WO2020103616A1 - Copper oxide/carbon nanotube/carbon nitride electrochemical sensor for detecting acetaminophen, preparation method therefor and application thereof - Google Patents

Copper oxide/carbon nanotube/carbon nitride electrochemical sensor for detecting acetaminophen, preparation method therefor and application thereof

Info

Publication number
WO2020103616A1
WO2020103616A1 PCT/CN2019/111754 CN2019111754W WO2020103616A1 WO 2020103616 A1 WO2020103616 A1 WO 2020103616A1 CN 2019111754 W CN2019111754 W CN 2019111754W WO 2020103616 A1 WO2020103616 A1 WO 2020103616A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
acetaminophen
electrochemical sensor
carbon nitride
copper oxide
Prior art date
Application number
PCT/CN2019/111754
Other languages
French (fr)
Chinese (zh)
Inventor
张菲菲
袁月环
王宗花
王海燕
Original Assignee
青岛大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 青岛大学 filed Critical 青岛大学
Publication of WO2020103616A1 publication Critical patent/WO2020103616A1/en

Links

Images

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Definitions

  • the present disclosure belongs to the field of electrochemical analysis and detection, and in particular relates to a copper oxide / carbon nanotube / carbon nitride electrochemical sensor for detecting acetaminophen and its preparation method and application.
  • Acetaminophen N-acetyl-P-aminophenol or acetaminophen
  • Acetaminophen does not have any serious side effects when taken at the prescribed dose.
  • excessive use of acetaminophen can lead to the accumulation of toxic metabolites, which can lead to liver toxicity and nephrotoxicity, which in turn can damage the liver and other organs of the kidney. Therefore, it is necessary to quickly and sensitively detect acetaminophen in clinical applications.
  • electrochemical sensing provides an application platform for its fast, accurate and convenient detection process.
  • a copper oxide / carbon nanotube / carbon nitride composite material is provided.
  • the preparation method includes: mixing carboxylated carbon nanotubes, carbon nitride and water uniformly, and performing ultrasonic treatment; then adding copper acetate, mixing and performing ultrasonic treatment; drying after ultrasonic treatment, and then inert gas atmosphere The calcination is carried out under the condition of copper oxide / carbon nanotube / carbon nitride composite material.
  • a copper oxide / carbon nanotube / carbon nitride composite material prepared by the above method is provided.
  • the application of the copper oxide / carbon nanotube / carbon nitride composite material in preparing an electrochemical sensor for detecting acetaminophen is provided.
  • an electrochemical sensor for detecting acetaminophen, the electrochemical sensor including a substrate electrode; and,
  • the above copper oxide / carbon nanotube / carbon nitride composite material is attached to the base electrode.
  • a method for preparing the electrochemical sensor for detecting acetaminophen includes the following steps:
  • the obtained copper oxide / carbon nanotube / carbon nitride composite material is washed with water, dried, and dispersed into a dispersion liquid with a concentration of 0.5 to 1.5 mg / ml in water: secondly, the base electrode is polished with aluminum powder Separately use ethanol and secondary water for ultrasonic cleaning. After blowing dry with nitrogen, apply the dispersed droplets to the electrode to prepare a copper oxide / carbon nanotube / carbon nitride modified electrode, which is used to detect acetaminophen. Chemical sensor.
  • the application of the electrochemical sensor in detecting acetaminophen is provided.
  • a method for detecting paracetamol including the step of performing electrochemical detection using the detection paracetamol electrochemical sensor.
  • gC 3 N 4 is compounded with carboxylated carbon nanotubes (CNT), and then copper acetate solution is added, and calcined at high temperature to obtain copper oxide / carbon nanotube / carbon nitride (CuO / CNT / gC 3 N 4 ) Composite materials.
  • CNT carboxylated carbon nanotubes
  • CuO / CNT / gC 3 N 4 copper oxide / carbon nanotube / carbon nitride
  • the lone pair of nitrogen atoms in carbon nitride has a conjugated effect on the ⁇ bond between the carbon nanotubes, allowing the carbon nanotubes to enter the carbon nitride layer, increasing the surface area of the composite material, and at the same time the overall composite material
  • the electrical conductivity of the material has been improved, which in turn enables the composite material to have enhanced catalytic capabilities.
  • a CuO / CNT / gC 3 N 4 composite modified electrode was prepared and used as an electrochemical sensor to detect acetaminophen. The electrochemical results show that the composite material has a good detection effect on acetaminophen.
  • Figure 1 shows the bare electrode (a), gC 3 N 4 (b), CuO (c), CNT (d), CNT / gC 3 N 4 (e), CuO / CNT / gC 3 N 4 (f) modified electrode
  • the acetaminophen concentration is 0.02 ⁇ M, 0.04 ⁇ M, 0.06 ⁇ M, 0.08 ⁇ M, 0.1 ⁇ M (A, B), 1 ⁇ M, 15 ⁇ M, 30 ⁇ M, 45 ⁇ M, 60 ⁇ M, 75 ⁇ M, 90 ⁇ M, 105 ⁇ M, 120 ⁇ M (C, D).
