CN112337424B - 一种Bi5O7I/煅烧水滑石复合材料及其制备方法 - Google Patents
一种Bi5O7I/煅烧水滑石复合材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种Bi5O7I/煅烧水滑石复合材料及其制备方法,属于化学化工与功能材料技术领域。Bi5O7I/煅烧水滑石复合材料为在煅烧水滑石基底上负载Bi5O7I;其中煅烧水滑石为锌铝铋煅烧水滑石(ZnAlBi‑LDO),其中Zn:Al:Bi的摩尔比为3:1‑x:x,0.01≤x≤0.1;复合材料中,Bi5O7I与锌铝铋水滑石(ZnAlBi‑LDHs)的质量比为1:5~1:15。本发明借助水滑石的“记忆效应”,当混合金属氧化物在水溶液中恢复层状结构时,可大幅提高对Cr(Ⅵ)的吸附,同时负载的Bi5O7I会扩宽复合材料的光吸收范围,使复合材料在可见光下具有光催化降解Cr(Ⅵ)的效果,使Cr(Ⅵ)被还原为无毒的Cr(Ⅲ)。本发明制备的Bi5O7I/煅烧水滑石复合型吸附催化材料,可实现产品性能更高、工艺简单,彻底解决变价重金属环境污染问题。
Description
技术领域
本发明涉及一种Bi5O7I/煅烧水滑石复合材料及其制备方法和应用,属于化学化工与功能材料技术领域。
背景技术
随着工业的迅速发展,环境污染情况加剧,水体污染成为急需解决的重要问题之一,而重金属铬(Cr)污染是其中一种比较严重的水体污染。在废水中重金属Cr主要以Cr(Ⅲ)和Cr(Ⅵ) 两种价态形式存在,其中Cr(Ⅵ)的毒性约为Cr(Ⅲ)的100倍,并且在自然条件下不易降解,非常容易被人体吸收,对人体健康有着严重的威胁。
目前对Cr(Ⅵ)常见的去除手段有膜分离法、吸附法、化学沉淀法、电解法、光催化降解法等。在这些方法中,吸附法由于其成本低廉、效率高等优点而被广泛使用。常用的吸附剂为层状双金属氢氧化物—水滑石,是一类结构类似于水镁石的二维阴离子黏土,其层板是由可调控的二价和三价金属阳离子构成,层间由可交换的阴离子来平衡电荷。水滑石由于其较大的比表面积、较好的离子交换性能和较好的热稳定性而备受关注。当水滑石在低温下煅烧后,会形成混合金属氧化物,由于水滑石的“记忆效应”,这种混合金属氧化物会在水溶液中恢复其层状结构,这种特性经常被用来吸附去除一些阴离子型污染物。
但吸附法也存在吸附剂吸附位点有限不能完全去除六价铬等缺点,并且吸附剂吸附后只是将Cr(Ⅵ)从水中转移,Cr(Ⅵ)仍然存在,后续仍需要对吸附剂进行一系列的处理,这使其也难以成为有效的去除Cr(Ⅵ)的方法。近年来,通过光催化将Cr(Ⅵ)还原为无毒的Cr(Ⅲ)的方法也引起了人们的广泛关注。Bi元素对可见光具有一定活性,近年来一系列的Bi基半导体在光催化领域引起了广泛关注,Bi3+的掺杂会在一定程度上提高光催化活性,降低电子空穴复合率。碘氧化铋是一种新型光催化剂,具有合适的禁带宽度,对可见光具有一定的响应,其中Bi5O7I型碘氧化铋由于其富铋富氧型结构,使其具有合适的导带位置,而引起了人们的广泛关注。为了提高光催化效果和Cr(Ⅵ)的去除率,研究者们选择将光催化剂负载在具有吸附效果的吸附剂载体上,以此来实现吸附和光催化共同去除Cr(Ⅵ)。
