CN108816283A - 一种金属负载型复合光催化剂及制备方法和应用 - Google Patents
一种金属负载型复合光催化剂及制备方法和应用 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
一种金属负载型复合光催化剂及制备方法和应用,其中光催化剂是由氧化钛(P25)和一种杂多酸的复合载体共同负载的贵金属组成。该光催化剂的制备方法主要是:将贵金属的盐酸盐溶解后加入聚乙烯醇及硼氢化钠,激烈搅拌,得到贵金属的负载前体溶液,再将氧化钛(P25)和一种杂多酸组成的复合载体加入到贵金属的负载前体溶液中,于80℃烘干得到催化剂。本发明的光催化剂用于清除废水中有机污染物,反应后催化剂可以回收。本发明的光催化剂为具有较高活性的氧化反应催化剂,具有高的稳定性。反应条件温和,反应效率很高。该催化剂用空气作为氧化剂,对废水中有机污染物的消除反应表现出很高活性,降解率可达90%以上。
Description
技术领域
本发明涉及一种光催化剂及制备方法和应用。
背景技术
随着人们生活水平和经济的快速发展,环境污染的问题也越来越严重。特别是水体污染,水体污染是指水体因某种物质的介入,超过了水体的自净能力,导致其物理、化学、生物等方面特征的改变,从而影响到水的利用价值,危害人体健康或破坏生态环境,造成水质恶化的现象,水体污染可分为化学型污染、物理型污染和生物型污染三种类型。有机化合物引起的环境污染,特别是人工合成的有机物,如染料、工业废水(如苯酚)等,一旦进入水体,当含有大量氮、磷等植物营养物质的生活污水、农田排水连续排入湖泊、水库、河水等处的缓流水体时,造成水中营养物质过剩,便发生富营养化现象,导致藻类大量繁殖,水的透明度降低,失去观赏价值。同时,由于藻类繁殖迅速,生长周期短,不断死亡,并被好氧微生物分解,消耗水中的溶解氧;也可被厌氧微生物分解,产生硫化氢等有害物质。从以上两方面造成水质恶化,鱼类和其他水生生物大量死亡。而利用半导体光催化氧化技术可以很好的降解有机物污染物引起的化学污染,而且这种方法具有普适性,节约能源和无二次污染的特点,使得半导体材料的光催化技术在诸多环境污染的治理技术方面是最有前途的方法之一。其中,TiO2是研究最广泛的光催化剂之一,主要是由于它具有较高的化学稳定性,无毒无害,较高的光电转换效率,成本低活性高的优点。纳米TiO2(P25)等光催化材料,甚至生物技术与光催化技术结合共同进行污水处理(Peternel I.T.et.al.,J.Hazard.Mater.,2007,148,477–484;Annadurai G.et.al.,J.Hazard.Mater.,2002,92,263–274;BaeE.et.al.,Environ.Sci.Technol.,2003,37,147–152),在西方国家尤其是日本,光催化功能材料的商品化研究开发特别快,已经有大量的相关产品开发成功并推向市场。但是由于TiO2本身存在不足之处,如利用太阳能的效率比较低,为了提高TiO2的光催化活性以及提高对太阳能的利用率,对TiO2进行改性研究,在一边将它的吸收光谱向红光方向移动的同时还致力于开发出一些复合光催化剂材料。总体上光生电子和空穴快速复合使得光催化效率受到了限制。
发明内容
本发明的目的在于提供一种利于反应分子扩散的、环境友好、工艺简单、易于回收的金属负载型复合光催化剂及制备方法和应用。
为实现上述目的,本发明采用的技术方案为:
1.一种金属负载型复合光催化剂,它是由氧化钛(P25)和一种杂多酸的复合载体共同负载的贵金属组成,其中氧化钛(P25)和一种杂多酸的质量比为1:3-3:1;贵金属和复合载体的质量比为1:1000-1:50,所述的贵金属选自Au、Pt、Pd中的一种,杂多酸是含有Co,W,Sn等金属的杂多金属氧酸盐CoW11O39SnOH8。
2、金属负载型复合光催化剂的制备方法:
a)将氧化钛(P25)和杂多酸以质量比为1:3-3:1混合,在室温下水中剧烈搅拌2h(转速1000转/分钟),过滤,于80℃干燥,得到氧化钛(P25)和一种杂多酸组成的复合载体;
