CN115069302B - 一种高效可见光催化材料及其制备方法和应用 - Google Patents
一种高效可见光催化材料及其制备方法和应用 Download PDFInfo
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- CN115069302B CN115069302B CN202210850837.XA CN202210850837A CN115069302B CN 115069302 B CN115069302 B CN 115069302B CN 202210850837 A CN202210850837 A CN 202210850837A CN 115069302 B CN115069302 B CN 115069302B
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Abstract
本发明公开了一种高效可见光催化材料及其制备方法和应用，涉及光催化材料技术领域。本发明将Ag@AgCl与海藻酸钙凝胶复合制备得到光催化材料Ag@AgCl/CA，该光催化材料呈小颗粒状，具有吸附能力强、光催化降解时间短、催化效率高、可见光波响应范围广以及易回收循环使用等优点。本发明制得的复合光催化材料Ag@AgCl/CA具有较好可见光吸收性能，在可见光条件下(λ≥420nm)具有高效降解土霉素废水的性能，在实际光催化剂生产中具有极大应用潜力。
Description
技术领域
本发明涉及光催化材料技术领域，特别是涉及一种高效可见光催化材料及其制备方法和应用。
背景技术
近几十年，抗生素类药物已被广泛应用于药物治疗和畜牧养殖业，由此引发的潜在危害也引起了越来越多的关注。四环素类(Tetracyclines，TCs)是使用量最大的抗生素之一，其作为抗菌剂和生长因子被广泛应用于药物治疗和畜牧养殖业，每年有大量四环素类抗生素废水排入水体，其大量排放到环境中易造成药物残留。土霉素(oxtetracycline，OTC)又称氧四环素，是四环素类抗生素的一种，因其性质稳定的特点，难分解，从而造成环境污染。常规的物理吸附、化学沉淀、生物降解对于抗生素废水的处理都不是很理想。
光催化氧化技术作为一种新兴技术，对四环素类抗生素废水有很强的降解效果。当前，用于土霉素光催化水降解研究中，比较多的是采用TiO2作为光催化剂及其复合光催化材料降解土霉素。然而TiO2只对紫外光响应的性质限制了它对太阳能的利用效率和作为光催化剂的规模工业化应用。因此开发新型高效可见光催化材料，提高光能转换效率和拓宽催化剂光响应范围是目前光催化材料研究的热点。
近年来，作为新型可见光催化材料，Ag@AgCl引起了广泛的关注。Ag@AgCl因Ag0具有表面等离子体共振效应(SPR)而对可见光有明显的吸收。但Ag@AgCl粉体材料具有易团聚、比表面积较小、吸附性能较差的缺点限制了材料的应用，一般是通过与g-C3N4、V2O5、MoO3等形成复合光催化材料来提高其光化学稳定性、光催化活性。但Ag@AgCl与海藻酸钙(CA)凝胶形成复合光催化材料用于抗生素的降解，尤其对土霉素的降解未见报道。
发明内容
本发明的目的是提供一种高效可见光催化材料及其制备方法和应用，以解决上述现有技术存在的问题，实现在可见光波响应范围内对土霉素的高效催化降解，并使制得的催化材料具有易回收循环使用的优势。
为实现上述目的，本发明提供了如下方案：
本发明提供一种高效可见光催化材料的制备方法，将Ag@AgCl与海藻酸钙凝胶复合制备得到Ag@AgCl/CA，即为所述高效可见光催化材料。
进一步地，制备方法包括以下步骤：将海藻酸钠与Ca2+进行交联，形成海藻酸钙凝胶，然后通过化学沉淀反应原位沉积AgCl，并通过光致还原制备得到Ag@AgCl/CA，即为所述高效可见光催化材料。