现有技术中报道了一些将光催化半导体与水滑石复合用于Cr(Ⅵ)去除的材料,例如,公开号为CN109529793A的中国专利文献报道先制备磁性ZnAl-LDHs后,再将磁性水滑石与二氧化钛(TiO2)复合得到复合材料,该方法制得的复合材料仅对紫外光具有吸收,无法利用可见光进行光催化降解Cr(Ⅵ);公开号为CN109569561A的中国专利文献报道将石墨烯与 ZnAlTi-LDHs复合,后再空气中煅烧得到复合材料,该方法制得的复合材料在可见光下降解Cr(Ⅵ)浓度较低,效果有限;Bin等人将g-C3N4与CoFe-LDHs复合,然后在空气中煅烧得到复合材料,该方法制得的复合材料具有较好的吸附和光催化去除Cr(Ⅵ)的效果,但是光催化降解时使用的是300W的氙灯,运行设备功率大,耗能高。
因此,如何制备一种对可见光有吸收,吸附光催化效果好,降解时耗能低的材料用于废水处理变得尤为重要。
发明内容
本发明解决的第一个技术问题是提供一种既可以吸附,又能在自然光下具有光催化性能去除Cr(Ⅵ)的材料。
Bi5O7I/煅烧水滑石复合材料:煅烧水滑石为锌铝铋煅烧水滑石(ZnAlBi-LDO),其中Zn: Al:Bi的摩尔比为3:1-x:x,0.01≤x≤0.1;复合材料中,Bi5O7I与锌铝铋水滑石(ZnAlBi-LDHs) 的质量比为1:5~1:15。
本发明Bi5O7I/煅烧水滑石复合结构不仅可以提供丰富的吸附位点,同时在可见光下具有光催化还原能力,可以将Cr(Ⅵ)还原为无毒的Cr(Ⅲ),显著提升了Cr(Ⅵ)去除能力。本发明的Cr(Ⅵ)去除能力优于单独的Bi5O7I和煅烧水滑石。
本发明解决的第二个技术问题是提供一种Bi5O7I/煅烧水滑石复合材料的制备方法。
Bi5O7I/煅烧水滑石复合材料的制备方法,包括以下步骤:
a、取Zn(NO3)2·6H2O和Al(NO3)3·9H2O溶解于水,Bi(NO3)3·5H2O溶解于HNO3,得到混合金属盐溶液,取NaOH和Na2CO3溶解于水,得到混合碱溶液,将混合金属盐溶液和混合碱溶液同时缓慢滴加搅拌混合,滴加过程中控制反应液的pH值为8~9,滴加结束后将反应液置于干燥箱内晶化,将晶化后的产物离心洗涤干燥,研磨后得到ZnAlBi-LDHs;
b、取Bi(NO3)3·5H2O溶解于乙二醇中,得到Bi(NO3)3溶液,将KI溶解于水中,得到KI溶液,将KI溶液缓慢滴加进Bi(NO3)3溶液中并搅拌,滴加完毕后,调节反应液的pH值,将反应液转移至内有聚四氟乙烯衬套的高压反应釜中,置于干燥箱内水热生长;
c、将步骤b中水热反应后的产物离心洗涤至上清液为中性,干燥研磨后得到Bi5O7I,将 Bi5O7I与步骤a中所得的ZnAlBi-LDHs置于水中,搅拌并超声复合1h后,即得到Bi5O7I/ZnAlBi-LDHs复合材料前体;
d、将步骤c所得的Bi5O7I/ZnAlBi-LDHs复合材料前体离心干燥研磨后,在空气中煅烧,即得到所述的Bi5O7I/煅烧水滑石复合材料。
在一种实施方式中,步骤a中,混合金属盐溶液中,Bi(NO3)3在总的三价金属硝酸盐中所占摩尔比为1%~10%;如果Bi(NO3)3浓度过大,则难以形成水滑石结构,影响吸附效果。
优选的,Bi(NO3)3在总的三价金属硝酸盐中所占摩尔比值为1%~5%;更优选的,Bi(NO3)3在总的三价金属硝酸盐中所占摩尔比值为3%,在该比值下,产品的综合效果最好。
在一种实施方式中,步骤a中,反应液的晶化温度为50~130℃;优选的,反应液的晶化温度为50℃。
在一种实施方式中,步骤b中,反应液的pH值为10~14;优选的,反应液的pH值为12~13。
在一种实施方式中,步骤b中,水热温度为120~180℃;优选的,水热温度为150℃。
在一种实施方式中,步骤c中,Bi5O7I与ZnAlBi-LDHs的质量比为1:5~1:15;优选的, Bi5O7I与ZnAlBi-LDHs的质量比为1:10。
