CN111659438A - 一种靶向吸附原位再生亲水型纳米分子印迹材料制备方法 - Google Patents
一种靶向吸附原位再生亲水型纳米分子印迹材料制备方法 Download PDFInfo
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Abstract
本发明涉及分子印迹材料领域，公开了一种靶向吸附原位再生亲水型纳米分子印迹材料制备方法，采用糖浆废水制备多基团纳米碳球，再采用溶胶‑凝胶法在纳米碳球表面上原位合成碳、氮共掺杂纳米TiO2@碳球，经过煅烧去除内核形成中空结构，提高表面分子印迹聚合物的产率、比表面积，结合位点多，传质速率快；以磺胺类和亚硝胺类污染物为目标分子，间苯二酚、三聚氰胺作为双功能单体，甲醛水溶液、TiO2作为双交联剂，乙腈作为致孔剂，形成纳米碳球表面分子印迹中空材料，提高分子印迹材料比表面积，实现更高的靶向吸附能力，操作简单，化学药剂使用量少；通过材料中的C,N‑TiO2光催化材料，直接利用可见光催化降解目标分子，实现分子印迹材料的原位再生和重复利用。
Description
技术领域
本发明涉及分子印迹材料领域，具体涉及一种靶向吸附原位再生亲水型纳米分子印迹材料制备方法。
背景技术
传统分子印迹聚合物存在几个缺点：
1、制备所用的试剂如功能单体(如甲基丙烯酸，乙二醇二甲基丙烯酸酯，5-乙烯基-8-羟基喹啉或原硅酸四乙酯等)，交联剂(如2,2-偶氮异丁腈，乙二醇二甲基丙烯酸酯，1,4-二丙烯酰基哌嗪或N，N'-1,4-苯二丙烯胺等)和致孔剂(如四氢呋喃)等均为有机试剂；
2、制备过程复杂，制备出的聚合物点位少，易塌陷，由于在有机溶剂中制备，亲水性差，在水溶液中的分子识别能力弱，限制了在食品，生物和环境领域的应用；
3、传统分子印迹聚合物为块状，需要进一步研磨、筛分得到一定大小的颗粒，颗粒物形态不规则，颗粒物大，比表面积小，识别位点不易接近，模板分子难以洗脱；
4、分子印迹材料使用前需要使用溶剂洗脱去除模板分子；
5、靶向吸附目标分子后无法再生或需要使用溶剂再生，过程复杂。
因此，传统分子印迹聚合物产量和结合能力低。
发明内容
基于以上问题，本发明提供一种靶向吸附原位再生亲水型纳米分子印迹材料制备方法，采用环境友好且具有中大量的葡萄糖、果糖和氨基亲水基团的糖浆废水制备多基团纳米碳球，再采用溶胶-凝胶法在纳米碳球表面上原位合成碳、氮共掺杂纳米TiO2@碳球，经过煅烧去除内核形成中空结构；无需外加碳源和氮源，使糖浆废水原生的N，C元素共掺杂TiO2，分子印迹识别位点负载在中空TiO2纳米颗粒内外层上，提高表面分子印迹聚合物的产率、比表面积及更容易获得的结合位点，传质速率快；以磺胺类和亚硝胺类污染物为目标分子，间苯二酚、三聚氰胺作为双功能单体，甲醛水溶液、TiO2作为双交联剂，乙腈作为致孔剂，形成纳米球形表面分子印迹中空材料，提高分子印迹材料比表面积，实现更高的靶向吸附能力，操作简单，化学药剂使用量少，有利于工业化应用；同时通过材料中的C,N-TiO2光催化材料，直接利用可见光催化降解目标分子，实现分子印迹材料的原位再生和重复利用。
为解决以上技术问题，本发明采用的技术方案是：
一种靶向吸附原位再生亲水型纳米分子印迹材料制备方法，包括如下步骤：
S1、利用糖浆废液和十二烷基硫酸钠经水热反应合成糖浆纳米碳球；
S2、每100mg的糖浆纳米碳球(DDSC)分散于20mL无水乙醇中，再加入2mL的钛酸四丁脂(TBOT)，在室温下搅拌24小时，然后抽滤、洗涤，并在80℃下真空干燥超过12小时，最后在400-600℃条件下煅烧1-3小时制得HollowC,N-TiO2@C微球；
S3、按质量份比例取甲醛水溶液1-2份、间苯二酚2-4份、超纯水40-60份加入到三颈烧瓶中，并在40℃下搅拌1h；
