CN106745180A - A kind of cupric oxide electrode material of porous nanometer structure, preparation method and applications - Google Patents
A kind of cupric oxide electrode material of porous nanometer structure, preparation method and applications Download PDFInfo
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229960004643 cupric oxide Drugs 0.000 title claims 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 23
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 13
- 229920000557 Nafion® Polymers 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000000527 sonication Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000005751 Copper oxide Substances 0.000 abstract description 34
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 34
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract description 12
- 239000002086 nanomaterial Substances 0.000 abstract description 11
- 229910021397 glassy carbon Inorganic materials 0.000 abstract description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- 238000006276 transfer reaction Methods 0.000 abstract description 3
- 238000003760 magnetic stirring Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 13
- 239000008103 glucose Substances 0.000 description 13
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
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- 238000011088 calibration curve Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- 108010015776 Glucose oxidase Proteins 0.000 description 1
- 239000004366 Glucose oxidase Substances 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229940116332 glucose oxidase Drugs 0.000 description 1
- 235000019420 glucose oxidase Nutrition 0.000 description 1
- 238000013095 identification testing Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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Abstract
一种多孔纳米结构的氧化铜电极材料、制备方法及其应用，属于新能源和电化学传感器电极技术领域，将醋酸铜水溶液滴加于草酸水溶液中，磁力搅拌条件下反应后，用去离子水和无水乙醇清洗并干燥处理，再经煅烧后，得到多孔纳米结构的氧化铜电极材料，材料呈多孔囊状三维结构，正面呈正方形，边缘为扁平状，中间凸起，侧面呈纺锤形。将材料分散在nafion溶液后涂履于经Al2O3悬浊液磨光并通过声波降解法处理的玻碳电极上，取得电化学传感器电极，能促进电子转移反应和提供具有良好的电化学活性且有利于电子的传输，具有潜在的应用价值。
A copper oxide electrode material with a porous nanostructure, a preparation method and its application, belonging to the technical field of new energy and electrochemical sensor electrodes, the copper acetate aqueous solution is added dropwise to the oxalic acid aqueous solution, and after the reaction under magnetic stirring conditions, the deionized water is used to After washing with absolute ethanol and drying, and calcining, the copper oxide electrode material with porous nanostructure is obtained. The material has a porous capsule-like three-dimensional structure, the front is square, the edge is flat, the middle is convex, and the side is spindle-shaped. The material is dispersed in nafion solution and then coated on the glassy carbon electrode polished by Al 2 O 3 suspension and treated by sonication to obtain an electrochemical sensor electrode, which can promote electron transfer reaction and provide good electrochemical performance. Active and conducive to the transport of electrons, it has potential application value.
Description
技术领域technical field
本发明属于新能源和电化学传感器电极技术领域，特别是多孔氧化铜材料的可控合成工艺。The invention belongs to the technical field of new energy and electrochemical sensor electrodes, in particular to a controllable synthesis process of a porous copper oxide material.
背景技术Background technique
为满足可移动新能源的巨大需求，研制出性能优异、安全价廉、环境友好且催化性能优异的电化学传感器已引起相关企业和业内专家的广泛关注。当前拥有特殊的物理和化学性质，纳米材料已经被广泛应用于化学传感器、生物传感器等领域。铜材料近年来迅速出现，与大多数贵金属相比，它们是廉价和丰富。与此同时，它们有能力促进电子转移反应和提供具有良好的电化学活性。直到现在，一些基于各种铜材料的传感器，已经用于对葡萄糖的检测研究。其中，p型半导体材料、铜氧化物和一个狭窄的和特殊的带隙能量已经吸引了研究者的注意。In order to meet the huge demand for mobile new energy, the development of electrochemical sensors with excellent performance, safety, low price, environmental friendliness and excellent catalytic performance has attracted widespread attention from relevant enterprises and industry experts. At present, with special physical and chemical properties, nanomaterials have been widely used in chemical sensors, biosensors and other fields. Copper materials have emerged rapidly in recent years, and they are cheap and abundant compared to most precious metals. At the same time, they have the ability to promote electron transfer reactions and provide good electrochemical activity. Until now, some sensors based on various copper materials have been used in the detection of glucose. Among them, p-type semiconductor materials, copper oxides, and a narrow and special band gap energy have attracted the attention of researchers.
