CN110090642A - 铜基底氧化锌复合材料及其制备方法和应用 - Google Patents
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 73
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 28
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- PDWBGRKARJFJGI-UHFFFAOYSA-N 2-phenylcyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1C1=CC=CC=C1 PDWBGRKARJFJGI-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
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- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明公开了一种铜基底氧化锌复合材料及其制备方法和应用,所述铜基底氧化锌复合材料由铜基底和附着在铜基底上的花簇状氧化锌棒构成;所述复合材料通过以下方法制备:步骤1,按照摩尔比(1‑2):(0.2‑0.4):(0.2‑0.4)取十六胺、葡萄糖、氯化铜均匀分散于去离子水中,然后于100‑140℃下保温10‑16h,过滤干燥得到基底铜;步骤2,将所述基体铜中加入硝酸锌、六亚甲基四胺和去离子水,其中硝酸锌、六亚甲基四胺与步骤1中氯化铜的摩尔比为(0.2‑0.4):(1‑1.5):(1‑1.5),于90‑100℃下搅拌2‑6h,过滤干燥得到铜基底氧化锌复合材料。所述铜基底氧化锌复合材料、铜基底氧化锌复合银材料都具有良好的光催化技术对水体中污染物的有效去除的应用。
Description
技术领域
本发明涉及金属无机复合材料技术领域,特别是涉及一种铜基底氧化锌复合材料及其制备方法和应用。
背景技术
近年来,由于我国的许多行业的快速发展(纺织、化妆品、造纸、皮革和制药等行业)每年都会产生大量的有机污染物,因此会产生大量的有机废水,这些废水排入河流湖泊等,直接对水产业和农业造成严重危害,不仅对人体的身体健康有严重的危害,而且对人们居住环境及生态环境也构成极大的威胁。传统的用于去除废水中有机物的方法包括物理吸附、生物净化、膜分离技术等,但这些方法都只是转移了有机物的位置,并没有从根本上去除有机物,可能会造成二次污染。近年来,人们对半导体光催化技术给予了极大的关注,半导体光催化技术被认为是最有效的无害化处理方法之一,可以充分利用可再生太阳能来解决环境问题和能源危机。因此开发新型光催化剂,减少环境污染具有重要意义。
半导体光催化技术可直接在光照下,激发半导体价带上的电子跃迁到导带上,而在价带上留下空穴,光生电子和空穴可将周围的水和氧气氧化成具有更高氧化性能的羟基自由基(·OH)和超氧自由基(·O2 -),这些自由基可以直接把废水中的有机物氧化分解,生成二氧化碳和水,从本质上将其去除。其中氧化锌是一种最常用的半导体之一,常温下禁带宽度为3.37eV,具有较大的结合能,并且其来源丰富、价格低廉,具有制备方法简单、热稳定性和化学稳定性好、无毒等特点,被公认为是当前最有应用价值的半导体光催化剂之一。
由于半导体光催化剂在光催化过程中,光生电子与空穴的高复合率严重影响其光催化效率,氧化锌作为其中之一也不例外,除此之外,光催化反应主要发生在催化剂的表面,因此光催化能力的大小与自身的形貌结构有很大的关系。现已有许多方法可以制备出各种形貌的氧化锌,像纳米棒、纳米花、纳米线等,但这些形貌的往往比表面积较小,影响晶体光催化效能。
发明内容
本发明的目的是针对现有技术中存在的技术缺陷,而提供一种铜基底氧化锌复合材料,通过对氧化锌材料的改性可以延缓电子与空穴复合,拓宽吸收光谱,促进催化剂表面的某些特定反应,提高光催化活性。并且通过合成不同形貌的铜来得到不同花簇状的氧化锌复合材料进而改变了氧化锌的比表面积。本发明还提供了所述铜基底氧化锌复合材料的制备方法及其在光催化降解化学有机污染物的中的应用。
为实现本发明的目的所采用的技术方案是:
一种铜基底氧化锌复合材料,所述复合材料由铜基底和附着在铜基底上的花簇状氧化锌棒构成;所述复合材料通过以下方法制备:
步骤1,按照摩尔比(1-2):(0.2-0.4):(0.2-0.4)取十六胺、葡萄糖、氯化铜均匀分散于去离子水中,然后于100-140℃下保温10-16h,过滤干燥得到基底铜;
步骤2,将所述基底铜中加入硝酸锌、六亚甲基四胺和去离子水,其中步骤1中氯化铜与所述硝酸锌和六亚甲基四胺的摩尔比为(0.2-0.4):(1-1.5):(1-1.5),于90-100℃下搅拌2-6h,过滤干燥得到铜基底氧化锌复合材料。
在上述技术方案中,所述步骤1中十六胺、葡萄糖、氯化铜的摩尔比为(5-6):1:1。
在上述技术方案中,所述葡萄糖和氯化铜的摩尔比为1:1,所述硝酸锌和六亚甲基四胺的摩尔比为1:1。
在上述技术方案中,所述复合材料的其比表面积为34.286-40.000m2·g-1,孔体积为0.162-0.200cm3·g-1,孔径为7.927-9.600nm。
在上述技术方案中,所述铜基底为铜纳米颗粒或铜纳米线。
在上述技术方案中,所述氧化锌棒的直径为20-30nm,长度为250-350nm。
本发明的另一方面,所述铜基底氧化锌复合材料作为复合光催化剂在降解水体中有机污染物中的应用。
在上述技术方案中,所述复合光催化剂在可见光下降解罗丹明B溶液时,降解35min后,降解率为79-82%。
本发明的另一方面,一种铜基底氧化锌复合材料的制备方法,包括以下步骤:
步骤1,按照摩尔比(1-2):(0.2-0.4):(0.2-0.4)取十六胺、葡萄糖、氯化铜均匀分散于去离子水中,然后于100-140℃下保温10-16h,得到基底铜;
步骤2,将所述基底铜中加入硝酸锌、六亚甲基四胺和去离子水,其中步骤1中氯化铜与所述硝酸锌和六亚甲基四胺的摩尔比为(0.2-0.4):(1-1.5):(1-1.5),于90-100℃下搅拌2-6h,过滤干燥得到铜基底氧化锌复合材料。
在上述技术方案中,所述葡萄糖和氯化铜的摩尔比为1:1,所述硝酸锌和六亚甲基四胺的摩尔比为1:1。
与现有技术相比,本发明的有益效果是:
1.在本发明中利用简单的分步合成以铜为基底的氧化锌复合材料制备出了3D花簇状氧化锌复合材料,所得到的铜基氧化锌复合材料形貌类似花簇,而且其中氧化锌的直径为25nm,长度为300nm。
2.铜基氧化锌复合材料的结构在很大程度上增大了催化剂与废水中有机物的接触面积,增大了光催化反应的反应活性位点。
3.本发明还提供了铜基氧化锌复合材料的制备方法和应用,由上述制备方法制备的氧化锌复合光催化剂,以及所述氧化锌复合光催化剂在模拟太阳光的条件下(氙灯照射,波长为320-780nm),用于在水体中降解有机物的应用。本发明中用罗丹明B来模拟水体中的有机污染物。对采用本发明方法制备的以铜为基底的氧化锌复合材料的光催化活性进行考察,远比纯的氧化锌高效,这对于氧化锌应用在处理有机污染废水方面具有良好的前景。
4.提高氧化锌粉末降解化学有机污染物的光催化活性,将纳米氧化锌的光吸收范围由紫外光区扩展至可见光区。
附图说明
图1以铜基底、铜基底氧化锌复合材料的SEM图(a,b为实施例3得到的基底铜的形貌,c,d为实施例3得到的铜基底氧化锌复合材料的形貌,e,f为实施例1得到的基底铜的形貌,g,h为实施例1得到的铜基底氧化锌复合材料的形貌)。
图2是铜基底氧化锌复合材料的XRD图。
图3是氙灯照射下光催化剂降解罗丹明B溶液的降解效率曲线图。
具体实施方式
以下结合具体实施例对本发明作进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1
步骤1,取0.04g CuCl2·2H2O溶于20mL的去离子水中,缓慢加入0.05g葡萄糖和0.40g十六胺(CuCl2·2H2O、葡萄糖和十六胺的摩尔比为1:1:8),磁搅拌强力搅拌6h,得到淡蓝色乳状液。然后将液体转入反应釜中,于120℃的烘箱中保温12h,冷却至室温后,离心过滤得到基底铜,进行真空干燥。
步骤2,0.34g Zn(NO3)2·6H2O和0.16g六亚甲基四胺溶于40mL的去离子水中。将以上得到的铜分散在溶液中,在95℃的油浴中保温6h。离心过滤后真空干燥,得到以铜为基底的花簇状氧化锌,即铜基底氧化锌复合材料(Cu@ZnO)。Cu@ZnO的比表面积和孔分布如表1所示
表1铜基底氧化锌复合材料的比表面积和孔分布
实施例2
重复实施例1,但把0.40g十六胺改成0.30g十六胺(CuCl2·2H2O、葡萄糖和十六胺的摩尔比为1:1:6),从而通过控制十六胺的量来控制所得到的铜的形貌。
实施例3
重复实施例1,但把0.40g十六胺改成0.27g十六胺(CuCl2·2H2O、葡萄糖和十六胺的摩尔比为1:1:5),从而通过控制十六胺的量来控制所得到的铜的形貌。
