CN110157018B - 一种TiO2/交联羧甲基淀粉复合材料的制备方法及其应用 - Google Patents
一种TiO2/交联羧甲基淀粉复合材料的制备方法及其应用 Download PDFInfo
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Abstract
本发明以玉米淀粉为原料,环氧氯丙烷为交联剂,氯乙酸为醚化剂,通过交联‑碱化‑醚化一系列反应制备了交联羧甲基淀粉(CCMS),并通过溶胶‑凝胶法,将纳米TiO2负载于交联羧甲基淀粉表面,得到TiO2/交联羧甲基淀粉复合材料。本发明以阳离子金黄X‑GL染料为目标污染物,研究TiO2/交联羧甲基淀粉复合材料的吸附‑光降解性能,结果表明发生了显著的吸附‑光降解协同作用。
Description
技术领域
本发明涉及复合材料制备及污水处理技术领域,更具体的说是涉及一种 TiO2/交联羧甲基淀粉复合材料的制备方法及其应用。
背景技术
近年来,水体中染料的污染已达到前所未有的高度。纺织行业中的印染工序作为最大的耗水量、废水排放量工序,在生产过程中大约有1%~15%的染料随废水排放。由于染料结构复杂,可生化性差,使得其进入水生态系统后,能够长期稳定的存在,严重威胁人类健康和动植物生存。去除染料的方法主要包括吸附法、膜分离法、混凝法、生物氧化法以及光催化降解法等,这些方法都存在一定的限制。其中,吸附法只是对染料进行了转移并未消除,易造成二次污染;光催化降解法是基于废水体系对光能量的吸收,被处理体系必须具有良好的透光性,而高浓度印染废水具色度高和透光性差的特点,反应难以进行,需要与其它方法联用。
目前用于光催化降解染料的光催化剂多为n型半导体材料的金属氧化物以及金属酸盐类物质,如TiO2、ZnO、CdS、WO3、Fe2O3、Bi2O3等。在众多半导体光催化剂中,TiO2以其高活性、安全无毒、化学性质稳定、成本低等优点,被认为是环境治污领域最具开发前途的环保型光催化材料。10nm锐钛型TiO2具有优良的光催化效应,但纳米TiO2一方面易团聚、不利于从溶液中分离,另一方面其对有机污染物吸附能力有限,制约其处理高浓度染料废水的能力。
淀粉是储存量最大的一种环境友好型天然可再生多糖类高分子化合物,其结构单元上的羟基活性强、易变性,可通过表面化学修饰而带有各种功能基团,从而极大地扩大其应用范围。交联羧甲基淀粉(CCMS)是天然淀粉通过交联-碱化-醚化一系列反应获得的改性淀粉,在淀粉分子中引入了羧甲基,从而使分子带负电荷,可以有效吸附阳离子染料。
因此,如何提供一种高效处理染料废水的TiO2/交联羧甲基淀粉复合材料是本领域技术人员亟需解决的问题。
发明内容
有鉴于此,本发明将传统的吸附法与光催化降解技术相结合用于处理染料废水,在吸附染料的同时,完成对染料的降解作用,达到对染料吸附-光降解的协同作用。采用溶胶-凝胶法,使纳米TiO2负载于交联羧甲基淀粉表面,得到对TiO2/交联羧甲基淀粉复合材料。
为了达到上述目的,本发明采用如下技术方案:
一种TiO2/交联羧甲基淀粉复合材料的制备方法,包括以下步骤:
(1)交联羧甲基淀粉的制备
以玉米淀粉为原料,环氧氯丙烷为交联剂,制备交联淀粉,交联淀粉经碱化后,以氯乙酸为醚化剂进行醚化反应,得到交联羧甲基淀粉;
(2)TiO2/交联羧甲基淀粉复合材料的制备
将所述交联羧甲基淀粉分散于蒸馏水中配制成淀粉乳液,转移至装有机械搅拌装置及冷凝装置的三口烧瓶中进行糊化,然后在搅拌条件下滴加经过超声分散的纳米TiO2悬浮液,反应结束后于室温下搅拌至形成凝胶,经冷冻、干燥后即得TiO2/交联羧甲基淀粉复合材料。
TiO2/交联羧甲基淀粉复合材料的制备示意图参见图9。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的制备方法中,步骤 (2)中纳米TiO2悬浮液与交联羧甲基淀粉的比例为25mL:10g。
上述技术方案的有益效果是:上述比例会影响后续冷冻干燥过程,由于冷冻干燥过程比较慢,增加悬浮液的体积,会使冷冻干燥时间不统一,或干燥程度不统一,在此比例下能达到最佳效果。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的制备方法中,步骤(2)中所述纳米TiO2悬浮液是在室温下强力搅拌2h,超声分散1h后得到的。
