CN113731496A - 一种CTF/BiVO4 II型异质结光催化剂的制备方法 - Google Patents
一种CTF/BiVO4 II型异质结光催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种CTF/BiVO4 II型异质结光催化剂的制备方法,包括以下步骤:1)CTF制备;2)BiVO4制备;3)BiVO4/CTF制备:称取CTF和纳米片BiVO4于烧杯中,加无水乙醇,搅拌后盖上保鲜膜,超声清洗,恒温搅拌,离心,将离心后的固体产物恒温真空干燥过夜,干燥后取出,得到纳米片BiVO4/CTF,研磨至粉末,得CTF/BiVO4异质结光催化剂。本发明方法基于表面易调制的共价三嗪有机框架构建吸附‑光催化双功能的II型异质结光催化材料,解决了传统单一光催化剂吸附VOCs性能差,光生载流子复合率高的问题,有效改善了VOCs的去除效率,实现VOCs彻底、高效、低能耗的去除。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及一种CTF/BiVO4 II型异质结光催化剂的制备方法。
背景技术
空气污染是继营养不良、饮食风险、高血压和烟草之后全球排名第五的人类健康风险因素。挥发性有机化合物(VOCs)的氧化可生成PM2.5的重要组分二次有机气溶胶,在NOx存在的情况下,该过程还会导致对流层O3浓度的增加,从而增加呼吸系统疾病死亡的风险。雾霾天气近年来频繁出现在我国大城市及其周边地区。VOCs成分复杂,有特殊气味且具有渗透、挥发及脂溶等特性,还具有毒性、刺激性及致畸致癌作用,尤其是苯、甲苯、二甲苯和甲醛对人体健康的危害最大,长期接触会使人患上贫血症与白血病。综上,发展有效的VOCs降解技术是现阶段解决大气PM2.5和臭氧污染问题的关键,可为打赢“蓝天保卫战”提供强有力的技术支撑,对治理空气污染和保障人体健康都具有重要意义。
VOCs的控制技术可分为源头削减技术、过程控制技术和末端治理技术,以末端治理技术为主。末端处理技术主要通过物理方法,利用目标污染物与其它组分的物理性质的差异使之得到分离,或者通过化学或生化反应将有机物转变成为CO2和水。吸收法的吸收剂需后续处理,吸附法的吸附材料需定期更换;生物处理法对可生化性差的VOCs去除率低;电子束法能耗大且对环境有害。相比较而言,光催化技术条件温和,可在常温常压进行,且设备简单、维护方便,已成为有前景的VOCs去除方法之一。
在光催化氧化VOCs过程中,本征TiO2除具有低的光子吸收率,其自身极性结构导致对VOCs具有相对较差的吸附能力。开发既能有效利用光能,又能强化VOCs吸附过程的光催化材料是高效光催化处理VOCs的有效途径。通过选择合适的窄带隙半导体,其能带结构需要满足自由基的产生电位,且能够拓宽半导体的光谱响应范围,使太阳光得到有效利用。而通过能带结构匹配形成的异质复合结构已被证明是优化光催化反应活性的有效途径。异质复合结构的建立不仅有利于光生电荷的形成,促进光生载流子的分离和转移,而且可使电子-空穴对的氧化还原能力最大化。因此,合理地组合光催化剂是制备高催化活性的异质结复合光催化剂的关键。
共价三嗪框架(CTFs)是近年来备受关注的一类共价有机框架(COFs)。经研究报道的COFs种类繁多,按形成的共价键可分为硼氧环、硼酸酯、三嗪和腙等种类。共价三嗪框架具有良好的可见光吸收、大的比表面积和高的孔隙率。其所具有的三嗪环结构使之较硼氧环和硼酸酯类具有更突出的可见光响应能力、以及化学和热稳定性。此外,三嗪环结构含有丰富的吡啶氮原子可在催化过程中提供丰富的活性中心,而大的比表面积也为污染物的预吸附提供更多的吸附位点,促进了污染物分子在其内部的扩散和流通,从而提高催化效率。然而单纯的CTFs仍存在光生载流子复合率高、量子效率低的问题。为克服这些缺点,且在不损失CTFs宽的可见光吸收范围和强的VOCs吸附能力的基础上,构筑基于CTFs的异质结光催化材料是实现VOCs去除的有效手段。
发明内容
针对现有技术中存在的问题,本发明设计的目的在于提供一种CTF/BiVO4 II型异质结光催化剂的制备方法。
本发明通过以下技术方案加以实现:
所述的一种CTF/BiVO4 II型异质结光催化剂的制备方法,其特征在于该制备方法包括以下步骤:
1)CTF制备:取适量的1,4-二氰基苯于25ml三氟甲磺酸中, 0℃环境下进行搅拌1.5h使其充分混合后置于100℃烘箱中烘干20min,之后取出冷却至室温后,于乙醇中研磨后转移至烧杯中进行多次洗涤离心,离心后的固体物质置于60℃烘箱内干燥过夜,待固体物质完全干燥后加入NaOH溶液,于在60℃烘箱内浸泡5h,后加入去离子水搅拌5min,离心5min,重复操作直到溶液洗涤至中性,再次放入60℃烘箱内干燥过夜,收集干燥好的CTF,研磨至粉末,备用;
2)BiVO4制备:取一定量的浓硝酸,向其中加入适量的Bi(NO3)3·5H2O,另取一定量的NaOH加入适量的NH4VO3,随后将两种溶液以Bi/V摩尔比为1:1的形式混合在一起,搅拌1h,通过滴加稀释的NaOH溶液调pH至11.0-12.0,得橙黄色浆状混合物,然后将混合物转移到200mL聚四氟乙烯内衬不锈钢高压釜中,加热至180℃;此温度保持6h后收集得到的沉淀物,用乙醇和去离子水洗涤,在空气中60℃干燥,得到纳米片BiVO4;
3)BiVO4/CTF制备:用电子分析天平分别称取一定量的 CTF和纳米片BiVO4,放入250ml烧杯中,加入适量的无水乙醇,搅拌后盖上保鲜膜,放入超声波清洗机内超声清洗30min,再将烧杯放入集热式恒温加热磁力搅拌器中50℃恒温搅拌2h,在超高速冷冻离心机处离心,将离心后的固体产物放入真空干燥箱中60℃恒温真空干燥过夜,待其干燥后取出,得到纳米片BiVO4/CTF,研磨至粉末,得CTF/BiVO4异质结光催化剂。
进一步地,步骤1)中1,4-二氰基苯的添加量为0.4-0.6g。
进一步地,步骤1)中多次洗涤离心是指先无水乙醇洗涤离心4次,再去离子水洗涤离心4次,每次洗涤离心均为洗涤后搅拌5min后再离心,每次离心的转速为12000r/min,每次离心时间为5min。
进一步地,步骤2)中浓硝酸与Bi(NO3)3·5H2O的添加比例为每10mL的浓硝酸中加入0.01 mol的Bi(NO3)3·5H2O。
进一步地,步骤2)中NaOH与NH4VO3,的添加比例为每10mLNaOH中加入0.01mol的NH4VO3,所述NaOH的浓度为5-7M。
进一步地,步骤3)中CTF、纳米片BiVO4与无水乙醇的料液比为:1mg:1mg:2ml。
进一步地,步骤3)中离心机的转速为12000r/min,离心时间为10min。
本发明方法基于表面易调制的共价三嗪有机框架构建吸附-光催化双功能的II型异质结光催化材料,解决了传统单一光催化剂吸附VOCs性能差,光生载流子复合率高的问题,有效改善了VOCs的去除效率,实现VOCs彻底、高效、低能耗的去除。
附图说明
图1为试验例对甲苯的去除效果图。
具体实施方式
以下结合具体实施例对本发明做进一步详细描述,以便更好地理解本技术方案。
实施例1:CTF制备
分别取0.513g的1,4-二氰基苯(DCB)与25ml三氟甲磺酸(TFMS)并进行混合,随后置于0℃环境下并进行搅拌1.5h,再将溶液放入100℃烘箱中20min。等待其冷却后在乙醇中研磨然后将转移入250ml烧杯加无水乙醇搅拌5min,再超高速冷冻离心机处离心,转速设置为12000r/min,离心时间为5min,将离心后的固体产物用无水乙醇冲洗后继续搅拌5min,随后再次离心,无水乙醇洗涤离心系列步骤反复操作4次。随后往离心固体中加入去离子水继续搅拌5min后再次离心5min,并重复系列操作4次。将获得的固体放入60℃烘箱内干燥过夜。等待固体完全干燥后加入0.5mol/LNaOH溶液60ml,在60℃烘箱内浸泡5h,后加入去离子水搅拌5min,离心5min,重复操作直到溶液洗涤至中性。放入60℃烘箱内干燥过夜。收集干燥好的CTF,研磨至粉末,备用。
实施例2:BiVO4制备
取40mL的浓硝酸,向其中加入0.04mol的Bi(NO3)3·5H2O,并取6MNaOH的40mL同时加入0.04mol的NH4VO3,随后将两种溶液以Bi/V摩尔比为1:1的形式混合在一起。然后在环境空气中剧烈搅拌1h。随后,通过滴加稀释的NaOH溶液,将pH调整为11.0−12.0,得到橙黄色浆状混合物。然后将混合物转移到200m L聚四氟乙烯内衬不锈钢高压釜中,加热至180℃;此温度保持6h。最后,收集得到的沉淀物,用乙醇和去离子水洗涤,在空气中60℃干燥,得到纳米片BiVO4。
实施例3:BiVO4/CTF制备
用电子分析天平分别称取100mgCTF和100mg纳米片BiVO4,放入250ml烧杯中,用量筒量取200ml无水乙醇加入250ml烧杯中,放入搅拌子,盖上保鲜膜,放入超声波清洗机内超声清洗30min,再将烧杯放入集热式恒温加热磁力搅拌器中50℃恒温搅拌2h,在超高速冷冻离心机处离心,转速设置为12000r/min,离心时间为10min,将离心后的固体产物放入真空干燥箱中60℃恒温真空干燥过夜。待其干燥后取出,得到纳米片BiVO4/CTF,研磨至粉末,得CTF/BiVO4异质结光催化剂,备用。
