CN108786794B - 一种可循环光电协同催化剂及其制备方法和应用 - Google Patents
一种可循环光电协同催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种可循环光电协同催化剂及其制备方法和应用。所述方法首先采用水热法将Cu镀在Ni表面生成Cu/Ni,再高温煅烧Cu/Ni生成Cu2O/Cu/Ni,最后用水热法将Ag镀在Cu2O/Cu/Ni表面形成Ag‑Cu/Cu2O/Ni可循环光电协同催化剂。本发明的Ag‑Cu/Cu2O/Ni催化剂同时具有光催化和电催化效果。金属Cu作为原电池的阳极,金属Ag作为原电池的阴极,光催化剂Cu2O生长在金属Cu的表面,在光照下,光催化和电催化同时进行。本发明的光电协同催化剂对有机染料的降解不仅呈现出很好的催化效果,而且能够重复多次使用,在有机染料废水处理中具有巨大的应用前景。
Description
技术领域
本发明属于光电催化剂的制备及水处理技术领域,具体涉及一种可循环光电协同催化剂及其制备方法,和其在染料废水处理中的应用。
背景技术
国民经济中,染料工业占着主导地位,其产品主要应用在皮革染料、文具油墨、食品、涂料、化妆品等领域。但是由于染料本身很难降解,未经处理或超标染料废水直接排放到自然水体中会引起严重的水体和土壤污染。因此,开发新的技术应用于有机染料废水处理迫在眉睫。
目前,光催化和电催化技术廉价而且高效,已被广泛研究用于降解染料。刘志国[物理化学学报,2009,25,1841~1846]等人用逐步水热法合成了Cu@Cu2O复合纳米材料,该催化剂对有机污染物的降解有一定的效果,但是由于光生电子和空穴的分离效率有限,因此得不到大规模的工业应用。赖波[Industrial&Engineering Chemistry Research,2014,53,2605~2613]等人合成了Fe/Cu双金属复合材料,虽然该材料对酸性橙有很高的降解效率,但是其经过长时间的使用后,阳极金属(Fe)被腐蚀,材料无法重复利用。
发明内容
针对现有的光催化和电催化技术中存在的降解效率低、重复使用率差的问题,本发明提供了一种可循环光电协同催化剂及其制备方法和应用。本发明通过将Cu镀在Ni表面生成Cu/Ni,再煅烧Cu/Ni生成Cu2O/Cu/Ni,最后将Ag镀在Cu2O/Cu/Ni表面形成Ag-Cu/Cu2O/Ni复合材料。该方法制备的Ag-Cu/Cu2O/Ni复合材料为可循环光电协同催化剂,对染料的降解催化效果良好。
本发明的技术方案如下:
一种可循环光电协同催化剂的制备方法,先用水热法将Cu镀在Ni表面生成Cu/Ni,再高温煅烧Cu/Ni生成Cu2O/Cu/Ni,最后用水热法将Ag镀在Cu2O/Cu/Ni表面形成Ag-Cu/Cu2O/Ni复合材料,具体步骤如下:
步骤1,将乙酸铜和柠檬酸溶于水中,搅拌,加入镍网,在120~130℃下进行水热反6~8h,反应结束后,用乙醇和水交替洗涤,干燥得到Cu/Ni;
步骤2,以5~7℃/min的升温速度,将Cu/Ni置于300~350℃下煅烧,保温3~5h,得到Cu2O-Cu/Ni;
步骤3,将硝酸银溶于体积浓度为71.4~78.6%的乙二醇的水溶液中,得到浓度为0.84~0.86g/L硝酸银溶液,按Cu2O-Cu/Ni与硝酸银的质量比为6.8~7.2:1,将Cu2O-Cu/Ni加入硝酸银溶液中,在150~160℃下水热反应18~20h,反应结束后,用乙醇和水交替洗涤,干燥得到Ag-Cu/Cu2O/Ni催化剂。
优选地,步骤1中,以摩尔比计,乙酸铜:柠檬酸=1.8~2.2:1,乙酸铜:镍网=0.6~0.8:1。
优选地,步骤1中,所述的乙酸铜的浓度为0.1~0.2mol/L。
优选地,步骤1中,所述的搅拌时间为1h,洗涤方式为乙醇和水交替洗涤3次,干燥温度为50~70℃,干燥时间为12~18h。
优选地,步骤3中,催化剂洗涤方式为乙醇和水交替洗涤3次,干燥温度为50~70℃,干燥时间为12~18h。
进一步地,本发明还提供上述方法制备得到的可循环光电协同催化剂。
更进一步地,本发明还提供上述可循环光电协同催化剂在催化降解有机染料中的应用。
