CN106582886A - 叠层壳聚糖/有机累托石/TiO2‑Ag@AgCl插层纳米复合光催化膜及其制备方法 - Google Patents
叠层壳聚糖/有机累托石/TiO2‑Ag@AgCl插层纳米复合光催化膜及其制备方法 Download PDFInfo
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- CN106582886A CN106582886A CN201611124299.7A CN201611124299A CN106582886A CN 106582886 A CN106582886 A CN 106582886A CN 201611124299 A CN201611124299 A CN 201611124299A CN 106582886 A CN106582886 A CN 106582886A
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Abstract
本发明公开了一种叠层壳聚糖/有机累托石/TiO2‑Ag@AgCl插层纳米复合光催化膜及其制备方法，属于环境保护材料制备技术领域。本发明首先利用溶胶‑凝胶法制备有机累托石/TiO2，再通过沉积法及光还原法制备有机累托石/TiO2‑Ag@AgCl，最后利用溶液法制备壳聚糖/有机累托石/TiO2‑Ag@AgCl插层纳米复合物，反复流涎‑冷冻‑干燥制备成物理交联的叠层复合膜。本发明制备的插层纳米复合光催化薄膜无毒、价廉，可生物降解，且稳定性好，可见光光催化活性高，不会造成资源浪费与形成二次污染，有望应用于工农业等领域有机废水及室内挥发性有机气体的处理。
Description
技术领域
本发明属于环境保护材料制备技术领域，具体涉及一种具有吸附-可见光光催化功能的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的制备方法。
背景技术
有机废水往往成分复杂，难以生物降解，在水体、土壤等自然环境中累积、蓄存，严重破坏了生态环境和人体健康。同样，由于楼房建筑、室内装修以及日用生活品的使用引起的室内污染问题也越来越严重。有效治理有机废水及去除室内挥发性有机污染气体是当前污染控制领域的研究重点和难点。传统处理有机污染物的方法主要有：物理处理技术、化学处理技术、生物处理技术。传统处理方法存在反应条件苟刻、应用范围窄、降解效率低、能耗高且易产生二次污染等问题。半导体光催化技术因对污染物选择性低、反应条件温和、反应速率快等优点而日益受到关注，在环境污染物的处理方面有良好的应用前景。TiO2因其氧化能力强、无毒和光化学稳定等优点在诸多领域得到应用，并取得了很好的研究成果。然而，TiO2带隙宽，导致太阳光利用率低、光生电子-空穴对易于复合而使量子效率下降，且TiO2纳米颗粒在水中难回收，使其应用受到很大限制。故拓宽光催化剂的光谱响应范围以提高太阳光的利用率、提高光催化剂的量子率和催化剂回收再利用迫在眉睫。
累托石是一种亲水性的、易分离成纳米级微片的天然矿物材料，既有良好的阳离子交换性、分散性、膨胀性、悬浮性和胶体性能，又耐高温、抗紫外，累托石表面积大，对有机污染物具有良好的吸附性，故可作为光催化剂的载体。我国湖北有品质优良的储藏量高达600多万吨的累托石矿藏，由于人们对其认识相对其它粘土较晚，对其进行高附加值的开发利用也较少。壳聚糖为阳离子型天然多糖，可生物降解，易成膜、无毒、价廉，含有丰富的羟基和氨基，对有机污染物吸附性强，可作为光催化剂的优良载体。
在拓宽光催化剂的光谱响应范围以提高太阳光利用率方面，研究人员展开了一系列研究，如掺杂、成“结”、沉积贵金属、染料敏化等均旨在获得宽谱响应的光催化材料。近年来，人们提出利用贵金属表面等离子体效应来提高光催化材料性能。如Xu等通过水热法制备了立方状的NaTaO3纳米粒，沉积AgCl在NaTaO3纳米粒表面，通过光还原将部分的Ag+还原为Ag0，得到等离子体光催化剂Ag/AgCl/NaTaO3，该催化剂相对于纯NaTaO3对亚甲基蓝、罗丹明B及苯酚均具有较高的可见光光催化活性(Dongbo Xu,Weidong Shi,Chengjie Song,etal.In-situ synthesis and enhanced photocatalytic activity of visible-light-driven plasmonic Ag/AgCl/NaTaO3 nanocubes photocatalysts.Applied Catalysis B:Environmental.2016(191)228-234)。
发明内容