上述技术方案的有益效果是:为了使纳米二氧化钛充分分散在水溶液中,先进行搅拌,再进行超声分散。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的制备方法中,步骤 (2)中所述糊化的温度为60~80℃,时间为1h。
上述技术方案的有益效果是:CCMS的水溶性很好,在较高温度就可以发生糊化,生成溶胶,60℃可以在更大程度上保持CCMS官能团的完整性。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的制备方法中,步骤 (2)中所述搅拌在60℃下进行4h。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的制备方法中,步骤 (2)中所述冷冻的温度为-20~-30℃,时间为6h。
上述技术方案的有益效果是:反应完成后在-30℃立即冷冻6h,可以使已经充分分散于凝胶中的纳米二氧化钛固定,得到负载更加均匀的TiO2/交联羧甲基淀粉复合材料。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的制备方法中,步骤 (2)中所述干燥时间为24h,使得材料充分干燥。
本发明还公开了一种根据上述方法制备得到的TiO2/交联羧甲基淀粉复合材料的应用,用于阳离子染料的吸附-光降解,具体包括以下步骤:
(1)将TiO2/交联羧甲基淀粉复合材料置于石英试管中,加入阳离子染料溶液,于光化学反应仪中搅拌一段时间后,在汞灯照射下进行光降解;
(2)吸附-光降解过程完成后,对染料溶液进行过滤,并用紫外-可见分光光度计测试滤液中染料浓度。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的应用中,所述阳离子染料为阳离子金黄X-GL染料。
上述技术方案的有益效果是:羧甲基淀粉携带负电荷,选用阳离子染料可以通过静电吸引充分体现出CCMS强大的吸附容量,以及最终的处理效果。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的应用中,步骤(1) 中TiO2/交联羧甲基淀粉复合材料与阳离子染料溶液的比例为0.01~0.05g:20mL,其中阳离子染料溶液的浓度为200~250mg·L-1。
上述技术方案的有益效果是:0.01g/250mg·L-1,可以充分体现TiO2/交联羧甲基淀粉复合材料对阳离子金黄染料的处理效果,使用量少,但处理染料废水浓度大。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的应用中,步骤(1) 中TiO2的含量占TiO2/交联羧甲基淀粉复合材料总量的0.5~7%,进一步优选为3%。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的应用中,步骤(1) 中通过0.1mol/L的HCl和/或NaOH控制pH值为3~8,进一步优选为5~7。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的应用中,步骤(1) 中TiO2/交联羧甲基淀粉复合材料的粒径为100-300目,进一步优选为300目。
上述技术方案的有益效果是:不同粒径对染料的处理结果影响很大,此处的探讨目数对染料去除率的影响。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的应用中,步骤(1) 于光化学反应仪中室温下磁力搅拌吸附10~30min后,在λ=265nm的250W汞灯照射下进行光降解20~120min。
上述技术方案的有益效果是:在实验时发现,在波长λ=265nm的250W 汞灯照射下进行光降解,降解效果最好。
优选的,在上述一种TiO2/交联羧甲基淀粉复合材料的应用中,步骤(2) 中通过0.22μm滤膜对染料溶液进行过滤。
上述技术方案的有益效果是:选用0.22μm滤膜可以使得复合材料充分过滤。