  • FIG 3 is a transmission electron micrograph of carbon nitride (A), carbon nanotube / carbon nitride (B), and copper oxide / carbon nanotube / carbon nitride (C).
  • a method for preparing a copper oxide / carbon nanotube / carbon nitride composite material includes the following steps: the carboxylated carbon nanotube, carbon nitride, and water Mix evenly and perform ultrasonic treatment; then add copper acetate, mix and perform ultrasonic treatment; after ultrasonic treatment, dry and then calcinate under an inert gas atmosphere to obtain copper oxide / carbon nanotube / carbon nitride composite materials after calcination.
  • the internal structure of gC 3 N 4 has a rich and uniform nitrogen coordination agent, which can provide more metal coordination sites as catalytic active sites during the electrocatalysis process.
  • the strong coordination between the N atom and Cu atom in gC 3 N 4 can increase the active site of the composite material, thereby improving the overall electrocatalytic activity of the material.
  • CuO / CNT / gC 3 N 4 composite materials prepared with different proportions of raw materials have different catalytic properties.
  • the ratio to copper acetate is (10-30) mg: (5-15) mg: (5-20) mL (5-6) mg. It has been verified by experiments that the above-mentioned ratio makes the CuO / CNT / gC 3 N 4 composite material have better catalytic performance and a good detection effect of acetaminophen.
  • the carboxylated carbon nanotubes, carbon nitride, and water are uniformly mixed, and the ultrasonic treatment time is 1 to 2.5 hours. Further, the sonication time is 2h.
  • the present disclosure When preparing a CuO / CNT / gC 3 N 4 composite material, the present disclosure first composites gC 3 N 4 with carboxylated carbon nanotubes so that the carbon nanotubes can enter the gC 3 N 4 layer, increasing the composite material At the same time, this operation makes the overall conductivity of the composite material well improved.
  • copper acetate is added and mixed, and the ultrasonic treatment time is 3 to 4 hours. Further, the sonication time is 3h.
  • the calcination temperature is 500-600 ° C, and the calcination time is 2-4h. Further, the calcination temperature is 520 ° C and the calcination time is 3h.
  • the inert gas is argon or helium.
  • a method for preparing carboxylated carbon nanotubes includes: mixing carbon nanotubes with concentrated nitric acid, then performing ultrasonic treatment, and then cleaning with water until neutral, Finally, the washed carbon nanotubes are dried, and then taken out to obtain dried carboxylated carbon nanotubes.
  • the purpose of carboxylation is to attach carboxyl groups on the surface of carbon nanotubes, and then combine with amino groups on the surface of carbon nitride to form a composite material.
  • the carbon nanotubes have a diameter of 40-60 nm and a length greater than 5 ⁇ m, and were purchased from Shenzhen Nanoport Technology Co., Ltd.
  • the selection basis is determined according to the size of the carbon nitride material (the size of the carbon nitride nanosheet is about 1-2 ⁇ m).
  • the diameter of the carbon nanotubes should not be too large, and the length should be as long as possible, which is conducive to the subsequent reaction.
  • the addition ratio of the carbon nanotubes and concentrated nitric acid is (30-50) mg: (15-25) mL; the mass fraction of the concentrated nitric acid is 95-98%.
  • a method for preparing carbon nitride includes:
  • the raw material is melamine.
  • the inert gas is argon.
  • the calcination temperature is 500-600 ° C., and the heating rate is 2.5-3.5 ° C./min.
  • the calcination temperature is 550 ° C, and the heating rate is 3 ° C / min.
  • the calcination time is 4.5 to 5.5 hours.
  • the calcination time is 5h.
  • the calcination time is 1.5 to 2.5 hours.
  • the purpose of secondary calcination under the protection of inert gas is to peel off the carbon nitride nanosheets.
  • the calcination time is 2h.
  • the lamellar micromorphology of gC 3 N 4 prepared by the above method provides the premise for uniform loading of copper oxide and the foundation for the insertion of carbon nanotubes.
  • a copper oxide / carbon nanotube / carbon nitride composite material prepared by the above method is provided.
  • Carbon nitride (gC 3 N 4 ) is a two-dimensional structure composed of nitrogen substituted carbon six ring units.
  • the inherently rich nitrogen active sites and excellent catalytic activity of gC 3 N 4 make it have broad application prospects in many fields.
  • copper oxide has potential application prospects in the fields of gas sensing, lithium ion batteries, and catalysis.
  • the strong complexation between the gC 3 N 4 N atoms and can be made of Cu atoms to CuO uniform loading surface 3 N 4 gC, and CuO while gC 3 N 4 heterojunction interface between reflector shape, which is conducive to enhance composite The catalytic performance of the material.
