CN111978565B - 纤维素水凝胶基纳米银/氯化银的制备方法及应用 - Google Patents
纤维素水凝胶基纳米银/氯化银的制备方法及应用 Download PDFInfo
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- CN111978565B CN111978565B CN202010786183.XA CN202010786183A CN111978565B CN 111978565 B CN111978565 B CN 111978565B CN 202010786183 A CN202010786183 A CN 202010786183A CN 111978565 B CN111978565 B CN 111978565B
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- tannic acid
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Abstract
纤维素水凝胶基纳米银/氯化银的制备方法及应用。本发明方法包括以下步骤:(1)搅拌条件下,向纤维素溶液中滴加单宁酸溶液形成反应液I,继续搅拌1~3h,调节反应液的pH,升温,然后加入戊二醛,继续搅拌,得反应液II;(2)向反应液II中滴加AgNO3溶液,继续搅拌,得反应液III,将反应液III滴加至剧烈搅拌的去离子水中,得絮状物悬浊液,抽滤,洗涤,滤饼为银/氯化银@纤维素纳米复合材料。本发明方法制备的银/氯化银@纤维素纳米复合材料不仅纳米银和氯化银分布均匀,团聚少,平均粒径较小,而且表现出了较高的催化效率,可在短时间内还原对硝基苯酚、邻硝基苯酚,对硝基苯胺以及多种有机染料。
Description
技术领域
本发明属于贵金属催化剂制备领域,具体涉及纤维素水凝胶基纳米银/氯化银的制备方法及应用。
背景技术
负载型贵金属催化剂由贵金属活性中心和载体构成。贵金属是活性中心,按照贵金属种类,负载型催化剂分为Pd基催化剂、Pt基催化剂、Au基催化剂、Ag基催化剂等等。Ag基催化剂由于银优越的成本优势,以及AgNPs独特的光学和电子特性,广受催化界关注。然而,与大多数金属纳米粒子一样,由于AgNPs具有高的表面能,存在严重的聚集问题,这会降低比表面积-体积比,从而影响催化性能。为了克服这一问题,通常将AgNPs固定在合适的载体材料上,如二氧化硅、金属氧化物、碳材料等,形成的杂化催化剂虽然避免了AgNPs的自聚集,在催化反应中分离也更方便,但是,值得注意的是,除了碳基材料外,这些杂化催化剂中贵金属的回收非常麻烦。并且,与传统的多相催化剂类似,仍然存在传质问题。所以,寻找一种理想的载体材料显得尤为迫切。
为了解决这些问题,水凝胶成为了固定AgNPs的可供替代的新兴载体材料。水凝胶是一种具有物理或化学交联的三维网络结构的聚合物,是一种高吸水、高保水性的亲水材料,使水溶液中的反应物能快速扩散到水膨胀的三维网络中,与AgNPs接触,进而促进催化反应。还有一点值得注意的是,通过在空气中简单的煅烧可以回收金属银,这也解决了上述提及的贵金属的回收问题。目前,利用各种水凝胶制备新型催化剂已成为众多研究的重点,在详细研究了文献中制备过程后,他们都致力于合成AgNPs,而且为获得均匀稳定的金属纳米材料,通常需要加入各种各样的封端剂、稳定剂和分散剂来控制AgNPs的尺寸和形状。
CN103722181A公开一种液相还原法使用分散剂制备纳米银粉的方法,其采用硝酸银和还原剂并添加丁二酸二甲酯为分散剂进行液相还原反应制备的纳米银粉。其中丁二酸二甲酯的加入量硝酸银质量的1%、2%和5%时,纳米银对应的尺寸分别为150~400nm、30~70nm和200~500nm。该方法不仅需要加入丁二酸二甲酯作为分散剂,制得最佳纳米银粒径仍然较大。
