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刘忠成, 倪学鹏, 牛萍. 多酸层层自组装复合材料应用的研究进展[J]. 应用化学, 32(3): 245-254
Zhongcheng LIU, Xuepeng NI, Ping NIU. Functional Polyoxometalate-Based Composite Materials via Layer-by-Layer Self-Assembly [J]. Chinese Journal of Applied Chemistry, 32(3): 245-254  
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多酸层层自组装复合材料应用的研究进展
刘忠成, 倪学鹏, 牛萍*
德州学院 山东省功能材料与配位化学高校重点实验室 山东 德州 253023
通讯联系人:牛萍,副教授; Tel:0534-8987865; Fax:0534-8985835; E-mail:np68@sina.com; 研究方向:复合材料组装及光催化性能
收稿日期:2014-07-04 修回日期:2014-09-02 接受日期:2014-10-07
基金:山东省自然科学基金高校、科研单位联合专项基金(ZR2013BL001); 德州学院人才引进课题(2003kjrc05);
摘要

多金属氧酸盐(简称多酸)具有独特的分子结构、性质的多样性和可调性,其在磁学、光电化学、材料化学、催化和生物医学等领域均有着潜在的应用。 近年来,层层自组装技术被广泛用于多酸超薄膜组装,进一步拓展了多酸的应用范围。 本文主要介绍基于静电相互作用的层层自组装方法制备的多酸基功能性超薄膜复合材料(平面薄膜、中空微胶囊和微球)在光催化、电催化、光致变色、电致变色、磁学、气体传感和光电催化等领域的研究进展并对其进行了展望。

关键词: 层层自组装; 多酸; 复合材料; 催化
中图分类号:O611.3 文献标志码:A 文章编号:1000-0518(2015)03-0245-10
Functional Polyoxometalate-Based Composite Materials via Layer-by-Layer Self-Assembly
Zhongcheng LIU, Xuepeng NI, Ping NIU
Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong,Dezhou University,Dezhou,Shandong 253023,China
Corresponding author:NIU Ping, associate professor; Tel:0534-8987865; Fax:0534-8985835; E-mail:np68@sina.com; Research interests:assembly and photocatalytic performance of nanocomposite material
Reveived:2014-07-04 Revised:2014-09-02 Accepted:2014-10-07
Fund:Supported by the Natural Science Foundation of Shandong Province(Combination Research Projects)(No.ZR2013BL001), Talent Introduction Subject of Dezhou University(No.2003kjrc05); }
Abstract

Polyoxomolybdates(POMs) have potential applications in photoelectrochemistry, magnetism, catalysis(photo- and electronic), materials science and biomedicine due to the diversity of the chemistry, structure and electron. In recent years, layer-by-layer self-assembly method has been widely used to build ultra thin films from POMs, which extends the application range of POMs. This work reviews the research progress of functional polyoxometalate-based composite materials(including plate multilayer films, microspheres and magnetic vesicles) via the layer-by-layer self-assembly. The applications in electrocatalysis, photocatalysis, electrochromism gas sensor and magnetic properties are also introduced. The research perspectives are presented.

Keyword: layer-by-layer self-assembly; polyoxometalates; composite materials; catalysis

多金属氧酸盐(polyoxometalates,POMs),通常被简称为多酸,是指由多金属原子和杂原子按一定的结构通过氧原子配位桥联而形成的一类簇合物的总称[1,2],被誉为当今最重要和最有前途的功能材料之一[3]。 早在1826年,Berzelius及其合作者[4]成功合成了第一个杂多化合物12-钼磷酸铵,至今多金属氧酸盐化学的研究已有近两百年的历史。 多酸分子不仅具有结构和组成的多样性、尺寸的可调变性,还具有独特的氧化还原性、强酸性、抗病毒、抗肿瘤、抗艾滋病等优异性能,在催化化学、电化学、光学、医学以及材料科学等领域具有广泛的应用。 此外,多酸中含有与杂多阴离子作为一整体的离域水合质子,这些离域的质子可流动,因此具有质子导电性,可作为高质子导体固体电解质[2,5,6,7,8],该特性使多酸在质子交换膜燃料电池、传感器和电显色装置等方面具有潜在的应用前景。 层层(layer-by-layer,LbL)自组装技术的研究始于1966年,Iler等[9]利用静电相互作用将带有正、负电荷的胶体粒子交替吸附在平板基底上得到了多层膜,然而该研究在当时并未引起人们的关注。 直到20世纪90年代初,在Iler等的工作基础上,法国化学家Decher等[10] 重新报道了这种基于静电吸附作用的交替沉积自组装技术,将相反电荷的线型聚电解质经静电相互作用组装到平板基底上制得了多层异质结构的超薄膜,并首次提出了LbL的概念,随后掀起了利用交替吸附自组装技术构筑多层膜的热潮。 经过20多年的发展,LbL自组装技术已成为制备纳米级多层膜的有效手段,受到了各国科研工作者的关注。该方法操作简单、成膜快,可以在分子水平上调控所得材料的尺寸、结构和形貌,并且成膜不受基底材质、大小和形状的限制。 到目前为止,用于多层膜组装的物质已从最初的聚电解质阴阳离子扩展到多种功能性的材料,如:无机纳米粒子、杂多酸、含有寡电荷的有机染料小分子、生物大分子如酶、蛋白质、DNA和细菌等、树枝状大分子、天然糖类等。 在该技术发展的早期,成膜的推动力主要是相反电荷离子间的静电相互作用,随着对该技术的深入研究,其组装的驱动力已从传统的作用力扩展至氢键[11]、配位键[12]、共价键[13]和电荷转移作用力[14]等。 利用LbL自组装技术得到的多层超薄膜材料在光催化、电化学、磁学、药物化学和生物传感器等方面具有广阔的应用前景。