最近，已有关于金属氧化物用于催化的报告。有报道显示，氧空位会加速表面氧化还原反应的动力学，提高材料的电化学性能。这些报告显示，氧空位会加速表面氧化还原反应的动力学，提高材料的电化学性能。根据相关报导表明：通过引入氧空位，缺氧的BiOI纳米片表现出更高的催化活性，可以达到10倍比未经处理的BiOI纳米片。氧气空缺有很大影响汇总用于超级电容器的电容性能。氧气空位也已经应用于各种领域，比如光催化、超级电容器等等。然而，几乎没有增强电化学催化活性的报道源于氧气空缺在电化学传感器。所以基于多孔氧化铜材料在无酶葡萄糖传感器电极中的应用及其可控合成在目前还没有相关研究。Recently, there have been reports on the use of metal oxides for catalysis. It has been reported that oxygen vacancies can accelerate the kinetics of surface redox reactions and improve the electrochemical performance of materials. These reports show that oxygen vacancies accelerate the kinetics of surface redox reactions and enhance the electrochemical performance of materials. According to related reports, by introducing oxygen vacancies, oxygen-deficient BiOI nanosheets exhibit higher catalytic activity, which can reach 10 times that of untreated BiOI nanosheets. Oxygen vacancies have a great influence on the capacitive properties of aggregated supercapacitors. Oxygen vacancies have also been applied in various fields, such as photocatalysis, supercapacitors, and so on. However, there are few reports of enhanced electrochemical catalytic activity originating from oxygen vacancies in electrochemical sensors. Therefore, the application and controllable synthesis of porous copper oxide materials in enzyme-free glucose sensor electrodes have not been studied so far.
葡萄糖氧化酶（气态氧），基础葡萄糖酶电极，可以氧化葡萄糖为葡糖酸直接电子转移与氧气的存在。然而，由于其不稳定性和灵敏度，气态氧是容易受湿度、pH、离子洗涤剂和其他环境因素。于是，许多研究进行了研究无酶葡萄糖传感器。无酶葡萄糖感应之一是由金属或金属氧化物纳米结构修改。该传感器基于现有氧气空位很少被报道的基础上进行这项工作的。在这个工作中，多孔粒子与氧空位的措成功由煅烧草酸铜可以获得通过简单一步合成在350℃。Glucose oxidase (gaseous oxygen), a glucose-based electrode, can oxidize glucose to gluconic acid with direct electron transfer in the presence of oxygen. However, due to its instability and sensitivity, gaseous oxygen is susceptible to humidity, pH, ionic detergents, and other environmental factors. Thus, many studies have been carried out to investigate enzyme-free glucose sensors. One of the enzyme-free glucose sensing is modified by metal or metal oxide nanostructures. The sensor is based on existing oxygen vacancies that have rarely been reported for this work. In this work, porous particles with oxygen vacancies co-calcined from copper oxalate can be obtained by a simple one-step synthesis at 350 °C.
发明内容Contents of the invention
为了克服以上现有技术缺陷，本发明提出一种可作为无酶葡萄糖传感器电极的多孔纳米结构的氧化铜电极材料。In order to overcome the above defects in the prior art, the present invention proposes a copper oxide electrode material with a porous nanostructure that can be used as an enzyme-free glucose sensor electrode.
本发明所述多孔纳米结构的氧化铜材料所述材料呈多孔囊状三维结构，正面呈正方形，边缘为扁平状，中间凸起，侧面呈纺锤形。The copper oxide material with a porous nanostructure in the present invention has a three-dimensional structure in the form of a porous capsule, with a square front, flat edges, a raised middle, and a spindle-shaped side.
