CN113769742A - 一种铜网集成Cu2O@FeO纳米阵列的制备方法 - Google Patents
一种铜网集成Cu2O@FeO纳米阵列的制备方法 Download PDFInfo
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- CN113769742A CN113769742A CN202110856949.1A CN202110856949A CN113769742A CN 113769742 A CN113769742 A CN 113769742A CN 202110856949 A CN202110856949 A CN 202110856949A CN 113769742 A CN113769742 A CN 113769742A
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- copper mesh
- feo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 10
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Abstract
本发明属于光催化降解及菌体灭活领域,提供一种铜网集成Cu2O@FeO纳米阵列的制备方法。本发明以铜网和九水合硝酸铁为原料,通过原位生长获得Cu(OH)2纳米阵列;通过铁离子的水解机制与铜网基底上原位制备的Cu(OH)2纳米阵列之间的相互作用,获得Cu(OH)2@Fe(OH)3纳米阵列前驱体;通过原位物相转变过程,在还原性气体的氛围中成功地在铜网基底上制备了具有异质结构的Cu2O@FeO纳米阵列。本发明还涉及铜网集成Cu2O@FeO纳米阵列及其应用,该材料在可见光照射下具有优异光降解和菌体灭活性能。本发明具有方法简单、操作步骤少、成本低廉且产物处理方便简洁等优势,适合于中等规模工业生产。
Description
技术领域
本发明属于光催化剂材料技术领域,涉及光催化降解及菌体灭活领域的光催化剂、其制备方法和应用。具体的,本发明涉及一种可用作光催化剂的双金属氧化物纳米阵列及其制备方法、应用。
背景技术
自1928年发现抗生素以来,抗生素在人类和动物疾病治疗中的应用在世界范围内呈指数级增长。然而,抗生素的滥用在水生环境中造成了严重的问题,如抗生素的积累、抗生素耐药菌以及体内相关耐药基因的富集和遗传。这些问题将增加细菌对抗生素的耐药性,降低治疗药物的有效性。因此,迫切需要寻找高效的途径来解决抗生素污染问题,包括抗生素的降解、抗生素耐药菌的灭活及其体内相关耐药基因的去除。
高级氧化工艺可利用太阳能天然和丰富的O2转化为具有强氧化性的·O2-,其原理在于半导体光催化利用在光源照射下产生的导带电子和价带空穴促进活性氧的产生。在目前众多的光催化剂中,具有交错(II型)能带排列的p-n异质结构体系因其高效的电荷分离效率而备受关注。铜,不仅具有无毒、低成本和储量丰富等优点,而且可以具有广泛的pH应用范围。氧化亚铜是一种在可见光范围内具有产生活性氧物种合适带隙(2.1-2.3eV)的p型半导体,这将为光催化分解抗生素污染物提供基础的保证。据报道,铜和氧化亚铜的复合材料具有显著的抗菌性能,这归因于荷质比和氧化应激效应。遗憾的是,氧化亚铜在光催化过程中光载流子的积累会导致氧化亚铜发生自氧化还原反应,即光腐蚀效应,导致氧化亚铜的光催化剂稳定性较差。针对这一问题,人们已经探索了各种策略,这也成为本领域的重要课题。
发明内容
本发明的目的在于提供一种铜网集成并含有铁的双金属氧化物纳米阵列及其制备方法。
一方面,具有高纵横比和垂直取向的一维纳米结构材料可以提高可见光的吸收和散射进而大大提高光催化性能。同时,具有一维纳米结构的材料尖端可以模拟粒子并启动内吞作用,从而导致质膜的弹性应变为驱动力时使其内陷,进而导致细胞破裂。另一方面,具有较大比表面积的二维金属基底可作为载流子的定向运输平台。因此,如果一维纳米结构可以垂直地集成到二维金属衬底上,形成一个多维的异质结构,那么该材料的可见光接触面积和利用效率就会大大提高。基于铁元素良好的生物相容性,通过引入铁氧化物与氧化亚铜构筑异质结可有效提高氧化亚铜的光催化稳定性;特别是氧化亚铁,其具有-0.17eV的导带电位和更为广泛可见光相应范围(550~650nm),在可见光下能促进过氧化氢转化为羟基自由基降解水中有机污染物。通过氧化亚铜与氧化亚铁的耦合获得的复合材料,有望成为处理抗生素等有机物污染的潜在材料。这有可能为可见光高效催化处理抗生素污染系统提供一个绿色解决方案。本发明基于上述发明构思完成。