本发明目的是提供一种在可见光下具有良好的光催化性的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜，以及该复合光催化膜的制备方法。
解决上述技术问题所采用的技术方案是该叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜由下述方法制备得到：
1、制备有机累托石
将累托石煅烧后用焦磷酸钠进行钠化处理，得到钠化累托石(NaREC)；将钠化累托石用十六烷基三甲基氯化铵进行有机化处理，得到有机累托石(OREC)。
2、制备有机累托石/TiO2-Ag@AgCl复合物
(1)将钛酸异丙酯和6mol/L盐酸混合，使混合液中钛离子与H+的摩尔比为1:(3～5)，室温下搅拌2～4小时，得到柱撑溶液。
(2)将有机累托石超声分散于体积分数为60％的乙醇水溶液中，配制成质量分数为1％～5％的有机累托石悬浮液。
(3)将柱撑溶液滴加入有机累托石悬浮液中，其中有机累托石的质量与柱撑溶液中钛离子的摩尔量之比为1g:8～15mmol，在超声条件下40～50℃反应20～30分钟，再在60～80℃恒温水浴下搅拌2～5小时，室温陈化20～30小时，过滤、去离子水洗涤、干燥，干燥后的固体在450～550℃下煅烧3～4小时，得到有机累托石/TiO2复合物(OREC/TiO2)。
(4)将有机累托石/TiO2复合物均匀分散于去离子水中，并加入0.1mol/LAgNO3水溶液，其中有机累托石/TiO2复合物的质量与AgNO3的摩尔量之比为1g:0.5～1.5mmol，室温搅拌20～30分钟，再加入0.1mol/L盐酸，搅拌20～30分钟，过滤、去离子水洗涤、干燥，所得固体产物分散于体积分数为40％的乙醇水溶液中，用波长>400nm的可见光照射30～90分钟，过滤、干燥，得到有机累托石/TiO2-Ag@AgCl复合物(OREC/TiO2-Ag@AgCl)。
3、制备壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物
将壳聚糖(CS)溶于质量分数为2％的醋酸水溶液中，配制成质量分数为1％～5％的壳聚糖溶液；将有机累托石/TiO2-Ag@AgCl复合物加入蒸馏水中，超声分散均匀，得到质量分数为1％～5％的有机累托石/TiO2-Ag@AgCl复合物悬浮液，然后加入甘油，继续超声20～30分钟，再在超声条件下逐滴加入质量分数为1％～5％的壳聚糖溶液，其中壳聚糖与有机累托石/TiO2-Ag@AgCl复合物、甘油的质量比为1:(0.02～0.10):(0.5～1.5)，在50～60℃下反应4～7小时，冷却至室温，得到壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物(CS/OREC/TiO2-Ag@AgCl)。
4、制备叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜
将壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物在玻璃板上经反复流涎-冷冻-干燥，得到叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜。
上述步骤1中，优选所述累托石的煅烧温度为850℃、时间为3小时，用焦磷酸钠进行钠化处理的温度为50～70℃、时间为2～3小时，用十六烷基三甲基氯化铵进行有机化处理的温度为60～70℃、时间为5～8小时，其中焦磷酸钠用量为累托石质量的3％～5％，十六烷基三甲基氯化铵用量为钠化累托石质量的3％～5％。
上述步骤2的(2)中，优选将有机累托石超声分散于体积分数为60％的乙醇水溶液中，配制成质量分数为3％的有机累托石悬浮液。
上述步骤2的(3)中，优选将柱撑溶液滴加入有机累托石悬浮液中，其中有机累托石的质量与柱撑溶液中钛离子的摩尔量之比为1g:10～12mmol，在超声条件下45℃反应20～30分钟，再在70℃恒温水浴下搅拌2～5小时，室温陈化20～30小时，过滤，用去离子水洗涤，干燥，干燥后的固体在450～550℃下煅烧3～4小时，得到有机累托石/TiO2复合物。
上述步骤2的(4)中，优选所述有机累托石/TiO2复合物的质量与AgNO3的摩尔量之比为1g:1.0mmol。
上述步骤3中，优选所述壳聚糖与有机累托石/TiO2-Ag@AgCl复合物、甘油的质量比为1:(0.05～0.08):(0.5～1.5)。
上述步骤4中，优选将壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物在玻璃板上以2.4mL/m2流涎，冷冻，60℃干燥成膜，反复流涎-冷冻-干燥3～5层。