  • Carbon nanotubes have a unique ⁇ -conjugated structure, high conductivity and large specific surface area. Its unique structure can be combined with other nanomaterials such as graphene, ionic liquids, nanoparticles, etc. Chemical sensitivity.
  • the application of the copper oxide / carbon nanotube / carbon nitride composite material in preparing an electrochemical sensor for detecting acetaminophen is provided.
  • an electrochemical sensor for detecting paracetamol includes a substrate electrode; and,
  • the copper oxide / carbon nanotube / carbon nitride composite material is attached to the base electrode.
  • the base electrode is a glassy carbon electrode.
  • a preparation method of the electrochemical sensor for detecting acetaminophen includes:
  • the obtained copper oxide / carbon nanotube / carbon nitride composite material is washed with water, dried, and dispersed into a dispersion liquid with a concentration of 0.5 to 1.5 mg / ml with water: secondly, the base electrode is first polished with aluminum powder, Separately use ethanol and water for ultrasonic cleaning. After blowing dry with nitrogen, apply the dispersed droplets to the electrode to prepare a copper oxide / carbon nanotube / carbon nitride modified electrode, which is an electrochemical sensor for detecting acetaminophen .
  • the application of the electrochemical sensor in detecting acetaminophen is provided.
  • a method for detecting acetaminophen for non-diagnostic purposes includes the following steps:
  • Example 2 Take 10 mL of the carbon nanotube aqueous solution in Example 2 (2 mg / mL), add 5 mL of the carbon nitride aqueous solution in Example 1 (2 mg / mL), take out after 5 hours of ultrasound, and vacuum-dry in a vacuum drying test box at 60 ° Transfer to a tube furnace, heat to 520 ° C at a heating rate of 4 ° C / min, and hold for three hours. During this process, argon gas must be passed to protect.
  • Example 2 Take 10 mL of the carbon nanotube aqueous solution in Example 2 (2 mg / mL), add 5 mL of the carbon nitride aqueous solution in Example 1 (2 mg / mL), after sonication for 2 hours, add 0.0053 g of copper acetate powder, and continue ultrasonic vibration 3 hour. After the ultrasound is completed, it is vacuum-dried in a vacuum drying test box at 60 ° C and then transferred to a tube furnace, heated to 520 ° C at a heating rate of 4 ° C / min, and maintained for three hours. During this process, it must be protected by argon gas. .
  • the carbon nitride nanosheet (in Example 1) exhibits a thin sheet-like structure, and its transmission electron microscope image is shown in FIG. 3A.
  • the results shown in FIG. 3B were obtained after sonication for a period of time. It can be seen from the figure that the carbon nanotubes were successfully incorporated into the surface of carbon nitride.
  • Figure 3C shows the transmission electron micrograph of the copper oxide / carbon nanotube / carbon nitride composite material in Example 4. As can be seen from the figure, when copper acetate is added to the ultrasonic stirring and calcination, there are Copper oxide particles appear, whose size is between 20-40nm.
  • the obtained copper oxide / carbon nanotube / carbon nitride composite material is dried in a vacuum drying oven and dispersed into a dispersion liquid with a concentration of 1 mg / ml with secondary water: secondly, the The base electrode was first polished with aluminum powder, ultrasonically cleaned with ethanol and secondary water, and dried with nitrogen, and then 6 microliters of the above dispersed droplets were applied to the electrode to prepare copper oxide / carbon nanotube / carbon nitride
  • the modified electrode is an electrochemical sensor for detecting acetaminophen.
  • This test uses cyclic voltammetry (CV) and square wave voltammetry (SWV).
  • the sweep speed is set to 100mV / s.
  • the reduction peak is not significant, indicating that the electron transfer rate occurring at the bare electrode due to the irreversible oxidation process is slow.
  • a pair of reversible redox peaks appeared between + 0.3V and + 0.4V.
  • the acetamido group of the CuO / CNT / gC 3 N 4 modified electrode Compared with the oxidation peak of the bare electrode, the peak current value of phenol is about 6 times that of the bare electrode.
  • the redox peak potential of the CuO / CNT / gC 3 N 4 modified electrode is shifted relative to the bare electrode, which also shows that the CuO / CNT / gC 3 N 4 modified electrode can effectively promote the oxidation of acetaminophen .
  • the position and intensity of the redox peak in the CV curve indicate that the prepared CuO / CNT / gC 3 N 4 modified electrode has a good catalytic effect on acetaminophen.
  • Example 7 A method for detecting acetaminophen
  • Fig. 2 shows that under the optimal conditions (0.1M phosphate buffer solution with pH 7), the electrochemical sensor of Example 5 was used to detect different concentrations of acetaminophen by square wave voltammetry. As shown in the figure, as the concentration of acetaminophen increases, the peak oxidation current gradually increases. It can be seen from Figures 2A and 2B that the peak current of oxidation is linearly related to the concentration of acetaminophen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A copper oxide/carbon nanotube/carbon nitride electrochemical sensor for detecting acetaminophen, a preparation method therefor and an application thereof. The method comprises: mixing carboxylated carbon nanotubes, carbon nitride, and water uniformly, and performing sonication; then adding copper acetate, mixing uniformly, and performing sonication; and drying after the sonication, and then calcining in an inert gas atmosphere to obtain a copper oxide/carbon nanotube/carbon nitride composite material. A CuO/CNT/g-C3N4 composite modified electrode is prepared and used as an electrochemical sensor for detecting acetaminophen. The electrochemical result shows that the composite material has a good detection effect on acetaminophen.