S4、取步骤S3中等量的甲醛水溶液，再按质量份比例三聚氰胺1-2份、超纯水15-20份一同加入到烧杯中，并在80℃下搅拌至溶液澄清，待温度降至40℃时，加入到步骤S3的三颈烧瓶中；再将4-6份步骤S1中制得的HollowC,N-TiO2@C微球和0.1-0.2份亚硝胺类和磺胺类作为目标分子依次加入到三颈烧瓶中并充分混合；在40℃的温度下搅拌至印迹模板溶解，然后加入3-5份乙腈，自组装反应30min后，升温至80℃水浴24h，过滤分离得到HollowC,N-TiO2@C-MIPs微球；
S5、将得到HollowC,N-TiO2@C-MIPs微球材料置于体积比为4:1的甲醇-水溶液中，超声波协同反应去除目标分子印迹模板，多次萃取后，过滤分离固体微球，最后将固体微球经60℃干燥12h得到HollowC,N-TiO2@C-MIPs。
进一步地，步骤S1中的糖浆纳米碳球的制备过程为：按质量份比例称取糖浆废液1000份和十二烷基硫酸钠(SDS)1份于烧杯中，恒温40℃条件下搅拌30min，然后转移到高压反应釜中，在180℃下加热8h；冷却至室温后抽滤，将产物用蒸馏水和无水乙醇清洗三次，并在80℃下真空干燥超过12h，制得糖浆纳米碳球。
进一步地，亚硝胺类包括亚硝基二甲胺(NDMA)、亚硝基二乙胺(NDEA)、亚硝基二丙胺(NDPA)、亚硝基二丁胺(NDBA)、亚硝基二苯胺(NDPhA)中的一种或多种；所述磺胺类包括磺胺嘧啶、磺胺甲氧嗪、磺胺异噁唑、磺胺噻唑、磺胺甲基嘧啶的一种或多种。
进一步地，抽滤过程的滤膜选用0.22um水系滤膜。
与现有技术相比，本发明的有益效果是：
1、利用糖浆废水中大量葡萄糖，果糖和氨基(CODcr>50000mg/L，TN>1000mg/L)，先采用水热法制备糖浆废液多基团纳米碳，然后采用溶胶-凝胶法在纳米碳球表面上原位合成中空碳、氮共掺杂纳米TiO2@碳(HollowC,N-TiO2@C)可见光纳米催化中空微球材料，无需外加碳源和氮源，操作简单，化学药剂用量少；
2、中空结构有利于吸附目标污染物，碳球表面的氨基、羟基、羧基、芳香环；TiO2表面羟基；交联剂，功能单体表面的羟基、苯环和氨基容易通过氢键和π-π相互作用吸附目标模板分子，构建更多的目标吸附点位；
3、HollowC,N-TiO2@C-MIPs微球表面的分子印迹层可以提供更多目标分子识别位点，通过分子“靶向”识别，提高对目标污染物去除能力；
4、HollowC,N-TiO2@C-MIPs具有很高的可重复使用性和稳定性，在可见光照射下，HollowC,N-TiO2@C能对分子空腔中特异性识别的磺胺类或亚硝胺类污染物进行光催化降解，实现“原位再生”。
附图说明
图1为实施例1和2中HollowC,N-TiO2@C微球制备示意图；
图2为实施例1和2中HollowC,N-TiO2@C-MIPs制备示意图；
图3为实施例2中相关原料、中间产物及HollowC,N-TiO2@C-MIPs的SEM图；
图4为实施例2中TiO2、HollowC,N-TiO2@C和HollowC,N-TiO2@C-MIPs球的紫外-可见吸收光谱图及Tauc曲线图；
图5为实施例2中HollowC,N-TiO2@C-MIPs的HRTEM图；
图6为实施例2中不同反应时间下pH对磺胺嘧啶的影响；
图7为实施例2中HollowC,N-TiO2@C-MIPs的稳定性试验结果图；
图8为实施例2中HollowC,N-TiO2@C-MIPs材料对磺胺类目标污染物饱和吸附量；
图9为实施例2中HollowC,N-TiO2@C-MIPs材料对亚硝胺类污染物饱和吸附量。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白，下面结合实施例和附图，对本发明作进一步的详细说明，本发明的示意性实施方式及其说明仅用于解释本发明，并不作为对本发明的限定。
实施例1：
