CN112725936B - 一种钼酸银纳米纤维材料及其制备方法 - Google Patents
一种钼酸银纳米纤维材料及其制备方法 Download PDFInfo
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- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000002121 nanofiber Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
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- 229910015667 MoO4 Inorganic materials 0.000 description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
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- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明提供了一种钼酸银纳米纤维材料及其制备方法。本发明提供的钼酸银纳米纤维材料由具有高纵横比的钼酸银纤维状纳米晶体及均匀生长在钼酸银纤维状纳米晶体上的Ag纳米粒子构成。本发明采用优化的均相沉淀法,首次使用具有超氧键的固体过氧钼酸作为钼源,生成一维的纳米纤维,克服了传统制备方法的缺陷,制备的钼酸银纳米纤维形貌均匀、表面银纳米颗粒的负载量较大,且粒径及分布均匀。
Description
技术领域
本发明涉及无机纳米材料技术领域,特别涉及一种钼酸银纳米纤维材料及其制备方法。
背景技术
钼酸银是一类银钼酸盐材料的统称,包括Ag2MoO4、Ag2Mo2O7、Ag2Mo4O13、Ag6Mo10O33以及钼酸银水合物等多种化合物,这一类材料由具有抗菌活性的银离子及对人体无毒害的钼酸根离子构成,这类化合物在水相溶液中具有特殊的“缓释”机理,可缓慢的释放出Ag+离子并保持其浓度在较低的范围内,因而被广泛的应用于无机抗菌材料的开发领域。
钼酸根离子的金属氧酸盐特性使其在不同的条件(如pH值、分散体系等)下发生不同程度的聚合现象,这一现象的存在使得钼酸银材料具有着丰富的晶体结构,且有部分材料可在适宜的条件下产生可逆相变(如充、放电过程),这些特性使得钼酸银材料在电化学领域获得了大量的关注,如应用于氨、乙醚等气体分子传感、电催化析氢、超级电容器等领域。
钼酸银材料中,Ag2MoO4具有较宽(约3.02eV)的能带间隙,对光的主要吸收集中在紫外波段,其他几种常见钼酸银材料的带隙均在1.9eV左右,在可见光催化领域有着潜在的应用价值。近年来,钼酸银材料或基于钼酸银材料的半导体异质结被广泛的应用于有机染料降解、光氧化燃芳香性硫化物降解以及抗生素光降解等模型反应的研究中。钼酸银材料虽具有光催化活性,但其光生载流子复合现象较为严重,且易产生光腐蚀现象,这些缺陷限制了钼酸银材料在光催化领域的应用,目前学界常采用贵金属负载、构建异质结、元素掺杂等方法对钼酸银材料的催化性能进行优化。
常用的钼酸银制备方法有沉淀法、水热法、固相法等,其中,沉淀法的操作较为复杂,且所制备的产物存在结晶度较差,形貌不均匀等问题。水热法得到的产物形貌相对理想,但粒径较大,催化活性较低。固相法能耗较高,且制备的材料不均一、颗粒较大,并不是理想的制备材料。除此之外,传统制备手段得到的产物往往需要进行额外的贵金属负载、沉积等过程,才能得到性能理想的材料,而现行的光沉积方法存在贵金属负载量较低、颗粒大小不均等缺点。因此,寻找简便、低能耗、产物质量高且无需进行额外负载处理的钼酸银类材料制备方法是十分必要的。
发明内容