Description

一种检测对乙酰氨基酚的氧化铜/碳纳米管/氮化碳电化学传感器及其制备方法与应用Copper oxide / carbon nanotube / carbon nitride electrochemical sensor for detecting acetaminophen and preparation method and application thereof 技术领域Technical field
本公开属于电化学分析检测领域,具体涉及一种检测对乙酰氨基酚的氧化铜/碳纳米管/氮化碳电化学传感器及其制备方法与应用。The present disclosure belongs to the field of electrochemical analysis and detection, and in particular relates to a copper oxide / carbon nanotube / carbon nitride electrochemical sensor for detecting acetaminophen and its preparation method and application.
背景技术Background technique
这里的陈述仅提供与本公开有关的背景信息,而不必然构成现有技术。The statements herein provide only background information related to the present disclosure and do not necessarily constitute prior art.
对乙酰氨基酚(N-乙酰基-P-氨基苯酚或对乙酰氨基酚)是最常用的止痛药物之一,被广泛用于缓解发烧,感冒,咳嗽和疼痛,如头痛,牙痛和背痛等病症。对乙酰氨基酚在照规定剂量食用时不会出现任何严重的副作用。然而,对乙酰氨基酚的过度使用会导致毒性代谢物的积累,这可能导致肝毒性和肾毒性,进而损伤肾的肝脏等器官。因此,在临床应用中快速灵敏地检测对乙酰氨基酚是必要的。检测对乙酰氨基酚的方法有很多,比如:滴定分析法、分光光度法、电化学方法、化学发光法、高效液相色谱法和高效毛细管电泳法等。与其他技术相比,电化学传感为其快速,准确和方便的检测过程提供了应用平台。Acetaminophen (N-acetyl-P-aminophenol or acetaminophen) is one of the most commonly used analgesics and is widely used to relieve fever, cold, cough and pain, such as headache, toothache and back pain, etc. Illness. Acetaminophen does not have any serious side effects when taken at the prescribed dose. However, excessive use of acetaminophen can lead to the accumulation of toxic metabolites, which can lead to liver toxicity and nephrotoxicity, which in turn can damage the liver and other organs of the kidney. Therefore, it is necessary to quickly and sensitively detect acetaminophen in clinical applications. There are many methods for detecting acetaminophen, such as: titration analysis, spectrophotometry, electrochemical method, chemiluminescence method, high performance liquid chromatography and high performance capillary electrophoresis. Compared with other technologies, electrochemical sensing provides an application platform for its fast, accurate and convenient detection process.
发明内容Summary of the invention
为丰富检测对乙酰氨基酚电化学传感器的种类以及获得对于对乙酰氨基酚具有良好的检测效果,在本公开的第一个方面,提供了一种氧化铜/碳纳米管/氮化碳复合材料的制备方法,该方法包括:将羧基化碳纳米管、氮化碳和水混合均匀,进行超声处理;然后加入醋酸铜,混匀,进行超声处理;超声处理后进行干燥,再在惰性气体氛围下进行煅烧,煅烧后得到氧化铜/碳纳米管/氮化碳复合材料。In order to enrich the types of acetaminophen electrochemical sensors and obtain a good detection effect for acetaminophen, in the first aspect of the present disclosure, a copper oxide / carbon nanotube / carbon nitride composite material is provided The preparation method includes: mixing carboxylated carbon nanotubes, carbon nitride and water uniformly, and performing ultrasonic treatment; then adding copper acetate, mixing and performing ultrasonic treatment; drying after ultrasonic treatment, and then inert gas atmosphere The calcination is carried out under the condition of copper oxide / carbon nanotube / carbon nitride composite material.
在本公开的第二个方面,提供采用上述方法制备得到的氧化铜/碳纳米管/氮化碳复合材料。In a second aspect of the present disclosure, a copper oxide / carbon nanotube / carbon nitride composite material prepared by the above method is provided.
在本公开的第三个方面,提供所述氧化铜/碳纳米管/氮化碳复合材料在制备检测对乙酰氨基酚电化学传感器中的应用。In a third aspect of the present disclosure, the application of the copper oxide / carbon nanotube / carbon nitride composite material in preparing an electrochemical sensor for detecting acetaminophen is provided.
