CN117861727A - 一种z型异质结光催化材料的制备方法、该光催化材料及其应用 - Google Patents
一种z型异质结光催化材料的制备方法、该光催化材料及其应用 Download PDFInfo
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Abstract
公开了一种Z型异质结光催化材料的制备方法、该光催化材料及其应用,该方法包括:(1)将三聚氰胺分次在氮气气氛下高温烧制获得碳氮纳米片(CNN);(2)将2‑氨基对苯二酸(NH2‑BDC)、N,N‑二甲基甲酰胺(DMF)与六水氯化铁(FeCl3·6H2O)均匀混合,得到异质结材料混合液:将CNN分散到混合液中,在140‑160℃的温度下反应一定时间,得到的Z型异质结光催化材料,其中CNN与NH2‑MIL‑101(Fe)的质量比为1:1‑1:8。本发明光催化材料结能够在可见光下有效地活化PMS加速水环境中PAEs的降解,为各类水中PAEs的中端控制和末端治理提供了解决方案。
Description
技术领域
本发明属于水污染治理领域,具体涉及一种Z型异质结光催化材料(MCNN)制备方法、该光催化材料以及利用该光催化材料耦合PMS高级氧化体系降解水中PAEs的应用。
背景技术
邻苯二甲酸酯(PAEs)作为一类重要的添加剂,常被用于提高商业塑料制品的延展性和耐久性,因此在包装、医疗器械、工业管道、农用塑料薄膜等塑料制品中广泛使用。2021年,全球PAEs使用量就高达为360万吨[1],由于PAEs仅通过分子间氢键或范德华力与聚合物相互作用,因此在塑料制品的制造、应用和处理过程中,PAEs很容易释放到环境中。目前,PAEs已广泛存在于各种环境介质中,尤其是在海水、淡水、饮用水及污水[9]等水生环境中。在世界范围内,PAEs在水生环境(如海水、淡水和废水)中的浓度可达102μg·L-1,大部分甚至超过环境质量标准[2-4]。
考虑到PAEs对环境和生物体健康的不利影响,如内分泌干扰、生殖毒性、免疫毒性、代谢毒性、神经毒性和发育毒性,人们越来越关注PAEs的环境行为,部分PAEs(如DEP、邻苯二甲酸二丁酯)已被美国、中国、加拿大和欧盟确定为优先控制污染物。在现有的研究中,邻苯二甲酸二异丁酯(DIBP,高分子量PAEs)和DEP(低分子量PAEs)是环境和生物体中最常检测到的高水平PAEs。然而,现有的污水处理厂往往无法完全降解PAEs,因此,污水处理厂被认为是PAEs进入水生环境的主要来源[5]。PAEs出水浓度往往达到μg·L-1,甚至高达mg·L-1,对生态***和生物健康构成潜在威胁[6]。综上,多环芳烃类有机污染物释放到水生环境之前,研究高效、环保的多环芳烃脱除技术具有重要意义。
现在各种非生物和生物降解技术被用于去除水中的PAEs,包括混凝/絮凝、吸附、高级氧化(AOPs)、光催化、微生物生物降解和植物修复等工艺。相比之下,基于过硫酸盐/过氧单硫酸盐(PS/PMS)的AOP被认为是一种很有前途的完全去除污染物的技术,因为它能形成了非选择性活性氧(ROS)—硫酸盐自由基(SO4 -·),且该方法能耗低,也能在污水处理厂中实际应用。然而,大多数常见的光催化剂携带金属或过渡元素,在实际应用中受到催化稳定性低和金属浸出的限制。因此,在PS/PMS活化过程中,有必要关注具有有效催化能力的低成本、生态友好型光催化剂。
