CN116116406B - 一种金属负载型液体光催化剂的制备和应用 - Google Patents
一种金属负载型液体光催化剂的制备和应用 Download PDFInfo
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Abstract
本发明公开了一种金属负载型液体光催化剂的制备方法和应用。其具体采用溶胶法制备TiO2胶体,并借助柠檬酸钠化学还原法获得纳米银胶体,然后利用紫外光诱导‑静电自组装组合法使纳米银胶体与TiO2胶体紧密结合,制得所述金属负载型液体光催化剂。与传统制备方法相比,本发明采用的制备方法简单易行,成本低廉,绿色环保,同时制备出的液体光催化剂具有较强的流动性、分散性,在紫外灯光照下具有较好的抗菌效果,因此在抗菌领域具有极大的应用价值。
Description
技术领域
本发明属于光催化技术领域,具体涉及一种金属负载型液体光催化剂的制备和应用。
背景技术
长期以来,每年有数百万人因病原微生物感染而致残或死亡。例如大肠杆菌是最常见的肠道病原体之一,其可破坏人类和其他动物的肠道。然而传统的消毒工艺(例如氯化和臭氧化)的消杀效率低下,同时还会造成二次污染,这使其应用场景存在一定的限制。
光催化技术近年来迅速发展并且对细菌有很强的消杀作用。TiO2作为最常见的一种无毒、无害、环保的光催化材料,在受到光激发时,其电子被激发到导带,并在价带中留下带正电的电子空位(空穴),从而产生活性自由基(ROS),例如•OH、O2 -和H2O2。这些ROS攻击吸附在二氧化钛表面的细菌,并通过氧化机制将细菌的细胞壁和细胞膜完全破坏。
公开银负载二氧化钛的制备方法有很多,例如,中国专利CN 113083353A公开了一种金属负载TiO2/ZSM-5的制备方法,但在其合成过程中经历了多次煅烧,并且引入了聚乙二醇等有机溶剂。中国专利CN 114455664A中介绍了一种可见光吸收的2D层板材料与Ag/TiO2材料复合的制备方法,但该方法中需要搅拌七天,周期过长,导致其实际应用中受到一定限制。中国专利CN 107159192A也公开了Ag/TiO2的制备方法,虽然该方法一步水热得到了Ag/TiO2,但水热法涉及到一定高温和压力,危险系数较大。中国专利CN 104923216A公开了一种负载贵金属的TiO2纳米棒的制备方法,其制备过程中经历了高压水热釜反应和煅烧,步骤繁琐的同时也造成了各种能量的消耗。因此就目前看,制备贵金属负载催化剂的方法都存在工艺繁琐、金属颗粒大、生产成本高等问题,某些方法还具有一定危险性,同时,现有各种各样的方法,但大都应用在固体催化剂上,而常见的固体光催化剂往往出现附着力弱、分离难、回收复杂等问题,从而极大限制固体光催化剂的使用场景。
发明内容
针对目前固体催化剂所存在的各种问题,本发明的目的在于提供一种金属负载型液体光催化剂的制备方法及应用,与其他现有方法不同,本发明利用光照使得TiO2表面带电性增强,再加入纳米银胶体进行静电自组装,可在不经煅烧或水热的条件下实现Ag/TiO2的制备,其操作简单,能量消耗低,且所得液体光催化剂在紫外光条件下具有很好的大肠杆菌灭活效果,可在各抗菌消毒场景中大规模使用。
为实现上述目的,本发明采用如下技术方案:
一种金属负载型液体光催化剂的制备方法,其是先采用溶胶法制备TiO2胶体,并借助柠檬酸钠化学还原法获得纳米银胶体,然后利用紫外光诱导-静电自组装组合法使纳米银胶体与TiO2胶体紧密结合,制得所述金属负载型液体光催化剂;其具体包括以下步骤:
(1)溶胶法制备TiO2胶体:将异丙醇钛加入到适量无水乙醇中并搅拌1h,再滴加一定量pH=1~2的稀酸溶液,滴加完后搅拌3h,再透析24h形成透明的TiO2溶胶;
(2)纳米银胶体的制备:将柠檬酸钠溶于超纯水中得到无色透明溶液,随后加入一定量的硝酸银溶液,80℃加热搅拌1.5h后冷却至室温,再透析24h得到纳米银胶体;
(3)光诱导-静电自组装组合法制备液体光催化剂:将步骤(1)制备的TiO2溶胶在室温下搅拌1h后,于紫外灯下光照1~3h,增强TiO2胶体表面带电性,再逐滴加入一定量步骤(2)得到的纳米银胶体进行静电自组装,即得所述金属负载型液体光催化剂。
