CN113649042A - 光催化电极制备方法、光催化反应器及污染流体处理方法 - Google Patents
光催化电极制备方法、光催化反应器及污染流体处理方法 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052802 copper Inorganic materials 0.000 claims abstract description 72
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 23
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 8
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 8
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
本发明公开了光催化电极制备方法、光催化反应器及污染流体处理方法,包括以下步骤:提供铜片;将铜片进行预处理去除表面氧化膜干扰;使用阳极氧化法在铜片上制得Cu2O薄膜;通过电化学沉积制得g‑C3N4/Cu/Cu2O光催化电极,即得Z型三元光催化电极。以g‑C3N4和Cu2O作为Z型光催化体系的两个半反应端,以Cu作为电子‑空穴对的复合中心,构建了高活性的Z型异质结,巧妙地设置了“还原脱氯——氧化降解”循环过程,此外对光催化电极板施加一定的外加偏压,能够把光催化的能量优势和电催化的可调控性协同起来,抑制光生电子‑空穴对的复合,进而提高光生电子的利用效率,促进有机污染物降解。
Description
技术领域
本发明涉及污染处理技术领域,尤其属于光催化电极制备方法、光催化反应器及污染流体处理方法。
背景技术
光催化技术有望成为解决二十一世纪能源与环境问题的重要技术之一。光催化技术的原理是利用光辐照催化剂产生活性自由基,将环境中的有机污染物降解和矿化。光催化技术具备环境友好、污染物降解彻底、无二次污染等优点,在有机污染物降解方面极具应用前景。但是,制约光催化技术在工业上的应用主要有以下几点:一是光催化反应为光激发反应,光激发产生的电子—空穴对极易复合,造成量子效率底下;二是传统光催化剂只对紫外光有响应,无法利用太阳光中的大部分可见光;三是非均相的光催化剂在降解有机污染物之后,难以实现光催化剂和水相的有效分离。
发明内容
为了克服现有技术中的部分缺陷,本发明提供了光催化电极制备方法、光催化反应器及污染流体处理方法,其能够有效的对低浓度含卤水体进行有效的净化,结构简单,使用方便。
本发明提供的技术方案如下一种光催化电极制备方法,包括以下步骤:
S1、提供铜片;
S2、对铜片进行预处理去除铜片表面的氧化膜干扰;
S3、使用阳极氧化法在铜片一侧制得Cu2O薄膜;
S4、通过液相沉积法在铜片另一侧制得g-C3N4薄膜,即得Z型三元光催化电极。
进一步地,所述步骤S2还包括:
(1)去污粉洗涤:将已准备好的铜片用去污粉进行洗涤,去除表面污渍,随后采用去离子水对铜片进行冲洗,完全去除铜片表面的污渍;
(2)酸洗:将去完污渍的铜片放置在40%的稀氢氟酸溶液中浸泡30s,对铜片表面的氧化层进行酸化,随后立即用去离子水冲洗,直至将铜片表面上残余的氢氟酸完全去除;
(3)打磨抛光:将铜片上的去离子水擦净,用400目的砂纸粗打磨,随后用1000目的砂纸将较明显的划痕打磨平,最后用2000目的砂纸细磨进行抛光,直至铜片光滑无痕,抛光好的铜片置于去离子水中保存待用;
(4)超声清洗:将保存在去离子水中的铜片先后依次浸泡于去离子水、无水乙醇、丙酮混合液、去离子水中,然后将铜片转移到超声波清洗器中超声清洗3min,清洗完成后即得去除氧化膜的铜片。
进一步地,所述步骤S3还包括以下步骤:
A1、在内衬有聚氯乙烯的电解槽中,以预处理后的铜片作为阳极,以铂片作为阴极,以Ag/AgCl(填充溶液为饱和氯化钠溶液)作参比电极,阳极铜片一面与阴极铜板相对且竖直平行放置,另一面用绝缘薄膜粘贴覆盖,以浓度为0.3~0.6mol/L的硼酸溶液作为电解液,在阳极表面电解生成Cu2O镀层薄膜;
A2、用去离子水冲洗负载有氧化亚铜薄膜的铜片,冲洗完成后将其放置在鼓风干燥箱中干燥20min,干燥温度为80℃-120℃,得到一面负载有Cu2O薄膜、另一面仍为未被氧化的铜片,即Cu/Cu2O光电极。
进一步地,所述步骤S4还包括以下步骤:
B1、去掉Cu/Cu2O光电极一侧的绝缘薄膜,在其表面涂敷三聚氰胺的甲醇溶液并晾干,涂敷和晾干过程重复10次以上;
B2、在氮气氛围的马弗炉中,将涂敷三聚氰胺的Cu/Cu2O光电极在550℃退火1h,即能在铜片表面一侧得到Cu2O结晶薄膜,另一侧得到g-C3N4结晶薄膜,即得到g-C3N4/Cu/Cu2O光催化电极。
进一步地,所述氯化钠溶液的温度为20~30℃、沉积电压为-0.6~0.3V、沉积时间10~120s。
本发明还提供了一种光催化反应器,包括上述光催化电极制备方法制作而成的Z型三元光催化电极,多个所述Z型三元光催化电极连接形成电极板,所述电极板连接在所述箱体内,相邻的所述电极板中心对称设置,电极板Cu2O薄膜一侧与相邻电极板的Cu2O薄膜一侧相对,反面的g-C3N4薄膜一侧则与后续相邻电极板中具有g-C3N4薄膜的一侧相对,所述电极板与相邻的所述电极板或所述箱体的内壁之间形成用于处理污染流体的廊道,在所述廊道内设置有紊流器,所述电极板连接有偏压电源。
进一步地,所述箱体上开设有流体输入口和流体输出口,所述流体输入口与所述流体输出口呈中心对称设置,所述流体输入口和所述流体输出口分别与所述廊道连通。
进一步地,所述箱体由耐卤素腐蚀的透明玻璃制作而成。
进一步地,所述卤代有机污染物流体为卤代有机污染物废气或卤代有机污染物废水。
本发明还提供了一种污染流体处理方法,应用于上述光催化反应器,包括以下步骤:首先,卤代有机污染物污染流体通过箱体上的流体输入口导入具有g-C3N4薄膜的廊道,在光照下实现还原脱卤;再转入两侧含有Cu2O薄膜的廊道,在光照下对脱卤有机产物氧化降解,“还原脱卤+氧化降解”过程在所述光催化反应器多个廊道中重复多次循环,最终通过流体输出口排出,最终实现污染流体中卤代有机物染物的彻底降解。
有益效果:
1.光催化电极板以g-C3N4和Cu2O作为Z型光催化体系的两个半反应端,以Cu作为电子-空穴对的复合中心,构建了高效光催化的Z型异质结,巧妙地设置了“还原脱氯——氧化降解”循环过程。
2.在光催化电极板加偏压电源,这种光电催化降解污染物的优势在于把光催化的能量优势和电催化的可调控性协同起来,对光催化电极板施加一定的外加偏压,促进光生电子的传移,抑制光生电子-空穴对的复合,进而提高光生电子的利用效率,促进有机污染物降解;
3.本发明采用多层细长廊道并且在廊道中间加入紊流器能够使卤代有机污染流体和光催化电极板充分的接触反应;
4.本发明使用的是自然光源且操作十分简便,使得光催化反应器的运营成本大幅度降低。
为让本发明的上述和其他目的、特征和优点能更明显易懂,下文特举较佳实施例,并配合所附图式,作详细说明如下。
附图说明
图1为本发明光催化电极制备方法的步骤示意图。
图2为光催化反应器的结构示意图。
具体实施方式
下面将结合附图以及具体实施例对本发明进行清楚完整地描述,显而易见的是,所列举的具体实施例仅仅是部分实施例,本领域的普通技术人员在没有付出创造性劳动的前提下所获得其他实施例,均属于本发明的保护范围。
参照图1-图2,一种光催化电极制备方法,包括以下步骤:
S1、提供铜片;
S2、对铜片进行预处理去除铜片表面的氧化膜干扰;
S3、使用阳极氧化法在铜片一侧制得Cu2O薄膜;
S4、通过液相沉积法在铜片另一侧制得g-C3N4薄膜,即得Z型三元光催化电极。
在上述实施例中,所述步骤S2还包括:
(1)去污粉洗涤:将已准备好的铜片用去污粉进行洗涤,去除表面污渍,随后采用去离子水对铜片进行冲洗,完全去除铜片表面的污渍;
(2)酸洗:将去完污渍的铜片放置在40%的稀氢氟酸溶液中浸泡30s,对铜片表面的氧化层进行酸化,随后立即用去离子水冲洗,直至将铜片表面上残余的氢氟酸完全去除;
(3)打磨抛光:将铜片上的去离子水擦净,用400目的砂纸粗打磨,随后用1000目的砂纸将较明显的划痕打磨平,最后用2000目的砂纸细磨进行抛光,直至铜片光滑无痕,抛光好的铜片置于去离子水中保存待用;
(4)超声清洗:将保存在去离子水中的铜片先后依次浸泡于去离子水、无水乙醇、丙酮混合液、去离子水中,然后将铜片转移到超声波清洗器中超声清洗3min,清洗完成后即得去除氧化膜的铜片。
在上述实施例中,所述步骤S3还包括以下步骤:
A1、在内衬有聚氯乙烯的电解槽中,以预处理后的铜片作为阳极,以铂片作为阴极,以Ag/AgCl(填充溶液为饱和氯化钠溶液)作参比电极,阳极铜片一面与阴极铂片相对且竖直平行放置,另一面用绝缘薄膜粘贴覆盖,以浓度为0.3~0.6mol/L的硼酸溶液作为电解液,在阳极表面电解生成Cu2O镀层薄膜;
