双子表面活性剂在纳米材料可控制备中的应用

双子表面活性剂在纳米材料可控制备中的应用 Applications of Gemini Surfactants in the Controllable Preparation of Nanomaterials 1 3 first-author 张莹方, 女, 硕士生, 现从事应用功能高分子的开发研究。 E-mail：yf_zhang@whu.edu.cn 张莹方, 女, 硕士生, 现从事应用功能高分子的开发研究。 E-mail：yf_zhang@whu.edu.cn yf_zhang@whu.edu.cn 2 3 1 3 corresp E-mail: whugzn@aliyun.com E-mail: whugzn@aliyun.com whugzn@aliyun.com 武汉大学 化学与分子科学学院 有机硅化合物及材料教育部工程研究中心,湖北 武汉 430072 武汉大学 化学与分子科学学院 有机硅化合物及材料教育部工程研究中心,湖北 武汉 430072 Engineering Research Center of Organosilicon Compounds and Materials of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China Engineering Research Center of Organosilicon Compounds and Materials of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China 复旦大学 高分子科学系 聚合物分子工程国家重点实验室,上海 200433 复旦大学 高分子科学系 聚合物分子工程国家重点实验室,上海 200433 State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University,Shanghai, 200433, China State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University,Shanghai, 200433, China 武汉大学 化学与分子科学学院 生物医用高分子材料教育部重点实验室,湖北 武汉 430072 武汉大学 化学与分子科学学院 生物医用高分子材料教育部重点实验室,湖北 武汉 430072 Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China 综述了双子表面活性剂(Gemini surfactants)作为软模板及稳定分散剂在纳米材料可控制备中的应用，重点介绍了Gemini表面活性剂在制备金纳米材料、银纳米材料、介孔硅基材料及其他一些纳米材料中的应用,并指出当前Gemini表面活性剂在纳米材料可控制备中存在种类不足、作用机理不明、难以量产等问题。 The soft template and stable dispersion of Gemini surfactants in the controllable preparation of nanomaterials were reviewed. The applications of Gemini surfactants in the synthesis of gold nanomaterials, silver nanomaterials, mesoporous silica materials and other nanomaterials were surveyed emphatically. The application situations of Gemini surfactants in the controllable preparation and synthesis of nanomaterials were discussed, such as insufficient types, unclear mechanism of action, difficulty in mass production, etc. 