CN106541149A公开一种精准尺寸控制超小纳米银颗粒的制备方法,该方法以硝酸银为前驱体,多元醇为溶剂兼为还原剂,在稳定剂聚乙烯吡咯烷酮和诱导剂硝酸镍作用下,使用微波辐照为热源,通过控制反应物浓度、比例、微波辐照时间和温度,快速、精准控制胶粒尺寸连续生长进程,达到超小粒径尺寸的精准控制,得到的纳米银颗粒粒径范围为1.91~30.5nm。该方法不仅需加入稳定剂聚乙烯吡咯烷酮和诱导剂硝酸镍,还需通过微波辐射,才可得到粒径范围为1.91和30.5nm纳米银颗粒。
CN101811664A公开一种纤维素/银纳米复合材料及其制备方法,该方法微晶纤维素溶液、银盐和还原剂为原料,以N,N-二甲基乙酰胺(DMAc)为溶剂,采用微波辐射处理法快速制备而成。该方法采用纤维素为基底,使得纳米银颗粒均匀分布在纤维素基底上,但该方法制备的复合材料上的纳米银颗粒的粒径仍较大,其最佳结果为100~150nm。
发明内容
本发明所要解决的技术问题是,克服以上不足,本发明方法制备的银/氯化银@纤维素纳米复合材料不仅纳米银和氯化银分布均匀,团聚少,平均粒径较小,而且表现出了较高的催化效率,可有效减少催化反应中还原剂的加入量,可在短时间内还原对硝基苯酚、邻硝基苯酚,对硝基苯胺以及多种有机染料。
本发明解决其技术问题所采用的技术方案如下:
一种绿色制备纤维素水凝胶基纳米银/氯化银的方法,其特征在,包括以下步骤:
(1)搅拌条件下,向纤维素溶液中滴加单宁酸溶液形成反应液I,继续搅拌1~3h,调节反应液的pH至6~7,升温至40~50℃,然后加入戊二醛,继续搅拌4~8h,得反应液II;
(2)保持40~50℃,向反应液II中滴加AgNO3溶液,继续搅拌10~24h,得反应液III,将反应液III滴加至剧烈搅拌的去离子水中,得絮状物悬浊液,抽滤,洗涤,滤饼为银/氯化银@纤维素纳米复合材料。
优选的,所述单宁酸与纤维素的质量比为2~9:5,优选为6:5。
优选的,所述AgNO3与纤维素的质量比为0.085~0.34:1,优选为0.255:1。
优选的,所述戊二醛与纤维素的质量比为0.474:1。
优选的,所述纤维素溶液是纤维素的LiCl/DMAC溶液,更为优选的,所述纤维素溶液中纤维素的质量百分数为1%。
优选的,所述单宁酸溶液是单宁酸的DMAC溶液,更为优选的,所述单宁酸溶液中单宁酸的质量浓度为0.02g/mL。
优选的,所述AgNO3溶液是AgNO3的DMAC溶液,更为优选的,所述AgNO3溶液中AgNO3的浓度为5~20mmol/L。
优选的,所述绿色制备纤维素水凝胶基纳米银/氯化银的方法,包括以下步骤:
(1)搅拌条件下,向50g 1wt%的纤维素溶液中滴加30mL 0.02g/mL的单宁酸溶液形成反应液I,继续搅拌1~3h,调节反应液的pH至6~7,升温至40~50℃,然后加入1mL质量百分浓度为25%的戊二醛,继续搅拌4~8h,得反应液II;
(2)保持40~50℃,向反应液II中滴加50mL 15mmol/L的AgNO3溶液,继续搅拌10~24h,得反应液III,将反应液III滴加至300mL去离子水中,并剧烈搅拌,得絮状物悬浊液,抽滤,洗涤滤饼,将滤饼重新分散在去离子水中,得到银/氯化银@纤维素纳米复合材料。
优选的,所述纤维素溶液的制备方法如下:
i.DMAC热活化:适量棉花中加入DMAC,160℃下热活化40min,得活化后的棉花;
ii.液压机压制:200℃下,将活化后的棉花压制1min,得到除掉DMAC的活化脱脂棉;
