CN110227526A - 氧化铋/碳酸氧铋/钼酸铋复合光催化材料及其制备方法 - Google Patents
氧化铋/碳酸氧铋/钼酸铋复合光催化材料及其制备方法 Download PDFInfo
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- CN110227526A CN110227526A CN201910555108.XA CN201910555108A CN110227526A CN 110227526 A CN110227526 A CN 110227526A CN 201910555108 A CN201910555108 A CN 201910555108A CN 110227526 A CN110227526 A CN 110227526A
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- Prior art keywords
- bismuth
- bismuth molybdate
- bismuthyl carbonate
- composite photocatalyst
- bismuth oxide
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- 239000000463 material Substances 0.000 title claims abstract description 115
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 63
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 62
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 61
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 10
- 239000004809 Teflon Substances 0.000 claims description 10
- 229920006362 Teflon® Polymers 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 36
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 12
- 238000000926 separation method Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 230000015556 catabolic process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 3
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 241001198704 Aurivillius Species 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
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- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
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- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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Abstract
本发明公开了一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料,包括钼酸铋光催化材料,该钼酸铋光催化材料的表面通过Na2CO3协助和焙烧引入碳酸氧铋和氧化铋纳米片。本发明还公开了该氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:步骤1,制备钼酸铋基催化材料;步骤2,通过Na2CO3协助和焙烧将碳酸氧铋和氧化铋纳米片引入步骤1得到的钼酸铋基催化材料的表面,制备得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。该材料无团聚,可见光响应范围宽,催化活性相比纯钼酸铋显著提高,重复使用性能良好,且制备工艺简单,条件温和,可控性好,操作方便。
Description
技术领域
本发明属于工业催化制备技术领域,特别是涉及一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料,还涉及一种该氧化铋/碳酸氧铋/钼酸铋复合光催化材料及其制备方法。
背景技术
Bi2MoO6(钼酸铋)作为一种结构最为简单的Aurivillius(奥里维里斯),是由(Bi2O2)2+层和(MoO4)2-层交替叠合构成层状结构的复合氧化物,Bi2MoO6的价带是由Bi6s和O2p轨道杂化而成,导带是Mo3d轨道形成,其禁带宽度约为2.5~2.8eV,最大吸收波长大约为490nm,可以吸收部分可见光而被激发,因此,Bi2MoO6光催化材料的研究和开发将为提高太阳光的利用率提供新的思路,在环境净化和新能源开发领域具有潜在的应用价值,已成为目前广泛研究的光催化剂之一。然而,Bi2MoO6仍然存在可见光响应较窄,光生电子-空穴对易于复合、寿命较短和迁移速率较慢等缺陷,极大地限制了Bi2MoO6光催化材料的实际应用。针对Bi2MoO6光催化材料存在的缺陷或者不足,采用改性策略对其改性,继而开发出可见光催化活性高且性能稳定的新材料是实际应用的关键。