A2、用去离子水冲洗负载有氧化亚铜薄膜的铜片,冲洗完成后将其放置在鼓风干燥箱中干燥20min,干燥温度为80℃-120℃,得到一面负载有Cu2O薄膜、另一面仍为未被氧化的铜片,即Cu/Cu2O光电极。
在上述实施例中,所述步骤S4还包括以下步骤:
B1、去掉Cu/Cu2O光电极一侧的绝缘薄膜,在其表面涂敷三聚氰胺的甲醇溶液并晾干,涂敷和晾干过程重复10次以上;
B2、在氮气氛围的马弗炉中,将涂敷三聚氰胺的Cu/Cu2O光电极在550℃退火1h,即能在铜片表面一侧得到Cu2O结晶薄膜,另一侧得到g-C3N4结晶薄膜,即得到g-C3N4/Cu/Cu2O光催化电极。
在上述实施例中,所述氯化钠溶液的温度为20~30℃、沉积电压为-0.6~0.3V、沉积时间10~120s。
本发明提供了一种光催化反应器,包括上述光催化电极制备方法制作而成的Z型三元光催化电极,多个所述Z型三元光催化电极连接形成电极板2,所述电极板2连接在所述箱体1内,相邻的所述电极板2中心对称设置,电极板2中Cu2O薄膜的一侧与相邻电极板2的Cu2O薄膜的一侧相对,反面的g-C3N4薄膜一侧则与后续相邻电极板2中具有g-C3N4薄膜的一侧相对,所述电极板2与相邻的所述电极板2或所述箱体1的内壁之间形成用于处理污染流体的廊道3,在所述廊道3内设置有紊流器4,所述电极板4连接有偏压电源5。
在上述实施例中,所述箱体1上开设有流体输入口11和流体输出口12,所述流体输入口11与所述流体输出口12呈中心对称设置,所述流体输入口11和所述流体输出口12分别与所述廊道3连通。
在上述实施例中,所述箱体1由耐卤素腐蚀的透明玻璃制作而成。
在上述实施例中,所述卤代有机污染物流体为卤代有机污染物废气或卤代有机污染物废水。
本发明还提供了一种污染流体处理方法,应用于上述光催化反应器,包括以下步骤:首先,卤代有机污染物流体通过箱体1上的流体输入口11导入具有g-C3N4薄膜的廊道3,在光照下实现还原脱卤;再转入两侧含有Cu2O薄膜的廊道3,在光照下对脱卤有机产物氧化降解,“还原脱卤+氧化降解”过程在所述光催化反应器多个廊道3中重复多次循环,最终通过流体输出口12排出,最终实现污染流体中卤代有机物染物的彻底降解。其中光照可以是自然光,也可以是经过调制的降解光线,在这里不对其进行具体的限制。
在实际应用中,首先在在光照的环境下打开光催化反应器的流体输入口11和流体输出口12,将电极板2通电。卤代有机污染物废气或卤代有机污染物废水通过流量泵控制流速进入光催化反应器进行深度处理,卤代有机污染物废气或卤代有机污染物废水进入箱体1内部,在紊流器4的作用下按照流向与电极板2充分接触。卤代有机污染物废气或卤代有机污染物废水开始降解,反应结束之后,关闭偏压电源5,将处理后的检测达标后的气体或水体从流体输出口12排出。
本发明中应用了具体实施例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想;同时,对于本领域的一般技术人员,依据本发明的思想,在具体实施方式及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本发明的限制。
Claims (10)
1.一种光催化电极制备方法,其特征在于,包括以下步骤:
S1、提供铜片;
S2、对铜片进行预处理去除铜片表面的氧化膜干扰;
S3、使用阳极氧化法在铜片一侧制得Cu2O薄膜;
S4、通过液相沉积法在铜片另一侧制得g-C3N4薄膜,即得Z型三元光催化电极。
2.根据权利要求1所述的光催化电极制备方法,其特征在于,所述步骤S2还包括:
(1)去污粉洗涤:将已准备好的铜片用去污粉进行洗涤,去除表面污渍,随后采用去离子水对铜片进行冲洗,完全去除铜片表面的污渍;
(2)酸洗:将去完污渍的铜片放置在40%的稀氢氟酸溶液中浸泡30s,对铜片表面的氧化层进行酸化,随后立即用去离子水冲洗,直至将铜片表面上残余的氢氟酸完全去除;
(3)打磨抛光:将铜片上的去离子水擦净,用400目的砂纸粗打磨,随后用1000目的砂纸将较明显的划痕打磨平,最后用2000目的砂纸细磨进行抛光,直至铜片光滑无痕,抛光好的铜片置于去离子水中保存待用;
(4)超声清洗:将保存在去离子水中的铜片先后依次浸泡于去离子水、无水乙醇、丙酮混合液、去离子水中,然后将铜片转移到超声波清洗器中超声清洗3min,清洗完成后即得去除氧化膜的铜片。
3.根据权利要求2所述的光催化电极制备方法,其特征在于,所述步骤S3还包括以下步骤:
A1、在内衬有聚氯乙烯的电解槽中,以预处理后的铜片作为阳极,以铂片作为阴极,以Ag/AgCl作参比电极,阳极铜片一面与阴极铂片相对且竖直平行放置,另一面用绝缘薄膜粘贴覆盖,以浓度为0.3~0.6mol/L的硼酸溶液作为电解液,在阳极表面电解生成Cu2O镀层薄膜,填充溶液为饱和氯化钠溶液;
A2、用去离子水冲洗负载有氧化亚铜薄膜的铜片,冲洗完成后将其放置在鼓风干燥箱中干燥20min,干燥温度为80℃-120℃,得到一面负载有Cu2O薄膜、另一面仍为未被氧化的铜片,即Cu/Cu2O光电极。
4.根据权利要求3所述的光催化电极制备方法,其特征在于,所述步骤S4还包括以下步骤:
B1、去掉Cu/Cu2O光电极一侧的绝缘薄膜,在其表面涂敷三聚氰胺的甲醇溶液并晾干,涂敷和晾干过程重复10次以上;
B2、在氮气氛围的马弗炉中,将涂敷三聚氰胺的Cu/Cu2O光电极在550℃退火1h,即能在铜片表面一侧得到Cu2O结晶薄膜,另一侧得到g-C3N4结晶薄膜,即得到g-C3N4/Cu/Cu2O光催化电极。
5.根据权利要求3所述的光催化电极制备方法,其特征在于,所述氯化钠溶液的温度为20~30℃、沉积电压为-0.6~0.3V、沉积时间10~120s。
6.一种光催化反应器,包括箱体,其特征在于,包括权利要求1-5任一项所述的光催化电极制备方法制作而成的Z型三元光催化电极,多个所述Z型三元光催化电极连接形成电极板,所述电极板连接在所述箱体内,相邻的所述电极板中心对称设置,电极板Cu2O薄膜一侧与相邻电极板的Cu2O薄膜一侧相对,反面的g-C3N4薄膜一侧则与后续相邻电极板中具有g-C3N4薄膜的一侧相对,所述电极板与相邻的所述电极板或所述箱体的内壁之间形成用于处理污染流体的廊道,在所述廊道内设置有紊流器,所述电极板连接有偏压电源。
7.根据权利要求6所述的光催化反应器,其特征在于:所述箱体上开设有流体输入口和流体输出口,所述流体输入口与所述流体输出口呈中心对称设置,所述流体输入口和所述流体输出口分别与所述廊道连通。
8.根据权利要求6所述的光催化反应器,其特征在于:所述箱体由耐卤素腐蚀的透明玻璃制作而成。
9.一种污染流体处理方法,其特征在于:应用于权利要求7-8任一项所述的光催化反应器,包括以下步骤:首先,卤代有机污染物流体通过光催化反应器箱体上的流体输入口导入具有g-C3N4薄膜的廊道,在光照下实现还原脱卤,获得脱卤有机产物;然后转入两侧含有Cu2O薄膜的廊道,在光照下对脱卤有机产物氧化降解,“还原脱卤+氧化降解”过程在所述光催化反应器多个廊道中重复多次循环,最终通过流体输出口排出,最终实现污染流体中卤代有机污染物的彻底降解。
10.根据权利要求9所述的污染流体处理方法,其特征在于:所述卤代有机污染物流体为卤代有机污染物废气或卤代有机污染物废水。
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US20030102227A1 (en) * | 1999-09-29 | 2003-06-05 | Europa Metalli S.P.A. | Electrochemical method for forming an inorganic covering layer on a surface of a copper material |
CN111841609A (zh) * | 2020-08-04 | 2020-10-30 | 杭州紫芯光电有限公司 | 一种Cu2O/C3N4/TiO2异质结可见光催化剂及其制备方法 |
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US20030102227A1 (en) * | 1999-09-29 | 2003-06-05 | Europa Metalli S.P.A. | Electrochemical method for forming an inorganic covering layer on a surface of a copper material |
CN111841609A (zh) * | 2020-08-04 | 2020-10-30 | 杭州紫芯光电有限公司 | 一种Cu2O/C3N4/TiO2异质结可见光催化剂及其制备方法 |
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