iii.高温搅拌:100℃下,将脱脂棉置于8.5%的LiCl/DMAC极性溶液中,搅拌3h,然后降至室温,继续搅拌至溶解,放置澄清,得到所述纤维素溶液。
上述方法制备的纤维素水凝胶基纳米银/氯化银作为催化剂在催化还原芳香硝基化合物中的应用。
上述方法制备的纤维素水凝胶基纳米银/氯化银在降解和吸附染料中的应用。
本发明的有益效果在于:
(1)本发明的方法采用单宁酸接枝在纤维素上,然后加入硝酸银,利用单宁酸的酚羟基螯合稳定分散银离子,再通过溶胶-凝胶法得到银/氯化银@纤维素纳米复合材料,得到的纳米银和氯化银均匀分布在纤维素基底上,无团聚,粒径较小;与其它的水凝胶基银纳米复合材料不同,可直接采用银/氯化银@纤维素纳米复合材料催化还原对硝基苯酚;在整个催化反应中,有毒的还原剂NaBH4不仅用量很低,而且发挥了双向作用,一方面,将银/氯化银@纤维素纳米复合材料还原为银@纤维素纳米复合材料;另一方面,作为这个反应中的还原剂提供电子,即“边还原边催化”。
(2)本发明的方法条件温和,对设备要求简单,一锅法即可完成,无论从原料还是从制备过程均符合绿色可持续发展的理念;而且相对其他贵金属催化剂,无论从载体原料还是金属前驱体,制备成本都相对低廉,可以广泛应用于工业发展;
(3)本发明制备的纤维素水凝胶基纳米银/氯化银可快速催化还原芳香硝基化合物,还原剂硼氢化钠用量比文献中低,合适的硼氢化钠的量低至0.3mL 0.05M(与反应底物的摩尔比为25:1);其还可有效降解甲基橙、刚果红、茜素黄和罗丹明-B等有机染料;本发明制备的纤维素水凝胶基纳米银/氯化银还可被涂布成膜,得到抗菌薄膜。
附图说明
图1是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.6g单宁酸)的TEM图;右上角插图为本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.6g单宁酸)中纳米银和氯化银颗粒的粒径分布图;
图2是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.6g单宁酸)的HRTEM图,右上角插图为局部放大图;
图3是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.2g单宁酸)的TEM图;右上角插图为本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.2g单宁酸)中纳米银和氯化银颗粒的粒径分布图;
图4是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.4g单宁酸)的TEM图;右上角插图为本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.4g单宁酸)中纳米银和氯化银颗粒的粒径分布图;
图5是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.8g单宁酸)的TEM图;右上角插图为本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.8g单宁酸)中纳米银和氯化银颗粒的粒径分布图;
图6是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.9g单宁酸)的TEM图;右上角插图为本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.9g单宁酸)中纳米银和氯化银颗粒的粒径分布图;
