CN113713821A - 一种钙钛矿复合材料及其制备方法、应用 - Google Patents
一种钙钛矿复合材料及其制备方法、应用 Download PDFInfo
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- B01J23/76—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
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Abstract
本发明公开的一种钙钛矿复合材料及其制备方法、应用,所述方法包括:将钙钛矿、硝酸钴、氟化铵、尿素溶解在水中,得到混合溶液;将所述混合溶液在预设条件下反应,得到反应中间体;煅烧所述反应中间体,得到所述钙钛矿复合材料。通过对钙钛矿进行改性,即在钙钛矿表面原位沉积生长纳米级的钴的氧化物,从而使得所制备得到的钙钛矿复合材料具有较高的比表面、表面载流子传输性好的特点。将其应用于内燃机尾气的处理,因其具有高比表面,高NOx吸附活性,因此能够很好的催化NOx和颗粒。
Description
技术领域
本发明涉及催化剂技术领域,尤其涉及的是一种钙钛矿复合材料及其制备方法、应用。
背景技术
随着人类经济发展,机动车需求量日益增长,机动车在提高人类生产效率的同时,其内燃机燃烧柴油/汽油也伴随着氮氧化物(NOx),颗粒物(PM)等有毒有害污染物的产生,这严重威胁着地球的生态平衡以及人类健康。
现有氮氧化物和颗粒物去除技术中,使用的协同催化剂包括铂族贵金属由于4电子传导机制在燃烧过程表现出极好的NOx和颗粒物去除效益,但由于价格昂贵而难以实际应用。铈基等过渡金属氧化物由于独特的金属价态变化(M3+与M2+)而具备不错的NOx吸附催化效果,但颗粒物催化效益低,往往需要掺杂其他金属实现协同催化。
钙钛矿由于丰富的离子价态以及A,B位金属可灵活替换(ABO3/A2BO4型金属氧化物,A位为碱土金属,B位为过渡金属)而成为研究热点,但其存在比表面低,载流子传输性差等缺点。
因此,现有技术存在缺陷,有待改进与发展。
发明内容
本发明要解决的技术问题在于,针对现有技术的上述缺陷,提供一种钙钛矿复合材料及其制备方法,旨在解决现有技术中用于催化氮氧化物,颗粒物的钙钛矿材料比表面低、载流子传输性能差的问题。
本发明解决技术问题所采用的技术方案如下:
第一方面,一种钙钛矿复合材料制备方法,其中,包括:
将钙钛矿、硝酸钴、氟化铵、尿素溶解在水中,得到混合溶液;将所述混合溶液在预设条件下反应,得到反应中间体;
煅烧所述反应中间体,得到所述钙钛矿复合材料。
可选地,所述的钙钛矿复合材料制备方法,其中,所述钙钛矿的化学式为La1.8Ba0.2CuO4;所述钙钛矿:硝酸钴:氟化铵:尿素的质量比为1:2:2:4或1:2:2:16。
可选地,所述的钙钛矿复合材料制备方法,其中,所述钙钛矿复合材料的通式为La1.8Ba0.2Cu-Co-y,其中,y=4,16。
可选地,所述的钙钛矿复合材料制备方法,其中,所述钙钛矿的制备方法包括:
按照La1.8Ba0.2CuO4的化学配比,分别称取La(NO3)3·6H2O、Ba(NO3)2、Cu(NO3)2加入到水中,得到混合溶液;
向所述混合溶液中加入有机配体后,调节所述混合溶液的pH至8-11,得到溶胶;所述有机配体与所述混合溶液中的金属离子的摩尔比为1:1.5;
将所述溶胶在200-300℃条件下反应,得到凝胶;