本发明多孔氧化铜材料可与氧气空缺作为改性材料，具有良好的电化学性能和催化性能，且具有良好的抗干扰能力。其中，多孔氧化铜材料是纳米级的。本发明的以上特征使制成的传感器的灵敏度为6240.50～10490.45 µA·(mM)-1·cm-2，响应时间小于3s，以利于电子的传输。The porous copper oxide material of the present invention can be used as a modified material with oxygen vacancies, has good electrochemical performance and catalytic performance, and has good anti-interference ability. Among them, the porous copper oxide material is nanoscale. The above characteristics of the present invention make the sensitivity of the manufactured sensor be 6240.50-10490.45 µA·(mM) -1 ·cm -2 , and the response time is less than 3s, which facilitates the transmission of electrons.
本发明还提出以上材料的制备方法。The present invention also proposes a preparation method of the above materials.
将醋酸铜水溶液滴加于草酸水溶液中，磁力搅拌条件下反应后，用去离子水和无水乙醇清洗并干燥处理，再经煅烧后，取得多孔纳米结构的氧化铜电极材料。The copper acetate aqueous solution is added dropwise to the oxalic acid aqueous solution, reacted under the condition of magnetic stirring, cleaned and dried with deionized water and absolute ethanol, and calcined to obtain the copper oxide electrode material with porous nanostructure.
本发明在充分利用氧化铜对葡萄糖的氧化具有优良的定向催化性以及材料成本低廉的基础上，通过可控合成特殊多孔纳米结构的氧化铜材料来提高比表面积，暴露更多的氧化活性位点，显现优良的氧缺陷结构，从而使传感器获得极高的灵敏度、较好的稳定性和抗干扰性等。其次，配位和前驱物法处理工艺简单、成本低廉、易于操作，适用于大规模生产。On the basis of making full use of the excellent directional catalytic performance of copper oxide on the oxidation of glucose and the low cost of materials, the present invention increases the specific surface area and exposes more oxidation active sites by controllably synthesizing copper oxide materials with special porous nanostructures , showing an excellent oxygen defect structure, so that the sensor can obtain extremely high sensitivity, good stability and anti-interference. Secondly, the coordination and precursor method is simple, low-cost, easy to operate, and suitable for large-scale production.
本发明的方法具有很好的可实施性，操作简单，价格便宜，具有很好的实用性。本发明的关键是多孔氧化铜材料可与氧气空缺作为改性材料，其中所用原料醋酸铜和草酸无特别要求。The method of the invention has good practicability, simple operation, low price and good practicability. The key point of the present invention is that the porous copper oxide material and oxygen vacancies can be used as modified materials, and there is no special requirement for the raw materials copper acetate and oxalic acid.
本发明的特点在于：The present invention is characterized in that:
1、该方法制得的氧化铜材料具有多孔结构，具有大的比表面积，与氧气空缺作为改性材料，有利于电子的传输，具有较好的催化性能和电化学性能。1. The copper oxide material prepared by this method has a porous structure and a large specific surface area, and the oxygen vacancy is used as a modified material, which is beneficial to the transmission of electrons, and has good catalytic performance and electrochemical performance.
2、反应时间短，重复率高，反应容易且成本低。2. The reaction time is short, the repetition rate is high, the reaction is easy and the cost is low.
另外，本发明所述醋酸铜水溶液中醋酸铜与草酸水溶液中草酸的投料摩尔比为1∶1。草酸具有一定的腐蚀性。但是如果草酸的量小于醋酸铜的量时，则得不到均一的颗粒状草酸铜。我们之前做过大量的对比试验，调控草酸和醋酸铜的摩尔比，最后实验结果表明，只有在醋酸铜与草酸的摩尔比为1∶1的情况下才能生成表面平滑的均一的草酸铜纳米颗粒。In addition, the molar ratio of copper acetate in the copper acetate aqueous solution of the present invention to oxalic acid in the oxalic acid aqueous solution is 1:1. Oxalic acid is somewhat corrosive. However, if the amount of oxalic acid is less than that of copper acetate, uniform granular copper oxalate cannot be obtained. We have done a lot of comparative experiments before, adjusting the molar ratio of oxalic acid and copper acetate. The final experimental results show that only when the molar ratio of copper acetate and oxalic acid is 1:1 can we generate uniform copper oxalate nanoparticles with smooth surface. .