在一种实施方式中,步骤d中,煅烧温度为200~500℃;
如果煅烧温度>500℃,煅烧水滑石形成尖晶石结构,失去“记忆效应”,煅烧温度< 200℃,层间阴离子和层间水无法完全去除,吸附效果无明显提升。
在一种具体的实施方式中,煅烧温度为300℃。当煅烧温度为300℃时,在空气中煅烧后的水滑石未出现尖晶石相,且具有最好的吸附效果。
在一种实施方式中,步骤d中,煅烧时间为2~5h;优选的,煅烧时间为4h。
本发明解决的第三个技术问题是提供了一种所述的Bi5O7I/煅烧水滑石复合材料的应用,将其用作Cr(Ⅵ)的去除。
本发明的有益效果:
1、本发明所述的Bi5O7I/煅烧水滑石复合材料,借助水滑石的“记忆效应”,当混合金属氧化物在水溶液中恢复层状结构时,可大幅提高对Cr(Ⅵ)的吸附,同时负载的Bi5O7I会扩宽复合材料的光吸收范围,使复合材料在可见光下具有光催化降解Cr(Ⅵ)的效果,使Cr(Ⅵ)被还原为无毒的Cr(Ⅲ),进一步的提升了Cr(Ⅵ)的去除能力。
3、本发明的制备方法中所用原材料来源广泛,光催化降解Cr(Ⅵ)时使用低功率的白炽灯,能耗低,操作简便。
附图说明
图1为实施例1所得的Bi5O7I/煅烧水滑石复合材料的XRD图。
图2为实施例1所得的Bi5O7I/煅烧水滑石复合材料的UV-Vis光谱图。
图3为实施例1所得的Bi5O7I/煅烧水滑石复合材料的Cr(Ⅵ)去除效率图。
图4为实施例1所得的Bi5O7I/煅烧水滑石复合材料随光照时间延长的Cr高分辨率XPS 光谱。
图5为实施例2所得的Bi5O7I/煅烧水滑石复合材料的Cr(Ⅵ)去除效率图。
图6为实施例3所得的Bi5O7I/煅烧水滑石复合材料的Cr(Ⅵ)去除效率图。
具体实施方式
下面结合实施例对本发明的具体实施方式做进一步的描述,并不因此将本发明限制在所述的实施例范围之中。
光催化活性测试
降解对象是100mL浓度为15mg/L的Cr(Ⅵ)溶液,在反应器中加入Bi5O7I/煅烧水滑石复合材料,于黑暗中磁力搅拌90min,使溶液中反应体系达到吸附-脱附平衡,随后打开功率为 40W白炽灯进行光催化降解,整个实验过程每隔15~30min取样,每次取样6ml,将样品离心取上清液,用二苯碳酰二肼分光光度法对Cr(Ⅵ)含量进行测定,用紫外-可见分光光度计测定在540nm波长处的吸光度值,并计算Cr(Ⅵ)的去除率。
实施例1
合成过程:
1)按化学计量比称取Zn(NO3)2·6H2O共3.5698g和Al(NO3)3·9H2O共1.4555g溶解于去离子水中,称取Bi(NO3)3·5H2O共0.0582g溶解于硝酸中,将Bi(NO3)3溶液与Zn(NO3)2和Al(NO3)3溶液混合得到混合金属盐溶液,称取NaOH共1.6798g和Na2CO3共0.84792g溶解于去离子水中得到混合碱溶液,将混合金属盐溶液和混合碱溶液同时缓慢滴加搅拌混合,滴加过程中控制反应液的pH值为8~9,滴加结束后将反应液置于干燥箱内50℃晶化,将晶化后的产物离心洗涤干燥,研磨后得到ZnAlBi-LDHs;其中,Bi(NO3)3在总的三价金属硝酸盐中所占摩尔比值为3%;
2)称取Bi(NO3)3·5H2O共1.2126g溶解于乙二醇中得到澄清溶液,称取KI共0.083g溶解于去离子水中得到KI溶液,将KI溶液缓慢滴加进Bi(NO3)3溶液中并搅拌,滴加完毕后,调节反应液的pH值为13,将反应液转移至内有聚四氟乙烯衬套的高压反应釜中,置于干燥箱内150℃水热生长;