本发明提供一种铜网集成Cu2O@FeO纳米阵列的制备方法。本发明以铜网和九水合硝酸铁为原料,通过原位生长和物相转变相结合的方法,成功地在铜网基底上制备了具有异质结构的Cu2O@FeO纳米阵列。本发明具有方法简单、操作步骤少、成本低廉且产物处理方便简洁等优势,适合于中等规模工业生产。
本发明的技术方案是:
(1)以铜网为基底,通过原位生长和铁离子的水解机制之间的协同作用获得Cu(OH)2@Fe(OH)3纳米阵列前驱体。
(2)在还原性气体的氛围中Cu(OH)2@Fe(OH)3前驱体通过原位物相转变过程制备Cu2O@FeO纳米阵列。
本发明提供了一种铜网集成Cu2O@FeO纳米阵列的制备方法,该方法包括如下步骤:
S1,以铜网为基底,通过原位生长获得Cu(OH)2纳米阵列;
S2,通过铁离子的水解机制与铜网基底上原位制备的Cu(OH)2纳米阵列之间的相互作用,获得Cu(OH)2@Fe(OH)3纳米阵列前驱体;
S3,在还原性气体的氛围中Cu(OH)2@Fe(OH)3纳米阵列前驱体通过原位物相转变过程制备Cu2O@FeO纳米阵列。
可选地,S1步骤包括:
S1.1,将铜网放置在一定浓度的盐酸溶液中进行超声洗;和
S1.2,在碱性环境中通过和氧化剂的作用下,原位生长Cu(OH)2纳米阵列。
通常,碱性环境是指pH值>7。本发明中,可以采用添加碱,关注反应体系的pH值实现。
可选地,步骤S1.2中的氧化剂可选自下列中的一种或者几种:过硫酸盐:过硫酸铵、过硫酸钾、过硫酸钠。
可选地,S1还包括通过去离子水的反复快速冲洗步骤S1.2制备的、原位生长的Cu(OH)2纳米阵列,获得无杂质的Cu(OH)2纳米阵列。
可选地,所述的步骤S1中,所述的盐酸浓度为1~2mol/L。
可选地,所述的超声时间为30~60分钟。
可选地,所述的碱性环境中,可加入强碱,例如氢氧化钠或者氢氧化钾,其浓度为1~3mol/L。
可选地,所述的氧化剂的浓度为0.1~1mol/L。
可选地,S2步骤包括:
S2.1,将铁盐)溶解在去离子水中;所述的铁盐可以是常见的硝酸铁或者氯化铁,例如本发明的优选例中采用一定质量的九水合硝酸铁,或者1mmol/L的六水合氯化铁。
S2.2,将在铜网上原位生成的Cu(OH)2纳米阵列材料置于步骤S2.1所配制的溶液中,搅动一定时间,得到Cu(OH)2@Fe(OH)3前驱体。
可选地,步骤S2还包括通过去离子水的反复快速冲洗S2.2制备的Cu(OH)2@Fe(OH)3前驱体,获得无杂质的Cu(OH)2@Fe(OH)3前驱体。
可选地,所述的步骤S2中,所述的九水合硝酸铁浓度为0.5~2mol/L。
可选地,所述的步骤S2中,所述的搅动时间为20~60秒钟。
可选地,S3步骤包括:
S3.1,具有Cu(OH)2@Fe(OH)3纳米阵列的铜网置于瓷舟中;
S3.2,将瓷舟放置于CVD管式炉中的石英管中央;管式炉也可以采用其他可维持还原性气氛环境的炉子。
S3.3,通入具有还原性的气流进行原位物相转变。
S3.4,在还原性气流的作用下,升温并保温。
S3.5,在还原性气流的保护下,冷却至室温。
本发明中,CVD管式炉的英文全称为Chemical Vapor Deposition。管式炉主要运用于冶金,玻璃,热处理,锂电正负极材料,新能源,磨具等行业,是测定材料在一定气温条件下的专业设备。
可选地,步骤S3还包括:通过去离子水的反复快速冲洗步骤S3.5制备的产物,真空干燥,获得无杂质的Cu2O@FeO纳米阵列。
可选地,所述的步骤S3中,所述的具有还原性的气流为氢气,气流流速为0.5L/min-0.8L/min。
可选地,所述的步骤S3中,所述的升温速率为5~10℃/min。
可选地,所述的步骤S3中,所述的原位物相转变反应温度为420~470℃。
可选地,所述的步骤S3中,所述的原位物相转变保温时间为3~6小时。
本发明还提供了一种铜网集成纳米阵列,即在铜网上形成了均匀或者异质结构的Cu2O@FeO纳米阵列。
可选地,所述的铜网集成纳米阵列由上述铜网集成Cu2O@FeO纳米阵列的制备方法制备。
本发明还提供了铜网集成纳米阵列的应用,根据上述方法制备的、以铜网为基底集成的Cu2O@FeO纳米阵列可应用于光催化领域。
所述的应用选自:
所述的铜网集成纳米阵列在制备抑菌药物或者试剂中的应用;
所述的铜网集成纳米阵列在制备抗生素替代品中的应用;或者
所述的铜网集成纳米阵列置于可见光下,通过光催化作用降解或者灭活细菌菌体。
由于采用上述方案,本发明的有益效果是:
1.本发明利用原位生成和物相转变的方法制备的Cu2O@FeO纳米阵列具有一定的普适性。本发明适用于光催化降解多种抗生素,且该方法可以推广至其他具有可水解为氢氧化物沉淀性质的金属,用于制备复合纳米材料。
2.分别采用简单廉价的原料作为反应物,原材料储量丰富,工业成本低。
3.依据该方法所制备的产物在可见光下具有良好的光催化降解及菌体灭活性能,有较为广阔的发展前景和应用空间。
4.本发明工艺简单,制备条件温和,且产物处理方便简洁,适合于中等规模工业生产。
5.本发明的方法可在二维金属基底上集成多元金属的纳米阵列,不仅可以增强可见光的利用效率,同时也充分的利用材料的结构特性,在利用绿色可再生能源领域将有重要的应用前景。
附图说明
图1为实施例1中所制备的铜网基底上原位制备Cu(OH)2的SEM照片及XRD图谱,其中:
A图为实施例1中制备铜网基底上原位制备Cu(OH)2过程中氢氧化钠浓度为1.0mol/L时的产物SEM照片;
B图为实施例1中制备铜网基底上原位制备Cu(OH)2过程中氢氧化钠浓度为2.0mol/L时的产物SEM照片;
C图为实施例1中制备铜网基底上原位制备Cu(OH)2过程中氢氧化钠浓度为2.5mol/L时的产物SEM照片;
D图为实施例1中制备铜网基底上原位制备Cu(OH)2过程中氢氧化钠浓度为3.0mol/L时的产物SEM照片
E图为实施例1中所制备的铜网基底上原位制备Cu(OH)2XRD图谱。
图2为实施例2中所制备铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体的SEM照片,其中:
A图为实施例2中制备铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体过程中九水合硝酸铁浓度为0.5mmol/L时的产物SEM照片;
B图为实施例2中制备铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体过程中九水合硝酸铁浓度为1mmol/L时的产物SEM照片;
C图为实施例2中制备铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体过程中九水合硝酸铁浓度为1.5mmol/L时的产物SEM照片;
D图为实施例2中制备铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体过程中九水合硝酸铁浓度为2.0mmol/L时的产物SEM照片。
图3为实施例3中所制备的铜网基底上集成Cu2O@FeO纳米阵列SEM照片、SAED照片、XRD图谱和EDS图谱,其中:
A和B图为实施例3中所制备的铜网基底上集成Cu2O@FeO纳米阵列SEM照片;
C图为实施例3中所制备的铜网基底上集成Cu2O@FeO纳米阵列SAED照片;
D图为实施例3中所制备的铜网基底上集成Cu2O@FeO纳米阵列XRD和RDS图谱。
图4为Cu2O@FeO纳米阵列光催化灭活抗生素抗性大肠杆菌的活性测试结果图。其中,
A图展示的抗生素光催化降解情况,在25min内,对于盐酸四环素、氨苄青霉素和卡那霉素三种抗生素均具有95%以上的光催化降解效率;
B图展示的抗生素抗性大肠杆菌的灭活情况,在10min内,已检测不到抗生素抗性大肠杆菌菌落,同时,180min内,在没有所制备的Cu2O@FeO纳米阵列的作用的情况下,仍有8个数量级的抗生素抗性大肠杆菌存活。
具体实施方式
以下结合附图所示实施例对本发明进行进一步详细说明。
实施例1
(1)铜网基底上原位制备Cu(OH)2
第一步,分别配制1mol/L、2mol/L、2.5mol/L和3mol/L的氢氧化钠溶液,将0.54g过硫酸铵溶于20mL的氢氧化钠溶液中,超声处理20min;
第二步,将经过1mol/L盐酸超声处理后的铜网加入到第一步所配制的溶液中,静置40分钟,观察到铜网表面呈现深蓝色;
第三步,铜网取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
(2)铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体
第一步,将上述制备的铜网基底上原位制备Cu(OH)2置于预先配制的1mmol/L九水合硝酸铁溶液中,搅动30秒钟,观察到溶液先变为淡绿色再变为浅黄色;
第二步,铜网取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
(3)铜网基底上原位物相转变制备Cu2O@FeO纳米阵列