进一步地，制备方法步骤如下：
(1)将阳离子乳化剂与海藻酸钠于溶液中混合，超声分散；
(2)向步骤(1)制得的混合液中依次加入AgNO3、Ca(NO3)2和NaCl，搅拌，静置，过滤，收集沉淀；
(3)将步骤(2)得到的沉淀加入水中，然后进行紫外灯照射，过滤，洗涤，冷冻干燥得到Ag@AgCl/CA，即为所述高效可见光催化材料。
进一步地，所述阳离子乳化剂为十六烷基三甲基溴化铵。
进一步地，步骤(2)中所述静置的时间为4～8h。
进一步地，所述海藻酸钠与AgNO3、Ca(NO3)2和NaCl的质量比为1:(2～3.5):4:(0.5～2)，优选的质量比为1:3:4:1。
进一步地，步骤(3)中所述紫外灯照射的功率为10W，时间为30min。
本发明技术方案之二：提供采用上述制备方法制备的高效可见光催化材料。
本发明技术方案之三：提供上述高效可见光催化材料在降解四环素类抗生素中的应用。
进一步地，所述四环素类抗生素为土霉素。
本发明主要针对AgCl稳定性差、易团聚、吸附能力不足以及难回收循环利用的问题，在阳离子乳化剂十六烷基三甲基溴化铵(CTAB)的分散作用下，通过海藻酸钠(SA)与二价阳离子(如Ca2+)的交联作用，形成稳定凝胶海藻酸钙(CA)作为模板，然后通过化学沉淀反应原位沉积AgCl，并通过光致还原制备得到Ag@AgCl/CA不溶性颗粒光催化材料。
本发明公开了以下技术效果：
本发明通过引入阴离子型天然高分子多糖水溶液与二价阳离子形成稳定凝胶的性质，采用化学偶联和原位沉积法负载AgCl，再通过光致还原制备而成Ag@AgCl/CA光催化材料；该光催化材料呈小颗粒状，具有吸附能力强、光催化降解时间短、催化效率高、可见光波响应范围广以及易回收循环使用等优点，可实际应用于土霉素废水的降解。
本发明制得的复合光催化材料Ag@AgCl/CA具有较好可见光吸收性能，在可见光条件下(λ≥420nm)具有高效降解土霉素废水的性能，在实际光催化剂生产中具有极大应用潜力。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1(a)、(b)分别为实施例1制备的光催化材料Ag@AgCl/CA不同放大倍数下的扫描电镜照片；
图2(a)、(b)分别为实施例1制备的光催化材料Ag@AgCl/CA不同放大倍数下的透射电镜照片；
图3为实施例1制备的光催化材料Ag@AgCl/CA的EDS图谱；
图4为实施例1制备的光催化材料Ag@AgCl/CA的主要元素面扫图；
图5为实施例1制备的光催化材料Ag@AgCl/CA的红外光谱；
图6为实施例1制备的光催化材料Ag@AgCl/CA的N2吸附-解吸等温线(a)和孔径分布图(b)；
图7为实施例1制备的光催化材料Ag@AgCl/CA的瞬态光电流响应(a)和电化学阻抗谱图(b)；
图8为实施例1制备的光催化材料Ag@AgCl/CA的电位图；
图9为实施例1制备的Ag@AgCl/CA和Ag@AgCl的UV-Vis DRS图；
图10为实施例1制备的Ag@AgCl/CA在可见光下对OTC光降解吸收光谱图；
图11为实施例1制备的Ag@AgCl/CA光催化OTC降解循环使用稳定性测试。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
实施例1
高效可见光催化材料Ag@AgCl/CA的制备步骤如下：
(1)取2g/L海藻酸钠(SA)溶液100mL，于该溶液中加入浓度为10g/L阳离子乳化剂十六烷基三甲基溴化铵(CTAB)16mL，超声分散30min，使CTAB与SA溶液充分混合；
(2)在磁力搅拌下，向步骤(1)的反应体系中缓慢滴加50g/L的AgNO3溶液12mL，滴加完毕，继续磁力搅拌15min后，于所得混合悬浮液中缓慢滴加20g/L的Ca(NO3)2溶液40mL。继续磁力搅拌15min后，再缓慢滴加20g/L的NaCl溶液10mL，滴加完毕，30min后停止搅拌，再静置4h。将反应体系利用双层纱布过滤，所得小颗粒沉淀物用去离子水洗涤5次；