图7是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.6g单宁酸)的XRD图;
图8是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.6g单宁酸)的FT-IR图;
图9是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.6g单宁酸)的XPS全谱图;
图10是本发明实施例1制备的纤维素水凝胶基纳米银/氯化银(0.6g单宁酸)的中的Ag 3d的分峰图;
图11是本发明实施例2中催化还原对硝基苯酚的紫外跟踪图;
图12是本发明实施例2中催化还原对硝基苯胺的紫外跟踪图;
图13是本发明实施例2中催化还原邻硝基苯酚的紫外跟踪图;
图14是本发明实施例2中催化还原对硝基苯酚的ln(Ct/C0)~t图;
图15是本发明实施例2中不同nNaBH4:n4-NP下,催化还原对硝基苯酚的ln(Ct/C0)~t的变化图;
图16是本发明实施例3中降解甲基橙的紫外跟踪反应图;
图17是本发明实施例3中降解刚果红的紫外跟踪反应图;
图18是本发明实施例3中降解茜黄素的紫外跟踪反应图;
图19是本发明实施例3中降解罗丹明-B的紫外跟踪反应图;
图20是本发明实施例3中降解模拟污水的紫外跟踪反应图;
图21是对比例1中中不加单宁酸的纤维素水凝胶基纳米银/氯化银的TEM图;
图22是对比例1中中不加单宁酸的纤维素水凝胶基纳米银/氯化银的催化还原对硝基苯酚的紫外跟踪图。
具体实施方式
以下结合实施例和附图对本发明进行进一步的说明。
实施例1
本发明绿色制备纤维素水凝胶基纳米银/氯化银包括以下步骤:
(1)纤维素溶液的制备
i.DMAC热活化:适量棉花中加入DMAC,160℃下热活化40min,得活化后的棉花。
ii.液压机压制:200℃下将活化后的棉花压制1min,得脱脂棉。
iii.高温搅拌:100℃下,将1g脱脂棉置于99g 8.5wt%的LiCl/DMAC极性溶液中,搅拌3h,降至室温,继续搅拌至溶解,放置澄清得纤维素溶液。
(2)向三颈瓶中加入50g纤维素溶液,0.6g单宁酸溶解于30mL DMAC中,25℃搅拌下,将单宁酸的DMAC溶液逐滴加入到三颈瓶中,混合液25℃搅拌2h,得反应液I,将反应液I的pH调为6.5,45℃下加入1mL戊二醛(质量分数25%),45℃下继续搅拌6h,得反应液II;
(3)将50mL,15mM AgNO3溶液逐滴加入反应液II中,45℃下继续搅拌13h,得反应液III,将反应液III逐滴滴加到盛有300mL去离子水并剧烈搅拌的烧杯中,得到絮状物悬浊液,抽滤水洗,洗掉多余的有机溶剂和氯离子(AgNO3检验),将抽滤水洗干净得到的滤饼为所述纤维素水凝胶基纳米银/氯化银(得到的纤维素水凝胶基纳米银/氯化银可重新分散在去离子水中(2mg/mL)供后续使用和保存)。
取本实施例制备的纤维素水凝胶基纳米银/氯化银进行电镜表征、X射线衍射分析、傅里叶变换-红外光谱分析和X射线光电子能谱分析。
电镜表征的结果如图1。由图1可以看出:近似球形的粒子比较均匀的分散在纤维素上,没有观察到严重的聚集现象。粒子的直径的统计如图1右上角插图所示,所形成颗粒的尺寸几乎在2.0-6.0nm范围内,平均直径为5.34nm。这些结果也证实了在制备过程中单宁酸的稳定及分散作用,单宁酸的结构中有众多酚羟基,可以起到螯合银离子从而达到分散的作用。单宁的分子骨架由刚性芳香环组成,芳香环提供空间效应,阻止纳米粒子的聚集,从而起到有效的稳定剂的作用。图2为高分辨透射电镜图,右上角插图为局部放大图,图中的晶格条纹间距为0.235nm,0.257nm对应于AgNPs的面心立方(fcc)结构的(111)平面和AgCl的(200)面。这些证实了AgNPs和AgCl以小尺寸(5.34nm)均匀分布,且无聚集的AgNPs和AgCl形成。