3)将步骤2)中水热反应后的产物离心洗涤至上清液为中性,干燥研磨后得到Bi5O7I,称取Bi5O7I共0.1g与步骤1)中所得的ZnAlBi-LDHs共1g置于水中,使Bi5O7I与ZnAlBi-LDHs 的质量比为1:10,搅拌30min后超声复合1h后,即得到Bi5O7I/ZnAlBi-LDHs复合材料前体;
4)将步骤3)所得的Bi5O7I/ZnAlBi-LDHs复合材料前体离心干燥研磨后,在空气中300℃煅烧4h,即得到所述的既具有吸附效果又具有光催化能力的Bi5O7I/煅烧水滑石复合材料。
图1为本发明实施例1所得Bi5O7I/煅烧水滑石复合材料的XRD图,由图1可知:实施例1所制得的Bi5O7I的XRD结果与标准衍射峰相符,未出现其他杂质峰,水滑石经煅烧后,层状结构被破坏,形成混合金属氧化物,XRD结果显示为ZnO,Al2O3未在XRD图谱中显示,主要是由于Al2O3以无定形态形式存在,Bi5O7I/煅烧水滑石复合材料的XRD图谱中既有 Bi5O7I的衍射峰又有ZnO的衍射峰,表明两者很好的复合在了一起。
图2为本发明实施例1所制得的Bi5O7I/煅烧水滑石复合材料的Uv-vis光谱,由图2可知:实施例1所制得的Bi5O7I/煅烧水滑石复合材料相较单独的煅烧水滑石其吸收波长发生红移,增强了对可见光的吸收。
图3为本发明实施例1所得的Bi5O7I/煅烧水滑石复合材料的Cr(Ⅵ)去除效率图,由图3 可知:实施例1在120min内去除浓度为15mg/L的Cr(Ⅵ)溶液的去除率为99.15%;在90min 内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为96.41%;在60min内去除浓度为15mg/L 的Cr(Ⅵ)溶液的吸附去除率为90.41%;在30min内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为79.80%;在15min内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为53.65%。
图4为本发明实施例1所得的Bi5O7I/煅烧水滑石复合材料随光照时间延长的Cr高分辨率XPS光谱,约在578和587eV处的峰属于Cr(Ⅵ),约在576和586eV处的峰属于Cr(Ⅲ),由图4可知:随着光照时间的延长,Cr(Ⅵ)的面积逐渐减小,Cr(Ⅲ)的面积逐渐增大,说明随着光照时间的延长越来越多的Cr(Ⅵ)被还原为无毒的Cr(Ⅲ)。
实施例2
合成过程:
1)按化学计量比称取Zn(NO3)2·6H2O共3.5698g和Al(NO3)3·9H2O共1.4555g溶解于去离子水中,称取Bi(NO3)3·5H2O共0.0582g溶解于硝酸中,将Bi(NO3)3溶液与Zn(NO3)2和Al(NO3)3溶液混合得到混合金属盐溶液,称取NaOH共1.6798g和Na2CO3共0.84792g溶解于去离子水中得到混合碱溶液,将混合金属盐溶液和混合碱溶液同时缓慢滴加搅拌混合,滴加过程中控制反应液的pH值为8~9,滴加结束后将反应液置于干燥箱内50℃晶化,将晶化后的产物离心洗涤干燥,研磨后得到ZnAlBi-LDHs;其中,Bi(NO3)3在总的三价金属硝酸盐中所占摩尔比值为3%;
2)称取Bi(NO3)3·5H2O共1.2126g溶解于乙二醇中得到澄清溶液,称取KI共0.083g溶解于水中得到KI溶液,将KI溶液缓慢滴加进Bi(NO3)3溶液中并搅拌,滴加完毕后,调节反应液的pH值为13,将反应液转移至内有聚四氟乙烯衬套的高压反应釜中,置于干燥箱内150℃水热生长;
