是纳米颗粒,高温易烧结,催化活性有待提高。中国专利CN102029167A公开了一种含有纳米钙钛矿型稀土氧化物的催化剂及其制备方法,该催化材料以堇青石蜂窝陶瓷为载体,涂覆含有纳米钙钛矿型稀土氧化物的涂层后负载贵金属Pd制备而成,该方法制备的催化剂抗结碳和抗高温烧结能力差,且易中毒,催化活性较低。因此制备具有多级孔结构的负载型钙钛矿催化剂以有效提高催化剂的比表面积、孔容积、低温还原性能和吸附氧物种浓度,进而提升其催化性能是目前亟待解决的问题。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂及其制备和应用。
本发明的目的可以通过以下技术方案来实现:
一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂,该催化剂分子组成为LaFe0.5M0.5O3-CA,其中M为Cu、Mn、Ni或Co。
一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的制备,该催化剂以PMMA为模板剂,以纤维素凝胶为载体,经过高温煅烧和碳化后制备得到,具体包括以下步骤:
(1)将甲醇、聚乙二醇和去离子水混合得到溶剂;
(2)将La(NO3)3、Fe(NO3)3以及金属硝酸盐,溶于步骤(1)所得的溶剂中,超声处理,获得透明溶液;
(3)将3gPMMA模板剂加入到步骤(2)所得透明溶液中搅拌,干燥后得到钙钛矿前驱体;
(4)将羧甲基纤维素、丙烯酰胺、过硫酸铵和亚甲基双丙烯酰胺依次加入去离子水溶解,并与步骤(3)得到的钙钛矿前驱体充分混合后,恒温水浴、干燥后得到复合干凝胶;
(5)将步骤(4)得到的复合干凝胶高温煅烧后得到三维多孔钙钛矿-纤维素碳凝胶复合催化剂。
作为上述技术方案的优选,步骤(1)和步骤(2)均在室温下进行,步骤(2)中:超声处理的时间为0.5~2h。
作为上述方案的优选,步骤(1)中:甲醇、聚乙二醇和去离子水的体积比为(5.0~10.0):(2.0~6.0):(5~10)。
作为上述方案的优选,步骤(2)中:所述金属M的硝酸盐为Cu(NO3)2、Mn(NO3)2、Ni(NO3)2、Co(NO3)2中的一种,La(NO3)3、Fe(NO3)3以及金属M的硝酸盐的摩尔比为2:1:1。
作为上述方案的优选,步骤(3)中:所述PMMA模板剂的加入量满足:La(NO3)3与PMMA模板剂的质量比为1:1。
作为上述方案的优选,步骤(4)中:羧甲基纤维素、丙烯酰胺、过硫酸铵、N-N'亚甲基双丙烯酰胺、去离子水与钙钛矿前驱体的比例为(0.1~0.5)g:(0.5~2.0)g:(0.1~0.3)g:(0.02~0.1)g:(10~40)mL:(0.6~2.0)g,恒温水浴的温度为25℃,时间为12~24h,干燥采用真空冷冻干燥,时间为24~48h。
作为上述方案的优选,步骤(5)中:煅烧温度为400~800℃,煅烧时间为2~6h。
一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的应用,该催化剂用于降解有机废水,向有机废水中加入所述LaFe0.5M0.5O3-CA催化剂,在微波作用下反应。
优选的,所述催化剂的加入量为0.2~0.8g/L,微波功率为300~600W,反应时间4~10min。
