CN108927138A - 一种Bi2O3/硅藻土复合光催化材料及其制备方法 - Google Patents
一种Bi2O3/硅藻土复合光催化材料及其制备方法 Download PDFInfo
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 title claims abstract description 46
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 10
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Abstract
本发明涉及一种Bi2O3/硅藻土复合光催化材料及其制备方法。本发明利用双氧水调控高烧失量硅藻土的有机质含量及表面荷电性,再通过水热方法负载Bi2O3,使得纳米片垂直生长于硅藻土表面,最终获得兼具优异的光催化性能和吸附性能的Bi2O3/硅藻土复合材料。该方法显著提升了高烧失硅藻土这种传统意义上劣质硅藻土的应用附加值,使硅藻土中的有机质得到有效利用,对设备要求低,原料成本低廉,节能减排,环境压力小,所得产品在催化、吸附、污水处理等领域具有广阔的应用前景。
Description
技术领域
本发明涉及一种Bi2O3/硅藻土复合光催化材料及其制备方法,该方法可显著提升光催化剂的活性与吸附性,属于矿物材料加工利用领域。
背景技术
Bi2O3晶体是一种重要的p-型半导体材料,禁带宽度较窄,可有效利用可见光进行有机污染物的光催化降解,是近年来受到广泛关注的新型可见光催化剂。虽然Bi2O3半导体纳米晶催化剂效率高,但从液相中分离回收困难,制约了其广泛应用。近年来,很多研究者尝试将纳米晶光催化剂固定或负载于不同载体得到负载型光催化剂,载体主要有:活性炭、硅胶、沸石、纤维等。硅藻土是一种非金属矿物,储量丰富,成本低,具有独特的多孔结构、强吸附性、大比表面积、化学性质稳定等优点,是一种较理想的光催化剂载体。
在氧化铋合成方面,董帆、李欣蔚等人在中国专利【CN107051422A】中公开了一种无定形氧化铋复合光催化剂、制备方法及使用方法。胡汉祥在《铋蒸气氧化法制备氧化铋纳米粉体的研究》一文中,采用金属蒸汽氧化法,通过加入助剂使Bi固体蒸发、气相氧化,从而制备了Bi2O3粉体。这种蒸汽氧化法对设备材质要求比较高,工业发展受限,这种方法制备氧化铋时遇到了铋的蒸气压不高、蒸发困难等问题,所以作者必须加入助剂,才能制备纳米氧化铋粉体,生产成本太高。
针对氧化铋与硅藻土的复合,林立、胡拥军等人在中国专利【CN107029757A】中公开了一种卤氧化铋#硅藻土复合光催化剂的制备方法。将原料精硅藻土为载体,以五水硝酸铋、氯化钾、溴化钾和碘化钾为前驱体,采用常温直接水解沉淀法合成卤氧化铋/硅藻土复合光催化材料,复合材料经过滤、洗涤、干燥后,得成品。潘道文、许蘅等人在中国专利【CN107199030A】中公开了一种蜂窝状多孔氧化铋的制备方法。采用真空冷冻干燥,霉变处理,煅烧处理,即得蜂窝状多孔氧化铋。李焕在《氧化铋/硅藻土复合光催化剂的制备及其可见光催化性能》一文中,将硅藻土分散在硝酸铋溶液中,经冷冻干燥后于空气中煅烧得到了Bi2O3/硅藻土质量比为0.10:1.00~0.60:1.00的一系列复合光催化剂。但是,这种冷冻干燥法得到的反应产物的结晶程度很差,一般都需要后续的煅烧处理来强化结晶、获得光催化性能,不仅拉高了生产过程的能源消耗,而且也容易破坏硅藻土多孔结构,给复合材料的催化活性带来不利影响。
硅藻土是生物成因的多孔SiO2质矿物,部分产地的硅藻土由于形成的历史条件差异而夹带大量生物质,被称为高烧失硅藻土。这种硅藻土中有机质含量往往高达20~50wt%,烧失量非常大,可利用的非晶态蛋白石产率很低,且煅烧处理过程也将产生严重的环境污染,因此高烧失量硅藻土一直被认为是难以利用的劣质硅藻土。肖森在中国专利【CN86107500】中公开了一种用劣质硅藻土制备的高活性多用途熟土与精土及其生产方法和用涂。利用SiO2的平均含量为52%的高烧失量型低品位硅藻土为原料,在低温下进行焙烧,从而生产出高活性熟土及精土。