经由上述的技术方案可知,与现有技术相比,本发明通过溶胶-凝胶法,将纳米TiO2负载于交联羧甲基淀粉表面,得到TiO2/交联羧甲基淀粉复合材料,在吸附染料的同时,完成对染料的降解作用,达到对染料吸附-光降解的协同作用,大大提高了对染料的处理效果。
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,下面将对实施例或现有技术描述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,还可以根据提供的附图获得其他的附图。
图1附图为本发明玉米淀粉、CCMS和TiO2/CCMS复合材料的XPS全谱图及氧和钛的高分辨率结合能分布图;
图2附图为本发明玉米淀粉、CCMS、TiO2/CCMS复合材料的XRD光谱图;
图3附图为本发明玉米淀粉、糊化CCMS、TiO2/CCMS复合材料的电镜图;
图4附图为本发明玉米淀粉、CCMS和TiO2/CCMS复合材料的N2吸附- 脱附等温线图;
图5附图为本发明阳离子金黄X-GL染料的吸附与光降解性能;
图6附图为本发明TiO2负载量对染料吸附-光降解去除率的影响;
图7附图为本发明pH对染料吸附-光降解去除率的影响;
图8附图为本发明TiO2/CCMS复合材料对阳离子金黄X-GL染料的吸附 -光降解动力学模型;
图9附图为本发明TiO2/交联羧甲基淀粉复合材料的制备示意图;
图10附图为本发明TiO2/CCMS复合材料对阳离子金黄X-GL染料吸附- 光降解原理图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明实施例公开了一种TiO2/交联羧甲基淀粉复合材料的制备方法,包括以下步骤:
(1)交联淀粉的制备
用碱性NaCl溶液(m氢氧化钠:m淀粉=2%,m氯化钠:m蒸馏水=5%) 配制10%的玉米淀粉糊,并转移至装有机械搅拌及冷凝装置的三口烧瓶中,置于50℃恒温水浴锅中;滴加3mL的环氧氯丙烷,反应8h后,用1mol/L盐酸溶液调节pH至7.0;静置一段时间,过滤,用50%乙醇洗涤,50℃真空干燥,制得交联淀粉(CS);
(2)交联羧甲基淀粉的制备
第一步:碱化反应
准确称取20.0g交联淀粉,溶解于80mL乙醇溶液中,移到250mL三口烧瓶中,在20mL水中溶解9.9g的NaOH(nNaOH:n氯乙酸=1:1),冷却至室温,用恒压滴液漏斗2~3分钟滴加至淀粉乳中,于35℃恒温水浴锅中搅拌反应1小时;
第二步:醚化反应
在50mL乙醇中溶解11.6g的氯乙酸(nAGU:n氯乙酸=1:1),碱化反应结束后,用恒压滴液漏斗5分钟滴加至淀粉乳中,在50℃下反应3h,反应结束后用1mol/L盐酸溶液调节淀粉乳pH值在6.5~7,将产物过滤,用体积比为80%的乙醇溶液洗涤产物至溶液中无氯离子,产物于50℃下烘干至恒重,得到交联羧甲基淀粉。
(3)TiO2/交联羧甲基淀粉复合材料的制备
首先,配制25mL一定质量分数的纳米TiO2悬浮液,于室温下强力搅拌 2h,超声分散1h备用;称取10g绝干CCMS分散于蒸馏水中,配制成10% (w/w)的淀粉乳液,并转移至装有机械搅拌及冷凝装置的三口烧瓶中,于 60℃糊化1h。随后,将分散好的纳米TiO2悬浮液缓慢滴加到淀粉糊中,保持搅拌于60℃反应4h。反应结束后,于室温下搅拌至形成凝胶。最后,将产物于-30℃冷冻6h后,进行冷冻干燥24h,最终产物经研磨过筛后备用。
对通过上述方法制备得到的TiO2/交联羧甲基淀粉复合材料进行物质的表征分析及TiO2/交联羧甲基淀粉复合材料对染料的吸附-光降解实验。
1、TiO2/CCMS复合材料的表征
1.1、样品喷金处理后,样品的表面化学成分用X-射线光电子能谱(XPS) 分析,得到的玉米淀粉、CCMS和TiO2/CCMS复合材料的XPS光谱图参见图 1。
具体的,图1为玉米淀粉(a)、CCMS(b)和TiO2/CCMS复合材料(c) 的XPS全谱图及氧和钛的高分辨率结合能分布图。一方面,由全谱图可以看出,CCMS中引入了-COONa,能谱图中出现了Na 1s峰;TiO2/CCMS复合材料能谱图中出现了Ti 2p峰。另一方面,由氧的结合能分布图可以看出,与玉米淀粉相比较,CCMS的能谱在531.2eV处出现了C=O键的特征峰;而TiO2/CCMS复合材料能谱图中在530.4eV处出现了Ti-O键的特征峰,XPS的结果进一步说明TiO2成功地负载到CCMS上,生成了TiO2/CCMS复合材料。