发明内容
本发明的第一个目的是提供一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料,该材料具有良好的可见光响应性能,并且能够促进光生电子-空穴对的分离,因此解决钼酸铋可见光催化活性不高的问题。
本发明的第二个目的是提供一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,用以制造上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
为了实现上述第一个目的,本发明所采用的技术方案是,一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料,包括钼酸铋,钼酸铋的表面通过Na2CO3协助和焙烧引入有碳酸氧铋和氧化铋纳米片。
为了实现上述第二个目的,本发明所采用的第二种技术方案是,一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1,制备钼酸铋光催化材料;
步骤2,通过Na2CO3协助和焙烧将碳酸氧铋和氧化铋纳米片引入步骤1得到的钼酸铋光催化材料的表面,制备得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
本发明的第二种技术方案,还具有以下特点:
所述步骤1具体包括:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中进行反应得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤和真空干燥处理后得到钼酸铋光催化材料。
在所述步骤1.2中,在电热恒温鼓风干燥箱中进行反应的温度为160℃,时间为12h。
在所述步骤1.2中,进行真空干燥处理的温度为60℃,时间为5h。
在所述步骤1.2中,所述反应釜为内衬特氟龙的不锈钢反应釜。
所述步骤2具体包括:
步骤2.1,先将步骤1得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.2,对步骤2.1制备得到的混合溶液B中滴加Na2CO3溶液,得到混合溶液C,其中Na2CO3与钼酸铋光催化材料的摩尔比为不大于0.3:1;
步骤2.3,对步骤2.2制备得到的混合溶液C进行恒温真空干燥,直到将水蒸干,待恒温真空干燥结束后将混合溶液C进行焙烧,最后采用蒸馏水进行水洗若干次,目的去除残留的Na2CO3溶液,于60℃下真空干燥处理5h后,最终得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
在所述步骤2.3中,进行恒温真空干燥的温度为50℃-70℃,时间为6h-8h。
在所述步骤2.3中,进行焙烧的温度为200℃-400℃,时间为1h-3h。
本发明的有益效果是:通过本发明的一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法得到的氧化铋/碳酸氧铋/钼酸铋复合光催化材料,无团聚,可见光响应范围宽,催化活性相比纯钼酸铋显著提高,重复使用性能良好,且制备工艺简单,条件温和,可控性好,操作方便。
附图说明
图1是钼酸铋光催化材料和本发明的制备方法获得的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的X射线粉末衍射图;
图2是钼酸铋光催化材料和本发明的制备方法获得的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的扫描电镜图;
图3是钼酸铋光催化材料和本发明的制备方法获得的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的TEM图;
图4是钼酸铋光催化材料和本发明的制备方法获得的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的固体紫外-可见吸收光谱图;
图5是钼酸铋光催化材料和本发明的制备方法获得的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的可见光催化活性对比图;
图6是钼酸铋光催化材料和本发明的制备方法不同焙烧温度获得氧化铋/碳酸氧铋/钼酸铋复合光催化材料的可见光催化活性对比图。
图7为钼酸铋光催化材料和本发明的制备方法不同焙烧温度获得氧化铋/碳酸氧铋/钼酸铋复合光催化材料去除苯酚中总有机碳(TOC)的浓度对比图。
图8是本发明的制备方法获得的氧化铋/碳酸氧铋/钼酸铋复合光催化材料使用4次后的可见光催化活性对比图和X射线粉末衍射图。
图中,BMO代表对比实施例1所得的钼酸铋光催化材料,BMO-N0代表对比实施例2中得到的焙烧后的钼酸铋光催化材料,Etched BMO-2代表对比实施例3中得到的刻蚀钼酸铋光催化材料,BMO-1代表实施例1中得到的氧化铋/碳酸氧铋/钼酸铋复合光催化材料,BMO-2代表实施例2中得到的氧化铋/碳酸氧铋/钼酸铋复合光催化材料。BMO-3代表实施例3中得到的氧化铋/碳酸氧铋/钼酸铋复合光催化材料,BMO-4代表实施例4中得到的氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
具体实施方式
以下结合附图说明和具体实施例对本发明的技术方案作进一步地详细说明。
本发明的一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料,包括钼酸铋,钼酸铋的表面通过Na2CO3协助和焙烧引入有碳酸氧铋和氧化铋纳米片。