本发明将光催化技术和电催化技术结合起来:选用金属Cu作为原电池的阳极,金属Ag作为原电池的阴极,光催化剂Cu2O生长在金属Cu的表面。在光照下,光催化和电催化同时进行,也就是说光催化剂Cu2O在产生光生电子和空穴的同时,阳极金属Cu也在失去电子生成Cu+。由于光催化剂Cu2O与金属Cu靠的近,因此光生电子很容易转移到金属Cu上,电子在金属Cu上一方面拓宽了金属Cu和金属Ag之间的电势差,使得电子由金属Cu转向金属Ag的趋势更大,这样便有效的抑制了光生电子和空穴的复合,因此该催化剂对染料的降解呈现出很好的催化效果。另一方面富集在金属Cu上的电子可以将Cu+还原为金属Cu,这样便抑制了阳极金属的腐蚀,从而提高了催化剂的使用寿命,因此该催化剂能够重复使用。
与现有技术相比,本发明具有以下优点:
1.金属Cu和Ag之间存在电势差,当Cu2O产生的光生电子到Cu上时,会很快转移到电势更高的Ag上,这样可以有效防止光生电子和空穴的复合,从而提高量子效率;
2.由于金属Cu和Ag之间存在电势差,电催化降解染料的过程中,金属单质Cu失去电子变成Cu+是一个自发的过程,但是半导体Cu2O在光照的条件下产生的光生电子会补给Cu+,使单质Cu得以再生,这样可以减缓阳极金属的腐蚀,从而提高了催化剂的寿命。
附图说明
图1为Ag-Cu/Cu2O/Ni催化剂的XRD图。
图2为Ag-Cu/Cu2O/Ni催化剂的SEM图。
图3为不同催化剂对AO7在不同条件下降解的紫外光谱图。
图4为在不同水热镀银温度时所合成的催化剂对AO7的降解紫外光谱图。
图5为Ag-Cu/Cu2O/Ni催化剂对AO7在光照下的循环降解图。
具体实施方式
下面结合实施例和附图对本发明作进一步详述。
实施例1
1.20g乙酸铜和0.58g柠檬酸溶解在60mL的去离子水中并搅拌1h。称取1g镍网于该混合液中,将混合物转移到100mL聚四氟乙烯反应釜中120℃水热反应6h,所制得的Cu/Ni用乙醇和水交替洗涤三次,然后50℃干燥12h。取0.42g Cu/Ni于马弗炉中按5℃/min速率升高至300℃煅烧,并恒温3h,得到Cu2O-Cu/Ni。称取0.056g硝酸银溶于醇水混合液中(50mL乙二醇+20mL水),将煅烧后的产物加入到硝酸银溶液中,该混合液在150℃条件下水热反应18h得到Ag-Cu/Cu2O/Ni。所得产物用醇水交替洗涤三次,然后50℃干燥12h。
实施例2
2.40g乙酸铜和1.15g柠檬酸溶解在60mL的去离子水中并搅拌1h。称取1g镍网于该混合液中,将混合物转移到100mL聚四氟乙烯反应釜中130℃水热反应8h,所制得的Cu/Ni用乙醇和水交替洗涤三次,然后70℃干燥18h。取0.42g Cu/Ni于马弗炉中按7℃/min速率升高至350℃煅烧,并恒温5h,得到Cu2O-Cu/Ni。称取0.060g硝酸银溶于醇水混合液中(55mL乙二醇+15mL水),将煅烧后的产物加入到硝酸银溶液中,该混合液在160℃条件下水热反应20h得到Ag-Cu/Cu2O/Ni。所得产物用醇水交替洗涤三次,然后70℃干燥18h。
图1为Ag-Cu/Cu2O/Ni的XRD图,从图中可以看出该催化剂中含有Ni,Cu,Ag,Cu2O相,图2为Ag-Cu/Cu2O/Ni的SEM图。
对比例1
取0.30g Cu2O/Cu/Ni催化剂于50mL 0.05mMAO7溶液中,黑暗条件下搅拌一个小时使之达到吸附-脱附平衡。将固体分离出,然后加入25mL 0.05mMAO7溶液于分离出的固体中,该混合液在可见光条件下搅拌30min。将反应后的液体取出,由紫外分光光度计测样可知染料废水的降解率在30min内达到20.1%。
对比例2
取0.30g Ag-Cu/Cu2O/Ni催化剂于50mL 0.05mMAO7溶液中,黑暗条件下搅拌一个小时使之达到吸附-脱附平衡。将固体分离出,然后加入25mL 0.05mMAO7溶液于分离出的固体中,该混合液在黑暗条件下搅拌30min。将反应后的液体取出,由紫外分光光度计测样可知染料废水的降解率在30min内达到77.2%。
对比例3
2.40g乙酸铜和1.15g柠檬酸溶解在60mL的去离子水中并搅拌1h。称取1g镍网于该混合液中,将混合物转移到100mL聚四氟乙烯反应釜中130℃水热反应8h,所制得的Cu/Ni用乙醇和水交替洗涤三次,然后70℃干燥18h。取0.42g Cu/Ni于马弗炉中按7℃/min速率升高至350℃煅烧,并恒温5h,得到Cu2O-Cu/Ni。称取0.060g硝酸银溶于醇水混合液中(55mL乙二醇+15mL水),将煅烧后的产物加入到硝酸银溶液中,该混合液在120℃条件下水热反应20h得到Ag120℃-Cu/Cu2O/Ni。所得产物用醇水交替洗涤三次,然后70℃干燥18h。图4为Ag120℃-Cu/Cu2O/Ni催化剂在30min内对AO7的降解图,由图可知其降解效率达到50.7%。
