CN113680384A - 一种TBA修饰g-C3N4基银掺杂光催化剂制备方法及应用 - Google Patents
一种TBA修饰g-C3N4基银掺杂光催化剂制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种TBA修饰g‑C3N4基银掺杂光催化剂制备方法,包括:将TCN材料研磨成细粉末,加入到纯水中,超声处理,获得TCN分散溶液;将硝酸银加入到所述TCN分散溶液中,在黑暗条件下剧烈搅拌使Ag+充分吸附,获得混合液;将所述混合液光照,形成悬浮液;将所述悬浮液抽滤,用纯水洗涤数次,干燥,获得TBA修饰g‑C3N4基银掺杂光催化剂。将其投加到待杀菌消毒水体种,可以在可见光或紫外光照射下激发产生强氧化性活性物质,对致病性细菌、病毒杀灭作用;该材料生产成本低,易于产业化;应用广泛。
Description
技术领域
本发明属于消毒材料领域,具体涉及一种TBA修饰g-C3N4基银掺杂光催化剂制备方法及其应用。
背景技术
随着自然水环境中微生物对抗生素的耐药性升高,人工水环境(如游泳池、水疗中心、水上公园)中的细菌菌株的耐药性问题也应当引起重视。游泳池水源通常是自来水,并用额外的消毒剂(氯化合物、臭氧等)处理。虽然现代游泳池有再循环系统,能有效地过滤和消毒,但相关研究表明,无论是循环净化系统还是消毒剂,都无法阻止有害病原体对泳池水的侵染。此外,存活的耐氯细菌也可能具有抗生素抗性,这一事实在处理过的饮用水和污水的细菌分离物中都已被证明。因此,游泳池等人工水环境也是传播抗生素耐药基因和抗生素耐药菌的途径之一,存在公共卫生风险。
目前,寻求更为有效的方法应对自然水体中日益严重的耐药菌群污染问题成为全世界共同关注的热点,采用半导体光催化灭活被认为是最有发展前景的手段之一,它克服了传统消毒方法的局限性,具有节能、生物安全、稳定性好、活性优越、对多种微生物病原菌有广泛杀灭能力等优势。当光照射半导体催化剂时,若入射光子的能量超过带隙能量,会产生电子-空穴对,电子(e-)将跃迁到导带,价带中产生空穴(h+)。部分e-和h+迁移到催化剂的表面,激发空气或水中的氧气并产生一系列强氧化性活性物质,例如h+,·O2 -/HO2·,·OH,1O2和H2O2,灭活水环境中的病原体,为开发经济、环保、可持续的新型耐药菌消毒方式带来希望与挑战。
因此,本发明研究一种TBA修饰g-C3N4基银掺杂光催化剂制备方法。
发明内容
本发明目的是提供一种TBA修饰g-C3N4基银掺杂光催化剂制备方法及其应用。
本发明的一种技术方案是:
一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,包括如下步骤:
(1)将TCN材料研磨成细粉末,加入到纯水中,超声处理,获得TCN分散溶液;
(2)将硝酸银加入到所述TCN分散溶液中,在黑暗条件下剧烈搅拌使Ag+充分吸附,获得混合液;
(3)将所述混合液光照,形成悬浮液;
(4)将所述悬浮液抽滤,用纯水洗涤数次,干燥,获得TBA修饰g-C3N4基银掺杂光催化剂。
进一步的,步骤(1)中所述TCN材料的制备方法为:
(a)将尿素、硫代巴比妥酸和纯水置于氧化铝坩埚内,在水浴锅中加热,混合均匀,然后将其干燥;
(b)将干燥后的材料置于带盖坩埚中加热并保温,待其自然冷却至室温,获得TCN。
进一步的,步骤(a)中所述尿素与硫代巴比妥酸的质量比为100:1;所述加热时间为8~12min;所述干燥具体为:在50~70℃的鼓风干燥箱内烘干2.5~3.5h。
进一步的,步骤(b)中所述加热为以4~6℃/min的递增速率升温至500~530℃,所述保温为在500~530℃的温度条件下保持1.5~2.5h。
进一步的,所述TCN材料与所述硝酸银的质量比4500:142~567。
进一步的,步骤(1)中所述超声处理的时间为25~40min。
进一步的,步骤(2)中所述搅拌的时间为25~35min。