双子表面活性剂 软模板 纳米材料 可控合成 Gemini surfactants soft template nanomaterials controllable synthesis 0　 引 言 1 纳米材料是由晶粒组成的、三维尺度上至少有一维的尺度在纳米级别(1~100 nm)的材料,具有宏观物质所没有的小尺寸、表面和界面、宏观量子隧道等效应,呈现出独特的物理和化学性质 [ 1 1 ] ,在光学、电学、磁学等领域有着重要的实用价值和广阔的应用前景 [ 2 2 ] 。通过对纳米材料的形貌和结构进行精确调控可实现其性能的可操控性。寻找简便方法合成特定均一形貌、结构独特的纳米材料具有重要意义。目前,纳米材料的合成方法主要有“自上而下”和“自下而上”两种途径 [ 3 3 ] 。其中,“自上而下”法是指将尺寸较大的材料通过物理方法使其尺寸达到纳米尺度。该过程涉及到较为复杂的仪器、苛刻的条件,且很难使产物达到均匀分布。而“自下而上”法指通过化学方法将单个分子聚集形成所需维度的纳米结构,主要包括模板法、化学还原法、晶种增长法、电沉积法等。 由于粒径较小,且具有较大的比表面积和表面能,纳米材料性质不稳定,容易发生自发团聚现象,导致尺寸、形貌发生变化而失去其独特的性质 [ 4 4 ] 。因此,在制备纳米材料的过程中,往往需要添加类似于表面活性剂等具有分散和稳定体系功能的物质。其中,在“自下而上”的化学合成方法中,以表面活性剂为软模板来导向合成纳米材料的制备过程简便、可操作性强,易实现原子或分子级别的组装,能更好地控制纳米材料的尺寸和形貌 [ 5 5 ] 。 表面活性剂可快速吸附在所形成的纳米晶表面,由于静电稳定机制和空间位阻机制,从而能有效地防止纳米材料的团聚现象,增加材料的稳定性 [ 6 6 ] 。此外,表面活性剂在溶液中可以形成不同形态的聚集体,如胶束、微乳液、囊泡、液晶等,这些聚集体就成为制备纳米材料的“微反应器”,起到软模板的作用,能较好地控制纳米粒子的尺寸与形貌 [ 7 7 ] 。常见用于制备纳米材料的表面活性剂有十六烷基三甲基溴化铵(CTAB)、十六烷基三甲基氯化铵(CTAC)、十二烷基磺酸钠(SDS)等小分子表面活性剂,以及聚乙烯基吡咯烷酮(PVP)等高分子表面活性剂。随着纳米科技的迅猛发展,上述表面活性剂已难以满足合成各种形貌纳米粒子的要求。双子表面活性剂(Gemini surfactants)是将2个传统表面活性剂在亲水头基(headgroups)或接近亲水头基处,由联接基团(spacer)通过化学键联接在一起形成的一类新型表面活性剂 [ 8 8 , 9 9 ] 。如 图1 图1 所示，通过改变其亲水头基、疏水尾链和中间联接链的种类、长度等，可以合成出不同结构的Gemini表面活性剂 [ 10 10 ] 。Gemini表面活性剂结构独特、性能优异,相较于传统的表面活性剂,具有以下特性: 1) 在溶液中可以形成种类丰富和更易调节的聚集体 [ 11 11 , 12 12 ] ； 2) 吸附聚集趋势更强,临界胶束浓度更低,表面活性更高 [ 13 13 ] ； 3) 水溶性更好，易于从产物表面去除,有利于产物表面洁净 [ 14 14 ] ； 4) 可设计性较强,可根据目标产物设计合成具有特定官能团或性能的Gemini表面活性剂 [ 15 15 ] 。 因此,Gemini表面活性剂在纳米材料的可控制备中具有明显的优势,其应用越来越广泛 [ 16 16 , 17 17 , 18 18 , 19 19 ] 。本文重点介绍Gemini表面活性剂在金纳米材料、银纳米材料、介孔氧化硅材料及其他一些纳米材料制备中的应用,并探寻其在纳米材料可控制备中存在的问题,展示其广阔的应用前景。 1　 Gemini表面活性剂在纳米材料制备中的应用 1 1.1　金纳米材料 2 金纳米材料作为化学性质最稳定的金属纳米材料,具有独特的光学、电学、磁学性质和良好的生物相容性等,在光学、电子、催化、生物传感及其他诸多领域应用前景广阔 [ 20 20 , 21 21 , 22 22 , 23 23 ] 。早在1998年, Esumi等 [ 24 24 ] 采用阳离子Gemini表面活性剂二亚甲基-1,2-双(十二烷基二甲基铵)二氯乙烷（C 12 -C 2 -C 12 ·Cl 2 , 其中,C 12 指2个疏水的十二烷基尾链,C 2 指中间联接链二亚甲基, Cl 2 指2个氯离子；下文中Gemini代表符号意义相同,仅尾链、中间联接链和反离子不同）作为软模板,在紫外光照射下还原氯金酸得到纤维状金纳米粒子,通过调整Gemini表面活性剂的浓度可以改变纤维状纳米产物的长度。