本发明的一种上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入内衬特氟龙的不锈钢反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中,于160℃下进行反应12h得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤后,于60℃下真空干燥处理5h后得到钼酸铋光催化材料;
步骤2.1,先将步骤1.2得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.2,对步骤2.1制备得到的混合溶液B中滴加Na2CO3溶液,得到混合溶液C,其中Na2CO3与钼酸铋光催化材料的摩尔比为不大于0.3:1;
步骤2.3,在50℃-70℃下对步骤2.2制备得到的混合溶液C进行恒温真空干燥6h-8h,直到将水蒸干,待恒温真空干燥结束后将混合溶液C在200℃-400℃下进行1h-3h的焙烧,最后采用蒸馏水进行水洗若干次,目的去除残留的Na2CO3溶液,于60℃下真空干燥处理5h后,最终得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
实施例1
本发明的一种上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入内衬特氟龙的不锈钢反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中,于160℃下进行反应12h得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤后,于60℃下真空干燥处理5h后得到钼酸铋光催化材料;
步骤2.1,先将步骤1.2得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.2,对步骤2.1制备得到的混合溶液B中滴加Na2CO3溶液,得到混合溶液C,其中Na2CO3与钼酸铋光催化材料的摩尔比为0.086:1;
步骤2.3,在50℃下对步骤2.2制备得到的混合溶液C进行恒温真空干燥6h,直到将水蒸干,待恒真空干燥结束后将混合溶液C在200℃下进行1h的焙烧,最后采用蒸馏水进行水洗若干次,目的去除残留的Na2CO3溶液,于60℃下真空干燥处理5h后,最终得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
实施例2
本发明的一种上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入内衬特氟龙的不锈钢反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中,于160℃下进行反应12h得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤后,于60℃下真空干燥处理5h后得到钼酸铋光催化材料;
步骤2.1,先将步骤1.2得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.2,对步骤2.1制备得到的混合溶液B中滴加Na2CO3溶液,得到混合溶液C,其中Na2CO3与钼酸铋光催化材料的摩尔比为0.115:1;
步骤2.3,在60℃下对步骤2.2制备得到的混合溶液C进行恒温真空干燥7h,直到将水蒸干,待恒温真空干燥结束后将混合溶液C在250℃下进行2h的焙烧,最后采用蒸馏水进行水洗若干次,目的去除残留的Na2CO3溶液,于60℃下真空干燥处理5h后,最终得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
实施例3
本发明的一种上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入内衬特氟龙的不锈钢反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中,于160℃下进行反应12h得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤后,于60℃下真空干燥处理5h后得到钼酸铋光催化材料;
步骤2.1,先将步骤1.2得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.2,对步骤2.1制备得到的混合溶液B中滴加Na2CO3溶液,得到混合溶液C,其中Na2CO3与钼酸铋光催化材料的摩尔比为0.144:1;
步骤2.3,在65℃下对步骤2.2制备得到的混合溶液C进行恒温真空干燥7h,直到将水蒸干,待恒温真空干燥结束后将混合溶液C在300℃下进行3h的焙烧,最后采用蒸馏水进行水洗若干次,目的去除残留的Na2CO3溶液,于60℃下真空干燥处理5h后,最终得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
实施例4
本发明的一种上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入内衬特氟龙的不锈钢反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中,于160℃下进行反应12h得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤后,于60℃下真空干燥处理5h后得到钼酸铋光催化材料;
步骤2.1,先将步骤1.2得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.2,对步骤2.1制备得到的混合溶液B中滴加Na2CO3溶液,得到混合溶液C,其中Na2CO3与钼酸铋光催化材料的摩尔比为0.230:1;
