CN109999917A - 一种降解水体中有机污染物的共价有机骨架基复合光催化剂及制备方法 - Google Patents
一种降解水体中有机污染物的共价有机骨架基复合光催化剂及制备方法 Download PDFInfo
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Abstract
本发明提供了一种降解水体中有机污染物的共价有机骨架基复合光催化剂及制备方法。将共价有机骨架CTF‑1溶液与4‑氨基苯甲酸溶液,经冰浴、搅拌、洗涤、真空干燥,制得苯甲酸功能化的CTF‑1,标记为CFB。通过球磨法将CFB和磷钨酸H3PW12O40按不同比例复合,得到H3PW12O40/CFB,即为降解水体中有机污染物的共价有机骨架基复合光催化剂。该方法通过对共价有机骨架CTF‑1进行苯甲酸功能化修饰,并将磷钨酸固载于其中,实现磷钨酸在分子水平上的单分散,有效提高了光催化活性,对有机物的降解效率明显提高,水中稳定性好,使用寿命长,同时工艺过程较为简单,原料易得,价格低廉,可工业化推广生产应用。
Description
技术领域
本发明涉及水体中有机污染物降解领域,具体涉及光催化剂的制备,特别是涉及一种降解水体中有机污染物的共价有机骨架基复合光催化剂及制备方法。
背景技术
随着现代工农业的发展,大量有毒有害的有机污染物进入水体中,给人类的生存和发展带来了巨大的威胁。目前污水处理的方法主要有如生物处理法、化学氧化法、物理吸附法、光催化氧化法等。其中,物理吸附法是利用多孔性的吸附剂将环境污染物富集转移到吸附剂表面进行去除的方法,具有成本较低、应用范围广、操作运行简便、无二次污染且吸附剂易再生等优点;另外光催化氧化法是一种新兴的污水处理技术,利用太阳能将水中所含多种有机污染物均可被完全降解为水和二氧化碳等,具有廉价、无毒、稳定及可以重复使用等优点。因而,兼具吸附和光催化性能的共价有机骨架材料受到人们的重视。共价有机骨架是一类沸石型的纯有机多孔晶态聚合物材料,由 C, H, N, O,B, Si 等第一、二周期的轻元素通过可逆的强共价键连接而成二维及三维结构。共价有机骨架材料兼具独特的优势:(1) 骨架密度低,质地轻;(2) 孔隙度大,比表面积大;(3) 筑基单元可调,孔结构灵活可调;(4) 优异的酸碱及热稳定性,其在气体存储分离,催化和光电等多方面展现出广阔的应用前景,同时独特的多孔结构和大比表面积使其可以作为复合光催化剂的载体。从共价有机骨架的合成反应大致可以将其分为含硼类、亚胺类、三嗪类及其他类等四种类型。
2008 年,P. Kuhn 等采用氰基自聚形成三嗪环结构合成了第一例共价三嗪骨架CTF-1 (Crystalline Triazine-based Organic Framework, CTFs,图 1)。另一方面,多金属氧酸盐 (Polyoxometalates, POMs) 简称多酸,是由高氧化态的过渡金属 (主要是 V V, Mo VI , W VI , Nb V 和 Ta V ) 通过氧原子桥连形成的多核簇合物。多酸在分子层面的特性(原子种类、金属-氧簇的尺寸、构型、酸性、氧化还原性及特殊的“准液相”性质等)决定了其作为一类新型高效的多功能绿色催化剂在能源光催化(如光催化制氢),工业光催化(如有机底物转化为有用的化学品)和环境光催化(污染物降解、灭菌)等领域呈现出潜在的应用价值。但因其存在带隙较宽,对可见光的利用率较低,多酸纳米簇的聚集使其比表面积较小(小于 10 m2/g),且多酸易溶于水,导致多酸从水体中难以被分离、回收再利用并且还可能导致金属残留等缺陷,这些极大地限制了多酸光催化降解水体中有机污染物的应用。所以,各种负载型多酸复合材料的多相光催化研究纷纷受到人们的广泛关注。
到目前为止,现有研究和技术中已存在诸多关于负载型多酸复合材料有机污染物降解和光催化技术的研究报道,例如:
专利公开号为CN105817241A的专利公开了一种磷钨酸铜@二氧化钛核壳结构纳米材料的制备方法。本发明提供了一种可见光响应的光催化剂,其工艺简便易行,纯度高,杂质含量低,成本低,性能优异,可以工业化批量生产。这种磷钨酸铜@二氧化钛核壳结构纳米材料光催化剂,在降解染料废水及室内有害气体,光催化消毒等领域具有广泛的应用前景。