第一步:将上述制备的铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体称置于瓷舟中;
第二步:将瓷舟放置于CVD管式炉中的石英管中央;
第三步:反应开始前,通入一定量的氢气并保持气体流速维持在0.5L/min;
第四步:在氢气氛围中以10℃/min的升温速率迅速从室温升高到450℃保温5小时;
第五步:等到反应体系自然冷却到室温,将瓷舟中的产物取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
如图所示,图1(A-D)展示在不同氢氧化钠浓度溶液环境中所制备的集成在铜网上的Cu(OH)2纳米阵列的SEM图。可以看出,随着氢氧化钠浓度的变化所制备的Cu(OH)2纳米阵列形貌有着明显的区别,当氢氧化钠的浓度为2.5mol/L时,铜网上形成了均匀的纳米阵列,且光滑度较好。通过对Cu(OH)2纳米阵列的X射线衍射分析(XRD)图谱分析,可以观察到在16.7°、23.8°、34.1°、38.3°、39.9°和53.5°处分别出现了Cu(OH)2的(020)、(021)、(002)、(022)、(130)和(150)晶面衍射峰,对应Cu(OH)2的PDF#13-0420卡片。证明了Cu(OH)2的成功合成。
实施例2
(1)铜网基底上原位制备Cu(OH)2
第一步,配制2.5mol/L的氢氧化钠溶液,将0.54g过硫酸铵溶于20mL的氢氧化钠溶液中,超声处理20min;
第二步,将经过1mol/L盐酸超声处理后的铜网加入到第一步所配制的溶液中,静置40分钟,观察到铜网表面呈现深蓝色;
第三步,铜网取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
(2)铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体
第一步,将上述制备的铜网基底上原位制备Cu(OH)2置于预先配制的0.5mmol/L、1mmol/L、1.5mmol/L和2mmol/L九水合硝酸铁溶液中,搅动30秒钟,观察到溶液先变为淡绿色再变为浅黄色;
第二步,铜网取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
(3)铜网基底上原位物相转变制备Cu2O@FeO纳米阵列
第一步:将上述制备的铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体称置于瓷舟中;
第二步:将瓷舟放置于CVD管式炉中的石英管中央;
第三步:反应开始前,通入一定量的氢气并保持气体流速维持在0.5L/min;
第四步:在氢气氛围中以10℃/min的升温速率迅速从室温升高到450℃保温5小时;
第五步:等到反应体系自然冷却到室温,将瓷舟中的产物取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
如图所示,图2(A-D)展示在不同九水合硝酸铁浓度溶液环境中所制备的集成在铜网上的Cu(OH)2@Fe(OH)3前驱体的SEM图。可以看出,随着九水合硝酸铁浓度的变化所制备的Cu(OH)2@Fe(OH)3前驱体形貌有着明显的区别,当九水合硝酸铁的浓度为1mmol/L时,Cu(OH)2@Fe(OH)3前驱体的纳米阵列保持良好,且表面可以观察到所负载的Fe(OH)3层。
实施例3
(1)铜网基底上原位制备Cu(OH)2
第一步,分别配制2.5mol/L的氢氧化钠溶液,将0.54g过硫酸铵溶于20mL的氢氧化钠溶液中,超声处理20min;
第二步,将经过1mol/L盐酸超声处理后的铜网加入到第一步所配制的溶液中,静置40分钟,观察到铜网表面呈现深蓝色;
第三步,铜网取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
(2)铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体
第一步,将上述制备的铜网基底上原位制备Cu(OH)2置于预先配制的1mmol/L九水合硝酸铁溶液中,搅动30秒钟,观察到溶液先变为淡绿色再变为浅黄色;
第二步,铜网取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
(3)铜网基底上原位物相转变制备Cu2O@FeO纳米阵列
第一步:将上述制备的铜网基底上原位制备Cu(OH)2@Fe(OH)3前驱体称置于瓷舟中;
第二步:将瓷舟放置于CVD管式炉中的石英管中央;
第三步:反应开始前,通入一定量的氢气并保持气体流速维持在0.5L/min;