非金属半导体氮化碳因其光响应效率高、成本低、易制备、环境友好等特点,在污染物处理领域的研究具有重要意义,且在可见光驱动下能有效活化PMS,从而提高成本效益,减少环境影响。然而,氮化碳对可见光的响应是有限的,且其界面反应活性位点少,空穴电子复合率快,这都限制了有机污染物的降解及对PMS的活化,现需针对性的改性材料,以期提高e-和h+分离效率及对可见光的吸收。利用构建异质结是提高e-和h+分离比最常用的方法之一,其中MOFs是一类可通过配体到金属的电荷转移效应促进电荷分离的三维有机无机复合材料,是制备异质结的优异原料。NH2-MIL-101(Fe)是具有代表性的铁基MOF,它不仅含有丰富的Fe-o团簇和可见辐射激发的-NH2,而且具有表面积大、孔隙率大、孔径可改变等诸多优点。含三嗪环的原始g-C3N4与MOF简单结合形成的异质结光催化剂的光催化性能有所提高,但是效果仍不尽人意。同时,利用异质结活化PMS降解有机污染物的相关研究(包括实际应用和降解产物)尚缺乏。
因此,针对日益剧增的水环境PAEs污染问题,亟待开发更多高效环保的催化工艺用于处理该问题,减少多环芳烃污染。
参考文献:
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发明内容
本发明的目的是为了解决上述现有研究中对水中有机污染物在自然条件下难于降解且降解速度缓慢等问题,提供了一种能够基于可见光响应的异质结材料的制备方法以及该材料耦合高级氧化高效降解水中有机污染物(例如PAEs)的应用,以弥补现有技术的不足。本发明以三聚氰胺、DMF、FeCl3·6H2O及NH2-BDC为主要原料,通过多段式热聚法耦合水热法得到Z型异质结光催化材料(CNN@NH2-MIL-101(Fe),以下称为MCNN),该材料可有效活化PMS高级氧化体系加速处理水中PAEs的污染状况。
根据本发明的一方面,提供一种Z型异质结光催化材料制备方法,包括以下步骤:
(1)利用多段式热聚法制备碳氮纳米片,包括:将三聚氰胺在氮气气氛下进行第一次高温烧制;对第一次烧制产物进行清洗并烘干;然后进行研磨并再次在氮气气氛下进行第二次高温烧制;对第二次烧制产物进行清洗并烘干,得到超薄碳氮纳米片(CNN);
(2)利用水热法原位制备Z型异质结光催化材料,包括:将NH2-BDC和FeCl3·6H2O以约1:2的摩尔比例混入在N,N-二甲基甲酰胺(DMF)中,进行搅拌和超声,以充分均匀混合得到混合液;将步骤(1)得到的CNN分散到所述混合液中,继续超声和搅拌后得到均匀的混合溶液;将所述混合溶液在100-130℃的温度下反应18~24小时,得到棕红色固体;清洗(使用DMF与乙醇)棕红色固体、烘干并研磨,从而得到所述Z型异质结光催化材料CNN@NH2-MIL-101(Fe)(MCNN),
其中,NH2-BDC和FeCl3·6H2O反应所得的NH2-MIL-101(Fe)与CNN质量比为8:1-1:1,优选为2:1。
根据本发明的实施方案,步骤(1)中,高温烧制的温度为400~600℃,,例如550℃,500℃,450℃,第一次烧制时间为3~5小时,优选4小时,升温速率为3~6℃/min,优选5℃/min;第二次烧制时间为1~4小时,优选2小时,升温速率为6~12℃/min,优选8℃/min;分段多次烧制,以得到超薄纳米片材料。
根据本发明的实施方案,步骤(1)中,分别使用乙醇与超纯水进行多次清洗操作。
根据本发明的实施方案,步骤(2)中,使用DMF与乙醇进行清洗,搅拌和超声的时间分别为约1小时。
根据本发明的实施方案,步骤(1)中,所得CNN具有超薄纳米片的片层结构,其比表面积为10-30m 2·g-1