本发明的有益效果如下：
1、本发明以吸附能力极佳的壳聚糖及有机累托石为载体，承载对可见光响应能力较高的TiO2-Ag@AgCl等离子体光催化剂，更大程度提高了壳聚糖/有机累托石/TiO2-Ag@AgCl复合膜光催化降解污染物的效率，且可重复使用。
2、本发明复合光催化膜制备方法操作简单，所用原料天然、价廉，反应可控，环境友好，适合于批量生产；有机/无机插层结构使膜具有良好的力学性能、热性能，叠层化处理提高了膜的使用寿命。
3、本发明叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜通过与污染物分子的相互作用实现特殊的转化，使周围的氧气、水分子及Cl-激发成氧化能力极强的氧自由基、羟基自由基及Cl0，达到降解有机污染物的目的，该方法不会造成资源浪费与二次污染，是一种绿色环保高效的有机污染物处理技术。
附图说明
图1是实施例1制备的有机累托石、有机累托石/TiO2-Ag@AgCl复合物、壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的XRD图。
图2是实施例1制备的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的扫描电镜图。
图3是实施例1制备的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的EDS图。
图4是实施例1制备的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物的透射电镜图。
图5是对比例1制备的壳聚糖/有机累托石复合膜、对比例2制备的壳聚糖/有机累托石/TiO2复合膜、实施例1制备的壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的紫外吸收光谱图。
图6是对比例1制备的壳聚糖/有机累托石复合膜、对比例2制备的壳聚糖/有机累托石/TiO2复合膜、实施例1制备的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜对甲其橙吸附-光催化降解动力学曲线。
图7是对比例1制备的壳聚糖/有机累托石复合膜、对比例2制备的壳聚糖/有机累托石/TiO2复合膜、实施例1制备的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜对罗丹明光催化降解动力学曲线。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
1、制备有机累托石
将5g累托石在850℃煅烧3小时，然后将煅烧后的累托石加入161.67g蒸馏水中配成质量分数为3％的累托石悬浮液，并加0.15g焦磷酸钠，在60℃下搅拌3小时，过滤、洗涤、干燥，得钠化累托石。将5g钠化累托石加入161.67g蒸馏水中，高速均质搅拌使其充分分散，再加入0.15g十六烷基三甲基氯化铵，在70℃下搅拌8小时，自然冷却，抽滤、水洗，将滤饼置于烘箱中90℃干燥8小时，研磨过筛，即得有机累托石。
2、制备有机累托石/TiO2-Ag@AgCl复合物
(1)将14mL(51.31mmol)钛酸异丙酯和36mL 6mol/L盐酸混合，室温下搅拌3小时，得到柱撑溶液。
(2)将5g有机累托石超声分散于162g体积分数为60％的乙醇水溶液中，配制成质量分数为3％有机累托石悬浮液。
(3)将步骤(1)得到的柱撑溶液以10滴/分钟的速度滴入到步骤(2)配制的有机化累托石悬浮液中，在超声条件下45℃反应30分钟，再在70℃恒温水浴下搅拌3小时，室温陈化24小时，过滤、去离子水洗涤、干燥，干燥后的固体放入马弗炉中在500℃下煅烧3小时，得到有机累托石/TiO2复合物。
(4)将5g有机累托石/TiO2复合物均匀分散于150mL去离子水中，并加入50mL0.1mol/L AgNO3水溶液，室温搅拌20分钟，过滤、去离子水洗涤、干燥后，所得固体产物分散于150mL体积分数为40％的乙醇水溶液中，用90W钠灯(平均波长589.3nm)照射60分钟，灯距为10cm，过滤，干燥，得到有机累托石/TiO2-Ag@AgCl复合物。
3、制备壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物