b)将贵金属的盐酸盐用去离子水溶解,浓度为0.1-1mmol/L,加入表面活性剂聚乙烯醇,聚乙烯醇与贵金属的质量比为0.5:1-3:1;再加入硼氢化钠,硼氢化钠与贵金属的质量比为0.5:1-3:1,室温下激烈搅拌2h,得到贵金属的负载前体溶液;
c)将步骤a)得到的复合载体加入到步骤b)得到的金属MI的负载前体溶液中,贵金属和复合载体的质量比为1:1000-1:50;室温下搅拌3h,过滤洗涤,于80℃烘干。
3、金属负载型复合光催化剂作为消除废水中有机污染物的应用,其操作步骤具体如下:将本发明光催化剂加入到有机污染物的溶液中,其中,催化剂与污染物的质量比为125:1,常压下,暴露于空气中,于10℃,光源为300W氙灯,光照下,搅拌反应30-300min,停止反应,分离回收催化剂。
本发明所涉及的有机污染物为罗丹明B、甲基橙、苯酚等污染物中的一种的含有有机污染物废水。
本发明与现有技术相比具有以下优点:
1.本发明设计合成了一种金属担载量较低的金属负载型催化剂,制备出具有较高活性的氧化反应催化剂,环境友好,可回收利用,具有高的稳定性。
2.该催化剂用空气作为氧化剂,对废水中有机污染物(苯酚、染料等)的消除反应表现出很高活性。反应条件温和,工艺流程简单,染料及苯酚的降解率可达90%以上。
具体实施方式
为了进一步说明本发明,列举以下实施实例,但它并不限制各附加权利要求所定义的发明范围。
实施例1
将氧化钛(P25)和杂多酸CoW11O39SnOH8,混合后在室温下水中剧烈搅拌2h
(转速1000转/分钟),其中氧化钛(P25)和CoW11O39SnOH8的质量比为1:3,过滤,于80℃干燥得到氧化钛(P25)和CoW11O39SnOH8组成的复合载体;将HAuCl4用去离子水溶解,浓度为0.1mmol/L,加入试剂聚乙烯醇,聚乙烯醇与Au的质量比为0.5:1,再加入试剂NaBH4,NaBH4与Au的质量比:0.5:1,室温下激烈搅拌2h,得到金属Au的负载前体溶液;
将得到的氧化钛(P25)和CoW11O39SnOH8组成复合载体加入到Au的负载前体溶液中,Au和氧化钛(P25)和CoW11O39SnOH8组成复合载体的质量比为1:1000;室温下搅拌3h,过滤洗涤,于80℃烘干,称为催化剂A。
实施例2
其余操作条件同实施例1,只是在制备复合载体时,氧化钛(P25)和一种杂多酸的质量比为1:1,最终得到催化剂B。
实施例3
制备复合载体时,氧化钛(P25)和一种杂多酸的质量比为3:1,其余操作步骤同实施例1,称为催化剂C。
实施例4
将HAuCl4用去离子水溶解,浓度为0.5mmol/L,其余操作步骤同实施例1,称为催化剂D。
实施例5
将HAuCl4用去离子水溶解,浓度为1mmol/L,其余操作步骤同实施例1,称为催化剂E。
实施例6
聚乙烯醇与Au的质量比为2:1,其余操作步骤同实施例1,称为催化剂F。
实施例7
聚乙烯醇与Au的质量比为3:1,其余操作步骤同实施例1,称为催化剂G。
实施例8
NaBH4与Au的质量比:2:1,其余操作步骤同实施例1,称为催化剂H。
实施例9
NaBH4与Au的质量比:3:1,其余操作步骤同实施例1,称为催化剂I。
实施例10
将得到的复合载体加入到Au的负载前体溶液中,Au和复合载体的质量比为1:500,其余操作步骤同实施例1,称为催化剂J。
实施例11
将得到的复合载体加入到Au的负载前体溶液中,Au和复合载体的质量比为1:200,其余操作步骤同实施例1,称为催化剂K。
实施例12
将得到的复合载体加入到Au的负载前体溶液中,Au和复合载体的质量比为1:50,其余操作步骤同实施例1,称为催化剂L。
实施例13
进行光催化氧化实验:
(1)将20mg催化剂A加入20ml 8mg/L罗丹明B溶液中,常压下,暴露于空气中,于10℃,光源(氙灯,300W)光照下,搅拌反应300min,停止反应,分离回收催化剂;
(2)将上述处理溶液离心分离回收催化剂,在UV-Vis分光光度计中检测,罗丹明B脱除率为80%。
实施例14
选用催化剂B,并且其加入量为20mg,甲基橙代替罗丹明B,其余操作条件同实施例13。应用结果UV-Vis分光光度计中检测,甲基橙脱除率为85.3%。
实施例15