目前存在的较为常用的钼酸银纳米纤维制备方法难以得到形貌均匀的产物,且一般方法制备的纳米纤维表面没有纳米级别的银颗粒,虽然可以通过光沉积的方法进行负载,但这一方法存在负载颗粒大小不均匀、负载量低、操作复杂等缺点。本发明的目的在于提供一种制备简便、形貌均匀、纵横比高、表面负载有均匀的纳米银颗粒、具有优良光催化性能及抗菌性能的钼酸银纳米纤维材料。
为实现上述目的,本发明提出了一种钼酸银纳米纤维材料,所述钼酸银纳米纤维材料由具有高纵横比的钼酸银纤维状纳米晶体及均匀生长在所述钼酸银纤维状纳米晶体上的Ag纳米粒子构成。
钼酸银系材料多为含银量较高的半导体材料,具有缓释Ag+离子的特性及较好的光催化活性,本发明制备的钼酸银系纳米纤维材料表面分布有均匀的纳米银颗粒,这些银颗粒可在可见光的辐射下产生局域表面等离子激元共振效应(Localized SurfacePlasmon Resonance)。上述共振效应具有以下特点:1)能够有效地促进半导体材料中光生空穴-电子的分离,提升半导体材料中光生载流子的迁移率,从而提升材料的光催化性能;2)纳米颗粒本身受可见光激发后亦可以产生具有光催化能力的热电子;3)不断的受激—退激过程可产生高效的光热转化效应。
优选地,所述钼酸银纤维状纳米晶体的长度为5~40um,宽度为40~100nm,所述Ag纳米粒子的直径为5~25nm。
优选地,所述钼酸银纤维状纳米晶体的长度为20~30um,宽度为50~80nm,所述Ag纳米粒子的直径为5~10nm。
优选地,所述钼酸银的化学组成包括:Ag2MoO4、Ag2Mo2O7、Ag2Mo4O13、Ag6Mo10O33中的至少一种。
为实现上述目的,本发明还提出一种钼酸银纳米纤维材料的制备方法,其特征在于,在避光条件下包括以下步骤:
(1)钼源的制备:在冰浴条件下,将钼粉缓慢加入剧烈搅拌的H2O2溶液中,待反应完全后得到灰绿色的液体,然后继续加入H2O2溶液直至溶液体系变为黄色,停止搅拌,将溶液体系蒸发结晶后得到橘黄色的H2MoO5固体;
(2)H2MoO5悬浊液的制备:称取适量H2MoO5晶体,研磨30min得到均匀的粉末,然后将其加入醇类溶剂中,搅拌并超声处理,得到分散均匀的H2MoO5-醇悬浊液;
(3)前驱体溶液的制备:将AgNO3溶于去离子水中,得到银源,将其逐滴加入剧烈搅拌下的H2MoO5-醇悬浊液中,滴加完毕后持续30min搅拌使溶液均匀混合,得到前驱体溶液;
(4)将前驱体溶液在85℃下持续剧烈搅拌,反应24h,反应结束后,将产物离心分离,并使用乙醇及丙酮洗涤产物,然后再45℃下真空干燥24h,即得到表面负载有均匀纳米银颗粒的钼酸银纳米纤维材料。
优选地,按质量分数计,步骤(1)中所述H2O2溶液的浓度为30%。
优选地,步骤(1)中控制溶液体系蒸发温度为45℃~75℃。
优选地,步骤(2)中所述醇类溶剂为无水乙醇或正丁醇中的一种。
在本发明技术方案中,选用乙醇及正丁醇的原因为以下两个方面:1、原料之一的固体过氧钼酸不能溶解于这两种醇,而这二者能较好的与适量的水均匀混合并形成共沸体系;2、若所选的醇碳链过长,则无法与反应必需用量的水形成均匀的体系,使反应无法正常进行。
优选地,步骤(2)中所述H2MoO5-醇悬浊液的浓度为8~10mol/L。
优选地,步骤(3)中所述AgNO3与步骤(2)中所述H2MoO5的摩尔比为1:1,步骤(3)中所述AgNO3与所述H2O的摩尔比为5:4。
与现有的技术相比,本发明采用优化的均相沉淀法,首次使用具有超氧键的固体过氧钼酸作为钼源,先通过超声分散的方法使固体过氧钼酸分散在醇类溶剂中形成稳定的悬浊液,固体过氧钼酸在水-乙醇混合溶液中溶解度较低,当温度升至85℃时,过氧钼酸分子中含有的过氧键与Ag+离子发生反应、断裂并产生自组装效应,从而生成一维的纳米纤维。本发明中使用的制备方法则克服了传统制备方法的缺陷,制备的钼酸银纳米纤维形貌均匀、表面银纳米颗粒的负载量较大,且粒径及分布均匀。
附图说明
图1为实施实例1所制得的钼酸银纳米纤维材料的HR-SEM图;