醋酸铜是一种高产物质，过高的浓度可能会导致反应不完全，然而过低的浓度又会造成结果产品的量少，因此所述醋酸铜水溶的中醋酸铜和浓度为0.1 M。Copper acetate is a kind of high-yield material, and too high concentration may cause incomplete reaction, yet too low concentration can cause the amount of result product again little, so the concentration of copper acetate in the described copper acetate water-soluble is 0.1 M.
同理，草酸铜是一种高产物质，过高的浓度可能会导致反应不完全，然而过低的浓度又会造成结果产品的量少，因此本发明所述草酸水溶液的中草酸的浓度为0.1 M。In the same way, copper oxalate is a high-yield substance, and too high concentration may cause incomplete reaction, but too low concentration will cause the amount of the result product to be small, so the concentration of oxalic acid in the oxalic acid aqueous solution of the present invention is 0.1 M.
所述煅烧条件为：在空气氛围中以每分钟1℃的升温速度升温至350℃，然后保持2个小时，再冷却至室温。草酸铜是含有一定结晶水的，每分钟升温1℃可以保持其原有的形态，而过快的升温速率则会导致草酸铜原样的形貌遭到破坏。经过分析得到草酸铜在320℃左右会存在一个质量的骤减，因此，将温度控制在350℃既能很好地对其进行煅烧，又能减少升温时间。保持2个小时是为了能让草酸铜完全煅烧，以防出现煅烧不完全的现象，从而影响后续工艺。The calcination conditions are as follows: in an air atmosphere, the temperature is raised to 350° C. at a rate of 1° C. per minute, then kept for 2 hours, and then cooled to room temperature. Copper oxalate contains a certain amount of crystal water, and its original shape can be maintained by raising the temperature by 1°C per minute, while an excessively fast heating rate will cause the original shape of copper oxalate to be destroyed. After analysis, it is found that there will be a sharp drop in the quality of copper oxalate at around 320°C. Therefore, controlling the temperature at 350°C can not only calcine it well, but also reduce the heating time. Keeping it for 2 hours is to allow the copper oxalate to be completely calcined, so as to prevent incomplete calcination, which will affect the subsequent process.
本发明还提出多孔纳米结构的氧化铜电极材料在电化学传感器中的应用。The invention also proposes the application of the porous nanostructured copper oxide electrode material in electrochemical sensors.
本发明通过声波降解法将多孔纳米结构的氧化铜电极材料均匀地分散在浓度为20mg/mL的nafion溶液中，得到多孔纳米结构的氧化铜电极材料的nafion混合溶液；将多孔纳米结构的氧化铜电极材料的nafion混合溶液涂履于经Al2O3悬浊液磨光并通过声波降解法处理的玻碳电极上，经干燥，取得电化学传感器电极。The present invention uniformly disperses the porous nanostructured copper oxide electrode material in a nafion solution with a concentration of 20 mg/mL by sonication to obtain a nafion mixed solution of the porous nanostructured copper oxide electrode material; the porous nanostructured copper oxide The nafion mixed solution of the electrode material is coated on the glassy carbon electrode polished by the Al 2 O 3 suspension and treated by the sonication method, and dried to obtain the electrochemical sensor electrode.
本发明以玻碳电极作为载体，将经过声波降解法均匀地分散在nafion溶液中，使用Al2O3悬浊液将玻碳电极（GCE）磨光并通过声波降解法处理的溶液滴在玻碳电极上，能促进电子转移反应和提供具有良好的电化学活性且有利于电子的传输，具有潜在的应用价值。In the present invention, the glassy carbon electrode is used as a carrier, and the sonication method is uniformly dispersed in the nafion solution, and the glassy carbon electrode (GCE) is polished using the Al 2 O 3 suspension, and the solution treated by the sonication method is dropped on the glass On the carbon electrode, it can promote the electron transfer reaction and provide good electrochemical activity and facilitate the transport of electrons, which has potential application value.