(3)取步骤(2)所得小颗粒沉淀物加入250mL三角瓶中，加入50mL去离子水，在磁力搅拌下，置于10W的紫外灯照射30min。双层纱布过滤后的颗粒用去离子水洗涤3次，真空冷冻干燥，即得到Ag@AgCl/CA光催化材料。
取Ag@AgCl/CA光催化材料0.2g加入100mL三角瓶中，然后加入60mL10mg·L-1的OTC溶液，调初始pH值6.0，温度控制在40℃，先于黑暗中搅拌30min，使达到吸附-解吸平衡，随后，磁力搅拌下，置于350W的氙灯可见光(420nm紫外截止滤光片过滤)催化降解10～30min。
图1和图2分别是高分辨场发射扫描电镜(SEM)和透射电子显微镜(TEM)观察到的实施例1制备的Ag@AgCl/CA光催化材料形貌图。图1(a)、(b)分别为不同放大倍数下Ag@AgCl/CA光催化材料的SEM图，图2(a)、(b)分别为不同放大倍数下Ag@AgCl/CA光催化材料透射电镜TEM图。
海藻酸钙(CA)凝胶结构中负载了大量呈不规则Ag@AgCl颗粒，部分重叠、堆积呈团簇状分布。Ag@AgCl颗粒类球型，粒径不均匀，为50～100nm。由此可见，Ag@AgCl粒子成功地负载在Ca2+交联的空隙内，凝胶网格状结构可充当隔板把团簇状Ag@AgCl颗粒进行有效分割，一定程度上有利于复合材料对OTC的吸附和快速降解，有效改善复合材料的光催化性能。
图3和图4分别为实施例1制备的光催化材料Ag@AgCl/CA的EDS谱图和主要元素面扫分布图。
结果表明，样品中含有Ag、Cl、C、O、N、Ca、Br等元素，其中Ag元素的质量浓度较大，仅次于C元素，同时Ag原子浓度也比较大，仅次于C和O，而Cl原子浓度约为Ag原子浓度的一半，即Ag:AgCl＝1:1，说明每个AgCl粒子表面大致有纳米Ag粒子附着。另外材料里含有一定的N和Br原子，表明所制备的催化材料里含有少量AgBr杂质粒子和CTAB阳离子成分，而少量AgBr粒子也能协同Ag@AgCl对污染物的催化降解。
图5为实施例1制备的光催化材料Ag@AgCl/CA的红外光谱。
图5中，在1030cm-1处的吸收峰归属于环氧基的C-O-C伸缩振动吸收峰，1597cm-1和1403cm-1出现的峰分别对应于SA中-COOH的C＝O的伸缩振动峰和-OH的弯曲振动峰，2915cm-1处为甲基(-CH3)伸缩振动吸收峰，2851cm-1处出现的吸收峰是CTAB分子烷烃链的亚甲基(-CH2-)的伸缩振动的表现。复合材料在3375cm-1附近均出现很强的峰吸收峰，为缔合羟基(-OH)伸缩振动峰，即含氧官能团O-H键的伸缩振动。
图6为实施例1制备的光催化材料Ag@AgCl/CA的N2吸附-解吸等温线(a)和孔径分布图(b)。
其等温线符合第Ⅳ类等温线，说明复合材料具有介孔(中孔)结构，有利于催化剂与OTC接触，也有利于可见光的吸收，减少电子-空穴的复合，提高了复合材料的光催化降解性能。该材料的比表面积为0.96553m2/g，平均孔径21.311nm，孔径分布在2～100nm之间。一定量的催化剂，其表面积是一定的，催化降解效果主要是由吸附在催化剂表面的污染物的多少决定的，根据光催化氧化机理，催化剂表面上光生电子和空穴的复合在小于10-9s内完成，但载流子被俘获的速率相对较慢，通常需要10-8～10-7s，因此，只有吸附在催化剂表面的污染物才有可能获得高活性的电子和空穴发生反应。将Ag@AgCl颗粒分散沉积在CA凝胶上，能有效增强该复合材料的吸附性能和催化降解性能。
图7(a)为实施例1制备的光催化材料Ag@AgCl/CA在每个开启和遮蔽光照的瞬态光电流响应特性。