煅烧所述凝胶,得到所述钙钛矿。
可选地,所述的钙钛矿复合材料制备方法,其中,所述有机配体选自柠檬酸、苹果酸、乳酸和乙二醇中的任一种。
可选地,所述的钙钛矿复合材料制备方法,其中,所述煅烧所述反应中间体,得到所述钙钛矿复合材料,其中,煅烧温度为500-700℃。
可选地,所述的钙钛矿复合材料制备方法,其中,所述煅烧所述凝胶,得到所述钙钛矿,其中,煅烧温度为900-1100℃。
可选地,所述的钙钛矿复合材料制备方法,其中,所述将所述混合溶液在预设条件下反应,得到反应中间体的步骤,具体包括:将所述混合溶液在100-200℃反应12-16小时,得到反应中间体。
第二方面,一种钙钛矿复合材料,其中,所述钙钛矿复合材料采用如上所述的钙钛矿复合材料制备方法制备而成。
第三方面,一种如上所述的钙钛矿复合材料的应用,用于催化内燃机尾气中的颗粒及氮氧化合物。
有益效果:本发明所提供的一种钙钛矿复合材料制备方法,包括:将钙钛矿、硝酸钴、氟化铵、尿素溶解在水中,得到混合溶液;将所述混合溶液在预设条件下反应,得到反应中间体;煅烧所述反应中间体,得到所述钙钛矿复合材料。通过对钙钛矿进行改性,即在钙钛矿表面原位沉积生长纳米级的钴的氧化物,从而使得所制备得到的钙钛矿复合材料具有较高的比表面、表面载流子传输性好的特点。
附图说明
图1是本发明中钙钛矿复合材料制备方法较佳实施例的流程图;
图2是本发明实施例所制备得到的钙钛矿复合材料升温NOx去除率图;
图3是本发明实施例所制备得到的钙钛矿复合材料升温COx的转化率图;
图4是实验测试示意图;
图5是本发明实施例所制备得到的钙钛矿复合材料XRD图;
图6是本发明实施例所制备得到的钙钛矿复合材料SEM图。
具体实施方式
为使本发明的目的、技术方案及优点更加清楚、明确,以下参照附图并举实施例对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
现有的对内燃机所排放的尾气进行净化处理时,多采用钙钛矿材料用作反应催化剂,但是该催化剂对尾气中的氮氧化合的吸附活性较低。经发明人研究发现,导致钙钛矿这类催化剂吸附活性低的原因是,现有的钙钛矿材料存在比表面低、载流子传输性差。
为了解决上述技术问题,本发明提供了一种钙钛矿复合材料,该钙钛矿复合材料,采用尿素水热沉积金属硝酸盐,通过氟化铵矿化诱导纳米沉积物修饰在钙钛矿表面,使得所得到的钙钛矿复合材料具有高比表面、高氮氧化物吸附活性。
在本实施例中,如图1所示,钙钛矿复合材料的制备方法包括如下步骤:
S10、将钙钛矿、硝酸钴、氟化铵、尿素溶解在水中,得到混合溶液。
具体来说,钙钛矿是指一类陶瓷氧化物,其分子通式为ABO3,钙钛矿结构的化学通式为ABX3,其中A通常为半径较大的稀土或碱土金属元素,如Ca、Sr、Ba;B位为半径较小的过渡金属元素,如Ti、Mn、Fe、Co等,由于其价态的多变性使其通常成为决定钙钛矿结构类型材料很多性质的主要组成部分;X位为O或卤素。示例性地,所述钙钛矿为La1.8Ba0.2CuO4。
在本实施例中,配制所述混合溶液时,所述钙钛矿、硝酸钴、氟化铵、尿素的加入量,可以按照质量比为1:2:2:4或1:2:2:16来进行称取,示例性地,如分别称取200g的化学式为La1.8Ba0.2CuO4的钙钛矿,400g的硝酸钴、400g的氟化铵以及800g的尿素,又或者是,如称取200g的化学式为La1.8Ba0.2CuO4的钙钛矿,400g的硝酸钴、400g的氟化铵以及3200g的尿素加入到水热反应罐中,然后加入50ml的去离子水,使原料全部溶解得到混合溶液。
