CN114177910B - 一种氧化铜氧化锌复合压电光催化材料及其制备方法和应用 - Google Patents
一种氧化铜氧化锌复合压电光催化材料及其制备方法和应用 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 60
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 30
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 28
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- GFCDJPPBUCXJSC-UHFFFAOYSA-N [O-2].[Zn+2].[Cu]=O Chemical compound [O-2].[Zn+2].[Cu]=O GFCDJPPBUCXJSC-UHFFFAOYSA-N 0.000 claims abstract description 30
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 244000005700 microbiome Species 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 150000001879 copper Chemical class 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 150000003751 zinc Chemical class 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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Abstract
本发明公开了一种氧化铜氧化锌复合压电光催化材料及其制备方法和应用，其中方法主要包括：(1)将氢氧化钠与纯水混合搅拌溶解完全，升温至45℃，并加入表面活性剂搅拌均匀；(2)将可溶性铜盐与可溶性锌盐溶液用纯水混合溶解完全；(3)将配置好的(2)铜锌溶液缓慢滴加至(1)溶液中，调节最终混合溶液PH为中性，升温至95℃反应2.5h；(4)将反应产物反复离心清洗、烘干即得到氧化铜氧化锌复合压电催化材料。本发明的氧化铜氧化锌复合压电光催化材料形态可控，结构稳定，催化效率高，具有良好的压电光电催化效应，能够在黑暗中实现有机污染物的高效降解及杀灭微生物，制备方法绿色和设备简单，成本低、便于大规模量产。
Description
技术领域
本发明涉及化合物制备技术领域，尤其涉及一种氧化铜氧化锌复合压电光催化材料及其制备方法和应用。
背景技术
压电催化材料在外加微弱的机械力作用下就可以诱导材料颗粒表面电荷的不对称分布；表面富集的非平衡电荷能够引发电化学反应，在温和条件下可实现水和氧气分子的活化以及活性氧物种(Reactive Oxygen Species,ROS)的产生，从而实现各类催化反应。
已报道的以BaTiO3为代表的压电催化材料展现出高效的催化效能，但其制备繁琐、昂贵，常需要电极极化的方式使材料产生压电效益，不宜于批量生产和应用。纳米氧化锌作为光催化半导体材料已被广泛报道。然而，氧化锌颗粒因为光生电子和空穴复合几率高，从而影响其光催化、抗菌功效。氧化铜作为掺杂纳米颗粒被用于改善上述问题，有效的提高了其光催化功效。然而，光催化剂的缺点是在光照下才能起到功效，大大限制了应用范围。发展压电催化剂可有效克服上述困难，具有广阔应用前景。
发明内容
本发明的目的在于提供一种绿色制备、成本可控、催化效能高、抗微生物性能高的氧化铜氧化锌复合压电光催化材料，解决了催化材料在黑暗中实现催化效能的关键技术问题，实现了压电催化材料绿色、低成本、批量化制备，同时发现了氧化铜氧化锌复合压电光催化材料的机械相应抗微生物效能。