对比例4
2.40g乙酸铜和1.15g柠檬酸溶解在60mL的去离子水中并搅拌1h。称取1g镍网于该混合液中,将混合物转移到100mL聚四氟乙烯反应釜中130℃水热反应8h,所制得的Cu/Ni用乙醇和水交替洗涤三次,然后70℃干燥18h。取0.42g Cu/Ni于马弗炉中按7℃/min速率升高至350℃煅烧,并恒温5h,得到Cu2O-Cu/Ni。称取0.060g硝酸银溶于醇水混合液中(55mL乙二醇+15mL水),将煅烧后的产物加入到硝酸银溶液中,该混合液在200℃条件下水热反应20h得到Ag200℃-Cu/Cu2O/Ni。所得产物用醇水交替洗涤三次,然后70℃干燥18h。图4为Ag200℃-Cu/Cu2O/Ni催化剂在30min内对AO7的降解图,由图可知其降解效率达到62.9%。
实施例3
取0.30g实例2中Ag-Cu/Cu2O/Ni催化剂于50mL 0.05mMAO7溶液中,黑暗条件下搅拌一个小时使之达到吸附-脱附平衡。将固体分离出,然后加入25mL 0.05mMAO7溶液于分离出的固体中,该混合液在可见光下搅拌30min。将反应后的液体取出,由紫外分光光度计测样可知染料废水的降解率在30min内达到88.6%,因此该催化剂呈现出很好的催化性能。与对比例1对比可知,电催化在有机染料废水降解过程中产生一定的作用。与对比例2对比可知,光催化在有机染料废水降解过程中产生一定的作用。由此可见,对于催化剂Ag-Cu/Cu2O/Ni,光催化和电催化同时参与了有机染料废水的降解,通过光电协同催化,Ag-Cu/Cu2O/Ni的催化效率显著提高。同时,其催化效果与对比例3和对比例4对比可知,水热镀银温度对催化剂的催化降解性能影响显著。
实施例4
取0.10g Ag-Cu/Cu2O/Ni催化剂于50mL 0.05mMAO7溶液中,黑暗条件下搅拌一个小时使之达到吸附-脱附平衡。将固体分离出,然后加入25mL 0.05mMAO7溶液并在可见光条件下鼓气6h。将反应后的液体取出,由紫外分光光度计测样可知染料废水的降解率内达到85%。再取25mLAO7于反应后的固体催化剂中,可见光条件下鼓气6h。将反应后的液体取出,由紫外分光光度计测样可知第二次的降解率达到79%。如此循环降解酸性橙24次。
图5为Ag-Cu/Cu2O/Ni催化剂对AO7在光照下的循环降解图。由图5可知,多次使用后,该催化剂对染料降解效果仍能达到56%,本发明的催化剂的循环使用性好。
Claims (7)
1.一种可循环光电协同催化剂的制备方法,其特征在于,具体步骤如下:
步骤1,将乙酸铜和柠檬酸溶于水中,搅拌,加入镍网,在120~130℃下进行水热反6~8h,反应结束后,用乙醇和水交替洗涤,干燥得到Cu/Ni;
步骤2,以5~7℃/min的升温速度,将Cu/Ni置于300~350℃下煅烧,保温3~5h,得到Cu2O-Cu/Ni;
步骤3,将硝酸银溶于体积浓度为71.4~78.6%的乙二醇的水溶液中,得到浓度为0.84~0.86g/L硝酸银溶液,按Cu2O-Cu/Ni与硝酸银的质量比为6.8~7.2:1,将Cu2O-Cu/Ni加入硝酸银溶液中,在150~160℃下水热反应18~20h,反应结束后,用乙醇和水交替洗涤,干燥得到Ag-Cu/Cu2O/Ni催化剂。
2.根据权利要求1所述的制备方法,其特征在于,步骤1中,以摩尔比计,乙酸铜:柠檬酸=1.8~2.2:1,乙酸铜:镍网=0.6~0.8:1。
3.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述的乙酸铜的浓度为0.1~0.2mol/L。
4.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述的搅拌时间为1h,洗涤方式为乙醇和水交替洗涤3次,干燥温度为50~70℃,干燥时间为12~18h。
5.根据权利要求1所述的制备方法,其特征在于,步骤3中,催化剂洗涤方式为乙醇和水交替洗涤3次,干燥温度为50~70℃,干燥时间为12~18h。
6.根据权利要求1至5任一所述的制备方法制得的可循环光电协同催化剂。
7.根据权利要求6所述的可循环光电协同催化剂在催化降解有机染料中的应用。
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