在本公开的第四个方面,提供一种检测对乙酰氨基酚电化学传感器,该电化学传感器包括基底电极;以及,In a fourth aspect of the present disclosure, there is provided an electrochemical sensor for detecting acetaminophen, the electrochemical sensor including a substrate electrode; and,
上述氧化铜/碳纳米管/氮化碳复合材料,该复合材料附着在所述基底电极上。The above copper oxide / carbon nanotube / carbon nitride composite material is attached to the base electrode.
在本公开的第五个方面,提供所述检测对乙酰氨基酚电化学传感器的制备方法,该方法包括以下步骤:In a fifth aspect of the present disclosure, a method for preparing the electrochemical sensor for detecting acetaminophen is provided. The method includes the following steps:
首先,将得到的氧化铜/碳纳米管/氮化碳复合材料用水洗涤之后,干燥,用水分散成浓度为0.5~1.5mg/ml的分散液:其次,将基底电极先用铝粉进行打磨,分别采用乙醇和二次 水进行超声清洗,用氮气吹干后,取所述分散液滴涂到电极上,制备氧化铜/碳纳米管/氮化碳修饰电极,即为检测对乙酰氨基酚电化学传感器。First, the obtained copper oxide / carbon nanotube / carbon nitride composite material is washed with water, dried, and dispersed into a dispersion liquid with a concentration of 0.5 to 1.5 mg / ml in water: secondly, the base electrode is polished with aluminum powder Separately use ethanol and secondary water for ultrasonic cleaning. After blowing dry with nitrogen, apply the dispersed droplets to the electrode to prepare a copper oxide / carbon nanotube / carbon nitride modified electrode, which is used to detect acetaminophen. Chemical sensor.
在本公开的第六个方面,提供所述电化学传感器在检测对乙酰氨基酚中的应用。In a sixth aspect of the present disclosure, the application of the electrochemical sensor in detecting acetaminophen is provided.
在本公开的第七个方面,提供一种检测对乙酰氨基酚的方法,该方法包括采用所述检测对乙酰氨基酚电化学传感器进行电化学检测的步骤。In a seventh aspect of the present disclosure, a method for detecting paracetamol is provided, the method including the step of performing electrochemical detection using the detection paracetamol electrochemical sensor.
与本发明人知晓的相关技术相比,本公开其中的一个技术方案具有如下有益效果:Compared with related technologies known to the inventor, one of the technical solutions of the present disclosure has the following beneficial effects:
本公开中,将g-C 3N 4与羧基化的碳纳米管(CNT)进行复合,其后加入醋酸铜溶液,在高温下煅烧得到氧化铜/碳纳米管/氮化碳(CuO/CNT/g-C 3N 4)复合材料。其中,g-C 3N 4中的N原子和Cu原子之间的强配位作用可以使CuO均匀的负载到g-C 3N 4表面。同时,氮化碳中氮原子的孤对电子与碳纳米管之间的π键产生共轭作用,使得碳纳米管进入到氮化碳的层间,增加了复合材料的表面积,同时复合材料整体的导电性能得到良好的改善,进而使复合材料具有增强的催化能力。制备CuO/CNT/g-C 3N 4复合修饰电极,并将其用作电化学传感器,用以检测对乙酰氨基酚,其电化学结果显示,该复合材料对于对乙酰氨基酚具有良好的检测效果。 In the present disclosure, gC 3 N 4 is compounded with carboxylated carbon nanotubes (CNT), and then copper acetate solution is added, and calcined at high temperature to obtain copper oxide / carbon nanotube / carbon nitride (CuO / CNT / gC 3 N 4 ) Composite materials. Wherein the strong complexation between the gC 3 N 4 N atoms and the Cu atom can even load CuO gC 4 to the surface 3 N. At the same time, the lone pair of nitrogen atoms in carbon nitride has a conjugated effect on the π bond between the carbon nanotubes, allowing the carbon nanotubes to enter the carbon nitride layer, increasing the surface area of the composite material, and at the same time the overall composite material The electrical conductivity of the material has been improved, which in turn enables the composite material to have enhanced catalytic capabilities. A CuO / CNT / gC 3 N 4 composite modified electrode was prepared and used as an electrochemical sensor to detect acetaminophen. The electrochemical results show that the composite material has a good detection effect on acetaminophen.
附图说明BRIEF DESCRIPTION
构成本公开一部分的说明书附图用来提供对本公开的进一步理解,本公开的示意性实施例及其说明用于解释本公开,并不构成对本公开的不当限定。The accompanying drawings forming part of this disclosure are used to provide a further understanding of this disclosure. The exemplary embodiments of this disclosure and their descriptions are used to explain this disclosure and do not constitute an undue limitation of this disclosure.
图1为裸电极(a)、g-C 3N 4(b)、CuO(c)、CNT(d)、CNT/g-C 3N 4(e)、CuO/CNT/g-C 3N 4(f)修饰电极在对乙酰氨基酚浓度为200μM的PBS缓冲溶液(pH=7.00)中的CV曲线,其扫速为100mV/s。 Figure 1 shows the bare electrode (a), gC 3 N 4 (b), CuO (c), CNT (d), CNT / gC 3 N 4 (e), CuO / CNT / gC 3 N 4 (f) modified electrode The CV curve in a PBS buffer solution (pH = 7.00) with a paracetamol concentration of 200 μM has a sweep rate of 100 mV / s.