根据本发明的实施方案,步骤(2)中,在利用NH2-BDC和FeCl3·6H2O制备NH2-MIL-101(Fe)的过程中加入CNN混合,采用前掺法制备材料,以奖NH2-MIL-101(Fe)有效结合至CNN表面,由此得到异质结材料,其中CNN:NH2-MIL-101(Fe)为1:1—1:8,例如1:1、1:2、1:4、1:8。
根据本发明的另一方面,提供一种Z型异质结光催化材料,其特征在于,利用本发明所述的方法制备。
根据本发明的又一方面,提供一种催化剂耦合PMS体系催化降解水中有机污染物例如PAEs的方法,其特征在于,包括以下步骤:
(1)将根据本发明所述的Z型异质结光催化材料(MCNN)加入含有PMS的待处理的水溶液,将溶液均匀混合,其中,MCNN的投加量为0.01-0.08g·L-1,例如0.01、0.02、0.04、0.08g·L-1,此外MCNN与PMS的摩尔比为1:20-1:160,例如为1:20、1:40、1:80、1:160。
(2)将步骤(1)所得混合物置于光源下,在搅拌的条件下进行光催化反应,以降解水中有机污染物。
根据本发明的实施方案,有机污染物为PAEs,例如为DIBP和DEP;光源为可见光,优选为氙灯;也可以采用其他的非可见光源,例如紫外光催化。
根据本发明的实施方案,步骤(2)中,可见光催化反应在常温下进行,反应时间为30-90分钟,优选60分钟。
根据本发明的实施方案,所述方法在反应60分钟后,有机污染物的降解效率大于80.0%,DEP降解效率大于82.0%,DIBP降解效率大于92.0%。
本发明带来的有益效果:
(1)使用超薄碳氮纳米片与NH2-MIL-101(Fe)结合的Z型异质结,光激发材料形成载流子具有更优异的输运能力,更低的界面电阻,进而更有效地分离e—和h+,还有效降低带隙能量,提高了合成材料的光催化性能,合成材料中的e-可以转移到PMS的e-受体上,在此与HSO5 -反应,产生更多的SO4 -·;
(2)本发明Z型异质结能够在可见光下有效地活化PMS加速水环境中PAEs的降解,为各类水中PAEs的中端控制和末端治理提供了解决方案,可以降低PAEs降解缓慢导致的累积。
附图说明
图1为根据本发明实施方案的CNN@NH2-MIL-101(Fe)(MCNN)的制备流程图;
图2为根据本发明实施方案的CNN、NH2-MIL-101(Fe)及MCNN的SEM图;
图3为根据本发明实施方案的CNN、NH2-MIL-101(Fe)及MCNN的XRD与FTIR图;
图4为根据本发明实施方案的CNN、NH2-MIL-101(Fe)及MCNN的XPS图;
图5为根据本发明实施方案的CNN与MCNN的BET图;
图6为根据本发明实施方案的CNN、NH2-MIL-101(Fe)及MCNN的UV图与带隙宽度计算结果;
图7为根据本发明实施方案的CNN与MCNN的PL图及电化学结果图;
图8为根据本发明实施方案的CNN与MCNN耦合PMS对DEP与DIBP降解结果图;
图9为根据本发明实施方案的MCNN/PMS/Vis体系降解过程中活性物质的检测图及降解机理推理;
图10为根据本发明实施方案的MCNN/PMS/Vis体系优化条件结果图。
具体实施方式
下面结合说明书附图和具体实施例对本发明做进一步解释,但应理解,本发明的范围不限于此。
实施例1-Z型异质结光催化材料MCNN的制备(图1)
分段热聚合法制备CNN:将三聚氰胺放入有盖坩埚中,随后放入管式炉中,通入纯N2(99.999%),以升温速率为5℃min-1升温至550℃,加热4h。得到原始块状氮化碳材料,自然冷却到室温,分别用无水乙醇和超纯水清洗固体,烘干(55℃)后在玻璃研钵中研磨成粉末。继续将粉末样品在纯N2中升温至550℃(8℃min-1)持续加热2小时。冷却后,研磨固体样品并用乙醇及超纯水冲洗三次。最后,在55℃下烘箱干燥24小时并收集得到CNN。
