CN108532290A - 一种光催化功能织物的制备方法及其应用 - Google Patents
一种光催化功能织物的制备方法及其应用 Download PDFInfo
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Abstract
本发明提供了一种光催化功能织物及其制备方法。先将沸石类咪唑骨架材料(ZIF‑8)处理到织物上,然后采用原位生长法,将钒酸铋(BiVO4)负载到用ZIF‑8处理的织物上,制备光催化功能织物。该功能织物在可见光照射下能高效催化降解有机污染物,可以用于印染废水处理以及空气净化。本发明制备工艺简单。制备的光催化功能织物,具有吸附性能好、催化效率高、稳定性好、可重复利用等优点。对活性黑KN‑B的光催化降解率可达85%以上,重复使用3次后的对活性黑KN‑B光催化降解率保持在65%以上。对空气中的甲醛降解率达到87%以上。
Description
技术领域
本发明属于光催化剂技术领域,涉及一种光催化功能织物的制备方法及其应用,特别涉及通过原位生长ZIF-8和BiVO4得到一种吸附性能好、可在可见光下催化分解有害物质的功能织物。
背景技术
随着经济快速发展和城市化进程的加速,全球性的环境污染和能源短缺日益成为人类面临的重大挑战,环境治理和太阳能的利用成为国内外科技工作者优先考虑的研究方向。印染废水因为有机污染物含量高、色度深、成分复杂,含有残留的染料、助剂、浆料、无机盐等,是目前难处理的工业废水之一;室内空气污染物的种类不断增多,其中最严重的就是化学污染,如室内装修散发出的甲醛、苯系物等。它们所引起的环境问题已经成为国内外关注的重大问题。为了人类的生存和发展,控制治理各种化学污染和开发利用太阳能显得极其重要。环境工作者一直以来都把开发化学污染清除技术为目标,但是这些技术要求高效率、低能耗、氧化能力强和适用范围大等特点。在这样的背景下,光催化技术逐渐兴起,半导体光催化技术在解决环境问题和能源问题上有很大的应用前景,能够将太阳能转化为对人类有利的氢能源,这样可以帮助人类解决温室效应以及化石能源枯竭带来的危机,并且在解决环境污染中,光催化降解有机污染物是比较廉价可行的技术。在众多半导体光催化材料研究中,因为二氧化钛具有价格廉价、氧化能力强、无毒性、光诱导性好和亲水性好等特点,从而研究最为广泛。但是二氧化钛吸收的禁带宽度太大(>3.2eV),仅在紫外光范围有响应,波长在400nm以下的紫外光部分不足太阳光总能量的5%,而在400nm~700nm的可见光范围,占太阳总能量的43%。
近年来,国内外研究专家在新型光催化材料的开发做了很多研究,其中钒酸铋(BiVO4)因其禁带宽度较窄,具有可见光催化活性,制备简单、无毒且不破坏环境的特点而得到广泛关注。研究表明单斜晶型结构的BiVO4具有较好的可见光光催化性能,其禁带宽度较窄(2.4eV),除了在紫外光区有吸收带外,在可见光区也存在明显的吸收带。钒酸铋作为新型光催化材料,虽然其可见光响应范围宽,但BiVO4产生的光生电子-空穴对容易在催化剂体相和表面复合、吸附性能差、比表面积小等缺点,导致光催化活性降低,同时,粉末状BiVO4光催化材料存在易沉淀、不易重复利用等缺点。为解决上述问题,制备负载型BiVO4光催化剂将有利于拓展其在污水处理、空气净化等方面的应用范围。如何延长BiVO4光催化剂光生电子和空穴的寿命以及通过复合和负载技术实现其循环利用具有重要的意义。
发明内容
发明目的:本发明根据现有光催化材料的不足,提供一种具有比表面积大、催化活性高、可多次重复使用的光催化功能织物的制备方法。
本发明的目的通过以下技术方案来实现:一种光催化功能织物的制备方法,包括下列步骤:
(1)织物的预处理:织物先用90~100℃热水煮10~15min,除去织物上残留的水溶性杂质,取出烘干后,将织物浸入丙酮中超声30min,进一步除去织物表面残留的杂质,再用蒸馏水清洗3次,烘干后备用。
(2)织物上原位生长ZIF-8:将4份2-甲基咪唑加入到400~500份的甲醇溶液中,用超声处理5~10min,得A溶液。将5~8份六水合硝酸锌加入到400~500份甲醇溶液中,用超声处理5~10min,得B溶液。然后将1份织物浸到A溶液中,用超声波处理20~30min,再将B溶液缓慢滴加至浸有织物的A溶液,用磁力搅拌,室温下反应20~25h,反应结束将织物取出,用甲醇溶液清洗三次,烘干。