为解决以上技术问题，本发明采用的技术方案是：一种氧化铜氧化锌复合压电光催化材料，所述氧化铜氧化锌复合压电光催化材料中的氧化铜、氧化锌具有针状结构。
所述氧化铜氧化锌复合压电光催化材料为具有压电催化效益的材料。
本发明还提供了上述氧化铜氧化锌复合压电光催化材料的制备方法，包括以下步骤：
(1)将氢氧化钠与纯水混合搅拌溶解完全，升温，并加入表面活性剂搅拌均匀；
(2)将可溶性铜盐与可溶性锌盐溶液用纯水混合溶解完全。
(3)将配置好的(2)铜锌溶液缓慢滴加至(1)溶液中，调节滴加速度，滴加完毕后，调节最终混合溶液pH为中性，升温反应一段时间；
(4)将反应产物反复离心清洗、烘干即得到氧化铜氧化锌复合压电催化材料。
优选的，所述表面活性剂为石油磺酸钾、十二烷基苯磺酸钠中的一种。
优选的，所述可溶性铜盐为硫酸铜、硝酸铜、氯化铜中的一种。
优选的，所述可溶性锌盐为硫酸锌、醋酸锌、氯化锌。
优选的，步骤(1)中升温至45℃；步骤(3)中升温到95℃反应0.5h。
本发明的氧化铜氧化锌复合压电光催化材料作为抗菌剂在黑暗环境中抗微生物的应用。
本发明的氧化铜氧化锌复合压电光催化材料作为催化剂在黑暗环境降解有机物的应用。
本发明的氧化铜氧化锌复合压电光催化材料作为催化剂在裂解水产氢气、氧气，还原固定二氧化碳中的应用。
综上所述，运用本发明的技术方案，具有如下有益效果：
(1)本发明采用水相、一步制备法，易于规模化、绿色环保、无需后续高温煅烧、所需设备简单、成本低；
(2)本发明的到氧化铜氧化锌复合压电催化材料具有良好的压电催化效益，能在黑暗中实现有机分子高效降解、杀灭微生物，光照对该催化效应具有增强作用
(3)本发明的到氧化铜氧化锌复合压电催化材料能够有效利用机械能，具有优良的抗微生物性能。
(4)本发明的氧化铜氧化锌复合压电光催化材料还具备裂解水产氢气、氧气，还原固定二氧化碳等催化效能。
附图说明
图1为实施例1中的氧化铜氧化锌复合压电材料扫描电镜图片(5um)；
图2为实施例1中的氧化铜氧化锌复合压电材料扫描电镜图片(2um)；
图3为实施例1中的氧化铜氧化锌复合压电材料XRD图谱；
图4为实施例3中的氧化铜氧化锌复合压电材料抑菌圈示意图；
图5为实施例1中的氧化铜氧化锌复合压电材料添加的塑料品；
图6为实施例1中的氧化铜氧化锌复合压电材料添加的塑料品后的扫描电镜图；
图7实施案例6压电材料添加塑料样品抑菌圈；
图8压电光催化材料的假设机理图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，但不构成对本发明保护范围的限制。
本发明利用纳米氧化铜颗粒的掺杂纳米氧化锌，通过发展绿色制备方法、控制反应条件，调控氧化铜氧化锌的稳定微观结构，制备能在黑暗环境下具有优良催化降解、高效抗菌功效的氧化铜氧化锌复合压电催化材料。
实施例1
将2L浓度为36mg/ml的氢氧化钠溶液，升温至45℃，加入80g石油磺酸钾搅拌溶解均匀。配置2L含60mg/ml硫酸铜、含60mg/ml硫酸锌的铜锌溶液。将铜锌溶液缓慢滴加至含十二烷基苯磺酸钠的氢氧化钠溶液中，滴加时长约1h。调节最终滴加后溶液pH为中性。升温至95℃反应0.5h。将反应产物反复离心清洗、晾干即得到氧化铜氧化锌复合压电催化材料。
参考附图1、2、8所示，本发明的氧化铜氧化锌复合压电光催化材料中的氧化铜、氧化锌具有柱状针状复合异质结结构，其中氧化铜显柱状结构，氧化锌显针状结构。针状氧化锌具有高比表面积、容易弯曲，可充分利用应力收集的空间，尽可能多的收集机械能；同时，柱状氧化铜异质结构被置于针状氧化锌根部，当在压电催化电极中形成压电势时，针状氧化锌发生形变、弯曲，进而引起表面电荷的转移，柱状氧化铜异质结提高还原或氧化电位，有效地促进压电载流子的分离，从而提高材料的压电催化效率。同时该异质结结构，也可促进光生电子、光生空穴的分离和抑制重组，提高该催化剂在光催化过程中量子产率，从而实现高压电光电催化效率。
在电子、空穴分离后，其可分别诱导产生活性氧物质，进而产生消毒杀菌、降解有机污染物的效能。