选用催化剂C,并且其加入量为20mg,其余操作条件同实施例13。应用结果UV-Vis分光光度计中检测,罗丹明B脱除率为89.8%。
实施例16
选用催化剂D,并且其加入量为20mg,甲基橙代替罗丹明B,其余操作条件同实施例13。应用结果UV-Vis分光光度计中检测,甲基橙脱除率为90%。
实施例17
选用催化剂E,并且其加入量为20mg,苯酚代替罗丹明B,反应时间为300分钟,其余操作条件同实施例13。应用结果UV-Vis分光光度计中检测,苯酚脱除率为100%。
实施例18
选用催化剂F,并且其加入量为20mg,苯酚代替罗丹明B,反应时间为30分钟,其余操作条件同实施例13。应用结果UV-Vis分光光度计中检测,苯酚脱除率为95.3%。
实施例19
选用催化剂G,并且其加入量为20mg,苯酚代替罗丹明B,反应时间为60分钟,其余操作条件同实施例13,应用结果UV-Vis分光光度计中检测,苯酚脱除率为80.1%。
实施例20
选用催化剂H,其余操作条件同实施例13,应用结果在UV-Vis分光光度计中检测,罗丹明B脱除率为91%。
实施例21
选用催化剂I,其余操作条件同实施例13,应用结果在UV-Vis分光光度计中检测,罗丹明B脱除率为95%。
实施例22
选用催化剂J,其余操作条件同实施例13,应用结果在UV-Vis分光光度计中检测,罗丹明B脱除率为93%。
实施例23
选用催化剂K,其余操作条件同实施例16,应用结果在UV-Vis分光光度计中检测,甲基橙脱除率为91%。
实施例24
选用催化剂L,其余操作条件同实施例18,应用结果在UV-Vis分光光度计中检测,苯酚脱除率为90.3%。
实施例25
将HPtCl4代替HAuCl4,其余操作步骤同实施例1,称为催化剂M。
实施例26
将Pd(NO3)3代替HAuCl4,其余操作步骤同实施例1,称为催化剂N。
实施例27
选用催化剂M,反应120分钟,其余操作条件同实施例13。应用结果在UV-Vis分光光度计中检测,罗丹明B脱除率为89.5%。
实施例28
选用催化剂N,反应120分钟,其余操作条件同实施例16。应用结果在UV-Vis分光光度计中检测,甲基橙脱除率为90%。
通过以上所有实施例,催化剂在温和条件下在染料及苯酚等污染物的光催化氧化反应中表现出了高活性,并且所有催化剂可以重复使用。反应后催化剂可以通过静置或者离心分离回收得到。
Claims (4)
1.一种金属负载型复合光催化剂,其特征在于:它是由氧化钛(P25)和一种杂多酸的复合载体共同负载的贵金属组成,其中氧化钛(P25)和一种杂多酸的质量比为1:3-3:1;贵金属和复合载体的质量比为1:1000-1:50,所述的贵金属选自Au、Pt、Pd中的一种,杂多酸是含有Co,W,Sn金属的杂多金属氧酸盐CoW11O39SnOH8。
2.权利要求1所述的金属负载型复合光催化剂的制备方法,其特征在于:
a)将氧化钛(P25)和杂多酸以质量比为1:3-3:1混合,在室温下水中剧烈搅拌2h,转速1000转/分钟,过滤,于80℃干燥,得到氧化钛(P25)和一种杂多酸组成的复合载体;
b)将贵金属的盐酸盐用去离子水溶解,浓度为0.1-1mmol/L,加入表面活性剂聚乙烯醇,聚乙烯醇与贵金属的质量比为0.5:1-3:1;再加入硼氢化钠,硼氢化钠与贵金属的质量比为0.5:1-3:1,室温下激烈搅拌2h,得到贵金属的负载前体溶液;
c)将步骤a)得到的复合载体加入到步骤b)得到的金属MI的负载前体溶液中,贵金属和复合载体的质量比为1:1000-1:50;室温下搅拌3h,过滤洗涤,于80℃烘干。
3.权利要求1所述的金属负载型复合光催化剂作为消除废水中有机污染物的应用,其操作步骤具体如下:将本发明光催化剂加入到有机污染物的溶液中,其中,催化剂与污染物的质量比为125:1,常压下,暴露于空气中,于10℃,光源为300W氙灯,光照下,搅拌反应30-300min,停止反应,分离回收催化剂。
4.根据权利要求1所述的金属负载型复合光催化剂作为消除废水中有机污染物的应用,其所涉及的有机污染物为罗丹明B、甲基橙、苯酚等污染物中的一种含有有机污染物废水。
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