在本实施例中,在步骤S10后包括步骤S20、将所述混合溶液在预设条件下反应,得到反应中间体。
具体来说,所述预设条件指的是反应温度为100℃至120℃,120℃至140℃,140℃至160℃,160℃至180℃,180℃至200℃。反应时间为12小时至13小时,13小时至14小时,14小时至15小时,15小时至16小时。示例性地,将所述混合溶液加热至120℃,在120℃温度下反应12小时。通过在该反应条件下反应,可以使尿素和金属硝酸盐得到充分的反应,将硝酸盐中的金属离子从溶液中沉积出来。需要说明的是,加热所使用的加热设备可以是烘箱、烤炉,当然也可以是根据需要选择其他的加热方式。具体的加热方式在此不做限定。
在本实施例中,在所述步骤S20之后还包括S30、煅烧所述反应中间体,得到所述钙钛矿复合材料。
具体来说,所述混合溶液在步骤S20所述的反应条件下反应后,得到反应中间体,将所述反应中间体放入煅烧设备中进行高温煅烧,经过煅烧后,得到钙钛矿复合材料。示例性地,可将所述反应中间体放入马弗炉中,加热至500℃至550℃,550℃至600℃,600℃至650℃,650℃至700℃。
在本实施例中,通过高温煅烧,可以将金属钴的氧化物原位生长在钙钛矿的表面,从而可以提高钙钛矿材料的比表面。
在本实施例的一种实现方式中,所述钙钛矿的制备可以采用溶胶-凝胶法进行制备,现以制备分子式为La1.8Ba0.2CuO4的钙钛矿的制备为例,对采用溶胶-凝胶法进行制备钙钛矿的方法做进一步的解释。
S100、按照La1.8Ba0.2CuO4的化学配比,分别称取La(NO3)3·6H2O、Ba(NO3)2、Cu(NO3)2加入到水中,得到混合溶液。
具体来说,按照上述配比分别称取77.9g的La(NO3)3·6H2O,5.2g的Ba(NO3)2、18.8g的Cu(NO3)2,加入到水中,得到混合溶液。
S110、向所述混合溶液中加入有机配体后,调节所述混合溶液的pH至8-11,得到溶胶;所述有机配体与所述混合溶液中的金属离子的质量比为1:1.5。
具体来说,所述有机配体包括但不限于柠檬酸、苹果酸、乳酸和乙二醇,所述有机配体与所述混合溶液中的金属离子的摩尔比为1:1.5,所加入的有机配体与金属组分离子形成配合物。通过控制反应温度和pH值使所得到的配合物溶解形成溶胶。示例性地,反应温度可以是150℃,反应时间为12小时,pH为11.0。
S120、将所述溶胶在200-300℃条件下反应,得到凝胶。
具体来说,将溶胶在200-300℃条件把内部的水份蒸发,随着水份的蒸发,溶胶变成凝胶。容易理解的是可以将溶胶放在如烘箱、烤炉上进行加热。
S130、煅烧所述凝胶,得到所述钙钛矿。
具体来说,将所得到的凝胶放入高温加热设备中进行高温煅烧,如将凝胶放入马弗炉中,温度升高至900-1100℃,得到钙钛矿La1.8Ba0.2CuO4。
基于相同的发明构思,本发明还提供一种钙钛矿复合材料,该钙钛矿复合材料采用上述所述的制备方法制备得到。具体的制备方法如上所述,在此不做赘述。
基于相同的发明构思,本发明还提供一种钙钛矿复合材料的应用,将钙钛矿复合材料应用于内燃机颗粒物和NOx去除等领域,如汽车尾气的处理。
下面通过具体的实施例,来对本发明所提供的钙钛矿复合材料及其制备方法、应用做进一步的解释说明。
实施例1