从图中可以看出，在可见光的照射下，Ag@AgCl/CA复合材料能产生快速而稳定的光电流，且具有良好的可逆性。因此，该催化材料具有很强的光敏性、较好的光电流响应性能、较高的光生电子传输效率以及光生电子-空穴对的分离效率，由此表明，所制备的复合光催化材料有较高的光催化活性。
图7(b)所示实施例1制备的光催化材料Ag@AgCl/CA的EIS表征结果表明，无光照时，圆弧半径较大；而光照时，圆弧半径明显减小。因此，在光辐射下，所制备的复合材光催化材料具有较小的光生电子转移电阻和较低的光生电子-空穴复合率，展现出良好的光催化性能。
图8显示，实施例1制备的Ag@AgCl/CA光催化材料pH4、5、6、7、8的Zeta电位分为-30.1mV、-32.7mV、-34.8mV、-30.9mV、-43.5mV，这说明催化材料在pH4～8时催化材料表面带负电荷，此时催化材料颗粒之间存在排斥作用，产生位阻效应，表明催化材料具有较强的稳定性。另外，研究表明，当溶液初始pH>7时，Ag+会与溶液中的氢氧根结合生成沉淀，使溶液变色，因此该催化剂在酸性条件下使用较好。
图9为实施例1制备的Ag@AgCl/CA和Ag@AgCl的UV-Vis DRS图。由图9可见，Ag@AgCl/CA催化材料不仅在350nm以下的紫外区有较强的吸收，而且在500～650nm的可见光区范围内也有比较强的吸收。据报道，AgCl间接能带隙为3.25eV左右，除了紫外区吸收带外，AgCl在400～800nm范围内几乎没有吸收性能。因此该催化材料在可见光区域有较强的吸收性能归因于Ag纳米粒子SPR效应产生的共振吸收带。
图10为实施例1制备的Ag@AgCl/CA催化材料在40℃，溶液初始pH6时，不同时间光催化降解OTC的吸收曲线。OTC有2个明显的吸收峰，分别在275nm和355nm处。暗处吸附30min后，吸收峰均大幅度降低，光照6min后275nm处的吸收峰消失，而355nm吸收峰明显减弱。随着光照时间的延长，355nm处的吸光度逐渐降低，吸收峰发生轻微蓝移。
实施例1制备的Ag@AgCl/CA催化材料循环5次的降解曲线如图11所示。光催化材料的活性没有明显变化，对OTC仍然具有大于90.0％以上的降解率，表明该催化材料具有良好的光催化稳定性及可重复使用性，作为一种可见光催化剂应用于实际生产中具有极大潜力。
以上所述的实施例仅是对本发明的优选方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。
Claims (7)
1.一种高效可见光催化材料的制备方法，其特征在于，制备方法步骤如下：
(1)将阳离子乳化剂与海藻酸钠于溶液中混合，超声分散；
(2)向步骤(1)制得的混合液中依次加入AgNO3、Ca(NO3)2和NaCl，搅拌，静置，过滤，收集沉淀；
(3)将步骤(2)得到的沉淀加入水中，然后进行紫外灯照射，过滤，洗涤，冷冻干燥得到Ag@AgCl/CA，即为所述高效可见光催化材料；
所述阳离子乳化剂为十六烷基三甲基溴化铵。
2.根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述静置的时间为4～8h。
3.根据权利要求1所述的制备方法，其特征在于，所述海藻酸钠与AgNO3、Ca(NO3)2和NaCl的质量比为1:(2～3.5):4:(0.5～2)。
4.根据权利要求1所述的制备方法，其特征在于，步骤(3)中所述紫外灯照射的功率为10W，时间为30min。
5.如权利要求1-4任一项所述制备方法制备的高效可见光催化材料。
6.如权利要求5所述的高效可见光催化材料在降解四环素类抗生素中的应用。
7.根据权利要求6所述的应用，其特征在于，所述四环素类抗生素为土霉素。
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