1.2、样品的结晶形态用X射线衍射(XRD)图谱分析,衍射角2θ为4~50°,测角仪步长为0.02°,玉米淀粉、CCMS、TiO2/CCMS复合材料的XRD光谱图参见图2。
具体的,由图2可知,玉米淀粉分别在15.2°、17.2°、18.1°和23.0°出现明显的衍射峰,其晶型是典型的A晶结构,玉米淀粉经一系列反应生成CCMS 后,A晶结构消失,在15°~23°范围内表现为一个宽谱峰,说明玉米淀粉的结晶区遭到破坏转变为无定形区。这是由于:a.淀粉分子中引入了-COO-,在同种电荷的互斥作用下,分子链间距增大,淀粉颗粒膨胀,结晶区被破坏;b. 在反应过程中,OH-作为亲核试剂(Lewis碱)与淀粉中的亲电试剂-OH(Lweis 酸)发生反应,使淀粉分子中的羟基数目降低,破坏了氢键的形成,淀粉的紧密结构被破坏,结晶度降低。TiO2/CCMS复合材料的光谱图中除CCMS的衍射峰外,在25.34°、37.67°、48.09°、53.91°、55.09°、62.46°、68.95°、70.27°和75.03°出现的衍射峰分别对应锐钛矿TiO2的(101)、(004)、(200)、(105)、(211)、 (204)、(116)、(220)和(215)特征晶面,说明锐钛矿TiO2负载到CCMS上,生成了TiO2/CCMS复合材料。
1.3、样品的表面形态使用台式扫面电镜(SEM)于加速电压10KV下进行观察,放大倍数为2000倍,玉米淀粉(a)、糊化CCMS(b)、TiO2/CCMS (c)复合材料的电镜图参见图3。
具体的,从图3中可以看出,玉米淀粉颗粒为多角形,表面光滑,规整程度较高,而糊化后的CCMS吸附剂颗粒受损,并且表面出现一个较大的孔洞。一方面,淀粉颗粒的完整性主要由其结晶结构决定,如果结晶区遭到破坏,则淀粉颗粒的宏观结构也会发生显著变化,这是与XRD分析结果相吻合的。另一方面,糊化后的淀粉采用的干燥方式为冷冻干燥,抽真空过程中,颗粒内外存在较大的压强差,导致颗粒出现一个较大的孔洞,与糊化后的 CCMS相比,TiO2/CCMS复合材料表面存在许多细微的颗粒,这是TiO2附着于CCMS表面造成的,此结果与XPS分析相一致。
1.4、样品的比表面积(BET)用介孔比表面物理吸附仪通过静态容量法测得,利用压力的变化,测得的玉米淀粉、CCMS和TiO2/CCMS复合材料的 N2吸附-脱附等温线如图4所示。
具体的,参照IUPAC的分类方法,图中的等温线为Ⅱ型,表明该吸附是由非孔或大孔固体产生的多分子层吸附。吸附等温线和脱附等温线产生明显的迟滞环,并且较高相对压力区域没有表现出吸附限制,说明该迟滞环为H3 型。玉米淀粉和CCMS的迟滞环大小以及吸附等温线高度相差不多,但明显小于和低于TiO2/CCMS复合材料,表明TiO2/CCMS复合材料的孔径较大且孔较多。
分别对玉米淀粉、CCMS和TiO2/CCMS复合材料的比表面积BET、平均孔径BJH以及比孔容积进行测定,结果参见表1:
表1样品的孔隙结构测定结果
从表中数据可以得出玉米淀粉和CCMS的比表面积、平均孔径以及比孔容积相差不多,说明玉米淀粉经一系列反应后,虽然结晶度降低,但结构依然较紧密;TiO2/CCMS复合材料的比表面积、平均孔径和比孔容积都增大,一方面是由于CCMS经高温下糊化后结构在一定程度上被破坏,另一方面是由于淀粉颗粒表面负载纳米级TiO2造成的。但总体而言,无论是CCMS还是 CCMS/TiO2复合材料,由于淀粉自身紧密的结构,与多孔材料相比,SBET 和比孔容积都相对非常小,因此对染料的吸附主要通过静电作用完成。
2、TiO2/CCMS复合材料的对染料的吸附-光降解试验
准确称取0.01g TiO2/CCMS复合材料置于试管中,加入0.02L阳离子金黄 X-GL染料溶液(250mg·L-1),于光化学反应仪中室温(25℃)下磁力搅拌吸附10min后,在250W汞灯(λ=265nm)照射下进行光降解实验。研究TiO2的负载量、染料溶液的pH(用0.1M HCl和0.1MNaOH调节)和光照时间 (20~120min)对TiO2/CCMS复合材料降解染料的影响。吸附-光降解实验完成后,用0.22μm滤膜对染料溶液进行过滤,并用紫外-可见分光光度计测试滤液中染料浓度。