1 多酸功能化平面多层膜
1.1 POMs多层膜光催化性质

多金属氧酸盐光催化降解水中有机污染物的研究始于20世纪80年代[15]。 多酸分子的催化性能来自其所具有的强Brönsted酸性和强氧化性,而其强氧化性源于分子中最高氧化态的W、Mo、V等配位原子;此外,多酸分子本身毒性小,催化反应副产物少,已成为光催化领域中广泛使用的绿色光催化剂。

图1 ( A)聚电解质、L和MW12(M=P,Co)团簇的结构;( B)阳离子L和MW12(M=P,Co)阴离子团簇交替沉积组装的多层膜示意图[16]Fig.1 ( A)Chemical structures of the polyelectrolyte, L, and MW12(M=P, Co) clusters, ( B)schematic diagram of the formation of the multilayer assemblies via alternating adsorption of cationic L and anionic MW12(M=P, Co) clusters[16]

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将自组装技术中的基底材料从平面模板换成球形胶体颗粒,就得到了超薄膜为壳层的微粒,然后将作为模板的胶体粒子溶剂溶解或高温分解,就可制备出自由的三维薄膜-一类全新结构的中空微胶囊。王恩波课题组[38]以聚苯乙烯纳米胶球为模板,将Keggin型多酸阴离子[SiW12O42]4-,取代型Keggin多酸阴离子[SiCoW11O40H2]6-、[SiNiW11O40H2]6-、[GeCoW11O40H2]6-以及具有荧光特性的[EuW10O36]9-(简称{EuW10})等作为壁材引入到胶囊中,从而得到功能性的微胶囊。 实验表明多酸引入后,所得微胶囊比聚电解质胶囊具有更高热稳定性,荧光多酸{EuW10}被组装到微胶囊中后,仍能保持其荧光特性。

高蕾[39]将过渡金属离子与聚电解质络合预先制备出聚电解质(PEI)-金属M(M=Ag+,Cu2+, Co2+, Ni2+)络合物,而后以聚苯乙烯胶球(PS) 为模板粒子,在其表面将Keggin型K4[β-SiWl2O40]·9H2O (SiW12)多酸阴离子和PEI-M交替沉积,直到达到所需层数,组装结束后用丙酮溶解除去PS模板制备出聚电解质/金属离子/多酸的三组分复合胶囊,经LbL组装后所得胶囊能提供一个还原环境,选用NaBH4为还原剂,原位成功获得了聚电解质/金属纳米粒子/多酸的复合胶囊,实现了金属纳米粒子的原位控制合成。

Cui等[40]将具有磁学性能的Keplerate型的多钼酸分子{Mo72Fe30}组装到微胶囊中,制备了磁性微胶囊。有趣的是,{Mo72Fe30}的水溶液却不能被分离,但是含有{Mo72Fe30}的微胶囊可以用磁铁进行分离。TEM表征说明含有{Mo72Fe30}的微球具有良好的磁响应性能,这样可以通过外界磁场对其进行调控。

2.2 多酸功能化微球

多金属氧酸盐(POMs)因其独特的分子结构、强Brönsted酸性和可逆的氧化还原能力,在许多化学反应中表现出优异的催化性能。然而,采用多金属氧酸盐作为均相催化剂时,由于其比表面积小(<10 m2/g)、热稳定性差且易溶水等缺陷,给催化反应后催化剂的分离回收造成了困难,因此限制了其在许多催化反应中的应用;为了更好地提高催化剂在有机污染物光降解过程中的效率,解决催化剂的回收难题,Gao等[41]将Keggin型多酸PW12和小分子染料硫瑾(TH)组装在石英片和MnCO3微球上,敏化剂的引入使PW12能在可见光下降解甲基橙和罗丹明B,与石英片上的(PW12-TH)10 复合膜相比,微球上的复合膜具有更高的光催化活性,效率提高的原因归为表面积的增大。