3)将步骤2)中水热反应后的产物离心洗涤至上清液为中性,干燥研磨后得到Bi5O7I,称取Bi5O7I共0.2g与步骤1)中所得的ZnAlBi-LDHs共1g置于水中,使Bi5O7I与ZnAlBi-LDHs 的质量比为1:5,搅拌30min后超声复合1h后,即得到Bi5O7I/ZnAlBi-LDHs复合材料前体;
4)将步骤3)所得的Bi5O7I/ZnAlBi-LDHs复合材料前体离心干燥研磨后,在空气中300℃煅烧4h,即得到所述的既具有吸附效果又具有光催化能力的Bi5O7I/煅烧水滑石复合材料。
图5为本发明实施例2所得的Bi5O7I/煅烧水滑石复合材料的Cr(Ⅵ)去除效率图,由图5 可知:实施例2在120min内去除浓度为15mg/L的Cr(Ⅵ)溶液的去除率为97.35%;在90min 内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为92%;在60min内去除浓度为15mg/L的 Cr(Ⅵ)溶液的吸附去除率为88.03%;在30min内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为78.34%;在15min内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为50.18%。
实施例3
合成过程:
1)按化学计量比称取Zn(NO3)2·6H2O共3.5698g和Al(NO3)3·9H2O共1.4555g溶解于去离子水中,称取硝酸铋(Bi(NO3)3·5H2O)0.0582g溶解于硝酸中,将Bi(NO3)3溶液与Zn(NO3)2和Al(NO3)3溶液混合得到混合金属盐溶液,称取NaOH共1.6798g和Na2CO3共0.84792g溶解于去离子水中得到混合碱溶液,将混合金属盐溶液和混合碱溶液同时缓慢滴加搅拌混合,滴加过程中控制反应液的pH值为8~9,滴加结束后将反应液置于干燥箱内50℃晶化,将晶化后的产物离心洗涤干燥,研磨后得到ZnAlBi-LDHs;其中,Bi(NO3)3在总的三价金属硝酸盐中所占摩尔比值为3%;
2)称取Bi(NO3)3·5H2O共1.2126g溶解于乙二醇中得到澄清溶液,称取KI共0.083g溶解于水中得到KI溶液,将KI溶液缓慢滴加进Bi(NO3)3溶液中并搅拌,滴加完毕后,调节反应液的pH值为13,将反应液转移至内有聚四氟乙烯衬套的高压反应釜中,置于干燥箱内150℃水热生长;
3)将步骤2)中水热反应后的产物离心洗涤至上清液为中性,干燥研磨后得到Bi5O7I,称取Bi5O7I共0.06g与步骤1)中所得的ZnAlBi-LDHs共0.9g置于水中,使Bi5O7I与ZnAlBi-LDHs的质量比为1:15,搅拌30min后超声复合1h后,即得到Bi5O7I/ZnAlBi-LDHs 复合材料前体;
4)将步骤3)所得的Bi5O7I/ZnAlBi-LDHs复合材料前体离心干燥研磨后,在空气中300℃煅烧4h,即得到所述的既具有吸附效果又具有光催化能力的Bi5O7I/煅烧水滑石复合材料。