郑水林在《酸浸和焙烧对硅藻土性能的影响》一文中,采用焙烧和酸浸法对临江硅藻土进行提纯处理,研究了原硅藻土和精硅藻土对罗丹明B溶液的吸附性质。对高烧失硅藻土表面有机质采用焙烧或者酸浸处理,直接影响硅藻土比表面积的大小,若采用工艺不当,特别是焙烧温度过高,破坏硅藻土的孔结构;对于酸浸,当酸浓度逐渐加大到一定值,硅藻体内部微孔孔壁因溶解使微孔连在一起,变成大孔,同样也破坏硅藻土的孔结构。这些专利主要关注了将劣质硅藻土转变为传统精制硅藻土的可行性,但针对高烧失量硅藻土中有机质的研究利用的报道还非常有限。赵以辛等在《内蒙产高烧失低品位硅藻土的提纯及碳化性能》一文中,关注了采用水洗-焙烧工艺,对内蒙产高烧失低品位硅藻土的提纯问题。如果能将高烧失硅藻土中的原位碳与功能性半导体相复合,将有望获得全新的硅藻土复合型半导体材料,但相关的研究极少。
如果充分利用硅藻土中的高含量有机质,在适当的氧化条件下,调控硅藻土内部有机质的含量及其碳化过程,将保留硅藻土自身的多孔结构,也有望有效提升Bi2O3/硅藻土复合材料的光催化性能,使得高烧失硅藻土作为活性组分参与到催化和吸附过程中,提升产品的性价比。因此,本专利提出了一种利用高烧失硅藻土制备Bi2O3/硅藻土复合光催化剂的方法,整个复合过程方法简单,原料廉价,不使用有机添加剂,无需煅烧即可获得理想的光催化性能,显著降低了生产能耗和废水处理难度。复合催化剂中不仅充分利用硅藻土中的高含量有机质,而且使Bi2O3直立生长在硅藻土表面,形状规则,均匀致密,同时又充分发挥了Bi2O3的可见光催化性能。
发明内容
本发明将针对上述问题,提出一种Bi2O3/硅藻土复合光催化剂的制备方法。本发明以高烧失硅藻土、铋盐为原料,使用水热法制备Bi2O3/硅藻土复合光催化剂。该发明克服了高烧失硅藻土可利用的非晶态蛋白石产率低,煅烧处理过程产生严重的环境污染等问题。充分利用硅藻土中的高含量有机质,在适当的氧化条件下,调控硅藻土内部有机质的含量及其碳化过程,使其产物适合在水热条件下实现对高结晶度、高活性、片状Bi2O3的负载,所得氧化铋在高烧失硅藻土表面直立生长,形状规则且分布均匀致密,所得Bi2O3/硅藻土复合材料兼具优良的吸附性能和光催化活性及稳定性。
本发明的目的是通过以下技术方案实现的:
1)原矿提纯。高烧失硅藻土原土,经常规方法进行粉碎、水浮选提,得到纯度大于75wt%、平均粒径小于15微米的硅藻土粉体(纯度以非晶态SiO2质量占其高温除碳灼烧品总质量的百分含量计)。
2)湿法氧化处理。将硅藻土粉体加水配制成5~15g/L的溶液,加入溶液体积1.6~6%的浓度为30%的H2O2,水浴温度控制在20℃-90℃范围内,搅拌4~5h,随后再加入溶液体积0.3~2.6%的浓度为30%的H2O2,搅拌4~5h,静置1~1.5h,弃去上层悬浊液,收集下层浆料洗涤、烘干、研磨,得到不同有机质含量的硅藻土。
3)水热复合。称取一定量的铋盐加水配成0.025~0.06mol/L的溶液,搅拌至全部溶解。将步骤2所得的硅藻土加入到铋盐溶液中,使得体系中Bi2O3与硅藻土载体的质量比在0.5~2.5的范围,充分搅拌后,逐滴加入碱性pH调节剂,将体系pH值调整为6~9,持续磁力搅拌1~2h,将料浆转移至密闭反应釜中,在160~200℃保温2~14h。待样品冷却后固液分离,洗涤沉淀,将沉淀在80~100℃下烘干,研磨后得到Bi2O3/硅藻土复合光催化材料。
所述的铋盐限定为:硝酸铋和乙酸铋中的任一种或两种。
有益效果:本发明充分利用高烧失硅藻土高含量有机质,克服了这种类型硅藻土烧失量大,可利用的非晶态蛋白石产率低,煅烧处理过程产生严重的环境污染等问题。本发明在适当的氧化条件下,调控高烧失硅藻土内部有机质的含量及其碳化过程,同时也活化了硅藻土的表面,很大程度的提升了硅藻土表面的吸附作用,并改变了其表面零点电位值。将氧化处理的高烧失硅藻土通过水热过程负载氧化铋,将硅藻土的吸附能力和Bi2O3的可见光催化性能有机的结合在一起,同时由于载体特殊的表面荷电性及吸附性,使得氧化铋在高烧失硅藻土表面直立生长,且形状规则、交错分布、均匀致密,进一步提高了Bi2O3/硅藻土复合光催化剂的吸附性能和可见光催化性能。该方法原料成本低、工艺简单、环境友好、制品分散性好、氧化铋形貌可控、且所得Bi2O3/硅藻土复合光催化剂易回收、可见光催化活性好、性能稳定。