TiO2/CCMS复合材料对染料的吸附-光降解协同去除率如下:
式中,R—去除率;C0、C1—吸附前后染料浓度,mg·L-1。
2.1、TiO2/CCMS复合材料的吸附和光降解性能
为了研究TiO2/CCMS复合材料对阳离子金黄X-GL染料吸附-光降解的协同作用,分别进行了吸附和光降解实验。
如图5所示,在黑暗中室温下,TiO2/CCMS复合材料对阳离子金黄X-GL 染料吸附20min基本达到吸附平衡,去除率为63.17%,表明该材料对阳离子金黄X-GL染料具有吸附速度快、吸附量大的特点。对于紫外光催化系统,在 TiO2光催化作用下去除率仅为9.34%,而在吸附-光催化作用下,去除率继续增加至84.98%,说明发生了显著的吸附-光降解协同作用。该复合材料通过 CCMS基体对阳离子金黄X-GL染料强大的吸附作用,迅速完成溶液中的染料在其表面的富集过程,使染料溶液脱色,同时利用所负载TiO2的光催化作用,将被吸附的染料彻底分解成CO2、H2O和无机小分子,染料分子被降解后,CCMS的活性位点重新裸露,继续捕集溶液中的染料,从而进一步提高对染料的去除率,这种吸附-降解的有机结合,大大提高了对染料的处理效果。
2.2、TiO2负载量对吸附-光降解协同作用的影响
TiO2负载量对染料吸附-光降解去除率的影响如图6所示。
可以看出,当TiO2含量由0.5%增至3%时,染料的去除率达到最大,随 TiO2含量继续升高,去除率不断下降。TiO2具有高光催化活性,当其负载量增大时,可利用的光催化活性位点增多,对染料的降解率提高。随着TiO2含量继续升高,一方面纳米TiO2易发生团聚,造成光催化活性位点减少,染料的降解率降低;另一方面,CCMS基体表面负载过多的TiO2,影响其与染料的接触,造成对染料的吸附量减少,为光催化反应提供的染料浓度降低,光催化反应效率降低。因此,最佳的TiO2负载量为3%。
2.3、pH对吸附和光降解协同作用的影响
pH对染料吸附-光降解去除率的影响如图7所示。
染料溶液的pH在吸附-光降解体系中是一个重要的因素,不仅影响CCMS 基体和TiO2的表面电荷,而且对染料在溶液中的状态产生影响。图7为pH 在3~8范围内,TiO2/CCMS复合材料对阳离子金黄X-GL染料的去除率变化,随着pH的增大,染料的去除率逐渐升高,当pH在5~7范围内时,染料的去除率达到较高的水平;pH>7后,去除率呈现明显的下降趋势。
溶液的pH较低时,CCMS基体和TiO2分别被质子化和离子化:
TiOH+H+→TiOH2 +
CCMS基体羧基数量减少,对阳离子金黄X-GL染料的吸附量降低,可被TiO2降解的染料浓度降低;同时由于携带正电荷,TiO2与阳离子金黄X-GL 染料发生静电排斥作用。随pH增大,溶液中H+数目减少,这种现象减弱,染料的去除率逐渐达到最高水平,当pH>7时,溶液中存在的大量OH-,发生如下反应:
TiOH+OH-→TiO-+H2O
TiO2在碱性环境中带负电荷,与阳离子金黄X-GL染料可发生静电吸引,有利于光催化降解反应的发生;然而阳离子金黄X-GL染料与碱发生反应,生成季铵碱,不但影响CCMS基体对其吸附作用,而且降低了光催化过程中羟基自由基(OH·)的形成,因此,在碱性环境中TiO2/CCMS复合材料对阳离子金黄X-GL染料去除率降低。
2.4、吸附-光降解动力学研究
本实施例以Langmuir-Hishelwood(L-H)动力学模型作为一个标准模型用来描述对染料的吸附-光降解行为,其简化表达式如下:ln(C0/Ct)=kt
式中:C0、Ct为染料溶液的初始浓度和处理t时间后的浓度,mg/L;
k为表观反应速率常数,min-1;t为紫外光照时间,min。
为了初步研究不同粒径TiO2/CCMS复合材料对阳离子金黄X-GL染料的吸附-光降解动力学,分别对100、200和300目的TiO2/CCMS复合材料进行动力学研究,对实验数据进行直线回归分析,结果如图8和表2所示。