本发明对所采用的各组分添加量进行了限定,由于制备得到的钙钛矿为LaFe0.5M0.5O3,因此按照化学式中各组分的特定摩尔比进行制备,即La(NO3)3、Fe(NO3)3以及金属M的硝酸盐的摩尔比为2:1:1。此外,本发明中La(NO3)3与PMMA模板剂的质量比为1:1为经过反复实验进行剂量优化得到的结果,若PMMA添加量过低则合成的钙钛矿产率过低,若添加量过高则无法使PMMA模板完全被负载,造成材料浪费。对于纤维素凝胶与钙钛矿前驱体添加量的限定,则是为了能够形成较好的三维多孔网络结构,添加量过多或过少对于材料形貌以及催化性能都有很大的影响。对于各原料组分的混合次序、加工温度等工艺参数等进行了限定,也均是基于反复实验验优化的结果,其中羧甲基纤维素、丙烯酰胺、过硫酸铵和亚甲基双丙烯酰胺依次加入,分别承担纤维素凝胶前驱体、功能单体、引发剂、交联剂的作用,其在凝胶材料制备过程中有特定的添加顺序,否则难以形成凝胶。
与现有技术相比,本发明具有以下优点:
一、本发明的催化剂具有比表面积大、孔隙率高、孔道整齐有序、孔形孔径分布均一、孔结构排列周期性强、孔尺寸均匀可调及整体结构三维有序等优势,并且可以有效提高催化剂的比表面积、孔容积、氧化性能和吸附氧物种浓度。
二、纤维素碳凝胶特有的三维网络交联结构和丰富的表面官能团对污染物具有优异的吸附、扩散和传质能力,并且其本身的碳质属性也具备很好的吸波和传热性能,从而对污染物的吸附和催化性能大大优于纳米颗粒或未负载的单一孔道钙钛矿催化剂。
三、以本发明提供的三维多孔钙钛矿-纤维素碳凝胶为微波催化剂,可直接通过钙钛矿B位元素化合价转化而在催化剂表面原位产生各种活性氧物种,结合纤维素碳凝胶的吸附和电子传递能力,在微波的协同作用下实现有机物的降解。
附图说明
图1为本发明中三维多孔钙钛矿-纤维素碳凝胶复合铜催化剂的扫描电镜图;
图2为本发明中三维多孔钙钛矿-纤维素碳凝胶复合铜催化剂在微波诱导下催化降解染料废水碱性品红的紫外-可见光谱图;
图3为本发明中三维多孔钙钛矿-纤维素碳凝胶复合铜催化剂在微波诱导下对染料废水碱性品红的催化降解效率。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
首先将La(NO3)3、Fe(NO3)3以及Co(NO3)2按摩尔比为2:1:1的比例,在室温下溶于5.0mL甲醇、2.0mL聚乙二醇和5.0mL去离子水中,超声处理1h后获得透明溶液。然后将1.0gPMMA模板剂加入到含金属硝酸盐溶液中搅拌3h,使金属盐充分浸渍入模版剂中,抽滤后得到负载有金属盐的PMMA,并在空气中干燥以得到钙钛矿前驱体。然后将0.1g羧甲基纤维素,0.5g丙烯酰胺,0.1g过硫酸铵和0.02gN-N'亚甲基双丙烯酰胺依次投加到10mL的去离子水中溶解,并加入0.6g上述钙钛矿前驱体充分混合。置于水浴锅中25℃恒温水浴12h后得到复合水凝胶,并真空冷冻干燥36h,制得复合干凝胶。最后将上述复合干凝胶放入马弗炉中于600℃下煅烧4h后得到三维多孔钙钛矿-纤维素碳凝胶复合催化剂。取50mL浓度为160mg/L的碱性品红溶液置于微波反应器中,加入0.2g/L制得的催化剂,在微波功率为300W下反应10min,根据吸光度计算碱性品红的降解率。
实施例2
首先将La(NO3)3、Fe(NO3)3以及Mn(NO3)2按摩尔比为2:1:1的比例,在室温下溶于6.0mL甲醇、3.0mL聚乙二醇和6.0mL去离子水中,超声处理0.5h后获得透明溶液。然后将2.0g PMMA模板剂加入到含金属硝酸盐溶液中搅拌2h,使金属盐充分浸渍入模版剂中,抽滤后得到负载有金属盐的PMMA,并在空气中干燥以得到钙钛矿前驱体。然后将0.2g羧甲基纤维素,1.0g丙烯酰胺,0.2g过硫酸铵和0.05g N-N'亚甲基双丙烯酰胺依次投加到20mL的去离子水中溶解,并加入1.0g上述钙钛矿前驱体充分混合。置于水浴锅中25℃恒温水浴16h后得到复合水凝胶,并真空冷冻干燥24h,制得复合干凝胶。最后将上述复合干凝胶放入马弗炉中于400℃下煅烧2h后得到三维多孔钙钛矿-纤维素碳凝胶复合催化剂。取50mL浓度为160mg/L的碱性品红溶液置于微波反应器中,加入0.4g/L上述制得的催化剂,在微波功率为400W下反应6min,根据吸光度计算碱性品红的降解率。