图6为本发明实施例3所得的Bi5O7I/煅烧水滑石复合材料的Cr(Ⅵ)去除效率图,由图6 可知:实施例3在120min内去除浓度为15mg/L的Cr(Ⅵ)溶液的去除率为94.79%;在90min 内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为93.26%;在60min内去除浓度为15mg/L 的Cr(Ⅵ)溶液的吸附去除率为80.91%;在30min内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为74.54%;在15min内去除浓度为15mg/L的Cr(Ⅵ)溶液的吸附去除率为50.43%。
Claims (10)
1.一种Bi5O7I/煅烧水滑石复合材料,其特征在于:煅烧水滑石为锌铝铋煅烧水滑石ZnAlBi-LDO,其中Zn:Al:Bi的摩尔比为3:1-x:x,0.01≤x≤0.1;复合材料中,Bi5O7I与锌铝铋水滑石ZnAlBi-LDHs的质量比为1:5~1:15。
2.如权利要求1所述的Bi5O7I/煅烧水滑石复合材料的制备方法,其特征在于,包括以下步骤:
a、取Zn(NO3)2·6H2O和Al(NO3)3·9H2O溶解于水,Bi(NO3)3·5H2O溶解于HNO3,得到混合金属盐溶液,取NaOH和Na2CO3溶解于水,得到混合碱溶液,将混合金属盐溶液和混合碱溶液同时缓慢滴加搅拌混合,滴加过程中控制反应液的pH值为8~9,滴加结束后将反应液置于干燥箱内晶化,将晶化后的产物离心洗涤干燥,研磨后得到ZnAlBi-LDHs;
b、取Bi(NO3)3·5H2O溶解于乙二醇中,得到Bi(NO3)3溶液,将KI溶解于水中,得到KI溶液,将KI溶液缓慢滴加进Bi(NO3)3溶液中并搅拌,滴加完毕后,调节反应液的pH值,将反应液转移至内有聚四氟乙烯衬套的高压反应釜中,置于干燥箱内水热生长;
c、将步骤b中水热反应后的产物离心洗涤至上清液为中性,干燥研磨后得到Bi5O7I,将Bi5O7I与步骤a中所得的ZnAlBi-LDHs置于水中,搅拌并超声复合1h后,即得到Bi5O7I/ZnAlBi-LDHs复合材料前体;
d、将步骤c所得的Bi5O7I/ZnAlBi-LDHs复合材料前体离心干燥研磨后,在空气中煅烧,即得到所述的Bi5O7I/煅烧水滑石复合材料。
3.根据权利要求2所述的Bi5O7I/煅烧水滑石复合材料的制备方法,其特征在于,步骤a所述混合金属盐溶液中,Bi(NO3)3在总的三价金属硝酸盐中所占摩尔比为1%~10%。
4.根据权利要求2所述的Bi5O7I/煅烧水滑石复合材料的制备方法,其特征在于,步骤a中,反应液的晶化温度为50~130℃。
5.根据权利要求2所述的Bi5O7I/煅烧水滑石复合材料的制备方法,其特征在于:步骤b中,反应液的pH值为10~14。
6.根据权利要求2所述的Bi5O7I/煅烧水滑石复合材料的制备方法,其特征在于:步骤b中,水热温度为120~180℃。
7.根据权利要求2所述的Bi5O7I/煅烧水滑石复合材料的制备方法,其特征在于:步骤c中,Bi5O7I与ZnAlBi-LDHs的质量比为1:5~1:15。
8.根据权利要求2所述的Bi5O7I/煅烧水滑石复合材料的制备方法,其特征在于:步骤d中,煅烧温度为200~500℃。
9.根据权利要求2所述的Bi5O7I/煅烧水滑石复合材料的制备方法,其特征在于:步骤d中,煅烧时间为2~5h。
10.一种权利要求1所述的Bi5O7I/煅烧水滑石复合材料或者权利要求2~9任一项所述制备方法制得的Bi5O7I/煅烧水滑石复合材料的应用,其特征在于,将其用作吸附和可见光下降解去除Cr(Ⅵ)。
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