CN110304659A - 一种wo3纳米线及其制备方法与应用 - Google Patents
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with 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
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
本发明涉及光催化材料技术领域,尤其涉及一种WO3纳米线及其制备方法与应用。本发明公开了一种WO3纳米线。本发明中,具有氧缺空位的非化学计量三氧化钨(W18O49)无毒,良好的化学稳定性,能更高效的吸收可见光和近红外光,具备较高的可见光催化活性,且W18O49直径小,可以组装孔径更小的高性能膜。另外,将钨酸与有机溶剂进行混合并超声处理,使得有机溶剂进入钨酸的层间,然后剥离剂通过中和反应除去过量的有机溶剂,在溶剂热的反应下,剥离剂进一步与钨酸层间的有机溶剂发生反应,剥离钨酸,使得钨酸剥离成更高浓度的WO6,有利于成核,并使得钨酸沿着一维方向结晶成超长超细的纳米线。
Description
技术领域
本发明涉及光催化材料技术领域,尤其涉及一种WO3纳米线及其制备方法与应用。
背景技术
日益严重的水资源短缺和水环境污染影响人民生活并且成为制约社会经济可持续发展的主要因素。膜分离技术是一种新兴的高效分离净化技术,在水处理领域有着无可比拟的优势。目前广泛使用的聚合物膜容易吸附有机污染物从而导致滤孔堵塞,导致水通量降低以及消耗更多的能源从而提高水处理成本;而且聚合物膜只能浓缩污染物需要进一步的后处理来清除污染物。相对于聚合物膜,无机光催化陶瓷膜具有更优异的热、化学和机械稳定性,同时兼具光催化降解污染物的功能近年来引发广泛关注。
目前无机光催化膜用在水处理中的主要是二氧化钛相关的光催化膜,可以有效的防止滤孔堵塞,同时具备杀菌,吸附重金属,降解污染物等多种优点。但是常用的二氧化钛纳米线的直径较大(100nm左右),目前只能组装到孔径50纳米的超滤膜,分离效率有限,只能过滤细菌和一些尺寸比较大的污染物,以及吸附少量的有机污染物,制约了其进一步的应用。而1-10纳米的纳滤膜就可以有效地截流住有机污染物,并且通过光催化的方法降解有机污染物,防止污染物堆积堵塞膜孔,造成膜污染。1-10纳米的纳滤膜还可以截流离子,用于海水淡化。想要得到孔径小于10纳米甚至1纳米的无滤孔堵塞的无机光催化膜,必须要合成微米长度且直径3纳米以下超细纳米线。
发明内容
本发明提供了一种WO3纳米线及其制备方法与应用,解决了二氧化钛纳米线的直径较大,且只能利用紫外光催化处理污染物的问题。
其具体技术方案如下:
本发明提供了一种WO3纳米线,所述W18O49纳米线的直径为1~10nm,优选为3nm,长度为0.5~10μm,优选为1.5μm。
三氧化钨类材料具有无毒,良好的化学稳定性,以及有相对窄的带隙可以利用波长小于450nm可见光等优点,而具有氧缺空位的非化学计量三氧化钨(W18O49)能更高效的吸收可见和近红外光,具备较高的可见光催化活性,且W18O49直径小,可以组装孔径更小的高性能膜。
所述W18O49纳米线由以下制备方法制得:
步骤1:将所述钨酸与有机溶剂进行混合,超声处理,得到钨酸混合物;