试验例
本实验以氙灯作为光源模拟太阳光。在用高纯度空气吹扫玻璃反应器并用UV预清洁光催化剂之后,将空气鼓泡通过含有去离子水的不锈钢瓶调节相对湿度,用高纯度空气稀释VOCs标准气体(甲苯)来调节浓度,通过调节循环夹套水温度控制反应器温度。在吸附恒定后开启UV灯并在预设的反应时间取样进行气相色谱仪(GC)分析。甲苯的初始浓度为50mg/m3,称取25 mg的光催化剂,随后打开氙灯,在设定的时间间隔每次抽取1 mL气体,采用GC分析样品。由图1可得CTF/BiVO4、CTF和BiVO4光催化反应240分钟后对甲苯的去除效率分别为100%、46.23%和60.12%。
Claims (7)
1.一种CTF/BiVO4 II型异质结光催化剂的制备方法,其特征在于该制备方法包括以下步骤:
1)CTF制备:取适量的1,4-二氰基苯于25ml三氟甲磺酸中, 0℃环境下进行搅拌1.5h使其充分混合后置于100℃烘箱中烘干20min,之后取出冷却至室温后,于乙醇中研磨后转移至烧杯中进行多次洗涤离心,离心后的固体物质置于60℃烘箱内干燥过夜,待固体物质完全干燥后加入NaOH溶液,于在60℃烘箱内浸泡5h,后加入去离子水搅拌5min,离心5min,重复操作直到溶液洗涤至中性,再次放入60℃烘箱内干燥过夜,收集干燥好的CTF,研磨至粉末,备用;
2)BiVO4制备:取一定量的浓硝酸,向其中加入适量的Bi(NO3)3·5H2O,另取一定量的NaOH加入适量的NH4VO3,随后将两种溶液以Bi/V摩尔比为1:1的形式混合在一起,搅拌1h,通过滴加稀释的NaOH溶液调pH至11.0-12.0,得橙黄色浆状混合物,然后将混合物转移到200mL聚四氟乙烯内衬不锈钢高压釜中,加热至180℃;此温度保持6h后收集得到的沉淀物,用乙醇和去离子水洗涤,在空气中60℃干燥,得到纳米片BiVO4;
3)BiVO4/CTF制备:用电子分析天平分别称取一定量的 CTF和纳米片BiVO4,放入250ml烧杯中,加入适量的无水乙醇,搅拌后盖上保鲜膜,放入超声波清洗机内超声清洗30min,再将烧杯放入集热式恒温加热磁力搅拌器中50℃恒温搅拌2h,在超高速冷冻离心机处离心,将离心后的固体产物放入真空干燥箱中60℃恒温真空干燥过夜,待其干燥后取出,得到纳米片BiVO4/CTF,研磨至粉末,得CTF/BiVO4异质结光催化剂。
2.如权利要求1所述的一种CTF/BiVO4 II型异质结光催化剂的制备方法,其特征在于步骤1)中1,4-二氰基苯的添加量为0.4-0.6g。
3.如权利要求1所述的一种CTF/BiVO4 II型异质结光催化剂的制备方法,其特征在于步骤1)中多次洗涤离心是指先无水乙醇洗涤离心4次,再去离子水洗涤离心4次,每次洗涤离心均为洗涤后搅拌5min后再离心,每次离心的转速为12000r/min,每次离心时间为5min。
4.如权利要求1所述的一种CTF/BiVO4 II型异质结光催化剂的制备方法,其特征在于步骤2)中浓硝酸与Bi(NO3)3·5H2O的添加比例为每10mL的浓硝酸中加入0.01 mol的Bi(NO3)3·5H2O。
5.如权利要求1所述的一种CTF/BiVO4 II型异质结光催化剂的制备方法,其特征在于步骤2)中NaOH与NH4VO3,的添加比例为每10mLNaOH中加入0.01mol的NH4VO3,所述NaOH的浓度为5-7M。
6.如权利要求1所述的一种CTF/BiVO4 II型异质结光催化剂的制备方法,其特征在于步骤3)中CTF、纳米片BiVO4与无水乙醇的料液比为:1mg:1mg:2ml。
7.如权利要求1所述的一种CTF/BiVO4 II型异质结光催化剂的制备方法,其特征在于步骤3)中离心机的转速为12000r/min,离心时间为10min。
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11244709A (ja) * | 1998-02-27 | 1999-09-14 | Shiseido Co Ltd | 光触媒体 |
CN102008892A (zh) * | 2010-09-29 | 2011-04-13 | 北京工业大学 | 一种光-热耦合催化氧化消除气态甲苯的方法 |