附图说明
图1为实施例1、2、3、4方法中Bi2O3/硅藻土复合光催化剂的X射线衍射图谱;
图2为实施例1、2、3、4方法中Bi2O3/硅藻土复合光催化剂对罗丹明B的光催化降解图谱。
具体实施方式
下面结合实施例作进一步详细说明:
实施例1
1)高烧失硅藻土原土(产地:内蒙古克什克腾旗;烧失量:24.3%),经常规方法进行粉碎,所得硅藻土粉体的平均粒径小于15微米。
2)取2.5g硅藻土粉体并加入500mL去离子水配成5g/L的硅藻土悬浊液,控制水浴温度为30℃,在溶液中分别加入8ml 30%H2O2(溶液体积1.6~6%),搅拌4h,随后再加入2ml30%H2O2(溶液体积0.3~2.6%),搅拌4.5h,静置1.5h,弃去上层悬浊液,收集下层浆料洗涤、烘干、研磨,得到不同有机质含量的硅藻土。
3)称取0.73g五水硝酸铋加60ml水配成0.025mol/L的硝酸铋溶液,搅拌至全部溶解,将步骤2所得的硅藻土称量0.7g,加入到硝酸铋溶液中,充分搅拌后,逐滴添加NaOH溶液,将体系pH值调整为6~6.5,持续搅拌2h,将料浆转移至密闭反应釜中,在160℃保温12h。待样品冷却后固液分离,洗涤沉淀,将沉淀在100℃下烘干,研磨后得到Bi2O3/30℃-硅藻土复合光催化材料。
4)Bi2O3/30℃-硅藻土的复合光催化材料,使Bi2O3在30℃-硅藻土表面充分分散与复合,解决了纳米Bi2O3光催化剂易团聚、附着力差等问题,在可见光下对罗丹明B的降解率达到55%以上,比纯氧化铋提升5%左右。
实施例2
1)高烧失硅藻土原土(产地:内蒙古克什克腾旗;烧失量:20.5%),经常规方法进行粉碎,所得硅藻土粉体的平均粒径小于15微米。
2)取2.5g硅藻土粉体并加入250mL去离子水配成10g/L的硅藻土悬浊液,控制水浴温度为50℃,在溶液中分别加入10ml 30%H2O2,搅拌5h,随后再加入3ml 30%H2O2,搅拌5h,静置1h,弃去上层悬浊液,收集下层浆料洗涤、烘干、研磨,得到不同有机质含量的硅藻土。
3)称取1.46g五水硝酸铋加60ml水配成0.05mol/L的硝酸铋溶液,搅拌至全部溶解,将步骤2所得的硅藻土称量0.35g,加入到硝酸铋溶液中,充分搅拌后,逐滴添加NaOH溶液,将体系pH值调整为8~8.5,持续搅拌1h,将料浆转移至密闭反应釜中,在180℃保温10h。待样品冷却后固液分离,洗涤沉淀,将沉淀在80℃下烘干,研磨后得到Bi2O3/50℃-硅藻土复合光催化材料。
4)Bi2O3/50℃-硅藻土的复合光催化材料,在可见光下对罗丹明B的降解率达到80%以上。比纯氧化铋提升30%左右。而且,8小时内的光催化降解速率均比纯氧化铋快。这是由于Bi2O3/50℃-硅藻土使罗丹明B降解包括Bi2O3/50℃-硅藻土表面Bi2O3光催化降解与50℃-硅藻土的吸附。其中,对罗丹明B降解中光催化占主导作用,相比纯Bi2O3,Bi2O3/50℃-硅藻土的复合光催化材料的光催化性能大幅度提高。
实施例3
1)高烧失硅藻土原土(产地:内蒙古克什克腾旗;烧失量:24.3%),经常规方法进行粉碎,所得硅藻土粉体的平均粒径小于15微米。
2)取3g硅藻土粉体并加入250mL去离子水配成12g/L的硅藻土悬浊液,控制水浴温度为70℃,在溶液中分别加入15ml 30%H2O2,搅拌5h,随后再加入6ml 30%H2O2,搅拌4h,静置1.5h,弃去上层悬浊液,收集下层浆料洗涤、烘干、研磨,得到不同有机质含量的硅藻土。
3)称取1.16g乙酸铋加60ml水配成0.05mol/L的乙酸铋溶液,搅拌至全部溶解,将步骤2所得的硅藻土称量0.7g,加入到乙酸铋溶液中,充分搅拌后,逐滴添加NaOH溶液,将体系pH值调整为7~7.5,持续搅拌1h,将料浆转移至密闭反应釜中,在200℃保温8h。待样品冷却后固液分离,洗涤沉淀,将沉淀在100℃下烘干,研磨后得到Bi2O3/70℃-硅藻土复合光催化材料。
4)Bi2O3/70℃-硅藻土的复合光催化材料,相比纯Bi2O3,Bi2O3/70℃-硅藻土的复合光催化材料的光催化性有所提高。对样品进行光催化测试,Bi2O3/70℃-硅藻土的复合光催化材料,在可见光下对罗丹明B的降解率达到65%以上,比纯氧化铋提升15%左右。