水热法制备异质结材料:将2.0mmol NH2-BDC和4.0mmol FeCl3·6H2O混合于40mLDMF中,磁搅拌和超声处理各1h使之充分混合得到混合液。随后,在混合液中加入上述CNN材料,继续搅拌和超声各1h使溶液均匀混合得到混合溶液。最后,将混合溶液转移到高温反应釜中,在110℃下保持20小时。经离心、DMF与无水乙醇洗涤,最后在60℃下烘干得到棕红色材料,研磨得到Z型异质结光催化材料MCNN。
在该步骤中,在利用NH2-BDC和FeCl3·6H2O制备NH2-MIL-101(Fe)的过程中加入CNN,采用前掺法制备材料,以期将NH2-MIL-101(Fe)有效结合至CNN表面,由此得到异质结材料,其中加入的CNN的量与:NH2-MIL-101(Fe)的量(NH2-BDC和FeCl3·6H2O反应所得)之比为1:2。
实施例2-NH2-MIL-101(Fe)的制备
采用水热法制备NH2-MIL-101(Fe):将上述实施例1中得到的一部分混合液转移到高温反应釜中,在110℃下保持20小时。经离心、DMF与无水乙醇洗涤,最后在60℃下烘干得到棕黑色材料,研磨得到NH2-MIL-101(Fe)。
实施例3-实施例1和实施例2所得材料的表征
将得到的CNN、NH2-MIL-101(Fe)及本发明的Z型异质结光催化材料CNN@NH2-MIL-101(Fe)分别进行理化表征。表征如下:通过测定CNN、NH2-MIL-101(Fe)、MCNN的结构、表面官能团,化学成分,分析改性前后的理化性质变化,具体测定方法及结果如下:
采用扫描电镜检测其表面形貌和结构性能,检测结果参见附图2,如图所示,CNN在图2a中呈现出超薄纳米片的片层结构,NH2-MIL-101(Fe)呈光滑的六方八面体,尺寸为400—600nm(图2b)。基于两种材料之间的相互作用,MCNN SEM图像(图2c)中可以感受到两组分之间的紧密接触,这可以有效地减少电子-空穴对的传输路径,加速电荷转移。此外,MCNN有褶皱和粗糙表面,这有助于吸附有机污染物。
采用X射线衍射仪和傅立叶透射红外光谱仪检测材料的化学成分、晶体结构及表面官能团,检测结果参见附图3,如图3a所示,合成材料中不仅包含CNN的三嗪单元(100)和面间π-π层(002)特征晶面,还存在NH2-MIL-101(Fe)的典型峰,表明异质结构的有效构建。所有材料的FTIR光谱如图3b所示。对于合成材料,同时存在属于CNN的三嗪单元(801cm-1)与NH2-MIL-101(Fe)的Fe-O键(519cm-1)。1350—1550cm-1处的强吸收带属于羧基,说明CNN表面被羧基化了。FTIR结果也进一步证实复合材料中同时存在CNN和NH2-MIL-101(Fe)。
采用X射线光电子能谱仪检测材料的表面元素和化学键组成。如图4a所示,合成材料中除了CNN中的C和N外,还掺杂了O和Fe,这表明NH2-MIL-101(Fe)与CNN有效结合。对于Fe2p的高分辨率光谱(图4b),合成材料中的Fe为Fe(Ⅲ)。对于C1s的高分辨率光谱(图4c),合成材料中的主峰(284.8eV)属于非定式碳(C-C),另两个弱峰286.1eV和288.6eV分别属于NH2-MIL-101(Fe)的C-O和O-C=O。在高分辨率N1s光谱中(图4d),sp2键的芳香环N(398.6eV)和N-(C)3中的叔氨基(399.3eV)存在证明了CNN的N键结合模式在合成材料中被保留。然而,由于NH2-MIL-101(Fe)的N中存在孤对e-会被CNN中的-COOH抽离,导致合成的催化剂正移。综上所述,XPS结果证实了CNN与NH2-MIL-101(Fe)之间的相互作用。