按照La1.8Ba0.2CuO4的配比分别称取77.9g的La(NO3)3·6H2O,5.2g的Ba(NO3)2、18.8g的Cu(NO3)2,加入到反应容器中,然后向反应容器中加入水,得到混合溶液。接着向所述反应容器中加柠檬酸,柠檬酸的加入量与金属离子的摩尔比为1:1,然后加入氨水将混合溶液的pH值调节至10.0,水浴加热至溶胶状。将得到的溶胶状物质放入烘箱,在150℃反应12小时,得到凝胶,将该凝胶放入马弗炉中加热至900℃反应,得到La1.8Ba0.2CuO4钙钛矿。
按照钙钛矿(La1.8Ba0.2CuO4):硝酸钴:氟化铵:尿素:=1:2:2:4,分别称取100g的钙钛矿,200g的硝酸钴,200g的氟化铵和400g的尿素加入水热反应罐中,加去离子水80ml,待溶解后置入反应釜中,烘箱120℃反应12h,马弗炉加热600℃反应2小时。制备得到LBC-Co-4(La1.8Ba0.2CuO4-Co3O4)催化剂。所制备得到的钙钛矿复合材料XRD图以及SEM图,如图5至图6所示。
实施例2
按照La1.8Ba0.2CuO4的配比分别称取77.9g的La(NO3)3·6H2O,5.2g的Ba(NO3)2、18.8g的Cu(NO3)2,加入到反应容器中,然后向反应容器中加入水,得到混合溶液。接着向所述反应容器中加柠檬酸,柠檬酸的加入量与金属离子的摩尔比为1:1,然后加入氨水将混合溶液的pH值调节至10.0,水浴加热至溶胶状。将得到的溶胶状物质放入烘箱,在200℃反应12小时,得到凝胶,将该凝胶放入马弗炉中加热至1100℃反应,得到La1.8Ba0.2CuO4钙钛矿。
按照钙钛矿(La1.8Ba0.2CuO4):硝酸钴:氟化铵:尿素:=1:2:2:16,分别称取100g的钙钛矿,200g的硝酸钴,200g的氟化铵和1600g的尿素加入水热反应罐中,加去离子水80ml,待溶解后置入反应釜中,烘箱120℃反应16h,马弗炉加热500℃反应2小时。制备得到LBC-Co-16催化剂。
实施例3
按照La1.8Ba0.2CuO4的配比分别称取155.8g的La(NO3)3·6H2O,10.4g的Ba(NO3)2、37.6g的Cu(NO3)2,加入到反应容器中,然后向反应容器中加入水,得到混合溶液。接着向所述反应容器中加柠檬酸,柠檬酸的加入量与金属离子的摩尔比为1:1,然后加入氨水将混合溶液的pH值调节至11.0,水浴加热至溶胶状。将得到的溶胶状物质放入烘箱,在200℃反应14小时,得到凝胶,将该凝胶放入马弗炉中加热至1000℃反应,得到La1.8Ba0.2CuO4钙钛矿。
按照钙钛矿(La1.8Ba0.2CuO4):硝酸钴:氟化铵:尿素:=1:2:2:4,分别称取200g的钙钛矿,200g的硝酸钴,400g的氟化铵和800g的尿素加入水热反应罐中,加去离子水120ml,待溶解后置入反应釜中,烘箱150℃反应14h,马弗炉加热700℃反应2小时。制备得到LBC-Co-4(La1.8Ba0.2CuO4-Co3O4)催化剂。
实施例4
Co3O4制备:
按照硝酸钴:氟化铵:尿素:=1:1:8的比例,分别称取硝酸钴100g,氟化铵100g,尿素800g加入水热反应罐中,加去离子水100ml,待溶解后置入反应釜中,烘箱120℃反应12h,马弗炉加热600℃反应2小时,得到Co3O4。
下面对上述实施例中所制备得到的钙钛矿、钙钛矿复合材料以及四氧化三钴NOx转化效率进行评估:
内燃机尾气排放主要成分为NOx和颗粒物,以500ppm/5%O2/N2混合气体为尾气,商业U碳代替颗粒物,模拟协同催化剂反应NOx与PM去除的真实情况,步骤流程如附图4,将80mg催化剂与20mgU碳机械混合加入催化反应床内。以50mL/min速率通入气体,以10℃/min程序升温。升温通气体分为两个阶段:室温-150℃,通纯N2,150-800℃通500ppm/5%O2/N2混合气体,质谱仪监测NOx与COx浓度变化,测试结果如表1,附图2、3示。实例一、二催化剂相比钙钛矿催化活性400℃时NOx反应去除率提升34.1%,T50%由587℃降至415℃;COx的T50%由539℃降至437℃,提升效果明显。
有关NOx,COx催化转化效率计算如下:
C1,C2进出口气体浓度mg/m3;Q1,Q2进出口标准状态下的气体流量m3/h。
表1
综上所述,本发明公开的一种钙钛矿复合材料及其制备方法、应用,所述方法包括:将钙钛矿、硝酸钴、氟化铵、尿素溶解在水中,得到混合溶液;将所述混合溶液在预设条件下反应,得到反应中间体;煅烧所述反应中间体,得到所述钙钛矿复合材料。通过对钙钛矿进行改性,即在钙钛矿表面原位沉积生长纳米级的钴的氧化物,从而使得所制备得到的钙钛矿复合材料具有较高的比表面、表面载流子传输性好的特点。将其应用于内燃机尾气的处理,因其具有高比表面,高NOx吸附活性,因此能够很好的催化NOx和颗粒。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (10)
1.一种钙钛矿复合材料制备方法,其特征在于,包括:
将钙钛矿、硝酸钴、氟化铵、尿素溶解在水中,得到混合溶液;
将所述混合溶液进行反应,得到反应中间体;
煅烧所述反应中间体,得到所述钙钛矿复合材料。
2.根据权利要求1所述的钙钛矿复合材料制备方法,其特征在于,所述钙钛矿的化学式为La1.8Ba0.2CuO4;所述钙钛矿:硝酸钴:氟化铵:尿素的质量比为1:2:2:4或1:2:2:16。
3.根据权利要求2所述的钙钛矿复合材料制备方法,其特征在于,所述钙钛矿复合材料的通式为La1.8Ba0.2Cu-Co-y,其中,y=4,16。
4.根据权利要求1所述的钙钛矿复合材料制备方法,其特征在于,所述钙钛矿的制备方法包括:
按照La1.8Ba0.2CuO4的化学配比,分别称取La(NO3)3·6H2O、Ba(NO3)2、Cu(NO3)2加入到水中,得到反应溶液;
向所述反应溶液中加入有机配体后,调节所述混合溶液的pH至8-11,得到溶胶;所述有机配体与所述混合溶液中的总金属离子的质量比为1:1.5;
将所述溶胶在200-300℃条件下反应,得到凝胶;
煅烧所述凝胶,得到所述钙钛矿。
5.根据权利要求4所述的钙钛矿复合材料制备方法,其特征在于,所述有机配体选自柠檬酸、苹果酸、乳酸和乙二醇中的任一种。
6.根据权利要求1所述的钙钛矿复合材料制备方法,其特征在于,所述煅烧所述反应中间体,得到所述钙钛矿复合材料,其中,煅烧温度为500-700℃。
7.根据权利要求4所述的钙钛矿复合材料制备方法,其特征在于,所述煅烧所述凝胶,得到所述钙钛矿,其中,煅烧温度为900-1100℃。
8.根据权利要求1所述的钙钛矿复合材料制备方法,其特征在于,所述将所述混合溶液进行反应,得到反应中间体的步骤,具体包括:将所述混合溶液在100-200℃反应12-16小时,得到反应中间体。
9.一种钙钛矿复合材料,其特征在于,采用权利要求1-8任一所述的制备方法制备得到。
10.一种权利要求9所述的钙钛矿复合材料的应用,用于催化内燃机尾气中的颗粒及氮氧化合物。
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