进一步的,步骤(3)中所述光照具体为:暴露于280~320W卤钨灯下光照25~35min,所述悬浮液的银含量为2~8%(质量百分比)。
进一步的,步骤(4)中所述干燥具体为:置于55~65℃的真空烘箱中干燥11~13h。
本发明的另一种技术方案是:一种TBA修饰g-C3N4基银掺杂光催化剂制备方法所制备的TBA修饰g-C3N4基银掺杂光催化剂在制备消毒剂中的应用。
本发明提供了TBA修饰g-C3N4基银掺杂光催化剂制备方法及其应用,其优点是:
(1)制备条件简单,经济,环保;
(2)能够灭活水环境中的病原体,是新型耐药菌消毒方式;
(3)耐药菌更容易被吸附在Ag/TCN表面,沉积的Ag可作为电子陷阱来获取、释放自由电子,从而降低载流子的复合率,提高光催化灭活效率。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。其中,
图1为一种TBA修饰g-C3N4基银掺杂光催化剂制备方法所制备的催化剂样品在不同光线条件下对耐药E.coli的灭活性能示意图,其中(a)为在黑暗条件下,(b)为在可见光照射下。
具体实施方式
g-C3N4是命名为CN的基础催化剂,既没有修饰也没有掺杂。大量文献都是基于该催化剂为基础,通过不同修饰和掺杂方式制备新型催化剂,本发明用硫代巴比妥酸修饰CN,再掺杂Ag,制备Ag/TBA/g-C3N4纳米催化剂。
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合具体实施方式和附图对本发明作进一步详细的说明。
首先,此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
其次,本发明利用结构示意图等进行详细描述,在详述本发明实施例时,为便于说明,示意图会不依一般比例作局部放大,而且所述示意图只是实例,其在此不应限制本发明保护的范围。此外,在实际制作中应包含长度、宽度及深度的三维空间。
实施例1
采用一锅热缩聚法制备TBA/g-C3N4。
将20g尿素、200mg硫代巴比妥酸、5mL纯水置于氧化铝坩埚内,在水浴锅中加热8min混合均匀,然后将其放置在50℃鼓风干燥箱内2.5h烘干。将干燥后的材料置于带盖坩埚中,以4℃/min的递增速率升温至500℃,并在此温度下保持1.5h,待其自然冷却至室温,获得的最终产物命名为TCN。
实施例2
采用一锅热缩聚法制备TBA/g-C3N4。
将20g尿素、200mg硫代巴比妥酸、5mL纯水置于氧化铝坩埚内,在水浴锅中加热10min混合均匀,然后将其放置在60℃鼓风干燥箱内3h烘干。将干燥后的材料置于带盖坩埚中,以5℃/min的递增速率升温至520℃,并在此温度下保持2h,待其自然冷却至室温,获得的最终产物命名为TCN。
实施例3
采用一锅热缩聚法制备TBA/g-C3N4。
将20g尿素、200mg硫代巴比妥酸、5mL纯水置于氧化铝坩埚内,在水浴锅中加热12min混合均匀,然后将其放置在70℃鼓风干燥箱内3.5h烘干。将干燥后的材料置于带盖坩埚中,以6℃/min的递增速率升温至530℃,并在此温度下保持2.5h,待其自然冷却至室温,获得的最终产物命名为TCN。
对比例
为了进行比较,在实施例2相同的工艺条件下,用尿素直接煅烧得到了纯g-C3N4,最终产物命名为CN。
实施例4
采用超声辅助光照还原法合成Ag/TBA/g-C3N4纳米催化剂。以实施例2制备所得的TCN为本实施例TCN材料。
将0.45g TCN材料在研钵中研磨成细粉末,加入到50mL纯水中,超声处理25min。待TCN溶液充分分散后,将硝酸银(0.0142、0.0283、0.0425和0.0567g)加入到悬浮液中,黑暗条件下剧烈机械搅拌25min促使Ag+充分吸附。随后,暴露于280W卤钨灯下光照25min,以形成具有不同银含量(2、4、6和8%)的悬浮液。最后,将该悬浮液抽滤,用纯水洗涤数次,置于55℃的真空烘箱中干燥11h。