以本发明的多孔纳米结构的氧化铜电极材料制成的传感器电极的灵敏度为6240.50～10490.45 µA·(mM)-1·cm-2，响应时间小于3s。The sensitivity of the sensor electrode made of the porous nanostructured copper oxide electrode material of the present invention is 6240.50-10490.45 µA·(mM) -1 ·cm -2 , and the response time is less than 3s.
所述Al2O3悬浊液中Al2O3粒径为0.3±0.005µm。该粒径的抛光粉既能保证不划伤玻碳电极，又能保证有很好的打磨效果。The particle size of Al 2 O 3 in the Al 2 O 3 suspension is 0.3±0.005 μm. The polishing powder with this particle size can not only ensure that the glassy carbon electrode will not be scratched, but also ensure a good polishing effect.
附图说明Description of drawings
图1为本发明制成的氧化铜电极材料S1样品的SEM图。Fig. 1 is the SEM image of the copper oxide electrode material S1 sample made in the present invention.
图2为本发明制成的氧化铜电极材料S1样品、S2样品和S3样品的XRD谱图。Fig. 2 is the XRD spectrum of the copper oxide electrode material S1 sample, S2 sample and S3 sample made in the present invention.
图3为本发明制成的氧化铜电极材料S1样品、S2样品和S3样品的EPR谱图。Fig. 3 is the EPR spectrum of the copper oxide electrode material S1 sample, S2 sample and S3 sample made in the present invention.
图4为本发明制成的氧化铜电极材料S1样品、S2样品和S3样品的核心级Cu 2P图。Fig. 4 is the core level Cu 2P diagram of the copper oxide electrode material S1 sample, S2 sample and S3 sample made in the present invention.
图5为本发明制成的氧化铜电极材料S1样品、S2样品和S3样品的O 1S XPS谱图。Fig. 5 is the O 1S XPS spectrum of the copper oxide electrode material S1 sample, S2 sample and S3 sample made in the present invention.
图6为本发明制成的氧化铜电极材料S1样品、S2样品和S3样品的的循环伏安曲线图。Fig. 6 is the cyclic voltammetry curves of copper oxide electrode materials S1 sample, S2 sample and S3 sample made in the present invention.
图7为本发明制成的氧化铜电极材料的响应时间图。Fig. 7 is a graph of response time of the copper oxide electrode material made in the present invention.
图8为本发明制成的氧化铜电极材料的稳定性图。Fig. 8 is a stability graph of the copper oxide electrode material produced in the present invention.
图9为本发明制成的氧化铜电极材料的抗干扰图。Fig. 9 is an anti-interference diagram of the copper oxide electrode material made in the present invention.
图10为本发明制成的氧化铜电极材料的高倍透射图。Fig. 10 is a high-magnification transmission diagram of the copper oxide electrode material produced in the present invention.
图11为本发明制成的氧化铜电极材料S1样品的响应电流校准图。Fig. 11 is a calibration diagram of the response current of the copper oxide electrode material S1 sample made in the present invention.
具体实施方式detailed description
一、制备工艺步骤：1. Preparation process steps:
（1）将浓度为0.1M的醋酸铜溶液50mL逐滴滴入50mL、浓度为0.1M的草酸溶液中，磁力搅拌1小时，直至体系完全变为蓝色沉淀物。(1) Add 50mL of 0.1M copper acetate solution dropwise into 50mL of 0.1M oxalic acid solution, and stir magnetically for 1 hour until the system completely turns into a blue precipitate.
（2）将蓝色沉淀物用去离子水和无水乙醇清洗三次，之后置于60℃烘箱中干燥处理。(2) The blue precipitate was washed three times with deionized water and absolute ethanol, and then dried in an oven at 60°C.