由相关系数R2可以看出TiO2/CCMS复合材料对阳离子金黄X-GL染料的吸附-光降解行为遵循L-H动力学模型。300目TiO2/CCMS复合材料的反应速率为0.0076min-1,明显高于100目和200目,说明粒径越小,越利于反应的发生。相比于100目颗粒,300目TiO2/CCMS复合材料更容易分散于染料溶液中;同时由于颗粒较小,有相对更多的有效官能团裸露在颗粒表面与染料接触,发生吸附和光降解反应。
表2不同粒径复合材料的回归直线系数
目数 | k<sub>1</sub> | R<sup>2</sup> |
100 | 0.0056 | 0.9993 |
200 | 0.0063 | 0.9954 |
300 | 0.0066 | 0.9980 |
上述XPS、XRD、SEM和BET结果共同表明了通过溶胶-凝胶法成功合成了具有更大比表面积的TiO2/CCMS复合材料,在吸附-光降解体系中,该复合材料通过CCMS基体对X-GL吸附量大且吸附速度快,迅速完成溶液中的染料在其表面的富集,然后利用所负载TiO2的光催化作用,将被吸附的染料降解,从而达到了吸附与光降解的协同作用,大大提高了对染料的处理效果。
本说明书中各个实施例采用递进的方式描述,每个实施例重点说明的都是与其他实施例的不同之处,各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言,由于其与实施例公开的方法相对应,所以描述的比较简单,相关之处参见方法部分说明即可。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (10)
1.一种TiO2/交联羧甲基淀粉复合材料的制备方法,其特征在于,包括以下步骤:
(1)交联羧甲基淀粉的制备
以玉米淀粉为原料,环氧氯丙烷为交联剂,制备交联淀粉,交联淀粉经碱化后,以氯乙酸为醚化剂进行醚化反应,得到交联羧甲基淀粉;
(2)TiO2/交联羧甲基淀粉复合材料的制备
将所述交联羧甲基淀粉分散于蒸馏水中配制成淀粉乳液,转移至装有机械搅拌装置及冷凝装置的三口烧瓶中进行糊化,然后在搅拌条件下滴加经过超声分散的纳米TiO2悬浮液,反应结束后于室温下搅拌至形成凝胶,经冷冻、干燥后即得TiO2/交联羧甲基淀粉复合材料。
2.根据权利要求1所述的一种TiO2/交联羧甲基淀粉复合材料的制备方法,其特征在于,步骤(2)中纳米TiO2悬浮液与交联羧甲基淀粉的比例为25mL:10g。
3.根据权利要求1所述的一种TiO2/交联羧甲基淀粉复合材料的制备方法,其特征在于,步骤(2)中所述糊化的温度为60~80℃,时间为1h;所述冷冻的温度为-20~-30℃,时间为6h。
4.一种根据权利要求1-3任一项所述的方法制备得到的TiO2/交联羧甲基淀粉复合材料用于阳离子染料的吸附-光降解的应用,其特征在于,包括以下步骤:
(1)将TiO2/交联羧甲基淀粉复合材料置于试管中,加入阳离子染料溶液,于光化学反应仪中搅拌一段时间后,在汞灯照射下进行光降解;
(2)吸附-光降解过程完成后,对染料溶液进行过滤,并用紫外-可见分光光度计测试滤液中染料浓度。
5.根据权利要求4所述的一种TiO2/交联羧甲基淀粉复合材料的应用,其特征在于,所述阳离子染料为阳离子金黄X-GL染料。
6.根据权利要求4所述的一种TiO2/交联羧甲基淀粉复合材料的应用,其特征在于,步骤(1)中TiO2/交联羧甲基淀粉复合材料与阳离子染料溶液的比例为0.01~0.05g:20mL,其中阳离子染料溶液的浓度为200~250mg·L-1。
7.根据权利要求4所述的一种TiO2/交联羧甲基淀粉复合材料的应用,其特征在于,步骤(1)中TiO2的含量占TiO2/交联羧甲基淀粉复合材料总量的0.5~7%。
8.根据权利要求4所述的一种TiO2/交联羧甲基淀粉复合材料的应用,其特征在于,步骤(1)中通过0.1mol/L的HCl和/或NaOH控制pH值为3~8。
9.根据权利要求4所述的一种TiO2/交联羧甲基淀粉复合材料的应用,其特征在于,步骤(1)中TiO2/交联羧甲基淀粉复合材料的粒径为100~300目。
10.根据权利要求4所述的一种TiO2/交联羧甲基淀粉复合材料的应用,其特征在于,步骤(1)于光化学反应仪中室温下磁力搅拌吸附10~30min后,在λ=265nm的250W汞灯照射下进行光降解20~120min。
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