将1g壳聚糖溶于32.33g质量分数为2％的醋酸水溶液中，制得质量分数为3％的壳聚糖溶液；将0.05g有机累托石/TiO2-Ag@AgCl复合物加入1.62g蒸馏水中，超声分散，得到质量分数为3％的有机累托石/TiO2-Ag@AgCl复合物悬浮液，然后加入1g甘油，继续超声20分钟，再在超声条件下逐滴加入质量分数为3％的壳聚糖溶液，在60℃下反应6小时，冷却至室温，得到壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物。
4、制备叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜
将玻璃板裁成2.5cm×7.5cm大小，浸没在新配制的铬酸洗液中2～3天，取出后用大量二次水冲洗干净，吹干后将其浸没在质量分数为98％的硫酸和质量分数为30％的双氧水按体积比为3:1的混合溶液中，将该混合溶液加热至80℃，活化2小时，自然冷却至室温，冷却后用大量二次水冲洗，吹干，得到洁净的活化玻璃板。将壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物在洁净的活化玻璃板上以2.4mL/m2流涎，-10℃冷冻1小时，60℃干燥成膜，反复流涎-冷冻-干燥3层，得到叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜。
采用X-射线衍射仪(XRD)来表征样品的相结构，XRD分析结果见图1。由图可见，有机累托石在2θ为3.64°处有一衍射峰，根据Bragg定律，可算出其d001值为2.4473nm。相比于有机累托石，有机累托石/TiO2-Ag@AgCl复合物的(001)与(002)峰强度变弱，同时在25.3°、27.4°、33.4°处出现了TiO2的锐钛矿、板钛矿及金红石的特征衍射峰，在27.4°、33.4°、46.2°、54.6°、57.2°、67.2°、74.1°及76.4°处出现AgCl的特征衍射峰，在38.30°及48.22°处出现Ag的特征衍射峰，表明成功获得有机累托石/TiO2-Ag@AgCl复合物。相对于有机累托石/TiO2-Ag@AgCl复合物，壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物的(001)峰发生了左移且峰强度大大降低，根据Bragg定律，算出d001值为3.0256nm，表明壳聚糖已成功插进有机累托石/TiO2-Ag@AgCl层间形成了壳聚糖/有机累托石/TiO2-Ag@AgCl复合物。
采用扫描电镜(SEM)来表征样品的形貌，利用其附件能谱仪(EDX)对样品表面所选区域进行组成成分分析，SEM及EDS分析结果见图2和3。由SEM图可知，有机累托石/TiO2-Ag@AgCl在壳聚糖基质中分散均匀，膜表面平整，由EDS图可看到膜材料中存在C、Si、O、Ti、Cl、Ag元素，表明膜中存在有机累托石/TiO2-Ag@AgCl。
采用透射电镜(TEM)来表征样品的微观形貌，TEM分析结果见图4，其中白色为壳聚糖基体，黑色为有机累托石、Ag@AgCl颗粒及TiO2聚集体。由TEM图可知，有机累托石在壳聚糖基质中进行了插层且被剥离，形成插层-剥离型复合材料。同时膜材料中分散着纳米级的Ag@AgCl颗粒及TiO2聚集体。TEM和EDX结果表明了叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜具有由壳聚糖和有机累托石/TiO2-Ag@AgCl形成的插层型复合结构。
对比例1
将1g壳聚糖溶于32.33g质量分数为2％的醋酸水溶液中，制得质量分数为3％的壳聚糖溶液；将0.05g有机累托石(按照是实施例1的方法制备)加入1.62g蒸馏水中，超声分散，得到质量分数为3％的有机累托石悬浮液，然后加入1g甘油，继续超声20分钟，再在超声条件下逐滴加入质量分数为3％的壳聚糖溶液，在60℃下反应6小时，冷却至室温，得到壳聚糖/有机累托石复合物。将壳聚糖/有机累托石复合物在洁净的活化玻璃板上以2.4mL/m2流涎，-10℃冷冻1小时，60℃干燥成膜，反复流涎-冷冻-干燥3层，得到壳聚糖/有机累托石复合膜。
对比例2
将1g壳聚糖溶于32.33g质量分数为2％的醋酸水溶液中，制得质量分数为3％的壳聚糖溶液；将0.05g有机累托石/TiO2复合物(按照是实施例1的方法制备)加入1.62g蒸馏水中，超声分散，得到质量分数为3％的有机累托石/TiO2复合物悬浮液，然后加入1g甘油，继续超声20分钟，再在超声条件下逐滴加入质量分数为3％的壳聚糖溶液，在60℃下反应6小时，冷却至室温，得到壳聚糖/有机累托石/TiO2复合物。将壳聚糖/有机累托石/TiO2复合物在洁净的活化玻璃板上以2.4mL/m2流涎，-10℃冷冻1小时，60℃干燥成膜，反复流涎-冷冻-干燥3层，得到壳聚糖/有机累托石/TiO2复合膜。