图2CuO/CNT/g-C 3N 4修饰电极在不同浓度的乙酰氨基酚的PBS缓冲溶液(pH=7.0)中测得的SWV曲线。其中,乙酰氨基酚浓度为0.02μM,0.04μM,0.06μM,0.08μM,0.1μM(A、B),1μM,15μM,30μΜ,45μΜ,60μM,75μM,90μM,105μM,120μM(C、D)。 Figure 2 SWV curves of CuO / CNT / gC 3 N 4 modified electrode measured in different concentrations of acetaminophen in PBS buffer solution (pH = 7.0). Among them, the acetaminophen concentration is 0.02 μM, 0.04 μM, 0.06 μM, 0.08 μM, 0.1 μM (A, B), 1 μM, 15 μM, 30 μM, 45 μM, 60 μM, 75 μM, 90 μM, 105 μM, 120 μM (C, D).
图3是氮化碳(A)、碳纳米管/氮化碳(B)和氧化铜/碳纳米管/氮化碳(C)的透射电镜图。3 is a transmission electron micrograph of carbon nitride (A), carbon nanotube / carbon nitride (B), and copper oxide / carbon nanotube / carbon nitride (C).
具体实施方式detailed description
应该指出,以下详细说明都是示例性的,旨在对本公开提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本公开所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanations of the present disclosure. Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this disclosure belongs.
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本公开的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图 包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作和/或它们的组合。It should be noted that the terminology used herein is for describing specific embodiments only, and is not intended to limit exemplary embodiments according to the present disclosure. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should also be understood that when the terms "comprising" and / or "including" are used in this specification, There are features, steps, operations, and / or combinations thereof.
在本公开的第一个典型的实施方式中,提供一种氧化铜/碳纳米管/氮化碳复合材料的制备方法,该方法包括以下步骤:将羧基化碳纳米管、氮化碳和水混合均匀,进行超声处理;然后加入醋酸铜,混匀,进行超声处理;超声处理后进行干燥,再在惰性气体氛围下进行煅烧,煅烧后得到氧化铜/碳纳米管/氮化碳复合材料。In a first typical embodiment of the present disclosure, a method for preparing a copper oxide / carbon nanotube / carbon nitride composite material is provided. The method includes the following steps: the carboxylated carbon nanotube, carbon nitride, and water Mix evenly and perform ultrasonic treatment; then add copper acetate, mix and perform ultrasonic treatment; after ultrasonic treatment, dry and then calcinate under an inert gas atmosphere to obtain copper oxide / carbon nanotube / carbon nitride composite materials after calcination.
g-C 3N 4的内在结构具有丰富均匀的氮配位剂,能够在电催化过程中提供更多的金属配位点作为催化活性位点。g-C 3N 4中的N原子和Cu原子之间的强配位作用可以提高增加复合材料的活性位点,进而提高材料整体的电催化活性。不同配比量的原料制备得到的CuO/CNT/g-C 3N 4复合材料的催化性能不同,在本公开的一个或一些具体的实施方式中,所述羧基化碳纳米管、氮化碳、水和醋酸铜的比例为(10~30)mg:(5~15)mg:(5~20)mL(5~6)mg。经试验验证,上述配比使得该CuO/CNT/g-C 3N 4复合材料的催化性能较好,获得良好的对乙酰氨基酚检测效果。 The internal structure of gC 3 N 4 has a rich and uniform nitrogen coordination agent, which can provide more metal coordination sites as catalytic active sites during the electrocatalysis process. The strong coordination between the N atom and Cu atom in gC 3 N 4 can increase the active site of the composite material, thereby improving the overall electrocatalytic activity of the material. CuO / CNT / gC 3 N 4 composite materials prepared with different proportions of raw materials have different catalytic properties. In one or some specific embodiments of the present disclosure, the carboxylated carbon nanotubes, carbon nitride, and water The ratio to copper acetate is (10-30) mg: (5-15) mg: (5-20) mL (5-6) mg. It has been verified by experiments that the above-mentioned ratio makes the CuO / CNT / gC 3 N 4 composite material have better catalytic performance and a good detection effect of acetaminophen.
在本公开的一个或一些具体的实施方式中,将羧基化碳纳米管、氮化碳和水混合均匀,超声处理时间为1~2.5h。进一步的,超声处理时间为2h。In one or some specific embodiments of the present disclosure, the carboxylated carbon nanotubes, carbon nitride, and water are uniformly mixed, and the ultrasonic treatment time is 1 to 2.5 hours. Further, the sonication time is 2h.