参见图1和图2，一种靶向吸附原位再生亲水型纳米分子印迹材料制备方法，包括如下步骤：
S1、利用糖浆废液和十二烷基硫酸钠经水热反应合成糖浆纳米碳球；
S2、每100mg的糖浆纳米碳球(DDSC)分散于20mL无水乙醇中，再加入2mL的钛酸四丁脂(TBOT)，在室温下搅拌24小时，然后抽滤、洗涤，并在80℃下真空干燥超过12小时，最后在400-600℃条件下煅烧1-3小时制得HollowC,N-TiO2@C微球；在制备过程中，为防止HollowC,N-TiO2@C微球被氧化，可以在煅烧时加保护气氛(如氮气)。
S3、按质量份比例取甲醛水溶液1-2份、间苯二酚2-4份、超纯水40-60份加入到三颈烧瓶中，并在40℃下搅拌1h；
S4、取步骤S3中等量的甲醛水溶液，再按质量份比例三聚氰胺1-2份、超纯水15-20份一同加入到烧杯中，并在80℃下搅拌至溶液澄清，待温度降至40℃时，加入到步骤S3的三颈烧瓶中；再将4-6份步骤S1中制得的HollowC,N-TiO2@C微球和0.1-0.2份亚硝胺类和磺胺类作为目标分子依次加入到三颈烧瓶中并充分混合；在40℃的温度下搅拌至印迹模板溶解，然后加入3-5份乙腈，自组装反应30min后，升温至80℃水浴24h，过滤分离得到HollowC,N-TiO2@C-MIPs微球；
S5、将得到HollowC,N-TiO2@C-MIPs微球材料置于体积比为4:1的甲醇-水溶液中，超声波协同反应去除目标分子印迹模板，多次萃取后，过滤分离固体微球，最后将固体微球经60℃干燥12h得到HollowC,N-TiO2@C-MIPs。
在本实施例中，HollowC,N-TiO2@C-MIPs对目标污染物具有良好的吸附和光催化性能。在黑暗环境下，HollowC,N-TiO2@C-MIPs表面吸附目标污染物，然后目标污染物进一步被分子印迹聚合物空穴内的作用位点特异性识别，最后在可见光照射下目标污染物被Hollow C,N-TiO2@C光催化降解，实现“原位再生”。HollowC,N-TiO2@C-MIPs的优异光催化性能来源于HollowC,N-TiO2@C，碳(C)和氮(N)的共掺杂可以协同促进可见光的吸收和光生电子-空穴对的分离，从而增强HollowC,N-TiO2@C光催化活性。HollowC,N-TiO2@C对特异性识别的目标污染物光催化降解后，空余的目标污染物印迹点位可以对目标污染物分子再识别，实现“靶向去除”和“重复利用”。因此采用分子印迹聚合物可实现Hollow C,N-TiO2@C-MIPs“靶向去除”、“原位再生”、“重复利用”的协同效能。
本实施例中，亚硝胺类包括亚硝基二甲胺(NDMA)、亚硝基二乙胺(NDEA)、亚硝基二丙胺(NDPA)、亚硝基二丁胺(NDBA)、亚硝基二苯胺(NDPhA)中的一种或多种；磺胺类包括磺胺嘧啶、磺胺甲氧嗪、磺胺异噁唑、磺胺噻唑、磺胺甲基嘧啶的一种或多种。
实施例2：
S1、利用糖浆废液和十二烷基硫酸钠经水热反应合成糖浆纳米碳球；
本实施例中的糖浆纳米碳球的制备过程为：称取50.00g糖浆废液和0.05g十二烷基硫酸钠(SDS)于烧杯中，恒温40℃条件下搅拌30min，然后转移到100mL高压反应釜中，在180℃下加热8h。冷却至室温后抽滤(0.22um水系滤膜)，将产物用蒸馏水和无水乙醇清洗三次，并在80℃下真空干燥超过12h，制得糖浆纳米碳球。
S2、每100mg的糖浆纳米碳球(DDSC)分散于20mL无水乙醇中，再加入2mL的钛酸四丁脂(TBOT)，在室温下搅拌24小时，然后抽滤(本实施例选用0.22um水系滤膜)，洗涤，并在80℃下真空干燥超过12小时，最后在600℃条件下煅烧两小时制得Hollow C,N-TiO2@C微球；
S3、将0.6mL甲醛水溶液、1.80g间苯二酚和30mL超纯水以(1:3:500,mL:g:mL)加入到三颈烧瓶中，并在40℃下搅拌1h；