为进一步研究单宁酸的量对纤维素水凝胶基纳米银/氯化银的中纳米银和氯化银颗粒粒径的调节作用,除单宁酸添加量更改为0.2g,0.4g,0.8g,0.9g按实施例1的制备方法分别制备纤维素水凝胶基纳米银/氯化银①②③④,并采用电镜表征它们,如图3发现当单宁酸的添加量为0.2g时起不到最佳的分散效果,粒子分布不均匀,粒径为7.16nm。如图4当单宁酸添加量增加到0.4g时,平均粒径为6.35nm,较之前明显减小。如图5而当单宁酸添加量增加到0.8g时,颗粒团聚,粒径增大到8.66nm,说明纤维素载体与单宁酸之间存在一定的平衡。一定量的载体只能接枝一定量的单宁酸。如图6当单宁酸进一步增加到0.9g时,颗粒的聚集更加严重。由此不难发现,单宁酸不仅可以控制颗粒的大小,而且对颗粒的分散起到重要作用。因此,从以上结果可以准确的得出单宁酸的最佳用量为0.6g,并选择其作为最佳催化剂。
X射线衍射分析结果如图7,XRD图的显示了本发明制备的纤维素水凝胶基纳米银/氯化银的组成和晶体结构,在图7中,纤维素(a)在2θ=21°表现出一种特征信号,这是纤维素II结晶形式造成的。单宁酸-纤维素(c)显示纤维素II的特征峰,并且在约24°处观察到一个较弱的肩峰,这表明少量纤维素分子上存在无定形碳,进而说明单宁酸成功连接到纤维素分子上。单宁酸-纤维素(c)的衍射峰与纤维素(a)相似,没有新的峰出现,表明化学修饰不会改变纤维素的完整化学结构。此外,纤维素水凝胶基纳米银/氯化银(d)的XRD图谱在27.8°,32.2°,46.3°,54.7°,67.5°,74.5°,76.6°处显示出附加的衍射峰,分别对应于AgCl的(111),(200),(220),(311),(222),(400),(331),(420)平面,同时在38°观察到相对弱的衍射峰,这是典型的立方相金属Ag的(111)面,这些表明成功形成了AgCl和AgNPs。
利用傅里叶变换-红外光谱分析表征纤维素与单宁酸接枝反应情况及在化学修饰过程中的结构完整情况。参见图8,当单宁酸接在纤维素上时,3400cm-1处的吸收峰变宽了,这是由于纤维素中的羟基与单宁酸的酚羟基通过戊二醛交联的结果,同时,在1180cm-1,1400cm-1处出现了新的吸附峰,这归因于单宁酸中酚羟基的C-O-H伸缩振动和酚羟基的面内形变振动,这些均表明单宁酸已成功接枝在了纤维素上,并且通过化学修饰纤维素的结构依然保持完整,这与XRD的结果相符。至于纤维素水凝胶基纳米银/氯化银(d)在3400cm-1处的单宁酸酚羟基拉伸振动比(c)的相对较窄,这是因为纳米复合材料中单宁酸的酚羟基与Ag+相互螯合的结果。
利用X射线光电子能谱分析纤维素水凝胶基纳米银/氯化银中银的化学状态,图9为纤维素水凝胶基纳米银/氯化银的XPS全谱图,显示出C1s,O 1s,Cl 2p,Ag 3p和Ag 3d的存在,没有其它明显的杂质。图10为Ag 3d的分峰图,如10所示,在368eV和374eV处的两个峰分别对应于Ag 3d5/2和Ag 3d3/2的结合能,两者差值为6.0eV,表明形成了AgNPs(Ag0)。另外,在367.6eV和373.6eV处的两个峰分别对应于Ag 3d5/2和Ag 3d3/2结合能,归因于Ag+。这些结果表明,Ag0和AgCl存在于复合物中,符合XRD的分析结果。因此,XPS和XRD分析表明样品为AgNPs/AgCl@TA-Cellulose纳米复合材料(纤维素水凝胶基纳米银/氯化银)。
实施例2
采用实施例1制备的纤维素水凝胶基纳米银/氯化银对芳香硝基类化合物进行还原。