步骤2.3,在70℃下对步骤2.2制备得到的混合溶液C进行恒温真空干燥8h,直到将水蒸干,待恒温真空干燥结束后将混合溶液C在400℃下进行3h的焙烧,最后采用蒸馏水进行水洗若干次,目的去除残留的Na2CO3溶液,于60℃下真空干燥处理5h后,最终得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
对比实施例1
为了方便对比,针对实施例2进行改进本发明的一种上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入内衬特氟龙的不锈钢反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中,于160℃下进行反应12h得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤后,于60℃下真空干燥处理5h后得到钼酸铋光催化材料;
对比实施例2
为了方便对比,针对实施例2进行改进本发明的一种上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入内衬特氟龙的不锈钢反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中,于160℃下进行反应12h得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤后,于60℃下真空干燥处理5h后得到钼酸铋光催化材料;
步骤2.1,先将步骤1.2得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.3,在60℃下对步骤2.1制备得到的混合溶液B进行恒温真空干燥7h,直到将水蒸干,待恒温真空干燥结束后将混合溶液C在250℃下进行2h的焙烧,最终得到焙烧后的钼酸铋光催化材料。
对比实施例3
为了方便对比,针对实施例2进行改进本发明的一种上述氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中再加入无水乙醇并搅拌均匀,然后再将其转入内衬特氟龙的不锈钢反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中,于160℃下进行反应12h得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤后,于60℃下真空干燥处理5h后得到钼酸铋光催化材料;
步骤2.1,先将步骤1.2得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.2,对步骤2.1制备得到的混合溶液B中滴加Na2CO3溶液,得到混合溶液C,其中Na2CO3与钼酸铋光催化材料的摩尔比为0.115:1;
步骤2.3,在60℃下对步骤2.2制备得到的混合溶液C进行恒温真空干燥7h,直到将水蒸干,待恒温真空干燥结束后,最后采用蒸馏水进行水洗若干次,目的去除残留的Na2CO3溶液,于60℃下真空干燥处理5h后,最终得到刻蚀钼酸铋光催化材料。
图1为BMO和BMO-2的粉末衍射图。从图1中可以看出BMO-2中出现的XRD特征衍射峰和BMO几乎一样,表明低温焙烧并不影响BMO的晶体结构。此外可以看出一系列新的特征衍射峰的出现,表明了(BiO)2CO3和Bi2O3的存在。
图2为BMO和BMO-2的扫描电镜图,其中(a)、(b)和(c)表示BMO,(b)、(c)是(a)的放大图,(d)、(e)和(f)表示BMO-2,(e)、(f)是(d)的放大图。由图2中的(a)、(b)和(c)可以看出,BMO是由大量的纳米片组装而成的三维球形分级结构,平均直径为1μm~2μm,而纳米片的厚度大约为10nm-20nm(图(c));由图2中(d)、(e)和(f)可以看出,BMO-2的形貌和尺寸与BMO基本相同,同时观察到BMO表面生成了(BiO)2CO3和Bi2O3超薄纳米片(图(e)和(f))。
图3中(a)表示BMO的TEM照片;(b)表示BMO的HR-TEM照片;(c)和(e)表示BMO-2的TEM照片;(d)和(f)表示BMO-2的HR-TEM图。由图3中的(a)、(c)和(e)可以看出,BMO和BMO-2是三维微球结构。由图3中的(c)和(e)可以看出,BMO-2是BMO三维微球结构、(BiO)2CO3和Bi2O3超薄纳米片组成。由图3中的(d)和(f)可以看出,晶面间距为0.315nm、0.27nm和0.32nm分别于正交晶系BMO的(131)晶面间距、(BiO)2CO3的(110)晶面间距和Bi2O3的(120)晶面间距相对应(曲线标记的部分),结果表明了Bi2O3/(BiO)2CO3/Bi2MoO6复合光催化材料成功制备。
图4为BMO和BMO-2的固体紫外-可见吸收光谱。从图4中可以看出,BMO的吸收边约为490nm,而BMO-2光催化材料表现出了与BMO相似的吸收边缘,带隙稍微变宽。
本发明制备的氧化铋/碳酸氧铋/钼酸铋复合光催化材料可用于苯酚的光催化降解。苯酚,又称石炭酸(Carbolic acid),是一种常见的化学品,是生产某些树脂、杀菌剂、防腐剂以及药物(如阿司匹林)的重要原料,并且是高分子芳香族碳氢化合物氧化的主要中间产物。含酚废水的来源非常广泛,主要来自于煤化工、石油化工、农药、酚醛树脂和焦化等企业,化工和炼油等行业的废水中酚类浓度均大于1000mg/L,此类废水中的酚类用常规的水处理方法很难去除,对人类健康和生态平衡构成了严重的威胁。酚类物质可以经过皮肤、口腔、呼吸道和粘膜进入体内,抑制中枢神经系统,损害肝和肾,吸入高浓度蒸汽可致头晕、头痛、乏力、视觉模糊和肺水肿等。人体摄入过量苯酚,可引起中毒,甚至死亡,严重威胁人类健康及生存环境。含酷废水不仅会对人类的健康造成严重威胁,也会对动植物产生危害。水中含酌含量达到时,鱼类就会出现中毒症状,超过时会引起鱼类大量死亡,甚至绝迹。含酷废水的毒性还可抑制水体中其它生物的自然生长速度,破坏生态平衡。因此,在我国地面水中规定挥发酌的最高允许浓度为0.1毫克升(V类水)。我国生活饮用水水质标准中规定挥发酣类不超过0.002毫克升。因此,对于人类、动植物的健康和环境的保护来说,能够有效去除废水中的酚类物质具有重要意义。