该类表面活性剂形成的棒状胶束为纳米材料的合成提供了软模板,可实现纤维状金纳米材料的可控合成。 Gemini表面活性剂在制备空心金纳米材料中具有独特的优势。Wang等 [ 25 25 ] 以C 12 -C 6 -C 12 ·Br 2 为软模板制备了多种空心的金纳米材料,包括球形、胶囊状和管状等( 图2 图2 )。由于Gemini表面活性剂具有较强的聚集能力,该模板在还原过程中保持稳定。而还原形成的金离子(Au + )大大降低了Gemini头基间的静电斥力,使C 12 -C 6 -C 12 ·Br 2 自组装成囊泡、囊状或管状聚集体,从而成为形成空心金纳米结构的模板。其中,中空的金纳米材料对甲醇氧化具有很好的催化效果。同年, 该课题组以相同的C 12 -C 6 -C 12 ·Br 2 为软模板,制备了长达数微米(宽40~50 nm)的新型一维“辫子状”金纳米线 [ 26 26 ] 。C 12 -C 6 -C 12 ·Br 2 与HAuCl 4 形成的球形聚集结构可以制备球形金纳米粒子,而由类蠕虫状和双层结构聚集体则可分别形成普通和辫子状金纳米线。由此可见,Gemini表面活性剂是控制金纳米粒子形貌形成的关键因素,而C 12 -C 6 -C 12 ·Br 2 头基和AuCl 4 - 之间静电相互作用的调控决定了聚集体的转变,进而决定了最终产物金纳米材料的形貌。Xu等 [ 27 27 ] 以季铵盐Gemini表面活性剂系列为导向剂,采用三步晶种增长法合成了长达4.4 μm、最大长径比达210的金纳米线。通过改变Gemini导向剂的中间联接链长度,实现了对纳米线长径比的精确调控 [ 27 27 ] ( 图3 图3 ),Gemini表面活性剂中间联接链的长度与纳米线的长度基本呈正相关。该研究为制备其他材料的一维纳米线提供了有力的支撑。此外,该课题组还开展了二维纳米片、三维枝状等结构的金微纳米材料的制备。 (a) C 16 -C 6 -C 16 ·Br 2 ; (b) C 16 -C 10 -C 16 ·Br 2 ; (c) C 16 -C 12 -C 16 ·Br 2 ; (d) C 16 -C 6 -C 16 ·Br 2 (Et) 除了在制备常规形态金纳米材料方面展现出显而易见的优势外,该类表面活性剂对控制高指数晶面的纳米颗粒及调控胶体纳米晶自组装也展现出独有的优势。夏衍等 [ 28 28 ] 报道以C 16 -C 6 -C 16 ·Br 2 为诱导剂可高产率制备多种不同形态的金纳米双锥,包括传统型、凹面型、截断型和哑铃型等。通过控制初产物的洗涤次数,使表面修饰有一定配体（保留的Gemini表面活性剂）的纳米双锥在硅基底上可形成长程有序的超晶体。同时,其普适性并未因产物形态的改变而改变。Gemini表面活性剂既充当导向剂,实现纳米晶形貌的有效控制,又充当诱导纳米晶组装的良配体,克服现行组装研究纳米晶（组装基元）的制备与组装过程相对独立的弊端。 因此,Gemini表面活性剂具备优越的调控产物形态以及诱导纳米晶组装的性能,为设计合成各种结构新颖和性能独特的金属纳米材料、超晶体材料,乃至于构建功能器件提供了一条简便有效的途径。 1.2　银纳米材料 2 银纳米材料不仅具有纳米材料固有的独特性能,还兼具优良的导电性、导热性、化学稳定性和抗氧化性等,使其在表面增强拉曼光谱 [ 29 29 , 30 30 ] 、催化剂 [ 31 31 ] 、抗菌杀菌 [ 32 32 ] 、柔性透明导电电极 [ 33 33 ] 等领域展现出巨大的应用价值。 Datta等 [ 34 34 ] 采用一系列Gemini咪唑表面活性剂合成银纳米粒子,并探究了中间联接链长度对银纳米结构形成的影响，发现中间为2个碳的Gemini表面活性剂易诱导形成瘦长结构的银纳米结构,而增加中间碳链的长度则趋向于形成球形的银纳米结构。该文献首次报道了Gemini咪唑表面活性剂所形成的胶束聚集体与银纳米粒子形貌之间的对应关系,制备过程中因使用咪唑鎓盐型Gemini表面活性剂能够得到单层银纳米材料,为合成单层纳米结构提供了一个新思路。 Negm等 [ 35 35 ] 合成了尾链长度为8~18个碳不等的磷酸烷基酯类阴离子Gemini表面活性剂,并以其为模板,柠檬酸三钠作为还原剂合成银纳米粒子，发现用Gemini保护的银纳米粒子抗菌效果更好,其抗菌效果与Gemini的种类有直接关系,而且具有更好的生物活性。此外,增加Gemini疏水链长度使得所合成的银纳米粒子的稳定性更佳。 