图2为实施实例1所制得的钼酸银纳米纤维材料的HR-TEM图;
图3为实施实例1所制得的钼酸银纳米纤维材料的EDS图;
图4为实施实例2所制得的钼酸银纳米纤维材料的HR-SEM;
图5为实施实例2所制得的钼酸银纳米纤维材料的HR-TEM图;
图6为实施实例2所制得的钼酸银纳米纤维材料的EDS图;
图7为实施例3所制得的钼酸银纳米材料的HR-SEM图;
图8为实施例4所制得的钼酸银纳米材料的HR-SEM图;
图9为实施例5所制得的钼酸银纳米材料的HR-SEM图;
图10为实施例6所制得的钼酸银纳米材料的HR-SEM图;
图11为实施例1-6所制得的各种钼酸银纳米材料的XRD图。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整的描述,显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。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他实施例,都属于本发明保护的范围。
应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
钼源的制备:在避光、冰浴条件下,将钼粉缓慢加入剧烈搅拌的浓度为30%H2O2溶液中,待反应完全后得到灰绿色的液体,然后继续加入H2O2溶液直至溶液体系变为黄色,停止搅拌,将溶液体系在45℃~75℃的温度条件下蒸发结晶,得到橘黄色的H2MoO5固体。
实施例1
在避光条件下制备钼酸银纳米纤维材料,包括以下步骤:
(1)称取0.178g固体过氧钼酸置于烧杯中,加入100ml乙醇,超声并持续搅拌3h,得到均匀的橙黄色过氧钼酸-乙醇悬浊液;
(2)称取硝酸银0.169g,将其溶于35ml去离子水中,然后将硝酸银溶液逐滴加入剧烈搅拌下的过氧钼酸-乙醇悬浊液中,持续搅拌30min,得到前驱体溶液;
(3)将前驱体溶液转移进烧瓶中,在85℃下持续油浴并剧烈搅拌,持续24h;
(4)待反应结束后,将体系自然冷却,将产物离心分离,使用乙醇洗涤3遍、丙酮洗涤2遍,然后在45℃下真空干燥24h,得到产品。
结合图1~3及图11可知,本实施例所制备材料是以Ag6Mo10O33为主的钼酸银纳米纤维,其长度在20μm以上,宽度为50nm左右,钼酸银纳米纤维上分布有直径小于10nm的纳米银颗粒。
实施例2
钼酸银纳米纤维材料的制备方法同实施例1,区别在于:将步骤(1)中使用的正丁醇改为乙醇。
结合图4~6及图11可知,本实施例所制备材料的主要成分为Ag2MoO4、含有少量Ag6Mo10O33、Ag2Mo2O7的钼酸银纳米纤维材料,材料表面载有均匀分布的纳米银颗粒,纤维的长度在5μm左右,宽度在50~100nm之间,纳米银颗粒粒径为5~25nm。
实施例3
材料的制备方法同实施例1,区别在于:将步骤(2)中使用的35ml去离子水改为使用45ml去离子水。
结合图7及图11可知,本实施例所制得的钼酸银纳米材料主要成分为Ag6Mo10O33,并含有少量的Ag2MoO4、Ag2Mo4O13成分,纳米纤维的长度为20μm左右,宽度在100nm以下,扫描电镜图显示制得的产物中有大量尺寸较大的块状产物,材料的表面较为光滑,不具有纳米银颗粒。
造成这种结果的原因可能是因为:随着反应体系中去离子水的用量增加,反应原料的溶解速度加快,反应体系中的原料浓度增高,影响了晶体的各向异性生长,从而使得产物的形貌更趋向于各向同性生长的结果。
实施例4
材料的制备方法同实施例1,区别在于,将步骤(1)中使用的正丁醇改为乙醇,将步骤(2)中使用的35ml去离子水改为使用10ml去离子水。
结合图8及图11可知,本实施例所制得的钼酸银块状材料组成为Ag6Mo10O33及少量Ag2MoO4、Ag2Mo2O7,扫描电镜结果显示材料的宽度200nm以上,直径在2μm左右,表面分布有直径20-50nm纳米的银颗粒。