（3）自烘箱中取出干燥的样品以去离子水和无水乙醇清洗三次清洗，再置于60℃烘箱中干燥，然后置于管式炉中煅烧。(3) Take out the dried sample from the oven, wash it three times with deionized water and absolute ethanol, then dry it in an oven at 60°C, and then place it in a tube furnace for calcination.
煅烧条件：在空气氛围中以每分钟1℃的升温速度升温至350℃，然后保持2个小时，自然冷却至室温，取得多孔纳米结构的氧化铜电极材料S1样品。Calcination conditions: in air atmosphere, the temperature was raised to 350°C at a rate of 1°C per minute, then kept for 2 hours, and naturally cooled to room temperature to obtain a sample of copper oxide electrode material S1 with a porous nanostructure.
平行试验1：在空气氛围中以每分钟1℃的升温速度升温至450℃，然后保持2个小时，自然冷却至室温，取得多孔纳米结构的氧化铜电极材料S2样品。Parallel test 1: In air atmosphere, the temperature was raised to 450°C at a rate of 1°C per minute, and then kept for 2 hours, and then naturally cooled to room temperature to obtain a sample of copper oxide electrode material S2 with a porous nanostructure.
平行试验2：在空气氛围中以每分钟1℃的升温速度升温至550℃，然后保持2个小时，自然冷却至室温，取得多孔纳米结构的氧化铜电极材料S3样品。Parallel test 2: in the air atmosphere, the temperature was raised to 550° C. at a rate of 1° C. per minute, then kept for 2 hours, and naturally cooled to room temperature to obtain a sample of copper oxide electrode material S3 with a porous nanostructure.
（4）将步骤（3）所得的样品通过声波降解法均匀地分散在浓度为20mg/mL的nafion溶液中，取得S1样品的nafion混合溶液。(4) The sample obtained in step (3) was uniformly dispersed in a nafion solution with a concentration of 20 mg/mL by sonication to obtain a nafion mixed solution of the S1 sample.
另外，使用Al2O3粒径为0.3±0.005µm的Al2O3悬浊液对玻碳电极（GCE）磨光，并通过声波降解法处理后待用。In addition, the glassy carbon electrode (GCE) was polished with an Al 2 O 3 suspension with an Al 2 O 3 particle size of 0.3±0.005 μm, and treated by sonication before use.
（5）将S1样品的nafion混合溶液滴于以上处理后的玻碳电极上，并置于室温中干燥，冷却后，取得电化学传感器电极。(5) Drop the nafion mixed solution of the S1 sample on the above-treated glassy carbon electrode, and dry it at room temperature. After cooling, the electrochemical sensor electrode is obtained.
二、产品鉴定试验及结果：2. Product identification test and results:
图1为S1样品的扫描电镜图，由图可见单个材料呈多孔囊状三维结构，正面呈边长为300nm的正方形，侧面呈纺锤形状，边缘为扁平状态，中间凸起，凸起部分高度为150nm。Figure 1 is the scanning electron microscope image of the S1 sample. It can be seen from the figure that the single material has a porous capsule-like three-dimensional structure. 150nm.
图2为S1样品、S2样品和S3样品（经过不同温度煅烧）的XRD谱图。由图可见：三个样品的XRD峰型都是一样的且与氧化铜的标准XRD峰相符合。这说明草酸铜经过不同煅烧温度，得到的产品都是一样的，均为氧化铜。Figure 2 shows the XRD patterns of S1 sample, S2 sample and S3 sample (calcined at different temperatures). It can be seen from the figure that the XRD peak types of the three samples are the same and consistent with the standard XRD peak of copper oxide. This shows that copper oxalate undergoes different calcination temperatures, and the products obtained are the same, all of which are copper oxide.
图3为S1样品、S2样品和S3样品的EPR图。由图可见：S1样品呈现出一个很明显的氧缺陷峰，而其余两个样品却没有。这说明S1样品确实存在氧缺陷。Fig. 3 is the EPR diagram of S1 sample, S2 sample and S3 sample. It can be seen from the figure that the S1 sample presents an obvious oxygen deficiency peak, while the other two samples do not. This shows that the S1 sample does have oxygen defects.