Xia课题组 [ 14 14 ] 以季铵盐Gemini表面活性剂C 16 -C 12 -C 16 ·Br 2 作导向剂,代替传统稳定剂,简便快速地合成了形状特异、单分散的花状银微纳米结构。仅通过改变实验参数,还可得到单分散的绣球状和蠕虫状等银微纳米结构。此外,还研究了银微纳米结构的形成机理以及Gemini表面活性剂在控制微纳米材料形貌中的作用( 图4 图4 )。而表面增强拉曼散射(SERS)测试显示,银微纳米花可以作为极其灵敏的SERS基片,可满足超痕量检测分析物的要求。 1.3　介孔硅基材料 2 介孔硅基材料是指孔径在2~50 nm范围内的多孔含硅材料,由于其具有更大的比表面积、有序的孔隙结构、较小的孔径和优异的生物相容性,受到越来越多的关注 [ 36 36 , 37 37 ] 。表面活性剂模板法是介孔硅基材料合成中研究最为广泛的合成方法,主要利用表面活性剂分子在溶液中形成的聚集体,如胶束、胶囊等形态作为模板合成所需形貌的介孔硅基材料。传统型表面活性剂的不对称性结构对胶束化过程和中间相类型有很大的影响,但其结构变化有限,限制了在介孔硅基材料制备中的使用。而Gemini表面活性剂结构变化丰富、性质独特,在介孔硅基材料的可控制备中具有广泛的应用前景。 Huo等 [ 38 38 ] 在研制介孔氧化硅材料时发现,相比于其他表面活性剂如十六烷基二甲基苄基氯化铵(CDBA)等,使用Gemini模板剂C 22 -C 12 -C 22 ·Cl 2 仅在室温下反应1 d时间就可以合成MCM-48,而无需加入有机物及在较高温度条件下进行反应。该课题组利用水热法合成介孔氧化硅发现,Gemini表面活性剂有利于形成立方相的MCM-48介孔氧化硅,其产物中间具有密度很大的长条状气孔 [ 39 39 ] 。Romero等 [ 40 40 ] 利用对称的Gemini表面活性剂C 12 -C 2 -C 12 ·Br 2 、C 10 -C 2 -C 10 ·Br 2 和不对称的Gemini表面活性剂C 8 -C 2 -C 16 ·Br 2 ,在酸性或中性环境中于室温下合成介孔氧化硅材料,发现C 12 -C 2 -C 12 ·Br 2 有利于合成MCM-50,而C 8 -C 2 -C 16 ·Br 2 则有利于合成MCM-41,且合成出的产物品质较高。相比于单链的表面活性剂,使用Gemini表面活性剂时反应条件更加温和。Han等 [ 41 41 ] 以阳离子Gemini表面活性剂C 12 -C 2 -C 12 ·Br 2 为软模板,通过乙酸乙酯控制反应溶液的酸碱性,并对硅源的硅酸钠与Gemini的摩尔比进行调控,合成了有序的立方介孔氧化硅材料MCM-48。Wang等 [ 42 42 ] 在研究Gemini中间联接链与介孔氧化硅材料空隙大小的关系时发现,Gemini联接链长增加,硅材料的气孔尺寸明显减小。 与传统的固体介孔纳米粒子相比,中空介孔氧化硅纳米材料（hollow mesoporous silica nanoparticles, HMSNs）因其独特的巨大空穴和介孔壳层结构,而具有较高的储存能力及在质量扩散和传输方面的优势,在生物矿化、催化、分离、药物释放等方面有着巨大的潜在应用前景。Li等 [ 43 43 ] 使用Gemini表面活性剂C 14 -C 2 -C 14 ·Br 2 作为模板,以四乙基原硅酸盐作为硅源,在碱性条件下加热至80 ℃反应2 h后去除表面活性剂模板,制得具有径向取向的中空介孔氧化硅材料,其微观形貌如 图5 图5 所示。 目前,纳米化学研究已经转向实现复杂的多功能纳米材料的制备,将2个或多个不同的特征以协同方式整合在单一的纳米系统中,从而赋予纳米粒子新的功能 [ 44 44 ] 。Yan等 [ 45 45 , 46 46 ] 将空心介孔和荧光特性结合在同一个SiO 2 纳米粒子结构中，构建了一种新型多功能含硅材料。他们首先设计合成具有聚合诱导发射(aggregation-induced emission，AIE)功能的Gemini表面活性剂,继而用之辅助制备形貌可控的荧光空心SiO 2 纳米粒子(AIE-SNs)。AIE-Gemini表面活性剂(C 16 -TPE-C 16 ·Br 2 ,其中TPE指四苯基乙烯)不仅为AIE-SNs提供了荧光团,而且还参与了十六烷基三甲基溴化铵(CTAB)的结构导向过程。通过适当调整CTAB与C 16 -TPE-C 16 ·Br 2 的摩尔比,可制备不同形貌和荧光性能的AIE-SNs,如 图6 图6 所示。