采用紫外可见分析仪对实施例1和对比例1和2的膜进行光学吸收特性表征，结果见图5。由图5可见，相比于壳聚糖/有机累托石复合膜，壳聚糖/有机累托石/TiO2复合膜及壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米光催化复合膜在波长为225～275nm区域对光吸收明显增加，其吸收带有明显红移现象。相比于壳聚糖/有机累托石/TiO2复合膜，壳聚糖/有机累托石/TiO2-Ag@AgCl复合膜在波长为340nm及380nm附近出现了两个新的吸收峰且吸收峰边缘达到430nm，在波长450nm至550nm区域有明显可见光吸收现象，说明等离子体Ag@AgCl拓展了叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的可见光响应范围。
为了证明本发明的有益效果，发明人分别采用实施例1制备的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜、对比例1制备的壳聚糖/有机累托石复合膜、对比例2制备的壳聚糖/有机累托石/TiO2复合膜作为光催化剂，光催化降解甲基橙和罗丹明，具体实验情况如下：
将0.1g叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜在室温下分别放入100mL初始浓度为50mg/L的甲基橙水溶液及10mg/L的罗丹明水溶液中，黑暗中搅拌120min，达到吸附平衡后取样4mL，同时再回补4mL蒸馏水。接着开启200W高压汞灯模拟可见光光源，每隔一定时间取样一次同时回补蒸馏水。取出的溶液用紫外分光光度计测定甲基橙及罗丹明浓度，以评价该复合光催化膜的光催化降解效果。实验结果表明，光照180min后，甲基橙的降解率达92.4％，罗丹明的降解率达60.4％，说明本发明制备的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜在可见光下光催化性能良好。
为研究等离子共振效应对光催化性能的影响，比较了不同光催化剂对甲基橙及罗丹明的光催化性能的影响，见图6及图7。从图6可看出，壳聚糖/有机累托石复合膜对甲基橙只有吸附性没有光催化降解性，壳聚糖/有机累托石/TiO2复合膜对甲基橙由于光催化导致的降解率只有40.2％，远小于壳聚糖/有机累托石/TiO2-Ag@AgCl复合膜，这点对于降解罗丹明也得到了相同的体现(图7)，这说明壳聚糖/有机累托石/TiO2-Ag@AgCl光催化膜中Ag@AgCl的表面等离子体效应有利于光催化反应的进行。
为研究流涎膜层数对光催化性能的影响，膜层数分别选1层、2层、3层和5层，其它反应条件均相同。实验结果表明，不同层数的复合膜对甲基橙及罗丹明都具有较好的光催化反应活性，对甲基橙的降解率分别为90.1％、91.3％、92.4％及91.0％，对罗丹明的降解率分别为58.1％、59.3％、60.4％及59.0％，只是流涎膜层数小于3，膜在甲基橙及罗丹明溶液中存在的稳定性不是太好，寿命不理想，故本发明中选用流涎膜层数为3。
为研究有机累托石/TiO2-Ag@AgCl复合物含量对复合膜光催化性能的影响，有机累托石/TiO2-Ag@AgCl用量分别取壳聚糖用量的2％、3％、5％和10％，其它反应条件均相同。实验结果表明，四种复合膜对甲基橙的降解率分别为87.7％、89.1％、92.4％及91.1％，对罗丹明的降解率分别为56.0％、57.1％、60.4％及58.9％，故本发明中选用有机累托石/TiO2-Ag@AgCl复合物含量为5％。
Claims (8)
1.一种叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的制备方法，其特征在于它由下述步骤组成：
(1)制备有机累托石
将累托石煅烧后依次用焦磷酸钠进行钠化处理、用十六烷基三甲基氯化铵进行有机化处理，得到有机累托石；
(2)制备有机累托石/TiO2-Ag@AgCl复合物
①将钛酸异丙酯和6mol/L盐酸混合，使混合液中钛离子与H+的摩尔比为1:(3～5)，室温下搅拌2～4小时，得到柱撑溶液；
②将有机累托石超声分散于体积分数为60％的乙醇水溶液中，配制成质量分数为1％～5％的有机累托石悬浮液；
③将柱撑溶液滴加入有机累托石悬浮液中，其中有机累托石的质量与柱撑溶液中钛离子的摩尔量之比为1g:8～15mmol，在超声条件下40～50℃反应20～30分钟，再在60～80℃恒温水浴下搅拌2～5小时，室温陈化20～30小时，过滤、去离子水洗涤、干燥，干燥后的固体在450～550℃下煅烧3～4小时，得到有机累托石/TiO2复合物；