S4、将0.6mL甲醛水溶液、0.6g三聚氰胺和10mL超纯水加入到烧杯中，并在80℃下搅拌至溶液澄清，待温度降至40℃时，加入到步骤S3的三颈烧瓶中；再将5.0g的Hollow C,N-TiO2@C微球和0.1g亚硝胺类和磺胺类作为目标分子依次加入到三颈烧瓶中并充分混合；在40℃的温度下搅拌至印迹模板溶解，然后加入5mL乙腈，自组装反应30min后，升温至80℃水浴24h，过滤分离得到HollowC,N-TiO2@C-MIPs微球；
S5、将得到HollowC,N-TiO2@C-MIPs微球材料置于体积比为4:1的甲醇-水溶液中，超声波协同反应去除目标分子印迹模板，多次萃取后，过滤分离固体微球，最后将固体微球经60℃干燥12h得到HollowC,N-TiO2@C-MIPs。
图3是本实施例中HollowC,N-TiO2@C和HollowC,N-TiO2@C-MIPs的SEM图。由图3(a-b)为TiO2的SEM图，纯TiO2呈絮状态且团聚现象严重。图3(c-d)为HollowC,N-TiO2@C的SEM图，HollowC,N-TiO2@C微球呈球形，表面比较粗糙，粒径比较均匀。图3(e-f)是HollowC,N-TiO2@C-MIPs微球的SEM图，可以看出HollowC,N-TiO2@C-MIPs是单分散的完整球型(粒径2–3um)，微球的表面粗糙并密布小裂缝，这是因为其表面附着了一层印迹聚合物所致。图4中(a)是TiO2、HollowC,N-TiO2@C和HollowC,N-TiO2@C-MIPs球的紫外-可见吸收光谱图，图4(b)TiO2、HollowC,N-TiO2@C和HollowC,N-TiO2@C-MIPs球的Tauc曲线图，图中表明HollowC,N-TiO2@C-MIPs光催化剂的吸收边与纯TiO2和Hollow C,N-TiO2@C相比发生了红移，在紫外和可见光区域均显示出更强的光吸收性，光催化活性越高。通过Tauc曲线的线性估算HollowC,N-TiO2@C-MIPs的Eg值约为0.78eV远低于纯TiO2(3.20eV)的Eg值。
图5(a-c)是HollowC,N-TiO2@C-MIPs球的TEM图像，扫描电镜和透射电镜都表明包裹分子印迹后的复合材料是单分散的完整微球(粒径2–3um)。而且从图5(d-f)可以清晰的看出分子印迹聚合物的表层有大量微小孔隙，这可以作为目标污染物良好的结合点。图5(g-i)是HollowC,N-TiO2@C-MIPs球HRTEM图像，可以看出该复合材料的微观结构：无晶型部分可以归因于碳核层和分子印迹层，晶型部分可以归因于锐钛矿TiO2晶体，0.35nm的晶格间距，其对应于锐钛矿型TiO2的(101)晶格间距。图5(g)是HollowC,N-TiO2@C-MIPs的mapping图，从图中可以明显的确定C、N、O、Ti和S元素的分布，Ti和S元素分散在整个样品中，C、N和O元素呈现球形分布。进一步证明分子印迹聚合物确实成功包覆在Hollow C,N-TiO2@C微球表面。
以磺胺嘧啶为目标污染物，利用HollowC,N-TiO2@C-MIPs对其进行吸附。图6为PH值HollowC,N-TiO2@C-MIPs光催化磺胺嘧啶性能影响曲线。20mg/L磺胺嘧啶，加入50mgHollow C,N-TiO2@C-MIPs，常温反应；试验数据表明：在pH＝7.0时，反应时间为120min，Hollow C,N-TiO2@C-MIPs对磺胺嘧啶达到最大值99.92％。