进一步地,步骤(1)中所用异丙醇钛、无水乙醇和稀酸溶液的体积比为1:4:1;所述稀酸溶液具体为稀硝酸溶液。所得TiO2溶胶的浓度为40g/mL。
进一步地,步骤(2)所述硝酸银溶液的浓度为15.8mg/mL,其用量按所用柠檬酸钠与硝酸银的质量比为20:79进行换算。所得纳米银胶体的浓度为1mg/mL。
进一步地,步骤(3)所用紫外灯的功率为300W,电流为16A。
进一步地,所得金属负载型液体光催化剂中含金属Ag的质量为0.5wt%。
上述方法制得的金属负载型液体光催化剂能够用于各光催化抗菌领域中。
本发明的优点在于:
(1)本发明采用光诱导-静电自组装组合法制备所述液体光催化剂,其具有操作简单、条件温和及绿色环保等特点,适合工业大规模生产,同时所得液体光催化剂性能稳定,克服了传统固体催化剂易团聚、吸附力弱等困难,可扩大其应用场景。
(2)本发明所制备的金属银负载型液体光催化剂可实现光生电子-空穴的有效分离,同时液体光催化剂不易聚沉,分散性好,可增大对细菌的捕捉和吸附能力,因而相较于普通TiO2光催化剂具有更强的杀菌效果。
(3)由于库仑力作用的存在,银离子与细胞膜上带负电的电解质相结合进而穿透细胞壁,在细胞膜内发生巯基反应,从而凝固细菌的蛋白质,破坏细菌的细胞和成酶活性,最终导致细胞丧失繁殖能力。因此,金属银可以抑制和杀死大量的细菌和微生物,是一种广谱抗菌剂。本发明制备的液体光催化剂中负载的金属颗粒尺寸均匀细小,具有更强的细菌破坏能力,可在短时间内实现高效的杀菌效果,符合工业生产的要求。
附图说明
图1为实施例制备的金属负载型液体光催化剂Ag/TiO2的TEM图。由图中可见,金属银均匀地负载在TiO2表面,且银颗粒的尺寸较小,约3~4nm。
具体实施方式
一种金属负载型液体光催化剂的制备方法,其具体包括以下步骤:
(1)溶胶法制备TiO2胶体:将异丙醇钛加入到适量无水乙醇中并搅拌1h,再滴加一定量pH=1~2的稀硝酸溶液,滴加完后搅拌3h,再透析24h形成浓度为40g/mL的透明TiO2溶胶;所用异丙醇钛、无水乙醇和稀酸溶液的体积比为1:4:1;
(2)纳米银胶体的制备:将柠檬酸钠溶于超纯水中得到无色透明溶液,随后加入一定量15.8mg/mL的硝酸银溶液,80℃加热搅拌1.5h后冷却至室温,再透析24h得到浓度为1mg/mL的纳米银胶体;所用柠檬酸钠与硝酸银的质量比为20:79;
(3)光诱导-静电自组装组合法制备液体光催化剂:将步骤(1)制备的TiO2溶胶在室温下搅拌1h后,于300W、16A的紫外灯下光照1~3h,增强TiO2胶体表面带电性,再逐滴加入步骤(2)得到的纳米银胶体进行静电自组装,即得含金属Ag 0.5wt%的金属负载型液体光催化剂Ag/TiO2。
采用场发射透射电子显微镜对液体光催化材料(Ag/TiO2)的形貌以及分布进行表征。
液体光催化剂的光催化活性通过紫外灯照射下对一定浓度细菌的消杀来进行测试。
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例
一种金属负载型液体光催化材料的制备,其包括以下步骤:
(1)溶胶法制备TiO2胶体:将12.8mL异丙醇钛与51.2mL无水乙醇混合并磁力搅拌1h,得溶液A;将2.5mL蒸馏水与10mL无水乙醇混合,加入0.3mL浓硝酸调节pH=1~2,得溶液B;随后将12.8mL溶液B逐滴加入到溶液A中,不断搅拌3h,最后将得到的胶体装入透析袋中,透析24h,得到40g/mL无色透明的TiO2溶胶;
(2)纳米银胶体的制备:称取20mg柠檬酸钠溶解于45mL去离子水中,室温下搅拌30min,然后逐滴加入5mL配制好的15.8mg/mL的硝酸银溶液,并在80℃条件下加热搅拌1.5h,待其冷却至室温后,装入透析袋,透析24h,得到1mg/mL的纳米银胶体;
(3)光诱导-静电自组装组合法制备液体光催化剂:量取50mL步骤(1)制备的TiO2溶胶,加入到石英反应器中,室温下搅拌1h后于300W、16A的紫外灯下光照1h,再逐滴加入10mL步骤(2)得到的纳米银胶体,从而得到含金属Ag 0.5wt%的液体光催化剂。
抗菌性能测试
以大肠杆菌为抗菌对象,将使用的试管、枪头、培养皿等仪器全部在高压无菌锅中经120℃灭菌30min。