相比实施例1,所制得的材料形貌较不均匀,造成这种情况的原因可能是由于体系中的去离子水量较低,较低的原料浓度使得材料的生长速度受到抑制,从而导致产物的纵向长度较短。
实施例5
在避光条件下制备钼酸银纳米纤维材料,包括以下步骤:
(1)称取0.178g固体过氧钼酸置于烧杯中,加入100ml正丁醇,超声并持续搅拌3h,得到均匀的橙黄色过氧钼酸-正丁醇悬浊液;
(2)称取硝酸银0.169g,将其一次性加入过氧钼酸-正丁醇悬浊液中,持续剧烈搅拌30min,得到前驱体溶液;
(3)将前驱体溶液转移进烧瓶中,在85℃下持续油浴并剧烈搅拌,持续24h;
(4)待反应结束后,将体系自然冷却,将产物离心分离,使用乙醇洗涤3遍、丙酮洗涤2遍,然后在45℃下真空干燥24h。
结合图9及图11可知,本实施例所制备的材料组成主要为Ag2MoO4,并含有少量Ag2Mo2O7、Ag6Mo10O33的梭形钼酸银纳米材料,钼酸银纳米晶体上分布有均匀的纳米银颗粒。所述钼酸银梭状纳米晶体的长度为2μm左右,中心宽度为100nm左右,所述Ag纳米粒子的直径为5~10nm,相比实施例1及实施例2制得的纳米纤维材料,梭状材料的比表面积相对较小,且尺寸较大。材料产生不同形貌的原因可能是由于:溶液体系的组成相较实施例1发生了较大的改变,溶剂的变化影响了原料的溶剂化效应,从而影响了作为钼酸银材料基本结构单元的钼氧八面体及银氧四面体进行自组装的过程,从而导致产物的组成及形貌均产生了较大的改变。
实施例6
材料的制备方法同实施例5,区别在于,步骤(1)中,加入100ml正丁醇改为加入100ml正己醇。
结合图10及图11可知,本实施例所制备的材料由3c相态的银及无定形成分构成。产物为无定形材料的原因可能是正己醇的极性较低,原料在溶剂中难以溶解,作为基本结构单元的钼氧八面体及银氧四面体难以进行自组装过程,而正己醇在加热的条件下具有还原性,从而将银离子还原成单质银颗粒,导致产物由大量的无定形物质及单质银纳米颗粒构成。
以上所述仅为本发明的部分实施例,并非因此限制本发明的专利范围,凡是在本发明的构思下,利用本发明说明书所作的等效结构变换,或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。
Claims (4)
1.一种钼酸银纳米纤维材料的制备方法,其特征在于,在避光条件下包括以下步骤:
(1)钼源的制备:在冰浴条件下,将钼粉缓慢加入剧烈搅拌的H2O2溶液中,待反应完全后得到灰绿色的液体,然后继续加入 H2O2溶液直至溶液体系变为黄色,停止搅拌,将溶液体系蒸发结晶后得到橘黄色的H2MoO5固体;
(2)H2MoO5悬浊液的制备:称取适量H2MoO5晶体,研磨30min得到均匀的粉末,然后将其加入醇类溶剂中,搅拌并超声处理,得到分散均匀的H2MoO5-醇悬浊液,所述醇类溶剂为无水乙醇或正丁醇中的一种;
(3)前驱体溶液的制备:将AgNO3溶于去离子水中,得到银源,将其逐滴加入剧烈搅拌下的H2MoO5-醇悬浊液中,滴加完毕后持续30min搅拌使溶液均匀混合,得到前驱体溶液,所述银源中硝酸银和去离子水的质量体积比为0.169g:35mL;
(4)将前驱体溶液在85℃下持续剧烈搅拌,反应24h,反应结束后,将产物离心分离,并使用乙醇及丙酮洗涤产物,然后再45℃下真空干燥24h,即得到表面负载有均匀纳米银颗粒的钼酸银纳米纤维材料。
2.如权利要求1所述的钼酸银纳米纤维材料的制备方法,其特征在于,按质量分数计,步骤(1)中所述H2O2溶液的浓度为30%。
3.如权利要求1所述的钼酸银纳米纤维材料的制备方法,其特征在于,步骤(1)中控制溶液体系蒸发温度为45oC~75oC。
4.如权利要求1所述的钼酸银纳米纤维材料的制备方法,其特征在于,步骤(2)中所述H2MoO5-醇悬浊液的浓度为8~10mol/L。
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