④将有机累托石/TiO2复合物均匀分散于去离子水中，并加入0.1mol/L AgNO3水溶液，其中有机累托石/TiO2复合物的质量与AgNO3的摩尔量之比为1g:0.5～1.5mmol，室温搅拌20～30分钟，再加入0.1mol/L盐酸，搅拌20～30分钟，过滤、去离子水洗涤、干燥，所得固体产物分散于体积分数为40％的乙醇水溶液中，用波长>400nm的可见光照射30～90分钟，过滤、干燥，得到有机累托石/TiO2-Ag@AgCl复合物；
(3)制备壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物
将壳聚糖溶于质量分数为2％的醋酸水溶液中，配制成质量分数为1％～5％的壳聚糖溶液；将有机累托石/TiO2-Ag@AgCl复合物加入蒸馏水中，超声分散均匀，得到质量分数为1％～5％的有机累托石/TiO2-Ag@AgCl复合物悬浮液，然后加入甘油，继续超声20～30分钟，再在超声条件下逐滴加入质量分数为1％～5％的壳聚糖溶液，其中壳聚糖与有机累托石/TiO2-Ag@AgCl复合物、甘油的质量比为1:(0.02～0.10):(0.5～1.5)，在50～60℃下反应4～7小时，冷却至室温，得到壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物；
(4)制备叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜
将壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物在玻璃板上经反复流涎-冷冻-干燥，得到叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜。
2.根据权利要求1所述的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的制备方法，其特征在于：在步骤(1)中，所述累托石的煅烧温度为850℃、时间为3小时，用焦磷酸钠进行钠化处理的温度为50～70℃、时间为2～3小时，用十六烷基三甲基氯化铵进行有机化处理的温度为60～70℃、时间为5～8小时，其中焦磷酸钠用量为累托石质量的3％～5％，十六烷基三甲基氯化铵用量为钠化累托石质量的3％～5％。
3.根据权利要求1所述的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的制备方法，其特征在于，在步骤(2)的②中，将有机累托石超声分散于体积分数为60％的乙醇水溶液中，配制成质量分数为3％的有机累托石悬浮液。
4.根据权利要求3所述的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的制备方法，其特征在于，在步骤(2)的③中，将柱撑溶液滴加入有机累托石悬浮液中，其中有机累托石的质量与柱撑溶液中钛离子的摩尔量之比为1g:10～12mmol，在超声条件下45℃反应20～30分钟，再在70℃恒温水浴下搅拌2～5小时，室温陈化20～30小时，过滤，用去离子水洗涤，干燥，干燥后的固体在450～550℃下煅烧3～4小时，得到有机累托石/TiO2复合物。
5.根据权利要求4所述的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的制备方法，其特征在于，在步骤(2)的④中，所述有机累托石/TiO2复合物的质量与AgNO3的摩尔量之比为1g:1.0mmol。
6.根据权利要求1所述的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的制备方法，其特征在于：在步骤(3)中，所述壳聚糖与有机累托石/TiO2-Ag@AgCl复合物、甘油的质量比为1:(0.05～0.08):(0.5～1.5)。
7.根据权利要求1所述的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜的制备方法，其特征在于：在步骤(4)中，将壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合物在玻璃板上以2.4mL/m2流涎，冷冻，60℃干燥成膜，反复流涎-冷冻-干燥3～5层。
8.权利要求1～7任意一项方法制备得到的叠层壳聚糖/有机累托石/TiO2-Ag@AgCl插层纳米复合光催化膜。
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