2012年,Yang等[42]以多孔的TiO2微球为模板,采用LbL方法成功制备了PW12和硫瑾(TH)复合材料,研究了可见光下微球催化剂对罗丹明B的光催化降解,TiO2模板的多孔结构为染料分子的吸附和光催化降解提供了大的比表面积,TH引入可将TiO2和PW12二者敏化,使其在可见光下均具有光催化活性,因此TiO2和PW12的结合使复合膜表现出比单一TiO2优异的光催化性能,所制备催化剂的催化性能和重复性与PW12-TH 双层的层数密切相关,该研究为探索多酸分子可见光下的光催化应用提供了有价值的参考。

2013年,Li等[43]采用层层自组装方法将Keggin型多酸PW12和TH成功组装在核壳结构的Fe3O4@SiO2磁性微球上,以甲基橙为模型污染物,研究了Fe3O4@SiO2@(PW12-TH) n 催化剂可见光下的光催化性质,与石英片沉积的复合膜相比,沉积在磁性微球上的(PW12-TH) n膜表现出更高的光催化活性、稳定性和重复使用性,该方法所得催化剂具有超顺磁性,因此可被磁性分离。磁性支撑物的使用,实现了催化剂降解污染物后方便、干净、快速和高效的分离。

3 LbL技术组装TiO2/POMs复合膜

将催化活性组分通过层层自组装技术固定在基底上,实现了催化剂的快速方便回收。但是TiO2的光生电子和空穴对易复合,从而导致催化剂的光量子产率较低。为了更好地提高二氧化钛纳米材料的催化效率,人们使用电子接受剂来(如多酸)转移TiO2导带中的电子,这种电子给-受体系可有效抑制光生载流子的快速复合。多酸是一类纳米尺度的功能性无机材料,具有较强的电子接受能力,经过可逆的多电子氧化还原反应仍能保持完整的结构,这些特性使多酸分子成为一种高效的电子清除剂,从而提高了复合材料光电化学响应性。

3.1 复合膜光催化性能

2008年,东京理工学院的Nakajima课题组[44]采用静电自组装技术制备了含PW12与TiO2多层膜,通过研究复合膜对2-丙醇气体的光催化降解效果,发现(PW12/TiO2)2对2-丙醇的降解速度明显高于单一组分的(TiO2)2和(PW12)2膜,说明多酸分子与TiO2纳米粒子间存在协同作用;随着多层膜层数的增加,(TiO2)6对2-丙醇的降解明显加快,而(PW12/TiO2)6复合膜对2-丙醇的降解率没有提高,说明膜内层催化剂对2-丙醇降解没有贡献。

此后,该课题组[45,46]又分别将Keggin型PW12、SiW12、H2W12和[PW xMo12- xO40]3-多酸分子组装到TiO2纳米粒子中得到了二者的杂化膜,以异丙醇为污染物模型,研究了杂化膜的光催化活性。光催化实验结果表明,H2W12/TiO2杂化膜在异丙醇气体的降解过程呈现出的最高活性,同时PW12/TiO2复合膜降解污染物的效率也提高了2.3倍;此外,除了多层膜层数可影响污染物的降解速度外,可见光和紫外光两种光源共存也促进了异丙醇降解。

山东大学郝京诚教授课题组[47,48,49,50]从功能性的多酸分子和TiO2纳米材料出发,创新性地将LbL技术组装的复合膜首次用于光催化降解染料废水的研究,发现由TiO2与多酸分子构建的复合膜催化活性远高于纯TiO2和纯POMs膜,主要归功于多层膜中TiO2和POMs间的协同作用。该课题组详细研究了多层膜双层层数、染料溶液浓度、染料种类、溶液pH值、金属阳离子、表面活性剂和电子接受剂等因素对染料降解效率的影响,对甲基橙光催化反应动力学研究发现,甲基橙的降解符合一级反应动力学模型,导致污染物降解主要氧化性物种为光生空穴。同时通过LbL自组装技术把光催化活性物种固定在平板基底上,不仅能解决悬浮体系中催化剂颗粒难以分离回收的困扰,避免了二次污染,还可显著降低印染废水处理的成本,该研究丰富了功能性多酸复合膜的研究领域,也为多酸盐光催化剂用于大规模净化工业污水提供了有价值的参考。

3.2 复合膜的光电催化性质

Sun等[51]采用静电自组装技术构筑了(P2Mo18/TiO2) n、(PW12/TiO2) n和(PSS/TiO2) n复合膜体系,复合膜的原子力显微镜(AFM)表征如图4所示。 光电流瞬时测定表明,(PW12/TiO2) n复合膜的光电流响应与膜的厚度密切相关, n=4时瞬态光电流值最大;此外,在所得的3种多层膜中,PW12与TiO2构筑的多层膜具有最高的瞬态光电流、能量转换效率和对甲醇的光电氧化活性,二者的结合有效的抑制了电子-空穴快速复合,从而提高了光电催化性能。