实施例5
采用超声辅助光照还原法合成Ag/TBA/g-C3N4纳米催化剂。以实施例2制备所得的TCN为本实施例TCN材料。
将0.45g TCN材料在研钵中研磨成细粉末,加入到50mL纯水中,超声处理30min。待TCN溶液充分分散后,将硝酸银(0.0142、0.0283、0.0425和0.0567g)加入到悬浮液中,黑暗条件下剧烈机械搅拌30min促使Ag+充分吸附。随后,暴露于300W卤钨灯下光照30min,以形成具有不同银含量(2、4、6和8%)的悬浮液。最后,将该悬浮液抽滤,用纯水洗涤数次,置于60℃的真空烘箱中干燥12h。根据负载银的质量不同将产物分别命名为Ag/TCN-2、Ag/TCN-4、Ag/TCN-6和Ag/TCN-8。
实施例6
采用超声辅助光照还原法合成Ag/TBA/g-C3N4纳米催化剂。以实施例2制备所得的TCN为本实施例TCN材料。
将0.45g TCN材料在研钵中研磨成细粉末,加入到50mL纯水中,超声处理40min。待TCN溶液充分分散后,将硝酸银(0.0142、0.0283、0.0425和0.0567g)加入到悬浮液中,黑暗条件下剧烈机械搅拌35min促使Ag+充分吸附。随后,暴露于320W卤钨灯下光照35min,以形成具有不同银含量(2、4、6和8%)的悬浮液。最后,将该悬浮液抽滤,用纯水洗涤数次,置于65℃的真空烘箱中干燥13h。
实验过程
本实验所采用的催化剂为实施例2所制得的TCN、对比例所制得的CN、实施例5所制得的Ag/TCN-2、Ag/TCN-4、Ag/TCN-6和Ag/TCN-8。
使用一个300W的Xe灯(Philips,Netherland)和紫外截止滤光片(λ>400nm)作为可见光光源。灭活实验在室温下进行,将5mg催化剂加入到49.5mL无菌水中,超声30min充分分散,将混合溶液转移至磁力搅拌器上。向其中加入新鲜E.coli菌悬液0.5mL(浓度1.0×109CFU·mL-1),打开磁力搅拌器,吸取0min样品,同时打开光源并开始计时。在不同的时间间隔(5、15、30、45、60min),从混合溶液中取样并用无菌水梯度稀释,稀释2次,每次10倍。取不同的时间间隔的最终稀释液100μL均匀涂布在LB固体平板上。
耐药E.coli在LB(Luria-Bertani)培养基上实现培养及传代过程,实验在超净工作台内操作。将1mL枪头、试管、LB液体培养基和LB固体培养基在121℃条件下高压灭菌20min。灭菌完成后放入60℃的烘箱中。实验开始前30min,打开超净工作台的紫外灯照射,然后关闭紫外线灯,打开吹风。操作过程中,需要戴上橡胶手套,并使用95%乙醇对手部进行消毒,然后进入超净工作台。将灭菌完成的LB固体培养基置于超净工作台上,倒平板,待其冷却固化,倒置存放。其他实验物品冷却至室温后使用。
将接种环在酒精灯上灼烧至发红,以确保无菌。在试管中加入3ml LB液体培养基,通过接种环从菌株中挑出少量细菌,转移到LB液体培养基中,用试管塞密封。在转速180rpm,温度37℃的恒温振荡培养箱中,培养18h。
用接种环从培养好的菌悬液中沾取少量菌液,在LB固体培养基上划线获得单个菌落。在37℃恒温培养箱中培养18小时。最后,将固体培养基倒置放在4℃的冰箱中,存放备用。
培养完成后采用平板计数法记录形成的菌落数量。
