CN117046502A - 一种介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法及其应用 - Google Patents
一种介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法及其应用,本制备方法首先制备介孔石榴状氮掺杂介孔碳球,然后利用该碳球制备得到介孔石榴状Bi4Ti3O12@MNC铁电材料,操作简便,成本廉价、无需复杂反应和试剂。该方法制备得到的复合材料孔径均匀、颗粒匀称、比表面积大,具有优异的可见光吸收能力和光压电催化活性,可较好的应用于光压电催化二氧化碳还原及降解污染物等领域。如光压电催化CO2还原为CO、降解塑料、裂解水制氢、催化生成H2O2溶液、净化污染水等。
Description
技术领域
本发明涉及一种铁电材料的制备方法及其应用。
背景技术
煤、石油、天然气的持续利用和开发打破了自然界的碳循环,造成了严重的环境污染问题。开发利用高效和绿色环保的催化技术以缓解全球气候变暖问题成为迫切的需要。众多催化技术中,半导体光催化技术因其绿色能源而受到广泛研究,可将CO2还原为含碳燃料。然而较高的光生载流子复合率限制了其催化能力,无法满足实际应用。近年来,已有报道利用压电效应提高光生电荷分离效率,利用机械能诱导材料内部产生内建电场,驱使光生载流子做定向移动,促进光生载流子的分离,从而提高催化效率。然而机械能转换效率低则成了新的问题。因此探索合成具有高效载流子分离效率和能量转换效率的压电光催化剂具有重要意义。
众多铁电半导体材料如BaTiO3、Bi4Ti3O12和LiNbO3等被报道展现出一定的光催化活性,同时也表现出良好的压电性能。为了进一步提高催化剂的电荷分离效率,研究者们提出了很多改性的方法,比如表面工程、异质结策略、助催化剂的负载等,都是以界面处形成局域电场驱使电荷做定向移动。同时反应活性位点也极大影响光催化反应活性,据报道,利用碳材料和铁电半导体混合能显著提高材料的光压电催化能力。然而,目前的报道大多都是简单的物理混合,不仅形貌不可控,往往伴随着比表面积低,吸附能力弱的缺点。因此,如何设计出比表面积大、活性位点丰富、具有较高的光压电性能的复合铁电材料,并将其应用于压电催化领域是十分有研究意义的。
发明内容
发明目的:针对上述现有技术,提出一种介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法及其应用,所制备得到的铁电材料比表面积大,孔径均匀,活性位点丰富,具有较高的光压电性能。
技术方案:一种介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法,包括:
S1:制备介孔石榴状氮掺杂介孔碳球,包括:按化学计量比将模板、胺源和聚合引发剂加入去离子水中进行搅拌混合,将所得样品经管式炉碳化;将碳化产物利用碱溶液刻蚀,刻蚀产物经洗涤、离心、烘干得到介孔石榴状氮掺杂介孔碳球;
S2:利用所述介孔石榴状氮掺杂介孔碳球制备介孔石榴状Bi4Ti3O12@MNC铁电材料,包括:按化学计量比将钛源、铋源分散在去离子水中,先后添加介孔石榴状氮掺杂介孔碳球和碱溶液并磁力搅拌均匀,将所得溶液倒进水热釜中加热反应,将反应产物经洗涤、离心、烘干得到所述介孔石榴状Bi4Ti3O12@MNC铁电材料。
进一步的,所述步骤S1中,所述搅拌速率为1800-2200r/min,管式炉加热温度为800-1000℃。
进一步的,所述步骤S1中,所述碱溶液为氢氧化钠溶液或氢氧化钙溶液,浓度4-6mol/L,刻蚀时间为12-15h。
进一步的,所述步骤S2中,所述加热反应的温度为160~240℃,反应时间为12~48h。