AIE-SNs具有单个荧光、空心或介孔纳米粒子所没有的优点,在生物医学中作为多功能纳米晶具有广阔的应用前景。该方法为制备多性质、多用途的纳米粒子提供了一种新的途径。 1.4　其他纳米材料 2 Gemini表面活性剂在其他纳米材料的可控制备中也有广泛应用,如合成纳米氧化物、复合材料等。 Lyu等 [ 47 47 ] 设计合成了含硅氧烷的Gemini表面活性剂,以其为软模板辅助合成了氧化锆、二氧化钛和氧化钒等介孔金属氧化物,如 图7 图7 所示。其中,含硅氧烷的Gemini表面活性剂在纳米材料形成过程中起着重要的支撑作用,直接煅烧去除后生成热稳定性较高的介孔金属氧化物。Yuan等 [ 48 48 ] 以含羟基和枝状侧链的非离子Gemini表面活性剂为结构定向模板合成介孔氧化钨,并用伏安法和分光光度法对其电致变色响应进行了研究。Ouyang等 [ 49 49 ] 以含硅氧烷的季铵盐Gemini表面活性剂为软模板,通过煅烧去除模板的策略合成了高度有序的介孔Ce 0.5 Zr 0.5 O 2 固溶体。该方法利用柠檬酸的配位能力,使无机源在温和的碱性溶液中共存,并利用H 2 O 2 的强氧化能力均匀地沉淀Ce和Zr阳离子。这种方法有效地避免了水溶液中无机-有机基团的结合。Song等 [ 50 50 ] 以C 16 -C 4 -C 16 ·Br 2 为稳定剂,采用一锅原位生长还原法制备了分布均匀的二维金属纳米粒子(MNPs)/石墨烯纳米复合材料。甚至一定浓度的Gemini表面活性剂在溶液中组装形成不同的聚集体,可诱导调控稀土纳米材料的形貌,如氧化铈 [ 51 51 ] 和氧化镧 [ 52 52 ] 等。 2　 现阶段主要问题 1 虽然使用Gemini表面活性剂软模板推进了纳米材料的可控制备,现阶段也取得了一些可喜的研究成果,然而仍存在着很多核心问题亟需解决。主要包括以下几个方面： 1） 缺乏具有特定官能团及结构的Gemini表面活性剂软模板。根据目标纳米材料的性能与特征,有针对性地设计和合成具有特定官能团和结构的Gemini软模板仍是一项极具挑战性的工作。根据需要,设计合成具有不同官能团,包括双官能团乃至多官能团的有机配体,如目前使用较少的巯基（—SH）、羧基（—COOH）等,以实现对不同种类纳米晶的有效修饰。此外,其新颖的空间结构可诱导纳米晶呈现更加丰富的组装行为,可期望得到结构新颖的超晶体结构,从而实现多种功能器件的制备。 2） Gemini表面活性剂在可控制备中的作用机理有待深入研究。虽然已实现用Gemini表面活性剂为软模板制备一些单分散和高产率的纳米材料,但对于其所起作用以及纳米材料的形成机理,尚未达成统一认识。进一步揭示其作用机理,对于后续纳米材料的可控制备研究具有重要的指导作用。 3） 合成方法与途径过于苛刻或复杂。纳米晶的形成对环境的敏感性较大,多种因素对其形成过程有重要的影响,例如试剂的加入顺序、加样速度、试剂浓度和种类以及反应温度甚至室温变化等。现阶段的许多制备方法仍仅局限于实验室,阻碍了纳米材料的广泛应用，需要继续寻找和改进有效适用的新制备方法,保证纳米材料可控制备的可重复性。 4） 纳米材料的量产制备及应用有待突破。尽管通过诸多高效的合成策略已经成功制备和调控得到多种不同形貌的纳米材料,但其量产制备一直是制约其应用的瓶颈。可合成克级、千克级纳米材料的方法极少,绝大多数仅维持在毫克级或更低量级,亟待开发可高效、量产和普适性的制备纳米材料新策略。此外,仅有少数纳米材料,如碳材料 [ 53 53 ] 、半导体材料 [ 54 54 ] 等已经在能源、催化等领域展现出优越的应用性能,很多的纳米材料尚未找到对应的应用,必须加大力度寻找各种纳米材料的有效应用,以发挥其应有的应用价值。 3　 结 语 1 Gemini表面活性剂拥有独特的双功能基团结构,在溶液中能形成丰富的有序聚集体,且聚集体结构具有可调控性。因此,Gemini表面活性剂适用于作为软模板进行纳米材料的可控制备,可获得不同形貌、结构、尺寸的纳米材料。目前,已使用Gemini表面活性剂可控制备了一些结构特殊、单分散、高产率的纳米材料,如金纳米材料、银纳米材料、介孔硅基材料及其他一些纳米材料。但尚有许多重要问题亟待解决。Gemini表面活性剂在纳米材料可控制备领域的深入研究,必将促使纳米材料合成技术的快速发展,进而拓宽纳米材料的应用领域和范围。 参考文献 HAN D , PARK J . 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