图1为一种TBA修饰g-C3N4基银掺杂光催化剂制备方法所制备的催化剂样品在不同光线条件下对耐药E.coli的灭活性能示意图。如图(a)所示,在黑暗条件下,E.coli的细胞密度几乎没有变化,表明CN和TCN催化剂对细菌的毒性可以忽略不计。虽然Ag+本身具有一定抗菌能力,但在黑暗条件下,Ag/TCN-8在60min时也仅导致0.4log CFU·mL-1E.coli的死亡,所以负载Ag后的催化剂在黑暗条件下对E.coli的细胞密度几乎无影响。如图b所示,在可见光激发下,CN和TCN显示出有限的灭活效果,而在TCN表面沉积Ag后,随着Ag含量的增加,同一时间内观察到的细菌菌落依次减少,表明Ag的加入使复合催化剂的光催化灭活E.coli活性显著提高。其中,Ag/TCN-6复合催化剂表现出最高的灭活性能,在60min内实现了6.2log CFU·mL-1E.coli的消杀,而CN、TCN分别仅达到1.6、2.5log CFU·mL-1E.coli的灭活。实验结果表明,E.coli更容易被吸附在Ag/TCN表面,沉积的Ag可作为电子陷阱来获取、释放自由电子,从而降低载流子的复合率,导致由光生电子与空穴产生的活性物种明显增加,这是其光催化灭活效率提高的主要原因。
应说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
1.一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于,包括如下步骤:
(1)将TCN材料研磨成细粉末,加入到纯水中,超声处理,获得TCN分散溶液;
(2)将硝酸银加入到所述TCN分散溶液中,在黑暗条件下剧烈搅拌使Ag+充分吸附,获得混合液;
(3)将所述混合液光照,形成悬浮液;
(4)将所述悬浮液抽滤,用纯水洗涤数次,干燥,获得TBA修饰g-C3N4基银掺杂光催化剂。
2.根据权利要求1所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于,步骤(1)中所述TCN材料的制备方法为:
(a)将尿素、硫代巴比妥酸和纯水置于氧化铝坩埚内,在水浴锅中加热,混合均匀,然后将其干燥;
(b)将干燥后的材料置于带盖坩埚中加热并保温,待其自然冷却至室温,获得TCN。
3.根据权利要求1所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于:步骤(a)中所述尿素与硫代巴比妥酸的质量比为100:1;所述加热时间为8~12min;所述干燥具体为:在50~70℃的鼓风干燥箱内烘干2.5~3.5h。
4.根据权利要求1所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于:步骤(b)中所述加热为以4~6℃/min的递增速率升温至500~530℃,所述保温为在500~530℃的温度条件下保持1.5~2.5h。
5.根据权利要求1所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于:所述TCN材料与所述硝酸银的质量比4500:142~567。
6.根据权利要求1所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于:步骤(1)中所述超声处理的时间为25~40min。
7.根据权利要求1所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于:步骤(2)中所述搅拌的时间为25~35min。
8.根据权利要求1所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于,步骤(3)中所述光照具体为:暴露于280~320W卤钨灯下光照25~35min,所述悬浮液的银含量为2~8%。
9.根据权利要求1所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法,其特征在于,步骤(4)中所述干燥具体为:置于55~65℃的真空烘箱中干燥11~13h。
10.根据权利要求1~9任意一项所述的一种TBA修饰g-C3N4基银掺杂光催化剂制备方法所制备的TBA修饰g-C3N4基银掺杂光催化剂在制备消毒剂中的应用。
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