在制备CuO/CNT/g-C 3N 4复合材料时,本公开首先将g-C 3N 4与羧基化的碳纳米管进行复合,使得碳纳米管能够进入g-C 3N 4的层间,增加了复合材料的表面积,同时,这样操作使复合材料整体的导电性能得到良好的改善。 When preparing a CuO / CNT / gC 3 N 4 composite material, the present disclosure first composites gC 3 N 4 with carboxylated carbon nanotubes so that the carbon nanotubes can enter the gC 3 N 4 layer, increasing the composite material At the same time, this operation makes the overall conductivity of the composite material well improved.
在本公开的一个或一些具体的实施方式中,加入醋酸铜,混匀,超声处理时间为3~4h。进一步的,超声处理时间为3h。In one or some specific embodiments of the present disclosure, copper acetate is added and mixed, and the ultrasonic treatment time is 3 to 4 hours. Further, the sonication time is 3h.
煅烧温度过高或过低均不能得到理想形貌的氧化铜/碳纳米管/氮化碳复合材料。在本公开的一个或一些具体的实施方式中,煅烧温度为500~600℃,煅烧时间为2~4h。进一步的,煅烧温度为520℃,煅烧时间为3h。If the calcination temperature is too high or too low, the copper oxide / carbon nanotube / carbon nitride composite material with ideal morphology cannot be obtained. In one or some specific embodiments of the present disclosure, the calcination temperature is 500-600 ° C, and the calcination time is 2-4h. Further, the calcination temperature is 520 ° C and the calcination time is 3h.
在本公开的一个或一些具体的实施方式中,所述惰性气体为氩气或氦气等。In one or some specific embodiments of the present disclosure, the inert gas is argon or helium.
在本公开的一个或一些具体的实施方式中,提供一种羧基化碳纳米管的制备方法,该方法包括:将碳纳米管和浓硝酸混合,然后进行超声处理,再用水清洗至中性,最后将清洗好的碳纳米管干燥,取出后得到干燥的羧基化碳纳米管。羧基化的目的是使碳纳米管表面接上羧基基团,进而与氮化碳表面氨基基团结合,形成复合材料。In one or some specific embodiments of the present disclosure, a method for preparing carboxylated carbon nanotubes is provided. The method includes: mixing carbon nanotubes with concentrated nitric acid, then performing ultrasonic treatment, and then cleaning with water until neutral, Finally, the washed carbon nanotubes are dried, and then taken out to obtain dried carboxylated carbon nanotubes. The purpose of carboxylation is to attach carboxyl groups on the surface of carbon nanotubes, and then combine with amino groups on the surface of carbon nitride to form a composite material.
进一步的,所述碳纳米管的直径为40-60nm,长度大于5μm,购自深圳纳米港科技有限公司。选择的依据是根据氮化碳材料的尺寸(氮化碳纳米片的尺寸大约为1-2μm)来确定的,碳纳米管直径不能太大,长度尽量长一些,这样有利于后续反应的进行。Further, the carbon nanotubes have a diameter of 40-60 nm and a length greater than 5 μm, and were purchased from Shenzhen Nanoport Technology Co., Ltd. The selection basis is determined according to the size of the carbon nitride material (the size of the carbon nitride nanosheet is about 1-2 μm). The diameter of the carbon nanotubes should not be too large, and the length should be as long as possible, which is conducive to the subsequent reaction.
进一步的,所述碳纳米管与浓硝酸的添加比例为(30~50)mg:(15~25)mL;所述浓硝酸的质量分数为95~98%。Further, the addition ratio of the carbon nanotubes and concentrated nitric acid is (30-50) mg: (15-25) mL; the mass fraction of the concentrated nitric acid is 95-98%.
在本公开的一个或一些具体的实施方式中,提供一种氮化碳的制备方法,该方法包括:In one or some specific embodiments of the present disclosure, a method for preparing carbon nitride is provided. The method includes:
以二氰二胺、尿素或三聚氰胺为原料,在惰性气体的气氛下进行一次煅烧得到浅黄色块状固体g-C 3N 4,然后制成粉末,再在惰性气体的气氛下进行二次煅烧得到深黄色粉末g-C 3N 4Using dicyandiamine, urea or melamine as raw materials, primary calcination under an inert gas atmosphere yields a pale yellow solid gC 3 N 4 , which is then powdered, followed by secondary calcination under an inert gas atmosphere. Yellow powder gC 3 N 4 .
进一步的,为了使g-C 3N 4的产率较高,所述原料为三聚氰胺。 Further, in order to make the yield of gC 3 N 4 higher, the raw material is melamine.
进一步的,所述惰性气体为氩气。Further, the inert gas is argon.
为得到表面积较大的g-C 3N 4,所述一次煅烧或二次煅烧中,煅烧温度为500~600℃,升温速率为2.5~3.5℃/min。 In order to obtain gC 3 N 4 with a large surface area, in the primary calcination or secondary calcination, the calcination temperature is 500-600 ° C., and the heating rate is 2.5-3.5 ° C./min.