实施例3
首先将La(NO3)3、Fe(NO3)3以及Ni(NO3)2按摩尔比为2:1:1的比例,在室温下溶于8.0mL甲醇、4.0mL聚乙二醇和8.0mL去离子水中,超声处理1.5h后获得透明溶液。然后将3.0g PMMA模板剂加入到含金属硝酸盐溶液中搅拌4h,使金属盐充分浸渍入模版剂中,抽滤后得到负载有金属盐的PMMA,并在空气中干燥以得到钙钛矿前驱体。然后将0.4g羧甲基纤维素,1.5g丙烯酰胺,0.15g过硫酸铵和0.08gN-N'亚甲基双丙烯酰胺依次投加到30mL的去离子水中溶解,并加入1.5g上述钙钛矿前驱体充分混合。置于水浴锅中25℃恒温水浴18h后得到复合水凝胶,并真空冷冻干燥48h,制得复合干凝胶。最后将上述复合干凝胶放入马弗炉中于500℃下煅烧5h后得到三维多孔钙钛矿-纤维素碳凝胶复合催化剂。取50mL浓度为160mg/L的碱性品红溶液置于微波反应器中,加入0.6g/L上述制得的催化剂,在微波功率为600W下反应4min,根据吸光度计算碱性品红的降解率。
实施例4
首先将La(NO3)3、Fe(NO3)3以及Cu(NO3)2的硝酸盐按摩尔比为2:1:1的比例,在室温下溶于10.0mL甲醇、6.0mL聚乙二醇和10.0mL去离子水中,超声处理2h后获得透明溶液。然后将4.0g PMMA模板剂加入到含金属硝酸盐溶液中搅拌6h使金属盐充分浸渍入模版剂中,抽滤后得到负载有金属盐的PMMA,并在空气中干燥以得到钙钛矿前驱体。然后将0.5g羧甲基纤维素,2.0g丙烯酰胺,0.3g过硫酸铵和0.1g N-N'亚甲基双丙烯酰胺依次投加到40mL的去离子水中溶解,并加入2.0g上述钙钛矿前驱体充分混合。置于水浴锅中25℃恒温水浴24h后得到复合水凝胶,并真空冷冻干燥48h,制得复合干凝胶。最后将上述复合干凝胶放入马弗炉中于800℃下煅烧6h后得到三维多孔钙钛矿-纤维素碳凝胶复合催化剂。取50mL浓度为160mg/L的碱性品红溶液置于微波反应器中,加入0.8g/L上述制得的催化剂,在微波功率为500W下反应8min,根据吸光度计算碱性品红的降解率。
图1为本发明中三维多孔钙钛矿-纤维素碳凝胶复合铜催化剂的扫描电镜图;从图中可以看出负载在碳气凝胶上的复合催化剂具有3维交联的网络结构,钙钛矿纳米粒子主要存在于碳气凝胶形成的孔隙之中,且分布较为均匀。
图2为本发明中三维多孔钙钛矿-纤维素碳凝胶复合铜催化剂在微波诱导下催化降解染料废水碱性品红的紫外-可见光谱图;从图中可以看出在微波诱导催化反应过程中,随着反应时间的推移,碱性品红的特征吸收峰(543.5nm)有明显的降低,其在4min以后基本消失,表明降解效果显著。
图3为本发明中三维多孔钙钛矿-纤维素碳凝胶复合铜催化剂在微波诱导下对染料废水碱性品红的催化降解效率。由图3可以看到,不添加催化剂时,微波降解对碱性品红几乎没有效果,降解率低于5%,然而添加本发明所制得的三维多孔钙钛矿-纤维素碳凝胶催化剂之后,降解率有显著提高,在微波时间4min时达到了98%以上的降解率,6min以后其降解率为100%。
把实施例1-4制备得到的钙钛矿-纤维素碳凝胶复合催化剂对染料废水碱性品红进行微波诱导催化降解实验。具体工艺参数和降解率如表1所示。
表1