CN103028390A (zh) * | 2012-12-24 | 2013-04-10 | 陕西科技大学 | 一种沿高活性(040)晶面取向生长圆饼片状N/BiVO4 光催化剂的制备方法 |
CN104148054A (zh) * | 2014-08-27 | 2014-11-19 | 哈尔滨工业大学 | 一种钒酸铋纳米棒束的制备方法 |
CN104998665A (zh) * | 2015-07-09 | 2015-10-28 | 三峡大学 | 一种钒酸铋-溴氧化铋异质结光催化剂,制备方法及其应用 |
CN105964277A (zh) * | 2016-05-13 | 2016-09-28 | 南京理工大学 | 一种CdS/BiVO4复合光催化剂及其制备方法 |
CN109776796A (zh) * | 2019-03-07 | 2019-05-21 | 中国科学技术大学 | 一种炔基功能化共价三嗪聚合物、其制备方法及应用 |
CN109985657A (zh) * | 2019-04-30 | 2019-07-09 | 燕山大学 | BiVO4/2D g-C3N4Z型异质结光催化剂的制备方法 |
CN110368924A (zh) * | 2019-07-22 | 2019-10-25 | 中山大学 | 一种钛酸铋/铋/钒酸铋复合物光催化剂及其在光热催化净化有机气体污染物中的应用 |
WO2020192722A1 (zh) * | 2019-03-26 | 2020-10-01 | 北京福纳康生物技术有限公司 | 富勒烯及其衍生物复合材料在降解甲醛、室内VOCs或抑菌中的应用 |
CN112675911A (zh) * | 2021-02-08 | 2021-04-20 | 福州大学 | 用于污水净化协同可见光催化还原二氧化碳的CTFs/Bi/BiOBr复合光催化剂 |
-
2021
- 2021-08-27 CN CN202110993469.XA patent/CN113731496B/zh active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11244709A (ja) * | 1998-02-27 | 1999-09-14 | Shiseido Co Ltd | 光触媒体 |
CN102008892A (zh) * | 2010-09-29 | 2011-04-13 | 北京工业大学 | 一种光-热耦合催化氧化消除气态甲苯的方法 |
CN103028390A (zh) * | 2012-12-24 | 2013-04-10 | 陕西科技大学 | 一种沿高活性(040)晶面取向生长圆饼片状N/BiVO4 光催化剂的制备方法 |
CN104148054A (zh) * | 2014-08-27 | 2014-11-19 | 哈尔滨工业大学 | 一种钒酸铋纳米棒束的制备方法 |
CN104998665A (zh) * | 2015-07-09 | 2015-10-28 | 三峡大学 | 一种钒酸铋-溴氧化铋异质结光催化剂,制备方法及其应用 |
CN105964277A (zh) * | 2016-05-13 | 2016-09-28 | 南京理工大学 | 一种CdS/BiVO4复合光催化剂及其制备方法 |
CN109776796A (zh) * | 2019-03-07 | 2019-05-21 | 中国科学技术大学 | 一种炔基功能化共价三嗪聚合物、其制备方法及应用 |
WO2020192722A1 (zh) * | 2019-03-26 | 2020-10-01 | 北京福纳康生物技术有限公司 | 富勒烯及其衍生物复合材料在降解甲醛、室内VOCs或抑菌中的应用 |
CN109985657A (zh) * | 2019-04-30 | 2019-07-09 | 燕山大学 | BiVO4/2D g-C3N4Z型异质结光催化剂的制备方法 |
CN110368924A (zh) * | 2019-07-22 | 2019-10-25 | 中山大学 | 一种钛酸铋/铋/钒酸铋复合物光催化剂及其在光热催化净化有机气体污染物中的应用 |
CN112675911A (zh) * | 2021-02-08 | 2021-04-20 | 福州大学 | 用于污水净化协同可见光催化还原二氧化碳的CTFs/Bi/BiOBr复合光催化剂 |
Non-Patent Citations (10)
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