实验条件如下:将苯酚溶于水配制浓度为10mg·L-1的降解液,加入催化剂粉体(浓度为1000mg·L-1),并将其置于黑暗中搅拌30min达到吸附平衡后,将光降解液置于光催化反应装置中进行光照,实验光源为金卤灯,模拟可见光(发射光谱380~800nm,加滤光片过滤掉420nm以下的光)。每隔30min取样离心,取上层清液,采用4-氨基安替比林分光光度法,于最大吸收波长507nm处测定苯酚的吸光度,采用光度法测定浓度变化,并以此来评价催化剂的光催化活性。
图5中(a)表示降解过程中苯酚的浓度变化,(b)表示苯酚的降解表观速率常数。由图5中的(a)可以看出,BMO-2的光催化活性最高,BMO的光催化活性最低,光照180min后,苯酚降解率分别为98.8%和3.71%。
图6中(a)表示不同焙烧温度获得氧化铋/碳酸氧铋/钼酸铋复合光催化材料降解过程中苯酚的浓度变化,(b)表示苯酚的降解表观速率常数。由图6中的(a)可以看出,250℃焙烧获得氧化铋/碳酸氧铋/钼酸铋复合光催化材料的光催化活性最高。
图7为BMO和BMO-2去除苯酚中总有机碳(TOC)的浓度变化。由图7可以看出,BMO-2的光催化去除苯酚中总有机碳(TOC)的效率最高,BMO的光催化效率最低,光照180min后,TOC降解率分别为67.50%和2.53%,结果表明,光催化降解苯酚的主要产物为CO2和H2O。
图8中(a)表示BMO-2使用4次后的可见光催化活性对比图,(b)表示BMO-2使用4次后的粉末衍射图。由图8可以看出,重复使用4次后,BMO-2的活性略有下降,说明该材料性能稳定,有良好的重复使用性。
Claims (9)
1.一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料,其特征在于,包括钼酸铋,钼酸铋的表面通过Na2CO3协助和焙烧引入有碳酸氧铋和氧化铋纳米片。
2.一种氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,其特征在于,具体按照以下步骤实施:
步骤1,制备钼酸铋光催化材料;
步骤2,通过Na2CO3协助和焙烧将碳酸氧铋和氧化铋纳米片引入步骤1得到的钼酸铋光催化材料的表面,制备得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
3.根据权利要求2所述的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,其特征在于,所述步骤1具体包括:
步骤1.1,按照2:1的摩尔比分别量取Bi(NO3)3·5H2O和Na2MoO4·2H2O,先将量取的Bi(NO3)3·5H2O溶解于乙二醇溶液中,然后再向乙二醇溶液中加入量取的Na2MoO4·2H2O,最后进行搅拌直至得到透明溶液;
步骤1.2,先向步骤1.1得到的透明溶液中加入无水乙醇并搅拌均匀,然后再将其转入反应釜内密封,之后再将反应釜放入电热恒温鼓风干燥箱中进行反应得到混合溶液A,待反应结束后将混合溶液A自然冷却至室温,再经离心分离、洗涤和真空干燥处理后得到钼酸铋光催化材料。
4.根据权利要求3所述的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,其特征在于,在所述步骤1.2中,在电热恒温鼓风干燥箱中进行反应的温度为160℃,时间为12h。
5.根据权利要求4所述的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,其特征在于,在所述步骤1.2中,进行真空干燥处理的温度为60℃,时间为5h。
6.根据权利要求5所述的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,其特征在于,在所述步骤1.2中,所述反应釜为内衬特氟龙的不锈钢反应釜。
7.根据权利要求3所述的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,其特征在于,所述步骤2具体包括:
步骤2.1,先将步骤1得到的钼酸铋光催化材料制成粉体状,之后再将其分散于去离子水中并进行超声处理,得到混合溶液B;
步骤2.2,对步骤2.1制备得到的混合溶液B中滴加Na2CO3溶液,得到混合溶液C,其中Na2CO3与钼酸铋光催化材料的摩尔比为不大于0.3:1;
步骤2.3,对步骤2.2制备得到的混合溶液C进行恒温真空干燥,直到将水蒸干,待恒温真空干燥结束后将混合溶液C进行焙烧,最后采用蒸馏水进行水洗若干次,目的去除残留的Na2CO3溶液,于60℃下真空干燥处理5h后,最终得到氧化铋/碳酸氧铋/钼酸铋复合光催化材料。
8.根据权利要求7所述的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,其特征在于,在所述步骤2.3中,进行恒温真空干燥的温度为50℃-70℃,时间为6h-8h。
9.根据权利要求4所述的氧化铋/碳酸氧铋/钼酸铋复合光催化材料的制备方法,其特征在于,在所述步骤2.3中,进行焙烧的温度为200℃-400℃,时间为1h-3h。
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