步骤2:将所述钨酸混合物与剥离剂混合,进行溶剂热反应,得到W18O49纳米线。需要说明的是,采用六氯化钨、乙氧基钨和羰基钨在胺配体保护下由下至上合成可以得到直径1-3纳米的超细W18O49纳米棒及纳米线,然而长度最大只有700nm,很难满足抽滤成高性能膜的实际操作需要,而且这些前驱体昂贵有毒,难以用于大规模可控合成W18O49纳米线。另外,采用钨酸氨水热法等只能得到直径20-43nm长达数微米的W18O49纳米线,难以得到超细W18O49纳米线。而将钨酸与有机溶剂进行混合并超声处理,使得有机溶剂进入钨酸的层间,然后剥离剂通过中和反应除去过量的有机溶剂,在溶剂热的反应下,剥离剂进一步与钨酸层间的有机溶剂发生反应,剥离钨酸,使得钨酸剥离成更高浓度的WO6单元,有利于WO6互相连接形成小小的W18O49晶核,在有机胺配体粘附在周围进行保护,导致晶核只能沿着棒核的两头增长,迅速结晶成超长超细的W18O49纳米线,较现有W18O49纳米线,本申请提供的W18O49纳米线长度和直径大大降低。而且分解长成的纳米线是非化学计量比的,含有氧缺空位,可以有效的帮助可见光吸收和提高催化活性。
所述剥离剂为10个碳原子以上的有机胺,优选为油胺、十七胺、十六胺和十九胺中的一种或多种,更优选为油胺;胺和层间的酸发生化学作用,这样增大了钨酸层间距离,有利于钨酸分解成WO6单元并进一步形成W18O49晶核。
所述有机溶剂为苄醇、苄酸或6个碳原子以下的羧酸或醇,优选为乙酸、丙酸、丁酸或甲酸,更优选为乙酸。具有-OH的醇或者酸,可以有效的取代水分子,与WO6单元的O进行化学作用。
本发明还提供了上述W18O49纳米线的制备方法,包括以下步骤:
步骤1:将所述钨酸与有机溶剂进行混合,超声处理,得到钨酸混合物;
步骤2:将所述钨酸混合物与剥离剂混合,进行溶剂热反应,得到W18O49纳米线。
本发明步骤1中,钨酸混合物为钨酸与乙酸的混合物;所述钨酸的制备方法为:将钨酸盐与强酸进行混合,超声分散,离心后取沉淀,得到所述钨酸;所述钨酸盐选自钨酸钠或钨酸铵;所述强酸选自硝酸、硫酸、盐酸或高氯酸;所述钨酸盐与所述强酸的质量体积比为(50~300)mg:(3~10)mL,优选为220:10mL;所述超声处理的时间为3~10min,优选为5min,功率为300~600W,优选为500W;所述离心的转速为8000-10000rpm,时间为3-10min。
本发明步骤1中,所述超声处理的时间为30min~120min,优选为30min,功率为500W。
本发明步骤2中,所述混合后,还包括:超声处理;所述超声处理的时间为30min~120min,优选为1h,功率为500W;所述溶剂热反应结束后,还包括:自然冷却至室温后,使用丙酮和乙醇洗涤除去离子和有机物。
所述剥离剂为10个碳原子以上的有机胺;
所述有机溶剂为苄醇、苄酸或6个碳原子以下的羧酸或醇。
优选地,所述钨酸与所述有机溶剂的摩尔比为(0.008~0.04):1,更优选为0.02:1。
优选地,所述钨酸混合物与所述剥离剂的摩尔比为(0.005~0.06):1,更优选为0.007:1。
优选地,所述溶剂热反应的温度为220℃~240℃,时间为24h~36h,更优选为220℃,24h。
本发明还提供了上述W18O49纳米线或上述制备方法制得的W18O49纳米线在光催化膜中的应用。
本发明还提供了一种NOBF4修饰的光催化膜,所述光催化膜由以下制备方法制得:
将上述W18O49纳米线或上述制备方法制得的W18O49纳米线与NOBF4溶液混合,超声处理、抽滤,得到NOBF4修饰的光催化膜。
由于上述W18O49纳米线表面还含有剥离剂,使其难溶于水,从而限制了其在水处理中的应用。本发明中,NOBF4与W18O49结合能力强,可以将W18O49表面的剥离剂完全置换从而使得W18O49纳米线在水中具有更好的分散性。
本发明还提供了一种石墨烯修饰的光催化膜,所述光催化膜由以下制备方法制得:
将银盐溶液与有机溶剂分散的上述W18O49纳米线或上述制备方法制得的W18O49纳米线进行混合后,加入水分散的石墨烯进行搅拌、离心和抽滤,得到石墨烯修饰的光催化膜。