实施例4
1)高烧失硅藻土原土(产地:内蒙古克什克腾旗;烧失量:17.3%),经常规方法进行粉碎,所得硅藻土粉体的平均粒径小于15微米。
2)取7.5g硅藻土粉体并加入500mL去离子水配成15g/L的硅藻土悬浊液,控制水浴温度为90℃,在溶液中分别加入25ml 30%H2O2,搅拌4h,随后再加入10ml 30%H2O2,搅拌5h,静置1h,弃去上层悬浊液,收集下层浆料洗涤、烘干、研磨,得到不同有机质含量的硅藻土。
3)称取1.39g乙酸铋加60ml水配成0.06mol/L的乙酸铋溶液,搅拌至全部溶解,将步骤2所得的硅藻土称量0.34g,加入到乙酸铋溶液中,充分搅拌后,逐滴添加NaOH溶液,将体系pH值调整为8~9,持续搅拌1.5h,将料浆转移至密闭反应釜中,在180℃保温10h。待样品冷却后固液分离,洗涤沉淀,将沉淀在80℃下烘干,研磨后得到Bi2O3/90℃-硅藻土复合光催化剂。
4)对样品进行光催化测试,Bi2O3/90℃-硅藻土的复合光催化材料,在可见光下对罗丹明B的降解率达到70%以上,比纯氧化铋提升20%左右。而且,8小时内的光催化降解速率均比纯氧化铋快。
Claims (3)
1.一种Bi2O3/硅藻土复合光催化材料,其特征在于,所述的复合材料中硅藻土选用烧失量高于15wt%且纯度大于75wt%的高烧失硅藻土(纯度以非晶态SiO2质量占其高温除碳灼烧品总质量的百分含量计)经湿法适度氧化获得,所述的复合材料中Bi2O3纳米片的制备与固载通过铋盐前驱体经一步水热晶化实现,所得Bi2O3片层垂直生长于湿法氧化硅藻土的表面,在复合材料中Bi2O3与硅藻土载体的质量比为0.5~2.5,优选的复合材料中硅藻土载体的质量占比为30~40wt%。
2.按照权利要求1所述的一种Bi2O3/硅藻土复合光催化材料,其特征在于,所述的铋盐前驱体为硝酸铋和乙酸铋中的任一种或两种。
3.按照权利要求1所述的一种Bi2O3/硅藻土复合光催化材料的制备方法,其特征在于,包括以下步骤:
1)高烧失硅藻土原矿,经常规方法进行粉碎、水浮选、烘干,得到纯度大于75wt%的高烧失硅藻土粉体;
2)将高烧失硅藻土粉体加水配制成5~15g/L的溶液,加入溶液体积1.6~6%浓度为30%的H2O2,水浴温度控制在20℃-90℃范围内,搅拌4~5h,随后再加入溶液体积0.3~2.6%浓度为30%的H2O2,搅拌4~5h,静置1~1.5h,收集下层浆料洗涤、烘干、研磨,得到不同程度湿法氧化的硅藻土载体;
3)将铋盐前驱体配成0.025~0.06mol/L的水溶液,加入适量步骤2所得的硅藻土载体,使得体系中Bi2O3与硅藻土载体的质量比在0.5~2.5的范围,充分搅拌后,滴加碱性调节剂,将体系pH值调整为6~9,持续磁力搅拌1~2h,将料浆转移至密闭反应釜中,在160~200℃保温2~14h,冷却后固液分离,洗涤沉淀,烘干研磨得到Bi2O3/硅藻土复合光催化材料。
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CN110560035A (zh) * | 2019-09-16 | 2019-12-13 | 吉林大学 | 一种Bi2O3/蒙脱石复合光催化材料及其制备方法 |
CN113996267A (zh) * | 2021-11-23 | 2022-02-01 | 西南科技大学 | 一种硅基纤维毡-铋基复合材料的制备方法及在放射性碘吸附中的应用 |
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CN114345301A (zh) * | 2022-01-19 | 2022-04-15 | 西南科技大学 | 用于放射性碘气体、气溶胶去除的Bi@纤蛇纹石气凝胶的制备及应用 |
CN114345301B (zh) * | 2022-01-19 | 2023-09-08 | 西南科技大学 | 用于放射性碘气体、气溶胶去除的Bi@纤蛇纹石气凝胶的制备及应用 |
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