图4是S1样品、S2样品和S3样品的Cu2p图。图中S1样品的结合能往低能级方向偏移了，这说明S1样品的Cu的价态发生了变化，进一步证实了氧缺陷的存在。Fig. 4 is the Cu2p diagram of S1 sample, S2 sample and S3 sample. In the figure, the binding energy of the S1 sample is shifted toward the lower energy level, which indicates that the valence state of Cu in the S1 sample has changed, further confirming the existence of oxygen vacancies.
图5为S1样品、S2样品和S3样品的O 1S XPS图。从峰强可以看出，S1样品的峰强偏弱，说明S1样品中氧的含量相对较少，进一步证实氧缺陷的存在。Fig. 5 is the O 1S XPS diagram of S1 sample, S2 sample and S3 sample. It can be seen from the peak intensity that the peak intensity of the S1 sample is weak, indicating that the oxygen content in the S1 sample is relatively small, further confirming the existence of oxygen defects.
图6为S1样品、S2样品和S3样品的循环伏安曲线图。从图中可以观察到，S1样品的伏安曲线要比另外两个样品明显，这说明S1样品有良好的电化学性能。Figure 6 is the cyclic voltammetry curves of S1 sample, S2 sample and S3 sample. It can be observed from the figure that the voltammetry curve of the S1 sample is more obvious than that of the other two samples, which indicates that the S1 sample has good electrochemical performance.
图7为S1样品修饰后的玻碳电极的响应时间。其响应时间小于3s，说明该样品比较灵敏。Figure 7 shows the response time of the glassy carbon electrode modified by the S1 sample. Its response time is less than 3s, indicating that the sample is relatively sensitive.
将玻碳电极至于0.1M的 NaOH溶液中，扫出稳定电流之后加入10µM的葡萄糖溶液。图8为加入10μM的葡萄糖后电流的稳定性图。在加入葡萄糖后的2800s后电流的减少仅为4.45%，这说明样品的稳定性较好。Place the glassy carbon electrode in 0.1M NaOH solution, and add 10µM glucose solution after sweeping out a steady current. Fig. 8 is a graph showing the stability of the current after adding 10 μM glucose. The decrease of current was only 4.45% after 2800s after adding glucose, which indicated that the stability of the sample was better.
图9为S1样品的抗干扰图。在加入葡萄糖后，加入同等量的AA,UA,DA,KCl，其电流均没有明显的波动，这进一步证实了S1样品的抗干扰性好。Figure 9 is the anti-interference diagram of the S1 sample. After adding glucose, adding the same amount of AA, UA, DA, and KCl, the current did not fluctuate significantly, which further confirmed the good anti-interference performance of the S1 sample.
图10为S1样品的高倍透射图。图中的曲线代表了原子的走向，说明确实存在缺陷使得原子的排列变得不整齐，并展示了优良的氧缺陷结构。Figure 10 is a high magnification transmission image of the S1 sample. The curve in the figure represents the orientation of atoms, indicating that there are indeed defects that make the arrangement of atoms irregular, and shows an excellent oxygen-deficient structure.
图11为S1样品的响应电流校准图。可通过校准曲线算得灵敏度。Figure 11 is a calibration diagram of the response current of the S1 sample. Sensitivity can be calculated from the calibration curve.
在0.6 V的电压下，将涂有S1样品的玻碳电极至于0.1 M的NaOH溶液中，向其中逐次滴加5 0，100，200，300，500，800µM的葡萄糖溶液，搜集其响应电流点并做校准曲线，可算出其灵敏度为灵敏度为：At a voltage of 0.6 V, place the glassy carbon electrode coated with the S1 sample in 0.1 M NaOH solution, add 5 0, 100, 200, 300, 500, 800 µM glucose solution dropwise to it, and collect the response current point And make a calibration curve, the sensitivity can be calculated as:
6240.50～10490.45µA·(mM)-1·cm-2。6240.50～10490.45µA·(mM) -1 ·cm -2 .
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Application publication date: 20170531 |