第四步:在氢气氛围中以10℃/min的升温速率迅速从室温升高到450℃保温5小时;
第五步:等到反应体系自然冷却到室温,将瓷舟中的产物取出用去离子水反复清洗,去除杂质后,将产物置于真空干燥箱中在60℃的条件下干燥24小时,取出后在惰性气氛下密封保存。
如图所示,图3(A-B)展示所制备的集成在铜网上的Cu2O@FeO纳米阵列的SEM图。由A图可以看出,铜网表面集成了密集的一维Cu2O@FeO纳米阵列,B图中可以观察到Cu2O纳米阵列表面有着一层致密的FeO层。Cu2O@FeO纳米阵列的SAED照片(C图)可以观察到,FeO的(211)晶面和Cu2O的(111)晶面的晶格条纹间距分别为0.19nm和0.20nm,同时在Cu2O和FeO之间的相界面上晶格条纹的取向发生了明显的变化,这表明异质结的形成。通过对Cu2O@FeO纳米阵列的XRD图谱分析,可以观察到在36.5°、42.4°、61.5°和73.7处分别出现了Cu2O的(111)、(200)、(220)和(311)晶面衍射峰,对应Cu2O的PDF#65-3288卡片;35.6°、37.7°、43.6°、61.4°和73.5°处分别出现了Cu2O的(003)、(101)、(102)、(104)和(105)晶面衍射峰,对应FeO的PDF#39-1088卡片。EDS图谱中可以清晰的观察到Cu、Fe和O元素的存在。上述结果证明了Cu2O@FeO纳米阵列的成功合成。
实施例4本发明Cu2O@FeO纳米阵列的光催化性能测试
(1)Cu2O@FeO纳米阵列光催化降解抗生素
第一步,分别配制一定浓度的盐酸四环素、氨苄青霉素和卡那霉素溶液,将生长着Cu2O@FeO纳米阵列的铜网置于上述抗生素溶液中;
第二步,利用光催化仪器模拟的可见光照射第一步中加入了铜网的抗生素溶液;
第三步,每隔一段时间取出一定量的抗生素溶液,利用紫外-可见光分光光度计测定吸光度的变化情况;
(2)Cu2O@FeO纳米阵列光催化灭活抗生素抗性大肠杆菌
第一步,在配制好的培养基中培养抗生素抗性大肠杆菌;
第二步,将生长着Cu2O@FeO纳米阵列的铜网置于培养完成的含有一定浓度抗生素抗性大肠杆菌的培养基中;
第三步,利用光催化仪器模拟的可见光照射第二步中加入了铜网的含有一定浓度抗生素抗性大肠杆菌的培养基;
第四步,每隔一段时间取出一定量的含有抗生素抗性大肠杆菌的培养基,利用平板涂步法检测抗生素抗性大肠杆菌的存活情况。
如图所示,图5A展示的抗生素光催化降解情况,在25min内,对于盐酸四环素、氨苄青霉素和卡那霉素三种抗生素均具有95%以上的光催化降解效率;图5B展示的抗生素抗性大肠杆菌的灭活情况,在10min内,已检测不到抗生素抗性大肠杆菌菌落,同时,180min内,在没有所制备的Cu2O@FeO纳米阵列的作用的情况下,仍有8个数量级的抗生素抗性大肠杆菌存活。
实施例5本发明与现在已经公开的光催化剂性能方面的对比结果
表1为所制备的集成在铜网上的Cu2O@FeO纳米阵列与已经公开的光催化在光催化降解抗生素方面的对比。
表1
表2为所制备的集成在铜网上的Cu2O@FeO纳米阵列与已经公开的光催化在光催化灭活抗生素抗性大肠杆菌方面的对比。
表2
如表中所示,所制备的集成在铜网上的Cu2O@FeO纳米阵列在光催化降解抗生素和灭活抗生素抗性大肠杆菌等领域内较已经公开的光催化剂在处理效率上有较大的优势。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于这里的实施例,在不脱离本发明的范畴的情况下所做出的修改都在本发明的保护范围之内。
Claims (20)
1.一种铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:该方法包括如下步骤:
S1,以铜网为基底,通过原位生长获得Cu(OH)2纳米阵列;
S2,通过铁离子的水解机制与铜网基底上原位制备的Cu(OH)2纳米阵列之间的相互作用,获得Cu(OH)2@Fe(OH)3纳米阵列前驱体;
S3,在还原性气体的氛围中Cu(OH)2@Fe(OH)3纳米阵列前驱体通过原位物相转变过程制备Cu2O@FeO纳米阵列。
2.根据权利要求1所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:
S1步骤包括:
S1.1,将铜网放置在盐酸溶液中进行超声洗;和
S1.2,在碱性环境中通过和氧化剂的作用下,原位生长Cu(OH)2纳米阵列。