本发明中,W18O49的W5+把硝酸银还原为单质银纳米颗粒,石墨烯将W18O49表面的剥离剂完全置换,且石墨烯作为载体。另外,石墨烯本身具有优异的电荷转移能力,能促进电荷分离,有助于污染物的降解。
需要说明的是,得到孔径小于10纳米甚至1纳米的无滤孔堵塞的无机光催化膜,必须要合成微米长度且直径3纳米以下超细纳米线之外,还需要W18O49纳米线有效的组装。本发明通过抽滤成膜W18O49纳米线被组装成一张膜,由于W18O49纳米线之间连接点有化学交联,从而可以形成稳定的过滤膜。
从以上技术方案可以看出,本发明具有以下优点:
本发明提供了一种WO3纳米线,WO3纳米线为W18O49纳米线;W18O49纳米线的直径为1~10nm,长度为0.5~10μm;WO3纳米线由以下制备方法制得:步骤1:将钨酸与有机溶剂进行混合,超声处理,得到钨酸混合物;步骤2:将钨酸混合物与剥离剂混合,进行溶剂热反应,得到WO3纳米线;剥离剂为10个碳原子以上的有机胺;有机溶剂为苄醇、苄酸或6个碳原子以下的羧酸或醇。
本发明中,三氧化钨类材料具有无毒,价格低廉,具有良好的化学稳定性,以及有相对窄的带隙可以利用波长小于450nm可见光等优点,而具有氧缺空位的非化学计量三氧化钨(W18O49)能更高效的吸收可见光和近红外光,具备较高的可见光催化活性,且W18O49直径小,可以组装孔径更小的高性能膜。另外,将钨酸与有机溶剂进行混合并超声处理,使得有机溶剂进入钨酸的层间,然后剥离剂通过中和反应除去过量的有机溶剂,在溶剂热的反应下,剥离剂进一步与钨酸层间的有机溶剂发生反应,剥离钨酸,使得钨酸剥离成更高浓度的WO6,有利于成核,并使得钨酸沿着一维方向结晶成超长超细的纳米线。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。
图1为本发明实施例1提供的W18O49纳米线的TEM图;
图2为本发明实施例2提供的NOBF4修饰的W18O49光催化膜的SEM图;
图3为本发明实施例2提供的NOBF4修饰的W18O49光催化膜的实物图;
图4为本发明实施例3提供的石墨烯修饰的光催化膜的TEM图;
图5为本发明实施例2提供的NOBF4修饰的W18O49光催化膜和实施例1提供的W18O49纳米线光催化降解罗丹明B的降解曲线图;
图6为本发明实施例3提供的石墨烯修饰的光催化膜和实施例1提供的W18O49纳米线光催化降解罗明丹B的降解曲线图;
图7为本发明实施例2提供的NOBF4修饰的W18O49光催化膜水通量的测试图。
具体实施方式
本发明实施例提供了一种WO3纳米线及其制备方法与应用,用于解决二氧化钛纳米线的直径较大,且只能利用紫外光催化处理污染物的问题。
为使得本发明的发明目的、特征、优点能够更加的明显和易懂,下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,下面所描述的实施例仅仅是本发明一部分实施例,而非全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
本实施例为W18O49纳米线的制备,具体步骤如下:
1、称取220mg的钨酸盐与10mL强酸混合,超声波分散约5min;
2、将混合物8000rpm离心5min,弃置上层清液,获得湿的钨酸沉淀;
3、将获得的钨酸沉淀加入10mL乙酸,超声波分散30min;
4、往分散好的钨酸混合物中,用注射器加入30mL油胺,继续超声波分散约1h;
5、将混合物转移至50mL的聚四氟乙烯高压反应釜中并注入氩气,放置于烘箱中,以220℃的温度溶剂热反应24h;