(1)磷酸盐缓冲溶液的配制:称取2.72g NaH2PO4•2H2O和5.68g NaHPO4•12H2O,加入适量去离子水,充分溶解后转移到2000mL的容量瓶中,定容备用。
(2)营养琼脂固定液的配制:称取16.5g营养琼脂溶解于500mL水中,备用。
(3)LB肉汤的配制:称取1.25g LB肉汤药品于试剂瓶中,加入50mL去离子水充分溶解,备用。
(4)用移液枪量取2mL步骤(3)配制的LB肉汤于试管中,加入50µL JM109大肠杆菌菌株,并在37℃条件下恒温培养24h,结束后放入冰箱备用。
(5)在培养皿中加入其体积的50-60%灭菌后的营养琼脂固定液,待其完全凝固后,移取适量步骤(4)得到的菌液于琼脂上,用T型棒涂布均匀后,放入恒温培养箱,37℃培养24h,得到形状均匀的菌落,随后放入冰箱备用。
(6)量取2mL灭菌后的LB肉汤于试管中,加入一颗步骤(5)得到的完好菌落,再次放入恒温箱,37℃条件下培养24h,然后加入18mL步骤(1)配置好的缓冲溶液,最后放入冰箱备用。
(7)在无菌条件下,量取4mL步骤(6)备好的菌液,加入36 mL步骤(1)的缓冲溶液进行稀释,随后加入液体光催化剂,在紫外灯下光照10 min,每1min计数一次,并按照η=(N0-N)÷N0×100%计算杀菌率,其中N0为未经紫外灯照射的菌落数,N为经过紫外灯照射后残留的菌落数。
对比例1
其操作步骤与实施例1基本相同,不同之处在于液体光催化剂改为未负载金属银的TiO2溶胶。
对比例2
其操作步骤与实施例1基本相同,不同之处在于将光源改为全波段氙灯,光照时间为90min,每30min计数一次。
表1 不同催化剂对大肠杆菌消杀效果的影响
表2 采用不同光照对大肠杆菌消杀效果的影响
从表中数据可以看出,在紫外光照射7min下,纯TiO2溶胶对大肠杆菌的灭杀效率仅为77.6%,Ag/TiO2液体光催化剂对大肠杆菌的灭杀效率可达到99.9%,同时也优于现有报道(现有制备的Ag/TiO2光催化剂一般需要在处理60min以上时,才能达到对大肠杆菌的灭杀效率达99%以上),且其在可见光照射下也表现出对大肠杆菌较高的灭杀效率。可见,本发明利用紫外光诱导-静电自组装组合法制备的Ag/TiO2光催化剂能够表现出优秀的快速杀菌效果。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (5)
1.一种金属负载型液体光催化剂的制备方法,其特征在于:先采用溶胶法制备TiO2胶体,并借助柠檬酸钠化学还原法获得纳米银胶体,然后利用紫外光诱导-静电自组装组合法使纳米银胶体与TiO2胶体紧密结合,制得所述金属负载型液体光催化剂;其包括以下步骤:
(1)溶胶法制备TiO2胶体:将异丙醇钛加入到适量无水乙醇中并搅拌1h,再滴加一定量pH=1~2的稀酸溶液,滴加完后搅拌3h,再透析24h形成透明的TiO2溶胶;
(2)纳米银胶体的制备:将柠檬酸钠溶于超纯水中得到无色透明溶液,随后加入一定量的硝酸银溶液,80℃加热搅拌1.5h后冷却至室温,再透析24h得到纳米银胶体;
(3)光诱导-静电自组装组合法制备液体光催化剂:将步骤(1)制备的TiO2溶胶在室温下搅拌1h后紫外灯下光照1~3h,再逐滴加入一定量步骤(2)得到的纳米银胶体进行静电自组装,即得所述金属负载型液体光催化剂;
步骤(1)中所用异丙醇钛、无水乙醇和稀酸溶液的体积比为1:4:1;所述稀酸溶液具体为0.1mol/L的稀硝酸溶液;
步骤(2)所述硝酸银溶液的浓度为15.8mg/mL,其用量按所用柠檬酸钠与硝酸银的质量比为20:79进行换算;
步骤(3)所得金属负载型液体光催化剂中含金属Ag的质量为0.5wt%。
2.根据权利要求1所述的金属负载型液体光催化剂的制备方法,其特征在于:步骤(1)所得TiO2溶胶的浓度为40mg/mL。
3.根据权利要求1所述的金属负载型液体光催化剂的制备方法,其特征在于:步骤(2)所得纳米银胶体的浓度为1mg/mL。
4.根据权利要求1所述的金属负载型液体光催化剂的制备方法,其特征在于:步骤(3)所用紫外灯的功率为300W,电流为16A。
5.一种如权利要求1所述方法制得的金属负载型液体光催化剂在光催化抗菌领域中的应用。
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