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂,其特征在于,该催化剂的分子组成为LaFe0.5M0.5O3-CA,其中M为Cu、Mn、Ni或Co。
2.根据权利要求1所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的制备,其特征在于,包括以下步骤:
(1)将甲醇、聚乙二醇和去离子水混合,得到混合溶剂;
(2)将La(NO3)3、Fe(NO3)3以及金属M的硝酸盐,溶于步骤(1)所得的混合溶剂中,超声处理,获得透明溶液;
(3)将PMMA模板剂加入到步骤(2)所得透明溶液中搅拌,干燥后得到钙钛矿前驱体;
(4)将羧甲基纤维素、丙烯酰胺、过硫酸铵和亚甲基双丙烯酰胺依次加入去离子水溶解,并与步骤(3)得到的钙钛矿前驱体充分混合后,恒温水浴、干燥后得到复合干凝胶;
(5)将步骤(4)得到的复合干凝胶高温煅烧后得到三维多孔钙钛矿-纤维素碳凝胶复合催化剂。
3.根据权利要求2所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的制备,其特征在于,步骤(1)和步骤(2)均在室温下进行;
步骤(2)中:超声处理的时间为0.5~2h。
4.根据权利要求2所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的制备,其特征在于,步骤(1)中:甲醇、聚乙二醇和去离子水的体积比为(5.0~10.0):(2.0~6.0):(5~10)。
5.根据权利要求2所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的制备,其特征在于,步骤(2)中:所述金属M的硝酸盐为Cu(NO3)2、Mn(NO3)2、Ni(NO3)2、Co(NO3)2中的一种;
La(NO3)3、Fe(NO3)3以及金属M的硝酸盐的摩尔比为2:1:1。
6.根据权利要求2所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的制备,其特征在于,步骤(3)中:所述PMMA模板剂的加入量满足:La(NO3)3与PMMA模板剂的质量比为1:1。
7.根据权利要求2所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的制备,其特征在于,步骤(4)中:羧甲基纤维素、丙烯酰胺、过硫酸铵、N-N'亚甲基双丙烯酰胺、去离子水与钙钛矿前驱体的比例为(0.1~0.5)g:(0.5~2.0)g:(0.1~0.3)g:(0.02~0.1)g:(10~40)mL:(0.6~2.0)g,恒温水浴的温度为25℃,时间为12~24h,干燥采用真空冷冻干燥,时间为24~48h。
8.根据权利要求2所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的制备,其特征在于,步骤(5)中:煅烧温度为400~800℃,煅烧时间为2~6h。
9.如权利要求1所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂在快速降解有机废水上的应用,其特征在于,催化剂用于降解有机废水时,向有机废水中加入所述LaFe0.5M0.5O3-CA催化剂,在微波作用下反应。
10.根据权利要求9所述的一种三维多孔钙钛矿-纤维素碳凝胶复合催化剂的应用,其特征在于,所述催化剂的加入量为0.2~0.8g/L,微波功率为300~600W,反应时间4~10min。
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