6、反应完成后,产物自然冷却至室温并转移至离心管中,用丙酮和乙醇多次洗涤,得到W18O49纳米线。
7、加入20mL甲苯保存。
如图1所示,本实施例W18O49纳米线的长度超过1.5微米,直径在3纳米以下。
实施例2
本实施例为NOBF4修饰的W18O49光催化膜的制备,具体步骤如下:
1、称取30mg NOBF4,然后溶解于20mL的N,N-二甲基甲酰胺(DMF)中;
2、将实施例1提供的W18O49纳米线10000rpm离心8min,弃置上层清液,然后加入配置好的NOBF4的DMF溶液,超声处理1h后,得到NOBF4修饰的W18O49纳米线;
3、将NOBF4修饰的W18O49纳米线减压抽滤,得到NOBF4修饰的W18O49光催化膜。
如图2和3所示,本实施例成功制备得到NOBF4修饰的W18O49光催化膜。从图3中可以看到NOBF4修饰的W18O49组装成一张稳定的光催化膜。
实施例3
本实施例为石墨烯修饰的光催化膜的制备,具体步骤如下:
1、称取40mg硝酸银,溶解于10mL的乙二醇中;
2、然后将硝酸银溶液加入到已经用甲苯分散好的实施例1提供的W18O49纳米线中,磁力搅拌12h;
3、将水分散的石墨烯(GO)加入到上述混合液,磁力搅拌6h;
4、搅拌完成后,10000rpm离心8min取固体,然后用丙酮和乙醇多次洗涤,抽滤后得到GO-W18O49-Ag光催化膜;
5、加入20mL乙醇保存。
如图4所示,银纳米颗粒负载在W纳米线上,而W18O49-Ag负载在GO上,表明成功制备得到GO-W18O49-Ag光催化膜。
实施例4
使用实施例1提供的W18O49纳米线、实施例2提供的NOBF4-W18O4和实施例3提供的GO-W18O49-Ag光催化膜降解罗丹明B:
1、分别取两组100mg实施例1W18O49纳米线、100mg W18O49-NOBF4、GO-W18O49-Ag分别分散在100mL的RhB溶液中,避光处理24小时后转移进反应管;
2、将反应管放置于光催化反应器中,300W高压汞灯照射反应;
3、隔一定时间取出反应清液,其中,W18O49-NOBF4每隔20分钟检测一次,GO-W18O49-Ag是每隔5分钟检测一次,第一组W18O49纳米线每隔5分钟检测一次,第二组W18O49纳米线每隔20分钟检测一次用紫外分光光度计检测反应清液的吸光度;
4、根据反应清液的吸光度来计算罗丹明B的清除程度;
如图5所示,与实施例1W18O49纳米线相比,实施例2W18O49-NOBF4光催化膜在光照120min表现出更好的罗丹明B的降解活性,表明NOBF4的修饰能提高W18O49光催化降解罗丹明B的能力。
如图6所示,与实施例1W18O49纳米线相比,GO-W18O49-Ag在光照下40min表现出更好的罗丹明B的降解活性,表明石GO修饰及Ag负载能提高W18O49光催化降解罗丹明B的能力。
实施例5
对实施例2提供的NOBF4-W18O4进行水通量测试:
1.将NOBF4-W18O4光催化膜置于过滤装置中;
2.加入纯水过滤,每隔5分钟把下方接有滤液的过滤杯进行重量称量;
3.加入RhB过滤,分别在避光及光照(300W氙灯放置于滤膜正上方照射)条件下进行,每隔5分钟把下方接有滤液的过滤杯进行称量重量;
4.根据所得数据计算获得其水通量数据。
如图7所示,在无光的条件下,水通量随着时间的推移而逐渐下降,因为RhB堵塞了孔道,而在光照下,过滤时大部分RhB被W18O49-NOBF4降解,从而使得相对于无光照下具有更好的水通量。
以上所述,以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种WO3纳米线,其特征在于,所述WO3纳米线为W18O49纳米线;