3.根据权利要求2所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:S1还包括通过去离子水的反复快速冲洗步骤S1.2制备的、原位生长的Cu(OH)2纳米阵列,获得无杂质的Cu(OH)2纳米阵列的步骤。
4.根据权利要求1所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:
S2步骤包括:
S2.1,将铁盐溶解在去离子水中;
S2.2,将在铜网上原位生成的Cu(OH)2纳米阵列材料置于步骤S2.1所配制的溶液中,搅动一定时间,得到Cu(OH)2@Fe(OH)3前驱体。
5.根据权利要求4所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:步骤S2还包括通过去离子水的反复快速冲洗S2.2制备的Cu(OH)2@Fe(OH)3前驱体,获得无杂质的Cu(OH)2@Fe(OH)3前驱体。
6.根据权利要求1所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:
S3步骤包括:
S3.1,具有Cu(OH)2@Fe(OH)3纳米阵列的铜网置于瓷舟中;
S3.2,将瓷舟放置于CVD管式炉中的石英管中央;
S3.3,通入具有还原性的气流进行原位物相转变;
S3.4,在还原性气流的作用下,升温并保温;
S3.5,在还原性气流的保护下,冷却至室温。
7.根据权利要求6所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:步骤S3还包括:通过去离子水的反复快速冲洗步骤S3.5制备的产物,真空干燥,获得无杂质的Cu2O@FeO纳米阵列。
8.根据权利要求2所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的步骤S1中,所述的盐酸浓度为1~2mol/L。
9.根据权利要求2所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的超声时间为30~60分钟。
10.根据权利要求2所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的碱性环境中含有氢氧化钠或者氢氧化钾;
氢氧化钠或者氢氧化钾的浓度为1~3mol/L。
11.根据权利要求2所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的氧化剂选自下列中的一种或者几种:过硫酸盐:过硫酸铵、过硫酸钾、过硫酸钠;
氧化剂的浓度为0.1~1mol/L。
12.根据权利要求5所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的步骤S2中,所述的铁盐是硝酸铁或者氯化铁;
铁盐的浓度为0.5~2mol/L。
13.根据权利要求5所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的步骤S2中,所述的搅动时间为20~60秒钟。
14.根据权利要求6所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的步骤S3中,所述的具有还原性的气流为氢气,气流流速为0.5L/min-0.8L/min。
15.根据权利要求6所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的步骤S3中,所述的升温速率为5~10℃/min。
16.根据权利要求6所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的步骤S3中,所述的原位物相转变反应温度为420~470℃。
17.根据权利要求6所述的铜网集成Cu2O@FeO纳米阵列的制备方法,其特征在于:所述的步骤S3中,所述的原位物相转变保温时间为3~6小时。
18.一种铜网集成纳米阵列,其特征在于:在铜网上形成具有异质结构的Cu2O@FeO纳米阵列。
19.根据权利要求18所述的铜网集成纳米阵列,其特征在于:所述的铜网集成纳米阵列由权利要求1-17中任意一种制备方法制备。
20.权利要求18所述的铜网集成纳米阵列的应用,其特征在于:所述的应用选自:
所述的铜网集成纳米阵列在处理抗生素污染水体中的应用;
所述的铜网集成纳米阵列在处理耐药菌中的应用;或者
所述的铜网集成纳米阵列置于可见光下,通过光催化作用降解或者灭活细菌菌体。
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