所述制备方法制得的介孔石榴状Bi4Ti3O12@MNC铁电材料在光压电催化中的应用。
进一步的,所述光压电催化包括催化CO2还原为CO、固氮合成氨、裂解水制氢、催化生成H2O2溶液、净化污染水。
有益效果:1、本发明制备的石榴状介孔Bi4Ti3O12@MNC铁电材料具有优异的压电光催化性能,尤其对CO2具有高效压电还原性能。
2、本发明通过溶剂热法合成的石榴状介孔Bi4Ti3O12@MNC铁电材料,成本低廉、无需复杂反应过程和试剂,反应物比表面积大,孔径均匀,活性位点丰富,具有较高的稳定性。
3、本发明首次利用碳球的均一介孔限域合成负载钛酸铋纳米颗粒,以形成石榴状的Bi4Ti3O12@MNC,限制钛酸铋在合成过程中的团聚效应,阻碍其形成片状,均一的分散在碳球的内部和表面。
4、本发明使用碱溶液取代酸溶液蚀刻碳球,从而调整PH以便于第二步复合材料的形成,以达到精准调控合成的目的。
附图说明
图1为本发明制备方法流程图;
图2为实施例1、实施例8、实施例9所得铁电材料的XRD图谱;
图3为实施例1及对比例所得铁电材料的XRD图谱;
图4为实施例1及对比例所得铁电材料的SEM图像;
图5为实施例1及对比例所得铁电材料的CO2还原性能图;
图6为实施例1、实施例2、实施例3的步骤S1搅拌所得聚苯胺的形貌图;
图7为实施例1、实施例4、实施例5的步骤S1煅烧所得碳球的形貌图;
图8为实施例1、实施例6、实施例7的步骤S2最终所得复合材料的形貌图。
具体实施方式
下面结合附图对本发明做更进一步的解释。
下述实施例及对比例的Bi4Ti3O12@MNC、Bi4Ti3O12+MNC、Bi4Ti3O12的性能评价方法如下:
1.物相评价方法:
X射线衍射(XRD):将制备的Bi4Ti3O12@MNC、Bi4Ti3O12+MNC、Bi4Ti3O12材料在德国Bruker公司D8 Advance系列广角X射线衍射仪分析样品的晶体结构,扫描速度为5°/min,扫描范围为10°~80°。
2.微观形貌评价方法:
扫描电镜(SEM):将制备的Bi4Ti3O12@MNC、Bi4Ti3O12+MNC、Bi4Ti3O12材料在日本JEOL公司JSM-IT300系列扫描电镜上测试,加速电压:5-20kV。
3.CO2压电光还原性能评价方法:
以Bi4Ti3O12@MNC压电光催化还原CO2反应为例,具体过程如下:首先在石英反应器中加入100ml的去离子水,然后再加入10mg的Bi4Ti3O12@MNC材料。将反应体系通过2XZ-2B型旋片式真空泵抽真空30min,并填充纯CO2气体至常压,置于KQ-400DE型数控超声波清洗器中,并在紫光光源下进行照射。CO2还原实验条件:在70kHz,260W的超声条件下,每30min扎针取一次样,共取4次样(即反应2h),反应过程中温度保持在25±5℃。所得气体样通过GC-7920气相色谱仪分析CO等产物的峰面积,由此判断CO2还原产物情况。Bi4Ti3O12+MNC、Bi4Ti3O12的CO2压电光还原性能评价方法同上。
实施例1
如图1所示,一种介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法,包括:
S1:制备介孔石榴状氮掺杂介孔碳球。
在室温下,按化学计量比2:1:4将二氧化硅、苯胺和过硫酸铵加入去离子水中进行搅拌混合,搅拌速率为2000r/min,搅拌时间为24h;然后将所得样品经管式炉碳化,加热温度为900℃,加热时间为2h;将碳化产物利用浓度为5mol/L的氢氧化钠溶液刻蚀12h,刻蚀产物经洗涤、离心、烘干得到介孔石榴状氮掺杂介孔碳球,简称为MNC。
S2:利用步骤S1制备得到的介孔石榴状氮掺杂介孔碳球制备介孔石榴状Bi4Ti3O12@MNC铁电材料。