(3)织物上负载BiVO4光催化材料:称取5~10mmol偏矾酸钠置于干燥洁净的烧杯,加入50~80mL蒸馏水,在50~60℃用磁力搅拌器搅拌至澄清,得溶液C。称取5~10mmol五水合硝酸铋和6~8mmol乙二胺四乙酸二钠盐置于干燥洁净的烧杯,加入40~60mL蒸馏水,再加入5~8mL浓硝酸溶液,用磁力搅拌器搅拌至澄清,用氨水将溶液pH值调节至7,得到溶液D。将步骤(2)处理的棉织物在溶液D中浸泡30min,再将溶液C通过恒压滴液漏斗以20~30d/s的速度滴加至溶液D,再用氨水或柠檬酸溶液调节混合溶液的反应pH值7,升温至90℃反应5~8h。反应结束后取出织物,用蒸馏水冲洗3次,洗去在织物表面附着的BiVO4,烘干。
作为优化:所述的织物为棉针织物和机织物。
一种根据所述的光催化功能织物的制备方法制备的光催化功能织物的应用,制备的钒酸铋光催化功能织物对染料的降解应用:将制得的0.5g光催化功能织物,在500W氙灯照射下,对200mL质量浓度为20mg/L的活性黑KN-B染料溶液进行光催化降解3h,降解率可达85%以上,重复使用3次后的对活性黑KN-B光催化降解率保持在65%以上。
一种根据所述的光催化功能织物的制备方法制备的光催化功能织物的应用,制备的钒酸铋光催化功能织物对空气中甲醛的降解应用:将制得的1g光催化功能织物绷在空气净化器中,置于有机玻璃制成的密闭容器中;取0.2mL浓度为20mg/L的甲醛溶液放在密闭容器中加热蒸发;蒸发后停止加热,将白炽灯放在密闭容器外直射布样表面,5h后测得对甲醛降解率达到87%以上。
有益效果:本发明将钒酸铋负载到用高比表面积、高空隙率且孔体积和孔径可调的ZIF-8预处理的织物上制成BiVO4光催化功能织物,金属络合物与半导体的集成,提高BiVO4光催化活性并有利于循环利用,在可见光照射下能高效催化降解废水有机污染物,降解甲醛,净化空气,具有很好的经济效益、社会效益和生态效益。
附图说明
图1是本发明的钒酸铋光催化功能织物对活性黑KN-B的降解率的结构示意图;
图2是本发明的钒酸铋光催化功能织物重复利用三次的光催化效率的结构示意图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,以使本领域的技术人员能够更好的理解本发明的优点和特征,从而对本发明的保护范围做出更为清楚的界定。本发明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的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。
实施例
一种光催化功能织物的制备方法,包括下列步骤:
(1)织物的预处理:将经过退煮漂的棉织物用90℃热水煮10min,除去织物上残留的水溶性杂质,取出烘干后,将织物浸入丙酮中超声30min,进一步除去织物表面残留的杂质,再用蒸馏水清洗3次,烘干后备用。
(2)织物上原位生长ZIF-8:将2.05g 2-甲基咪唑置于250mL甲醇溶液中,用超声处理10min,得A溶液。将3.67g六水合硝酸锌置于250mL甲醇溶液中,用超声处理10min,得B溶液。然后将0.5g棉织物浸到A溶液中,用超声波处理30min,再将B溶液缓慢滴加至浸有棉织物的溶液A,用磁力搅拌,室温下反应25h,反应结束将织物取出,用甲醇溶液清洗三次,然后在80℃下烘干备用。
(3)织物上负载BiVO4光催化材料:称取偏矾酸钠0.732g(6mmol)置于干燥洁净的烧杯,加入50mL蒸馏水,在50℃下用磁力搅拌器搅拌至澄清,得到溶液C。称取五水合硝酸铋2.911g(6mmol)和乙二胺四乙酸二钠盐2.5g置于干燥洁净的烧杯,加入45mL蒸馏水,再加入5mL浓硝酸溶液,50℃下用磁力搅拌器搅拌至澄清,用氨水将溶液pH值调节至7,得到溶液D。将步骤(2)处理的棉织物在溶液D中浸泡30min,再将溶液C通过恒压滴液漏斗以20-30d/s的速度滴加至溶液D,再用氨水或柠檬酸溶液调节混合溶液的反应pH值7,升温至90℃反应6h。反应结束后取出织物,用蒸馏水冲洗3次,洗去在织物表面附着的钒酸铋,烘箱70℃烘干。
制备的钒酸铋光催化功能织物对染料的降解应用:
选择活性黑KN-B染料,测定钒酸铋光催化功能织物的光催化性能,测试条件为0.5g纤维基钒酸铋光催化复合材料,在500W氙灯照射下,对200mL质量浓度为20mg/L的活性黑KN-B染料溶液进行光催化降解3h,实验每隔0.5h测定溶液的吸光度。根据下列公式计算染料的降解率:
式中,A0为降解前染液的吸光度;A1为降解后染液的吸光度。
将用于染料降解测试后的钒酸铋光催化功能织物用蒸馏水冲洗三次,置于烘箱中烘干。按上述方法进行重复降解染料实验,测定光催化功能织物的循环使用效果。