实施例2
配置2.5L含60mg/ml硫酸铜、含60mg/ml硫酸锌的铜锌溶液。升温至45℃，加入90g石油磺酸钾搅拌溶解均匀。配置1.5L浓度为36mg/ml的氢氧化钠溶液。将氢氧化钠溶液缓慢滴加至含十二烷基苯磺酸钠的铜锌溶液中，滴加时长约1h。调节最终滴加后溶液pH为中性。升温至95℃反应0.5h。将反应产物反复离心清洗、晾干即得到氧化铜氧化锌复合压电催化材料。
实施例3
采用抑菌圈实验测试氧化铜氧化锌复合压电光催化材料的抗菌性能。先取大肠杆菌培养液(约1.0×106CFU/ml)涂布在营养琼胶平板上，在板中央分别放上0.1克实施例1中的氧化铜氧化锌复合材料，在避光下，不经过任何处理，放入培养箱中经过24小时培养，取出测量其抑菌圈为2.0cm。如图4所示，可以看到，氧化铜氧化锌复合压电光催化材料具有强力的抗菌功效。
实施例4
取0.1g实施例1中氧化铜氧化锌复合压电光催化材料投入100ml约1.0×106CFU/ml大肠杆菌液中，避光环境下在不同的搅拌速度下震荡培养24小时后，进行大肠杆菌菌落数的测试。如表一所示，证明该氧化铜氧化锌复合压电光催化材料有较强的抗菌能力。同时，增加实验中的震荡速度，可以提升材料的抗菌性能(抗菌率从96.8％提升至99.1％)，再次证明了该材料的压电抗菌性能。
表一：氧化锌石墨烯压电材料在不同搅拌速度下的抗菌功效
实施例5：配置5mg/L的亚甲基蓝溶液，分别取50ml亚甲基蓝溶液并加入0.1g实施例2氧化铜氧化锌复合压电光催化材料，在不同条件下处理后，用分光光度计测其催化效应。结果如下表所示：
通过实施例5说明，氧化铜氧化锌复合压电光催化材料通过在黑暗中搅拌、超声即可催化降解亚甲基蓝溶液，光照能够进一步加强其催化效能。
实施例6：将氧化铜氧化锌复合压电光催化材料按1％的添加量加入到PP塑料接头的注塑材料中(如图5所示)，通过共混注塑制得复合PP塑料接头。通过扫描电镜可以看到，氧化铜氧化锌复合压电光催化材料颗粒被均匀的分散到塑料中(如图6所示)，再取一小块塑料，通过抑菌圈实验可以观察到复合PP塑料还具有抑菌圈(如图7所示)，说明氧化铜氧化锌复合压电光催化材料被融入PP塑料后还能够通过催化产生活性氧物质，从而对周边的微生物产生杀灭的作用。
以上所述是本发明的优选实施方式，应当指出，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，这些改进和润饰也视为本发明的保护范围。
Claims (2)
1.氧化铜氧化锌复合压电催化材料作为抗菌剂在黑暗环境中抗微生物的应用，其特征在于：所述氧化铜氧化锌复合压电催化材料中的氧化铜、氧化锌具有柱状针状复合异质结结构，其中氧化铜显柱状结构，氧化锌显针状结构，由以下方法制得：将2L浓度为36mg/mL的氢氧化钠溶液，升温至45℃，加入80g石油磺酸钾搅拌溶解均匀；配置2L含60mg/mL硫酸铜、含60mg/mL硫酸锌的铜锌溶液；将铜锌溶液缓慢滴加至含十二烷基苯磺酸钠的氢氧化钠溶液中，滴加时长约1h；调节最终滴加后溶液pH为中性；升温至95℃反应0.5h；将反应产物反复离心清洗、晾干即得到氧化铜氧化锌复合压电催化材料。
2.氧化铜氧化锌复合压电催化材料作为催化剂在黑暗环境降解有机物的应用，其特征在于：所述氧化铜氧化锌复合压电催化材料中的氧化铜、氧化锌具有柱状针状复合异质结结构，其中氧化铜显柱状结构，氧化锌显针状结构，由以下方法制得：将2L浓度为36mg/mL的氢氧化钠溶液，升温至45℃，加入80g石油磺酸钾搅拌溶解均匀；配置2L含60mg/mL硫酸铜、含60mg/mL硫酸锌的铜锌溶液；将铜锌溶液缓慢滴加至含十二烷基苯磺酸钠的氢氧化钠溶液中，滴加时长约1h；调节最终滴加后溶液pH为中性；升温至95℃反应0.5h；将反应产物反复离心清洗、晾干即得到氧化铜氧化锌复合压电催化材料。
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