实施例1中步骤1得到的是铜纳米颗粒如图1中e,f所示。实施例2中步骤1得到的是铜纳米线如图1中a,b所示。由铜纳米线得到Cu@ZnO的比表面积比较大,催化活性位点多。
测量实施例2和实施例3得到的铜基底氧化锌复合材料的比表面积和孔分布,得到类似结果,其比表面积为34.286-40.000m2·g-1,孔体积为0.162-0.200cm3·g-1,孔径为7.927-9.600nm。
从得到的SEM照片(图1中c,d,g,h)、XRD图谱(图2)结果可知,所得到的Cu@ZnO类似于花簇且粒径较小,通过对制备的Cu@ZnO的XRD图谱分析可知铜的(111)、(200)和(220)晶面的衍射峰,氧化锌的(100)、(002)、(101)、(102)、(110)、(103)、(200)、(112)、(201)、(004)和(202)晶面的衍射峰清晰可见。由此可知合成的产物为Cu@ZnO复合材料,且结晶度较高。
实施例4
配制2份50mL、质量分数为100g/L的罗丹明B溶液,分别置于编号为A、B的100mL的烧杯中。向A、B烧杯中分别加入ZnO(硝酸锌和六亚甲基四胺按摩尔比为1:1配制成0.25M的溶液,然后在95℃的油浴中保温6h。离心过滤后真空干燥)和按照实施例3的方法所制备的Cu@ZnO光催化剂20mg,然后将上述2只烧杯置于氙灯(波长为320-780nm)下照射,氙灯距离液面约10cm高,在室温下进行光催化降解罗丹明B的实验。每隔5min取样,在离心机中以5000rpm的转速离心分离15min后,取上层清液,用紫外可见分光光度计测其吸光度。计算不同时间下的光催化降解率,计算公式如下:
实验结果如表2所示。
表2氙灯照射下Cu@ZnO光催化剂降解罗丹明B溶液的降解效率
以上所述仅是本发明的优选实施方式,应当指出的是,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种铜基底氧化锌复合材料,其特征在于,所述复合材料由铜基底和附着在铜基底上的花簇状氧化锌棒构成;所述复合材料通过以下方法制备:
步骤1,按照摩尔比(1-2):(0.2-0.4):(0.2-0.4)取十六胺、葡萄糖、氯化铜均匀分散于去离子水中,然后于100-140℃下保温10-16h,过滤干燥得到基底铜;
步骤2,将所述基底铜中加入硝酸锌、六亚甲基四胺和去离子水,其中步骤1中氯化铜与所述硝酸锌和六亚甲基四胺的摩尔比为(0.2-0.4):(1-1.5):(1-1.5),于90-100℃下搅拌2-6h,过滤干燥得到铜基底氧化锌复合材料。
2.如权利要求1所述的铜基底氧化锌复合材料,其特征在于,所述步骤1中十六胺、葡萄糖、氯化铜的摩尔比为(5-6):1:1。
3.如权利要求1所述的铜基底氧化锌复合材料,其特征在于,所述葡萄糖和氯化铜的摩尔比为1:1,所述硝酸锌和六亚甲基四胺的摩尔比为1:1。
4.如权利要求1所述的铜基底氧化锌复合材料,其特征在于,所述复合材料的其比表面积为34.286-40.000m2·g-1,孔体积为0.162-0.200cm3·g-1,孔径为7.927-9.600nm。
5.如权利要求1所述的铜基底氧化锌复合材料,其特征在于,所述铜基底为铜纳米颗粒或铜纳米线。
6.如权利要求1所述的铜基底氧化锌复合材料,其特征在于,所述氧化锌棒的直径为20-30nm,长度为250-350nm。
7.如权利要求1-6任一项所述的铜基底氧化锌复合材料作为复合光催化剂在降解水体中有机污染物中的应用。
8.如权利要求7所述的应用,其特征在于,所述复合光催化剂在可见光下降解罗丹明B溶液时,降解35min后,降解率为79-82%。
9.一种铜基底氧化锌复合材料的制备方法,其特征在于,包括以下步骤:
步骤1,按照摩尔比(1-2):(0.2-0.4):(0.2-0.4)取十六胺、葡萄糖、氯化铜均匀分散于去离子水中,然后于100-140℃下保温10-16h,得到基底铜;
步骤2,将所述基底铜中加入硝酸锌、六亚甲基四胺和去离子水,其中步骤1中氯化铜与所述硝酸锌和六亚甲基四胺的摩尔比为(0.2-0.4):(1-1.5):(1-1.5),于90-100℃下搅拌2-6h,过滤干燥得到铜基底氧化锌复合材料。
10.如权利要求9所述的制备方法,其特征在于,所述步骤1中十六胺、葡萄糖、氯化铜的摩尔比为(5-6):1:1。
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