其对活性黑KN-B染料溶液的光催化降解率测试结果如下图1所示。从图1中可以看出,在可见光照射条件下,原棉织物对染料几乎没有吸附降解作用,而钒酸铋光催化功能织物对活性黑KN-B溶液明显的降解作用,随着光照时间增加,降解率逐渐增大,在光照3h后,活性黑KN-B的光催化降解率达到85.9%,说明钒酸铋光催化功能织物能够降解废水中的染料。
钒酸铋光催化功能织物重复利用三次的光催化效率如图2所示。从图2中可以看出,重复使用后的钒酸铋光催化功能织物的光催化效率下降了很少,重复使用3次后的对活性黑KN-B光催化降解率保持在67.4%以上,说明钒酸铋光催化功能织物可以重复利用,具有潜在的实际应用意义。
制备的钒酸铋光催化功能织物对空气中甲醛的降解应用:
将1g钒酸铋光催化功能织物绷在空气净化器中,置于有机玻璃制成的密闭容器中;取0.2mL浓度为20mg/L的甲醛溶液放在密闭容器中加热蒸发;蒸发后停止加热,将白炽灯放在密闭容器外直射布样表面。每隔1h用大气采样仪进行一次采样,通过乙酰丙酮显色法,计算空气中甲醛含量。测得不同时间下钒酸铋光催化功能织物对甲醛的降解率如表1所示。
表1不同时间下钒酸铋光催化功能织物对甲醛的降解率
降解时间/h | 0 | 1 | 2 | 3 | 4 | 5 |
降解率/% | - | 49.6 | 64.5 | 78.1 | 86.0 | 87.1 |
从表1中可以看出,钒酸铋光催化功能织物5h对0.2mL浓度为20mg/L的甲醛降解率达到了87.1%,有效的净化了空气,可显著改善空气质量。
Claims (5)
1.一种光催化功能织物的制备方法,其特征在于:织物经过预处理除杂后,先将沸石类咪唑骨架材料(ZIF-8)处理到织物上,然后采用原位生长法,将钒酸铋(BiVO4)负载到用ZIF-8处理的织物上,制得光催化功能织物。
2.根据权利要求1所述的光催化功能织物的制备方法,其特征在于:具体步骤如下:
(1)织物的预处理:织物先用90~100℃热水煮10~15min,除去织物上残留的水溶性杂质,取出烘干后,将织物浸入丙酮中超声30min,进一步除去织物表面残留的杂质,再用蒸馏水清洗3次,烘干后备用;
(2)织物上原位生长ZIF-8:将4份2-甲基咪唑加入到400~500份的甲醇溶液中,用超声处理5~10min,得A溶液;将5~8份六水合硝酸锌加入到400~500份甲醇溶液中,用超声处理5~10min,得B溶液;然后将1份织物浸到A溶液中,用超声波处理20~30min,再将B溶液缓慢滴加至浸有织物的A溶液,用磁力搅拌,室温下反应20~25h,反应结束将织物取出,用甲醇溶液清洗三次,烘干;
(3)织物上负载BiVO4光催化材料:称取5~10mmol偏矾酸钠置于干燥洁净的烧杯,加入50~80mL蒸馏水,在50~60℃用磁力搅拌器搅拌至澄清,得溶液C;称取5~10mmol五水合硝酸铋和6~8mmol乙二胺四乙酸二钠盐置于干燥洁净的烧杯,加入40~60mL蒸馏水,再加入5~8mL浓硝酸溶液,用磁力搅拌器搅拌至澄清,用氨水将溶液pH值调节至7,得到溶液D;将步骤(2)处理的棉织物在溶液D中浸泡30min,再将溶液C通过恒压滴液漏斗以20~30d/s的速度滴加至溶液D,再用氨水或柠檬酸溶液调节混合溶液的反应pH值7,升温至90℃反应5~8h;反应结束后取出织物,用蒸馏水冲洗3次,洗去在织物表面附着的BiVO4,烘干。
3.根据权利要求2所述的光催化功能织物的制备方法,其特征在于:所述的织物为棉针织物和机织物。
4.一种根据权利要求2所述的光催化功能织物的制备方法制备的光催化功能织物的应用,其特征在于:制备的钒酸铋光催化功能织物对染料的降解应用:
将制得的0.5g光催化功能织物,在500W氙灯照射下,对200mL质量浓度为20mg/L的活性黑KN-B染料溶液进行光催化降解3h,降解率可达85%以上,重复使用3次后的对活性黑KN-B光催化降解率保持在65%以上。
5.一种根据权利要求2所述的光催化功能织物的制备方法制备的光催化功能织物的应用,其特征在于:制备的钒酸铋光催化功能织物对空气中甲醛的降解应用:将制得的1g光催化功能织物绷在空气净化器中,置于有机玻璃制成的密闭容器中;取0.2mL浓度为20mg/L的甲醛溶液放在密闭容器中加热蒸发;蒸发后停止加热,将白炽灯放在密闭容器外直射布样表面,5h后测得对甲醛降解率达到87%以上。
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