专利公开号为 CN104525262B 的专利公开了一种光催化剂及其制备方法。本发明提供了一种光催化剂,其工艺简单,成本低,易回收,光催化效果明显,适于大批量生产。这种光催化剂以类石墨烯氮化碳作为多酸载体,利用氮化碳分子中的氨基,使磷钨酸和氨基发生中和反应制备其复合光催化剂,既解决了磷钨酸光催化剂不易回收,又提高了其光催化效果。
专利公开号为 CN105562110B 的专利公开了一种 AgX@MIL(Fe)复合光催化剂的制备方法,所述 AgX@MIL(Fe)复合光催化剂中 MIL(Fe)为 MIL-53(Fe)、MIL-88B(Fe)或MIL-100(Fe)中的一种,AgX 为 AgCl、AgBr 或 AgI 中的一种,本发明首先采用溶剂热法制备磷钨酸@MIL(Fe)复合材料,再通过双溶剂法在MIL(Fe)材料的孔中合成 AgX(X=Cl、Br、I),以得到具有优良光催化性能的AgX@MIL(Fe)复合光催化剂。以分子状态存在于 MIL(Fe)材料孔道中的磷钨酸,具有良好的电子转移性能,且由于其分子较大而难以从 MIL(Fe)材料孔中溶出;MIL(Fe)材料能高效吸附富集水中有机污染物,有利于 AgX 与有机污染物的接触;此外,AgX@MIL(Fe)复合光催化剂可充分发挥 AgX 和 MIL(Fe)之间的协同光催化效应,从而有效促进水中有机物的催化氧化降解效率。所以,本发明为处理有机废水提供广阔的前景。
根据上述,现有方案中的磷钨酸载体多样化,不同载体形成的复合材料光催化性能差异较大,目前还未见共价有机骨架用作多酸的载体形成复合材料的报道,本发明提出了一种用于降解水体中有机污染物的共价有机骨架基复合光催化剂及制备方法,充分发挥共价有机骨架 CTF-1 层状材料的良好光吸收、大的比表面积和良好的导电性;磷钨酸的氧化催化、光活性及电子“储存器”的特性,大大提高光生电子和空穴分离效果和利用率,实现“磷钨酸-CTF-1”之间结构和电荷的有效匹配,从而构建具有高效、稳定的有机污染物光催化降解体系。
发明内容
本发明的目的在于合成一种用于降解水体中有机污染物的共价有机骨架基复合光催化剂。本发明所制备的复合光催化剂对水体中有机污染物兼具吸附和光催化性能、在水中的稳定性好、使用寿命长、操作方便等优点。
本发明的技术方案是:一种降解水体中有机污染物的共价有机骨架基复合光催化剂,其特征在于,所述复合光催化剂为苯甲酸功能化修饰的共价有机骨架CTF-1,即CFB与磷钨酸H3PW12O40组成的H3PW12O40/CFB复合光催化剂。
一种降解水体中有机污染物的共价有机骨架基复合光催化剂,其特征在于,所述H3PW12O40/CFB复合光催化剂为先将共价有机骨架CTF-1苯甲酸功能化修饰,再与磷钨酸经球磨的方法制备得到,主要步骤为:
(1)预先合成一定量的共价有机骨架 CTF-1;
(2)通过与 4-氨基苯甲酸反应制得苯甲酸功能化的 CTF-1,即CFB;
(3)通过球磨法与磷钨酸H3PW12O40按照不同比例复合,以得到目标共价有机骨架基复合光催化剂H3PW12O40/CFB。
一种用于降解水体中有机污染物的共价有机骨架基复合光催化剂的制备方法,具体步骤为:
(1)苯甲酸功能化的 CTF-1 即 CFB 的制备:
(i) 将 200mL 21.3mg/mL 1,4-二氰基苯的三氯甲烷溶液通过分液漏斗缓慢滴加至氩气保护下、冰浴至 0 ºC、40~60 mL 体积比为 5:2 的三氯甲烷/三氯甲磺酸混合物溶液中,先后经 0 ºC 和40 ºC 分别搅拌 2h 和 48h,冷却至室温后,加 34mL 氨水和 660mL 去离子水继续搅拌 2h,后经抽滤,洗涤,真空干燥,制得共价有机骨架 CTF 前驱体;
(ii) 将2.00~2.30g CTF前驱体与1.787g ZnCl2置于氩气保护下400ºC管式炉中煅烧10 分钟,冷却后将产物先后倒入 150mL 水和 0.1mol/L HCl 中,60ºC 搅拌12h并抽滤,后经洗涤、真空干燥,制得共价有机骨架 CTF-1;