所述W18O49纳米线的直径为1~10nm,长度为0.5~10μm;
所述W18O49纳米线由以下制备方法制得:
步骤1:将钨酸与有机溶剂进行混合,超声处理,得到钨酸混合物;
步骤2:将所述钨酸混合物与剥离剂混合,进行溶剂热反应,得到WO3纳米线;
所述剥离剂为10个碳原子以上的有机胺;
所述有机溶剂为苄醇、苄酸或6个碳原子以下的羧酸或醇。
2.根据权利要求1所述的WO3纳米线,其特征在于,所述剥离剂为油胺、十七胺、十六胺和十九胺中的一种或多种;
所述有机溶剂为乙酸、丙酸、丁酸或甲酸。
3.权利要求1或2所述的WO3纳米线的制备方法,其特征在于,包括以下步骤:
步骤1:将钨酸与有机溶剂进行混合,超声处理,得到钨酸混合物;
步骤2:将所述钨酸混合物与剥离剂混合,进行溶剂热反应,得到WO3纳米线;
所述剥离剂为10个碳原子以上的有机胺;
所述有机溶剂为苄醇、苄酸或6个碳原子以下的羧酸或醇。
4.根据权利要求3所述的制备方法,其特征在于,所述钨酸与所述有机溶剂的摩尔比为(0.008~0.04):1。
5.根据权利要求3所述的制备方法,其特征在于,所述钨酸混合物与所述剥离剂的摩尔比为(0.005~0.06):1。
6.根据权利要求3所述的制备方法,其特征在于,所述溶剂热反应的温度为220℃~240℃,时间为24h~36h。
7.根据权利要求3所述的制备方法,其特征在于,所述超声处理的时间为3~10min,功率为300~600W。
8.权利要求1所述的WO3纳米线在光催化膜中的应用。
9.一种NOBF4修饰的光催化膜,其特征在于,所述光催化膜由以下制备方法制得:
将权利要求1或2所述的WO3纳米线与NOBF4溶液混合,超声处理、抽滤,得到NOBF4修饰的光催化膜。
10.一种石墨烯修饰的光催化膜,其特征在于,所述光催化膜由以下制备方法制得:
将银盐溶液与有机溶剂分散的权利要求1或2所述的WO3纳米线进行混合后,加入水分散的石墨烯进行搅拌、离心和抽滤,得到石墨烯修饰的光催化膜。
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CN111702902A (zh) * | 2020-06-24 | 2020-09-25 | 王怀远 | 一种木质基选择性近红外吸收材料的制备方法 |
CN114392741A (zh) * | 2021-12-28 | 2022-04-26 | 安徽大学 | 一种富空位用于提高可见光及近红外光动力抑菌的银负载氧化钨纳米线及制备与应用 |
CN115025794A (zh) * | 2022-03-02 | 2022-09-09 | 华南理工大学 | 具有可见光响应的ocn/w18o49复合光催化剂及其制备方法与应用 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111702902A (zh) * | 2020-06-24 | 2020-09-25 | 王怀远 | 一种木质基选择性近红外吸收材料的制备方法 |
CN114392741A (zh) * | 2021-12-28 | 2022-04-26 | 安徽大学 | 一种富空位用于提高可见光及近红外光动力抑菌的银负载氧化钨纳米线及制备与应用 |
CN115025794A (zh) * | 2022-03-02 | 2022-09-09 | 华南理工大学 | 具有可见光响应的ocn/w18o49复合光催化剂及其制备方法与应用 |
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