对HollowC,N-TiO2@C-MIPs光催化剂进行重复6次的光催化降解实验，每次实验后通过抽滤的方式回收溶液中HollowC,N-TiO2@C-MIPs光催化剂；为了去除未完全降解的目标分子，将固体微球加到200mL去离子水中，用125W汞灯照射4小时以保证残余的目标分子去除完全；最后在烘箱120℃下烘干，重新进行光催化降解磺胺嘧啶实验。HollowC,N-TiO2@C-MIPs光催化剂经6次重复光催化降解实验后，结果如如图7，HollowC,N-TiO2@C-MIPs对磺胺嘧啶目标分子的去除率仍高于90％，仅表现出轻微降低的光催化活性。这表明了HollowC,N-TiO2@C-MIPs在分离过程中很容易从溶液中分离和回收，并且重复使用率很高。
分别按前述制备方法制备亚硝胺类：亚硝基二甲胺(NDMA)、亚硝基二乙胺(NDEA)、亚硝基二丙胺(NDPA)、亚硝基二丁胺(NDBA)、亚硝基二苯胺(NDPhA)和磺胺类：磺胺嘧啶、磺胺甲氧嗪、磺胺异噁唑、磺胺噻唑、磺胺甲基嘧啶，采用本实施例制得的Hollow C,N-TiO2@C-MIPs材料吸附去除目标污染物，结果如图8和图9。HollowC,N-TiO2@C-MIPs材料对各类目标污染物均具有较高的处理能力。
如上即为本发明的实施例。上述实施例以及实施例中的具体参数仅是为了清楚表述发明验证过程，并非用以限制本发明的专利保护范围，本发明的专利保护范围仍然以其权利要求书为准，凡是运用本发明的说明书及附图内容所作的等同结构变化，同理均应包含在本发明的保护范围内。
Claims (4)
1.一种靶向吸附原位再生亲水型纳米分子印迹材料制备方法，其特征在于，包括如下步骤：
S1、利用糖浆废液和十二烷基硫酸钠经水热反应合成糖浆纳米碳球；
S2、每100mg的糖浆纳米碳球(DDSC)分散于20mL无水乙醇中，再加入2mL的钛酸四丁脂(TBOT)，在室温下搅拌24小时，然后抽滤、洗涤，并在80℃下真空干燥超过12小时，最后在400-600℃条件下煅烧1-3小时制得Hollow C,N-TiO2@C微球；
S3、按质量份比例取甲醛水溶液1-2份、间苯二酚2-4份、超纯水40-60份加入到三颈烧瓶中，并在40℃下搅拌1h；
S4、取步骤S3中等量的甲醛水溶液，再按质量份比例三聚氰胺1-2份、超纯水15-20份一同加入到烧杯中，并在80℃下搅拌至溶液澄清，待温度降至40℃时，加入到步骤S3的三颈烧瓶中；再将4-6份步骤S1中制得的Hollow C,N-TiO2@C微球和0.1-0.2份亚硝胺类和磺胺类作为目标分子依次加入到三颈烧瓶中并充分混合；在40℃的温度下搅拌至印迹模板溶解，然后加入3-5份乙腈，自组装反应30min后，升温至80℃水浴24h，过滤分离得到Hollow C,N-TiO2@C-MIPs微球；
S5、将得到Hollow C,N-TiO2@C-MIPs微球材料置于体积比为4:1的甲醇-水溶液中，超声波协同反应去除目标分子印迹模板，多次萃取后，过滤分离固体微球，最后将固体微球经60℃干燥12h得到Hollow C,N-TiO2@C-MIPs。
2.根据权利要求1所述的靶向吸附原位再生亲水型纳米分子印迹材料制备方法，其特征在于，步骤S1中的糖浆纳米碳球的制备过程为：按质量份比例称取糖浆废液1000份和十二烷基硫酸钠(SDS)1份于烧杯中，恒温40℃条件下搅拌30min，然后转移到高压反应釜中，在180℃下加热8h；冷却至室温后抽滤，将产物用蒸馏水和无水乙醇清洗三次，并在80℃下真空干燥超过12h，制得糖浆纳米碳球。
3.根据权利要求1或2所述的靶向吸附原位再生亲水型纳米分子印迹材料制备方法，其特征在于，所述亚硝胺类包括亚硝基二甲胺(NDMA)、亚硝基二乙胺(NDEA)、亚硝基二丙胺(NDPA)、亚硝基二丁胺(NDBA)、亚硝基二苯胺(NDPhA)中的一种或多种；所述磺胺类包括磺胺嘧啶、磺胺甲氧嗪、磺胺异噁唑、磺胺噻唑、磺胺甲基嘧啶的一种或多种。
4.根据权利要求3所述的靶向吸附原位再生亲水型纳米分子印迹材料制备方法，其特征在于，抽滤过程的滤膜选用0.22um水系滤膜。
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