取实施例1制备的纤维素水凝胶基纳米银/氯化银分散在去离子水中,配制为2mg/mL的催化剂悬浊液。分别向3mL 0.2mM的对硝基苯酚、对硝基苯胺和邻硝基苯酚硝中加入0.5mL制备的催化剂,通氮气20分钟,然后将反应液转到比色皿中,加入0.3mL,0.05MNaBH4,室温下反应。紫外跟踪反应结果分别如图11、图12和图13。在图11中通过记录400nm处4-NP特征吸收带随反应时间的变化来监测催化反应过程。在400nm处的吸收峰强度随着时间的推移逐渐减小,在约为5min后(不进行任何搅拌)吸收峰完全消失,同时在298nm处出现一个新的吸收峰,吸收峰强度逐渐增大。这个新的峰归因于对4-氨基苯酚的典型吸收。图11的UV-vis光谱显示了280nm和314nm处的两个等深点。这一结果表明,4-硝基苯酚的催化还原反应只生成4-氨基苯酚,不产生任何副产物。同理,在图12约10min后对硝基苯胺的吸收峰消失,图13约5min后邻硝基苯酚的吸收峰消失。
在过量NaBH4的情况下,该反应遵循拟一级动力学,t时刻4-NP浓度记为Ct,t=0时初始浓度记为C0,Ct/C0由吸光度的相对强度(At/A0)测量。根据图14可知,ln(Ct/C0)与反应时间t呈线性关系,一阶模型描述为:ln(Ct/C0)=ln(At/A0)=-kappt,斜率为纳米复合材料的kapp值,约为0.4611min-1。
图15在不同的nNaBH4:n4-NP下,ln(Ct/C0)~t的变化图,可以看出反应速率常数Kapp随NaBH4浓度的增大而增大,为了更准确的控制反应时间,将nNaBH4:n4-NP定位25:1,这低于我们所查阅的文献。而且针对我们的这项研究,在对硝基苯酚的催化还原反应中,NaBH4起着原位还原与催化还原的双重作用,为“边还原边催化”,部分硼氢化钠还用于还原催化剂中的AgCl,所以实际上真正用于该反应的NaBH4与4-NP的比值低于25:1,这也从另一个角度说明了我们制备的纳米杂化复合材料的催化活性好。
实施例3
采用实施例1制备的纤维素水凝胶基纳米银/氯化银降解有机染料。
取实施例1制备的纤维素水凝胶基纳米银/氯化银分散在去离子水中,配制为2mg/mL的催化剂悬浊液。分别向3mL 0.2mM甲基橙、刚果红、茜素黄和罗丹明-B中加入加入0.5mL(2mg/mL)制备的催化剂,通氮气20分钟,然后将反应液转到比色皿中,加入0.3mL,0.02M,0.1M,0.2M NaBH4,室温下反应。紫外跟踪反应结果。紫外跟踪反应结果分别如图16、图17、图18和图19。由图可知在约4min,7min,13min,3min(无任何搅拌)后甲基橙、刚果红、茜素黄和罗丹明-B均全部还原。
由于污水中通产含有多种有机染料,因此,采用混合染料AY+Rh-B+MO(茜素黄+罗丹明-B+甲基橙各1mL 0.2mM)模拟污水,进一步研究本发明制备的纤维素水凝胶基纳米银/氯化银的处理污水的催化性能。另外,三种有机染料混合模拟污水:将AY、MO、Rh-B(分别为1mL)的0.2M混合,加入0.5mL(2mg/mL)催化剂悬浮液,氮气通过20min去除氧气。然后将上述混合物转移到比色皿中,加入新鲜配制的NaBH4(0.3mL,0.05M),室温下反应。并记录紫外-可见吸收光谱,监测催化反应。其紫外跟踪反应结果如图20,在约9min后,三种染料的特征峰均观察不到,说明混合有机染料在9min后能全部还原。
对比例1
为了进一步证实单宁酸的重要性,我们在与实施例1相同条件下制备了不含单宁酸的纳米复合材料进行比较。电镜表征的结果如图21,由图我们可以清楚的看到,平均粒径为7.10nm的粒子尺寸分布不均,有大有小,有明显的聚集现象,与最优催化剂对比很好的证实了单宁酸的分散作用。