图4 ( A)(PSS/TiO2)3和( B)(PW12/TiO2)3多层膜的AFM图[51]Fig.4 AFM images of ( A)the (PSS/TiO2)3 film and ( B)the (PW12/TiO2)3 film on silicon wafer[51]

3.3 复合膜的电致变色性质

Liu等[52]首次利用LbL自组装技术构筑了由P2W18、TiO2和PAH组成的电致变色复合膜,TiO2纳米粒子的加入可提高LbL多层膜的电致变色稳定性,研究发现该复合膜还具有高光反差、短响应时间和低操作电压等优点。因此,该多层膜有望用于光学存储、灵巧窗和显示器件上。

3.4 复合膜的气体传感性

TiO2和POM均可作为气敏材料,为了扩展TiO2作为气敏材料的应用及提高其气敏特性,Li等[53]将功能性多酸分子掺杂到TiO2中,考察了POM/TiO2复合膜对NH3、NO2、C2H5OH和C6H6等气体的气敏性能。与TiO2相比,对有毒性气体NO2和NH3而言,POM/TiO2复合膜不仅工作温度较低,还具有较高的气敏性能。 POM/TiO2复合膜气敏性能提高主要归功于膜上POM的电子受体功能以及膜吸附能力的提高。 此研究为POM/TiO2复合膜作为气敏材料的应用提供了理论依据。

4 POMs与其它半导体构建的复合膜

Ma等[54]采用层层自组装方法制得了由Keggin型[SiW9V3O40]7-分子和Bi2O3纳米粒子组成的多功能多层复合膜,并首次研究了同时含多酸和纳米粒子的复合膜的电致变色和光致变色性质,结果表明,纳米粒子插入到多层膜后改变了膜的光致发光性质,同时还发现该复合膜具有电催化活性,不仅可以还原N O-2还可以氧化 L-半胱氨酸。

董绍俊课题组[55] 利用静电相互作用,将聚电解质修饰的磁性Fe3O4纳米粒子和Preyssler型的(NH4)14Na[P5W30O110]·31H2O(P5W30)多酸分子组装到多层膜中,电化学实验发现,复合膜中的Fe3O4层对碘酸盐的还原没有贡献,膜的电催化活性主要来自于多层膜中的多酸分子P5W30,Fe3O4纳米粒子在多层膜中虽然没有氧化还原活性,仅仅作为导电层,没有阻碍P5W30的电子转移。但经聚电解质修饰的Fe3O4纳米粒子提高了复合膜的析氢电催化活性和膜的稳定性,使得含有Fe3O4和P5W30的LbL多层膜有望成为有效、持久的燃料电池的阴极。

Sun等[56]利用交替沉积自组装方法,成功将Dawson型多酸P2W18和PAH修饰的半导体 CdS 制备成复合膜。与CdS-PAH/PSS 膜相比,无论在全光还是可见光的照射下,CdS-PAH/P2W18复合膜均展示了更高的光电流响应强度和能量转换效率,其光电流响应强度要大于单独 CdS 膜和 P2W18膜光电流之和,能量转换效率提高了1.5倍。 利用荧光和表面光电压测试对机理给出了解释,发现在 CdS 和 P2W18的界面上发生了光生电荷转移,降低了光生电子和空穴对的复合几率,从而提高了 CdS 的光电性能。

5 结论与展望

层层自组装技术是一种简单有效的多层膜构筑技术,可以在纳米水平上精确控制薄膜的厚度和结构,从而获得质量高且具有特殊功能的超薄复合材料。 该技术构筑的多酸基平面薄膜、中空微胶囊和微球等有序结构材料不仅保持了多酸分子原本的结构和性质,更重要的是将纳米粒子插入到多层膜中,由于二者之间的协同作用,复合材料的性质得到进一步的提升,例如:提高了多层膜催化剂对气相异丙醇、染料等有机污染物的光催化降解能力、甲醇的光电氧化活性、电催化活性、电致变色稳定性,也改变了膜的荧光性质;且将多酸固定在各种载体上后,方便了器件的组装和其作为催化剂时的回收。 但多酸化学的发展还需要更多的化学工作者的共同努力,采用先进的手段设计并合成出更多结构新型、性能优异的多酸,再通过修饰、组装和功能化,创新性研究出更多的功能性多酸复合材料,利用多酸与其它化合物间的协同作用诱导产生光、电、磁等特性,为纳米反应器、传感器、发光或磁性纳米和微米器件的开发提供可能的应用。

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