采用BET仪测定材料的比表面积、孔隙率及孔隙分布特征。如图5所示,与CNN(比表面积为13.71m2·g-1)相比,MCNN合成材料的孔体积和比表面积(361.33m2·g-1)显著增加,有利于吸附污染物,提高催化活性。另外,本发明将MOF附到CNN上有效增加了比表面积,达到增加材料活性位点的目的。
利用紫外-可见漫反射分光光度计检测材料在200—800nm范围内的光吸收特性,如图6a所示,因为NH2-MIL-101(Fe)中存在Fe3-μ3-O团簇,促进了-NH2基团与有机BDC连接器的紧密连接,所以MCNN比CNN多了一条可见光吸收边,增加了可见光吸收。随后利用Tauc图得到材料的带隙宽度(Eg)为2.76eV(CNN)、2.43eV(NH2-MIL-101(Fe))与1.66eV(MCNN)。本发明合成材料的带隙窄,这表明本材料可以提供更多的光生e-和h+,从而提高了合成材料的光吸收能力。此外,CNN的价带和导带分别为1.80eV和-0.96eV,而NH2-MIL-101(Fe)的分别为1.17eV和-1.26eV(图6)。由于NH2-MIL-101(Fe)的CB高于CNN,因此当合成材料暴露在可见光下时,CNN产生的e-会转移到NH2-MIL-101(Fe)中,从而延迟了光诱导载流子的重组比率,增加了光催化活性。
采用稳态光致发光光谱(PL)仪在375nm的光激发下测定材料的发光性能,并利用电化学站测试材料的电化学性能,如图7a所示,合成材料的PL强度低于CNN,这是有助于载流子的分离。合成材料的光电流密度明显强于CNN(图7b),说明异质结界面处的载流子具有优异的传输能力。同时,在Nyquist图中(图7c),异质结呈现较低的半圆半径,这也表明MCNN具有较低的界面阻力和对e-和h+的有效分离性能。
实施例4-DIBP及DEP在MCNN/PMS/Vis体系中的降解
采用实例1、2所得的CNN、NH2-MIL-101(Fe)、MCNN,及各材料耦合PMS高级氧化体系降解在水中PAEs,具体操作如下:
1)将CNN、NH2-MIL-101(Fe)及MCNN材料加到含有PAEs(DIBP和DEP)中,在黑暗条件下磁力搅拌30分钟,磁力搅拌转速设置为200rpm。
(2)将一部分混合后的反应体系转移至光反应器中,在500w氙灯下进行光照,并对体系继续进行磁力搅拌,每15分钟测定DIBP和DEP的去除率,按照如下公式计算:降解率(%)=(处理组PAEs浓度-原始组PAEs浓度)/原始组PAEs浓度×100%。同时,保持其他实验条件和光催化体系不变,将另一部分体系放置于黑暗环境下作为对照组进行对比实验。
(3)对采样的水样进行分析,采用高效液相色谱仪测定PAEs的浓度,采用ZORBAXEclipse Plus C18色谱柱(4.6mm*100mm,3.5μm,Agilent),二极管阵列检测器(DAD)波长分别为228nm和230nm,流动相为ACN和水的混合物。
MCNN/PMS/Vis体系的降解结果如图8所示,该体系具有良好的催化性能,在60分钟后,DIBP的去除率超过94.5%,DEP的去除率超过83.4%。
实施例5-水中PAEs的降解机理
通过猝灭实验和EPR实验来确定活性物质在该体系中DIBP和DEP光降解中的作用,结果如图9a所示,h+和SO4 -·在DIBP降解中起关键作用,h+是该体系降解DEP的主要活性物质。根据相关反应推测MCNN/PMS/Vis体系降解PAEs的机理。
实施例6-MCNN/PMS/Vis体系的优选