取对比例1制备的纤维素水凝胶基纳米银/氯化银分散在去离子水中,配制为2mg/mL的催化剂悬浊液。分别向3mL 0.2mM的对硝基苯酚加入0.5mL制备的催化剂,通氮气20分钟,然后将反应液转到比色皿中,加入0.3mL,0.05M NaBH4,室温下反应。紫外跟踪反应结果如图22,在约8min40 s后,400nm处的对硝基苯酚的特征峰消失,说明8min40 s时对硝基苯酚全部还原为对氨基苯酚。相比于添加单宁酸的最优催化剂(5min),两者之间的差值也进一步证实了单宁酸稳定分散的作用。
Claims (8)
1.纤维素水凝胶基纳米银/氯化银的制备方法,其特征在于,包括以下步骤:
(1)搅拌条件下,向纤维素溶液中滴加单宁酸溶液形成反应液I,继续搅拌1~3h,调节反应液的pH至6~7,升温至40~50℃,然后加入戊二醛,继续搅拌 4~8h,得反应液II;
(2)保持40~50℃,向反应液II中滴加AgNO3溶液,继续搅拌10~24h,得反应液III,将反应液III滴加至剧烈搅拌的去离子水中,得絮状物悬浊液,抽滤,洗涤,滤饼为银/氯化银@纤维素纳米复合材料即纤维素水凝胶基纳米银/氯化银;
所述纤维素溶液是纤维素的LiCl/DMAC溶液;
所述单宁酸与纤维素的质量比为6:5;
所述AgNO3与纤维素的质量比为0.085~0.34:1;所述戊二醛与纤维素的质量比为0.474:1。
2.根据权利要求1所述纤维素水凝胶基纳米银/氯化银的制备方法,其特征在于,所述纤维素溶液中纤维素的质量百分数为1%。
3.根据权利要求1所述纤维素水凝胶基纳米银/氯化银的制备方法,其特征在于,所述单宁酸溶液是单宁酸的DMAC溶液;所述单宁酸溶液中单宁酸的质量浓度为0.02 g/mL。
4.根据权利要求1所述纤维素水凝胶基纳米银/氯化银的制备方法,其特征在于,所述AgNO3溶液是AgNO3的DMAC溶液;所述AgNO3溶液中AgNO3的浓度为5~20 mmol/L。
5.纤维素水凝胶基纳米银/氯化银的制备方法,其特征在于,包括以下步骤:
(1)搅拌条件下,向50 g 1 wt%的纤维素溶液中滴加30 mL 0.02 g/mL的单宁酸溶液形成反应液I,继续搅拌1~3 h,调节反应液的pH至6~7,升温至40~50 ℃,然后加入1 mL质量百分浓度为25%的戊二醛,继续搅拌 4~8 h,得反应液II;
(2)保持40~50 ℃,向反应液II中滴加50 mL 15 mmol/L 的AgNO3溶液,继续搅拌10~24 h,得反应液III,将反应液III滴加至300 mL去离子水中,并剧烈搅拌,得絮状物悬浊液,抽滤,洗涤滤饼,将滤饼重新分散在去离子水中,得到银/氯化银@纤维素纳米复合材料即纤维素水凝胶基纳米银/氯化银;
所述纤维素溶液是纤维素的LiCl/DMAC溶液。
6.根据权利要求1~5任一项所述纤维素水凝胶基纳米银/氯化银的制备方法,其特征在于,所述纤维素溶液的制备方法如下:
i:DMAC热活化:适量棉花中加入DMAC,160 ℃下热活化40 min,得活化后的棉花;
ii:液压机压制:200 ℃下,将活化后的棉花压制1 min,得到除掉DMAC的活化脱脂棉;
iii:高温搅拌:100 ℃下,将脱脂棉置于8.5 wt%的LiCl/DMAC极性溶液中,搅拌3 h,然后降至室温,继续搅拌至溶解,放置澄清,得到所述纤维素溶液。
7.权利要求1~6任一项所述方法制备的纤维素水凝胶基纳米银/氯化银作为催化剂在催化还原芳香硝基化合物中的应用。
8.权利要求1~6任一项所述方法制备的纤维素水凝胶基纳米银/氯化银在降解和吸附染料中的应用。
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