(iii) 将 100~120mg重量比为 50:3 的 CTF-1/十二烷基磺酸钠溶于 200mL 水中,超声后冰浴至 0.5ºC,迅速加入 4-氨基苯甲酸溶液(900–1000mg 4-氨基苯甲酸加入 80 mL3.5mg/mL 氢氧化钠水溶液中,后缓慢加入 500–600 mg 亚硝酸同时冰至 0.5 ºC,快速加入 6mL 20% HCl 后搅拌),先后经冰浴和室温各搅拌 4h,后洗涤、真空干燥,制得苯甲酸功能化的 CTF-1,标记为 CFB。
(2)共价有机骨架基复合光催化剂H3PW12O40/CFB 的制备:将不同比例的CFB 和磷钨酸通过球磨复合,转速为 180~250 r/min,球磨时间 4~8h,乙醇洗涤、干燥,制得磷钨酸含量分别为 10%~60%的共价有机骨架基复合光催化剂H3PW12O40/CFB;为了对比实验结果,利用相同方法复合制得H3PW12O40/CTF-1复合光催化剂。
本发明所述共价有机骨架基复合光催化剂H3PW12O40/CFB 降解水体中有机污染物的具体过程为:在常温下,分别向 50 mL 浓度为 10mg/L 的四环素水溶液中加入 10mg 上述复合光催化剂,并进行磁力搅拌;在水面正上方 10 cm、功率 20 W、波长 450 nm 的 LED灯照射下,对水中有机污染物四环素进行降解实验,每隔 10min 取一次样,用紫外分光光度计分别在λ = 357 下测量吸光度,最后计算四环素的降解率。研究发现,当复合比例为50%H3PW12O40/CFB时,降解效果最为优异,反应 10min 后,四环素降解率为 75%,反应 20min后达稳定,降解率维持在 80%左右;然而复合光催化剂 50%H3PW12O40/CTF-1反应 20min 后四环素降解率才约为 38%,反应 50min 也未达稳定,此时降解率为 55%;对比研究发现,通过对 CTF-1 与 4-氨基苯甲酸进行修饰,即苯甲酸功能化,使其带上亲水性基团,从而更好地与磷钨酸复合在一起,有效地提高其吸附和降解污染物的效果。
本发明的有益之处主要体现在:(1)共价有机骨架 CTF-1 层状材料具有大的比表面积,良好光吸收、导电性和化学稳定性;能够吸附富集水中的有机物,有利于有机污染物与光催化剂的接触;其多孔结构使得该复合材料具有良好的渗透性,有利于反应物和产物的传质;
(2)磷钨酸H3PW12O40具有独特的类半导体特性、氧化催化、光活性及电子“储存器”的特性,大大提高光生电子和空穴分离效果和利用率,具有良好光催化降解有机污染物特性;
(3)考虑到磷钨酸H3PW12O40均相催化过程中存在易聚集及溶于水的不足,将磷钨酸固载于 CTF-1 中,实现磷钨酸在分子水平上的单分散,将磷钨酸固载于 CTF-1 上获得的复合材料将具有良好光吸收、光生电子-空穴对有效分离以及优异光催化降解有机污染物的能力。
(4)经试验发现直接将磷钨酸和CTF-1进行球磨复合的效果不是很好,导致在降解时磷钨酸会从CTF-1负载上脱落下来,从而影响降解效果。通过对CTF-1与4-氨基苯甲酸进行修饰,即苯甲酸功能化,使其带上亲水性基团,从而更好地与磷钨酸复合在一起,达到吸附和降解的效果。
(5)本发明合成工艺流程简单,可操作性强,所制备的复合光催化剂对水体中有机污染物兼具吸附和光催化性能、在水中的稳定性好、使用寿命长、在实际应用中易于推广。
附图说明
图 1 为共价有机骨架 CTF-1 的合成及结构示意图;
图2为本发明的共价有机骨架基复合光催化剂H3PW12O40/CFB的光催化降解四环素的效能分析。
具体实施方式
本发明的共价有机骨架基复合光催化剂H3PW12O40/CFB 的合成是采用球磨技术,首先通过CTF-1与 4-氨基苯甲酸反应,即CTF-1苯甲酸功能化修饰制得 CFB,使其带上亲水性基团,从而增强与磷钨酸 H3PW12O40的复合,具体操作步骤为:
首先根据上述合成路线(图 1)制备一定量的 CTF-1 材料,将 100~120mg重量比为50:3 的 CTF-1/十二烷基磺酸钠溶于 200mL 水中,超声后冰浴至 0.5ºC,迅速加入 4-氨基苯甲酸溶液(900–1000mg 4-氨基苯甲酸加入 80 mL 3.5mg/mL 氢氧化钠水溶液中,后缓慢加入 500–600 mg 亚硝酸同时冰浴至 0.5 ºC,快速加入 6mL 20% HCl 后搅拌),先后经冰浴和室温各搅拌 4h,后洗涤、真空干燥,制得苯甲酸功能化的 CTF-1,标记为 CFB。将不同比例的 CFB 和磷钨酸通过球磨复合,转速为 180~250 r/min,球磨时间 4~8h,乙醇洗涤、干燥,制得磷钨酸含量分别为 10%~60% 的共价有机骨架基复合光催化剂H3PW12O40/CFB。
对上述共价有机骨架基复合光催化剂H3PW12O40/CFB 进行光催化性能评价:在常温下,分别向 50 mL浓度为 10mg/L 的四环素水溶液中加入 10mg 上述复合光催化剂,并进行磁力搅拌;在水面正上方 10 cm、功率 20 W、波长450 nm 的 LED 灯照射下,对水中有机污染物四环素进行降解实验,每隔 10min取一次样,用紫外分光光度计分别在λ = 357 下测量吸光度,最后计算四环素的降解率,结果显示(如图 2 ),共价有机骨架基复合光催化剂50%H3PW12O40/CFB,降解效果最为优异,反应 10min后,四环素降解率为 75%,反应 20min后达稳定,降解率维持在 80%左右。
Claims (4)
1.一种降解水体中有机污染物的共价有机骨架基复合光催化剂,其特征在于,所述复合光催化剂为苯甲酸功能化修饰的共价有机骨架CTF-1,即CFB与磷钨酸H3PW12O40组成的H3PW12O40/CFB复合光催化剂。
2.根据权利要求1 所述一种降解水体中有机污染物的共价有机骨架基复合光催化剂,其特征在于,所述H3PW12O40/CFB复合光催化剂为先将共价有机骨架CTF-1苯甲酸功能化修饰,再与磷钨酸经球磨的方法制备得到,主要步骤为:
预先合成一定量的共价有机骨架 CTF-1;
通过与 4-氨基苯甲酸反应制得苯甲酸功能化的 CTF-1,即CFB;
通过球磨法与磷钨酸H3PW12O40按照不同比例复合,以得到目标共价有机骨架基复合光催化剂H3PW12O40/CFB。
3.一种根据权利要求1所述的降解水体中有机污染物的共价有机骨架基复合光催化剂的制备方法,其特征在于:具体步骤为:
(1) 将 200mL 21.3mg/mL 1,4-二氰基苯的三氯甲烷溶液通过分液漏斗缓慢滴加至氩气保护下、冰浴至 0 ºC混合物溶液中,充分搅拌,洗涤,真空干燥,制得共价有机骨架CTF前驱体;
(2) 将2.00~2.30g的CTF前驱体与 1.787g ZnCl2置于氩气保护下400ºC 管式炉中煅烧10 分钟,冷却后将产物先后倒入150 mL水和 0.1 mol/L HCl中,60ºC 搅拌 12h 并抽滤,后经洗涤、100~150℃真空干燥12~15h,制得共价有机骨架 CTF-1;
(3) 将重量比为 50:3 的 CTF-1/十二烷基磺酸钠溶于 200mL 水中,超声后冰浴至0.5 ºC,迅速加入4-氨基苯甲酸溶液,充分搅拌后进行洗涤、真空干燥,制得苯甲酸功能化的 CTF-1,标记为 CFB;
(4) 将不同比例的 CTF-1 和磷钨酸通过球磨复合,球磨机转速180~250r/min,球磨时间 4~8h,洗涤、干燥,制得磷钨酸含量分别为 10%~60%的共价有机骨架基复合光催化剂H3PW12O40/CTF-1;
(5) 将不同比例的 CFB 和磷钨酸通过球磨复合,球磨机转速180~250r/min,球磨时间4~8h,洗涤、干燥,制得磷钨酸含量分别为 10%~60%的共价有机骨架基复合光催化剂H3PW12O40/CFB。
4.根据权利要求3所述一种用于降解水体中有机污染物的共价有机骨架基复合光催化剂的制备方法,其特征在于:步骤(3)中4-氨基苯甲酸溶液为900~1000mg 4-氨基苯甲酸加入80 mL 3.5 mg/mL 氢氧化钠水溶液中,后缓慢加入 500~600 mg 亚硝酸同时冰浴至 0.5ºC,快速加入 6mL 20% HCl 后搅拌。
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