经过探究异质结材料的掺杂比、投加量、与PMS的摩尔比以及体系的初始pH对PAEs的去除率的影响,优选出最佳降解体系,结果如图10所示,当CNN:NH2-MIL-101(Fe)掺杂比为1:2,投加异质结材料量为0.04g·L-1,且材料与PMS摩尔比达到1:40时,MCNN/PMS/Vis体系的降解效果最优,且该体系在pH为3—9都有良好的降解效率。
以上所述仅是本专利的优选实施方式,应当指出的是,对于本领域的普通技术人员来说,在不脱离本专利的前提下,还可以做出若干改进,这些改进也应视为本专利的保护范围。
Claims (10)
1.一种Z型异质结光催化材料的制备方法,包括以下步骤:
(1)利用多段式热聚法制备碳氮纳米片,包括:将三聚氰胺在氮气气氛下进行第一次高温烧制;对第一次烧制产物进行清洗并烘干;然后进行研磨并再次在氮气气氛下进行第二次高温烧制;对第二次烧制产物进行清洗并烘干,得到超薄碳氮纳米片(CNN);
(2)利用水热法原位制备Z型异质结光催化材料,包括:将NH2-BDC和FeCl3·6H2O以约1:2的摩尔比例混入在N,N-二甲基甲酰胺(DMF)中,进行搅拌和超声,以充分均匀混合得到混合液;将步骤(1)得到的CNN分散到所述混合液中,继续超声和搅拌后得到均匀的混合溶液;将所述混合溶液在100-130℃的温度下反应18~24小时,得到棕红色固体;清洗(使用DMF与乙醇)棕红色固体、烘干并研磨,从而得到所述Z型异质结光催化材料CNN@NH2-MIL-101(Fe),
其中,NH2-BDC和FeCl3·6H2O反应所得的NH2-MIL-101(Fe)与CNN质量比为8:1-1:1,优选为2:1。
2.根据权利要求1所述的方法,其特征在于,步骤(1)中,高温烧制的温度为400~600℃,优选550℃,第一次烧制时间为3~5小时,优选4小时,升温速率为3~6℃/min,优选5℃/min;
第二次烧制时间为1~4小时,优选2小时,升温速率为6~12℃/min,优选8℃/min。
3.根据权利要求1所述的方法,其特征在于,步骤(1)中,分别使用乙醇与超纯水进行多次清洗操作。
4.根据权利要求1所述的方法,其特征在于,步骤(2)中,使用DMF与乙醇进行清洗,搅拌和超声的时间分别为约1小时。
5.根据权利要求1所述的方法,其特征在于,步骤(1)中,所得CNN具有超薄纳米片的片层结构,其比表面积为10-30m 2
-1
·g。
6.一种Z型异质结光催化材料,其特征在于,根据权利要求1-5中任一项所述的方法制备。
7.一种耦合PMS降解水中有机污染物的方法,其特征在于,包括以下步骤:
(1)将根据权利要求6所述的Z型异质结光催化材料加入含有PMS的待处理的水溶液中,并且在黑暗条件下搅拌一定时间,使之均匀混合;其中,Z型异质结光催化材料的投加量为0.01-0.08g·L-1,Z型异质结光催化材料与PMS的摩尔比为1:20-1:160;
(2)将步骤(1)所得混合物置于光源下,在搅拌的条件下进行光催化反应,以降解水中有机污染物。
8.根据权利要求7所述的方法,其特征在于,有机污染物为PAEs,例如为DIBP和DEP;光源为可见光,优选为氙灯。
9.根据权利要求8所述的方法,其特征在于,步骤(2)中,可见光催化反应在常温下进行,反应时间为30-90分钟,优选60分钟。
10.根据权利要求8所述的方法,其特征在于,在反应60分钟后,有机污染物的降解效率大于80.0%,DEP降解效率大于82.0%,DIBP降解效率大于92.0%。
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