在室温下,首先将0.1902g Bi(NO3)3·5H2O、0.1100g C16H36O4Ti、0.1000g MNC分散在30mL的去离子水中;其次加入4.800g NaOH进行磁力搅拌1h;最后将所得悬浮液转移到内衬为聚四氟乙烯不锈钢反应釜中加热反应,反应温度为160℃,反应30h;反应结束后用去离子水清洗离心3次,60℃下烘12h,得到介孔石榴状Bi4Ti3O12@MNC铁电材料。
上述方法制备的石榴状介孔Bi4Ti3O12@MNC铁电材料在催化领域的应用,包括压电光催化CO2还原为CO、固氮合成氨、裂解水制氢、催化生成H2O2溶液、净化污染水等。
本发明介孔石榴状Bi4Ti3O12@MNC铁电材料的压电光催化原理为:介孔石榴状Bi4Ti3O12@MNC铁电材料其晶体结构是非中心对称,当受到外界应力时,可以将机械能转化为化学能。其具体原理如下:在超声振动下,周期性空化气泡的猝灭会产生108Pa压力并作用材料表面。材料表面容易弯曲变形,内部会产生极化电场并形成电位差。当光照激发价带电子跃迁到导带时,光生载流子受极化电场驱使定向迁移至材料的两极界面,经碳球传导加速载流子的分离至材料表面,由此与材料吸附的CO2等物质发生氧化还原反应,实现催化目的。
对比例1
制备铋系层状铁电Bi4Ti3O12材料及其性能测试:
在室温下,首先将1.9403g Bi(NO3)3·5H2O、1.100g C16H36O4Ti分散在30mL的去离子水中,其次加入4.800gNaOH磁力搅拌1h,最后将所得悬浮液转移到内衬为聚四氟乙烯不锈钢反应釜中,200℃反应20h。反应结束后用去离子水清洗离心3次,60℃下烘12h得到Bi4Ti3O12材料。
对比例2
制备Bi4Ti3O12和MNC物理混合材料及其性能测试:
将100mg MNC、100mg对比例1Bi4Ti3O12放入石英研钵中物理研磨,得到Bi4Ti3O12+MNC物理混合材料。
如图3所示,基于XRD测试表征,实施例1、对比例1和对比例2都与Bi4Ti3O12的标准卡片PDF﹟35-0795对应,说明材料中存在Bi4Ti3O12且为纯相,无其他杂质。
如图4所示,基于SEM测试表征,可以发现对比例1和对比例2都有片状纳米片堆叠而成的纳米花球,厚约为15-50nm,此外实施例1和对比例2均看到介孔球,孔径为18-22nm,在催化过程中会吸附更多的CO2,同时暴露更多活性位点,有利于CO2充分与催化剂接触而发生还原反应。
如图5所示,通过对样品进行CO2还原测试性能测试,可以看出在超声作用2h后,Bi4Ti3O12@MNC对CO2还原CO的速率为58.79μmol g-1h-1;Bi4Ti3O12的还原产物速率为5.41μmol g-1h-1;Bi4Ti3O12+MNC的还原产物速率为35.06μmol g-1h-1。相较于对比例1和对比例2,本发明实施例1具有优异的压电光催化CO2还原的性能。
实施例2
与实施例1的区别仅在于,步骤S1中,搅拌速率为1800r/min。
实施例3
与实施例1的区别仅在于,步骤S1中,搅拌速率为2200r/min。
实施例4
与实施例1的区别仅在于,步骤S1中,管式炉加热温度为800℃。
实施例5
与实施例1的区别仅在于,步骤S1中,管式炉加热温度为1000℃。
实施例6
与实施例1的区别仅在于,步骤S1中,氢氧化钠溶液的浓度为4mol/L。
实施例7
与实施例1的区别仅在于,步骤S1中,氢氧化钠溶液的浓度为6mol/L。
实施例8
与实施例1的区别仅在于,步骤S2中,加热反应的温度为180℃,反应时间为48h。
实施例9
与实施例1的区别仅在于,步骤S2中,加热反应的温度为240℃,反应时间为12h。
如图2所示,基于XRD测试表征,实施例1、实施例8、实施例9不同温度下制备的复合材料,发现200℃下制备的晶型较好,实施例10则有其他杂峰,因此最佳制备温度为200℃。
如图6所示,在S1中仅改变搅拌速率,对比实施例1、实施例2、实施例3发现,所得聚苯胺的形貌有略微差异,2000r/min的搅拌速率下合成的聚苯胺形貌是最好的,实施例2中较慢的搅拌速率球形聚苯胺中局部出现分散现象,实施例3中较快的搅拌速率使球形聚苯胺发生团聚,因此其最佳搅拌速率为2000r/min。
如图7所示,在S1中仅改变管式炉煅烧温度,对比实施例1、实施例4、实施例5发现,煅烧所得碳球的形貌略有差异,在900℃下的煅烧温度下合成的碳球形貌是最好的,实施例4中的石榴状碳球有部分杂质,实施例5中的石榴状碳球则出现了部分模板脱落的现象,因此其最佳煅烧温度为900℃。
如图8所示,在S1中仅改变碱溶液的浓度,对比实施例1、实施例6、实施例7发现,所得复合材料的形貌有较大差异,5mol/L刻蚀下的复合材料钛酸铋分散均匀,形貌良好,实施例6中钛酸铋在碳球中的数量较少,实施例7中较多的钛酸铋纳米颗粒会发生团聚,因此其最佳碱溶液浓度为5mol/L。
需要说明的是,本发明制备方法的步骤S1中,模板为二氧化硅、介孔沸石、纳米管中至的一种,二氧化硅为最佳;胺源为苯胺、乙胺、乙二胺、二乙胺中的一种,苯胺为最佳;聚合引发剂为过硫酸铵、过硫酸钾、过氧化氢中的一种,过硫酸铵为最佳;碱溶液为氢氧化钠和氢氧化钙中的一种。步骤S2中,铋源选自氧化铋、溴化铋、碳酸铋、五水合硝酸铋、磷酸铋中的至少一种,五水合硝酸铋为最佳;钛源选自二氧化钛、钛酸正丁酯、偏钛酸钡、硫酸钛中的至少一种,钛酸正丁酯为最佳,碱溶液为氢氧化钠和氢氧化钙中的一种。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法,其特征在于,包括:
S1:制备介孔石榴状氮掺杂介孔碳球,包括:按化学计量比将模板、胺源和聚合引发剂加入去离子水中进行搅拌混合,将所得样品经管式炉碳化;将碳化产物利用碱溶液刻蚀,刻蚀产物经洗涤、离心、烘干得到介孔石榴状氮掺杂介孔碳球;
S2:利用所述介孔石榴状氮掺杂介孔碳球制备介孔石榴状Bi4Ti3O12@MNC铁电材料,包括:按化学计量比将钛源、铋源分散在去离子水中,先后添加介孔石榴状氮掺杂介孔碳球和碱溶液并磁力搅拌均匀,将所得溶液倒进水热釜中加热反应,将反应产物经洗涤、离心、烘干得到所述介孔石榴状Bi4Ti3O12@MNC铁电材料。
2.根据权利要求1所述的介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法,其特征在于,所述步骤S1中,所述搅拌速率为1800-2200r/min,管式炉加热温度为800-1000℃。
3.根据权利要求2所述的介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法,其特征在于,所述步骤S1中,所述碱溶液为氢氧化钠溶液或氢氧化钙溶液,浓度4-6mol/L,刻蚀时间为12-15h。
4.根据权利要求1-3任一所述的介孔石榴状Bi4Ti3O12@MNC铁电材料的制备方法,其特征在于,所述步骤S2中,所述加热反应的温度为160~240℃,反应时间为12~48h。
5.根据权利要求1-4任一所述制备方法制得的介孔石榴状Bi4Ti3O12@MNC铁电材料。
6.根据权利要求1-4任一所述制备方法制得的介孔石榴状Bi4Ti3O12@MNC铁电材料在光压电催化中的应用。
7.根据权利要求6所述的应用,其特征在于,所述光压电催化包括催化CO2还原为CO、固氮合成氨、裂解水制氢、催化生成H2O2溶液、净化污染水。
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