进一步的,所述煅烧温度为550℃,升温速率为3℃/min。Further, the calcination temperature is 550 ° C, and the heating rate is 3 ° C / min.
进一步的,所述一次煅烧中,煅烧时间为4.5~5.5h。Further, in the primary calcination, the calcination time is 4.5 to 5.5 hours.
更进一步的,所述煅烧时间为5h。Furthermore, the calcination time is 5h.
进一步的,所述二次煅烧中,煅烧时间为1.5~2.5h。在惰性气体的保护下进行二次煅烧目的是剥离氮化碳纳米片。Further, in the secondary calcination, the calcination time is 1.5 to 2.5 hours. The purpose of secondary calcination under the protection of inert gas is to peel off the carbon nitride nanosheets.
更进一步的,所述煅烧时间为2h。Furthermore, the calcination time is 2h.
通过以上方法制备得到的片层状微观形貌的g-C 3N 4,为氧化铜均匀负载提供前提以及为碳纳米管插入提供基础。 The lamellar micromorphology of gC 3 N 4 prepared by the above method provides the premise for uniform loading of copper oxide and the foundation for the insertion of carbon nanotubes.
在本公开的第二个典型的实施方式中,提供采用上述方法制备得到的氧化铜/碳纳米管/氮化碳复合材料。In a second typical embodiment of the present disclosure, a copper oxide / carbon nanotube / carbon nitride composite material prepared by the above method is provided.
氮化碳(g-C 3N 4)是由氮取代碳六环单元组成的二维结构。g-C 3N 4固有的丰富的氮活性位点和优异的催化活性使得其在众多领域具有广阔的应用前景。作为p型半导体金属氧化物,氧化铜在气体传感,锂离子电池和催化等领域具有潜在的应用前景。g-C 3N 4中的N原子和Cu原子之间的强配位作用可以使CuO均匀的负载到g-C 3N 4表面,同时CuO与g-C 3N 4间形异质结界面,这有利于提升复合材料的催化性能。但由于导电性差,CuO/g-C 3N 4的潜在电化学催化性能大大降低,这也导致其在电化学传感器的应用方面受到限制。碳纳米管由于具有独特的π-共轭结构,高导电性和大的比表面积,其独特的结构可以与其他纳米材料如石墨烯、离子液体,纳米颗粒等复合,产生协同作用,进一步提高电化学灵敏度。 Carbon nitride (gC 3 N 4 ) is a two-dimensional structure composed of nitrogen substituted carbon six ring units. The inherently rich nitrogen active sites and excellent catalytic activity of gC 3 N 4 make it have broad application prospects in many fields. As a p-type semiconductor metal oxide, copper oxide has potential application prospects in the fields of gas sensing, lithium ion batteries, and catalysis. the strong complexation between the gC 3 N 4 N atoms and can be made of Cu atoms to CuO uniform loading surface 3 N 4 gC, and CuO while gC 3 N 4 heterojunction interface between reflector shape, which is conducive to enhance composite The catalytic performance of the material. However, due to poor conductivity, the potential electrochemical catalytic performance of CuO / gC 3 N 4 is greatly reduced, which also limits its application in electrochemical sensors. Carbon nanotubes have a unique π-conjugated structure, high conductivity and large specific surface area. Its unique structure can be combined with other nanomaterials such as graphene, ionic liquids, nanoparticles, etc. Chemical sensitivity.
在本公开的第三个典型的实施方式中,提供所述氧化铜/碳纳米管/氮化碳复合材料在制备检测对乙酰氨基酚电化学传感器中的应用。In a third typical embodiment of the present disclosure, the application of the copper oxide / carbon nanotube / carbon nitride composite material in preparing an electrochemical sensor for detecting acetaminophen is provided.
在本公开的第四个典型的实施方式中,提供一种检测对乙酰氨基酚电化学传感器,该 电化学传感器包括基底电极;以及,In a fourth exemplary embodiment of the present disclosure, an electrochemical sensor for detecting paracetamol is provided, the electrochemical sensor includes a substrate electrode; and,
所述氧化铜/碳纳米管/氮化碳复合材料,该复合材料附着在所述基底电极上。The copper oxide / carbon nanotube / carbon nitride composite material is attached to the base electrode.
在本公开的一个或一些具体的实施方式中,所述基底电极为玻碳电极。In one or some specific embodiments of the present disclosure, the base electrode is a glassy carbon electrode.
在本公开的第五个典型的实施方式中,提供所述检测对乙酰氨基酚电化学传感器的制备方法,该方法包括:In a fifth typical embodiment of the present disclosure, a preparation method of the electrochemical sensor for detecting acetaminophen is provided. The method includes:
首先,将得到的氧化铜/碳纳米管/氮化碳复合材料用水洗涤之后,干燥,用水分散成浓度为0.5~1.5mg/ml的分散液:其次,将基底电极先用铝粉进行打磨,分别采用乙醇和水进行超声清洗,用氮气吹干后,取所述分散液滴涂到电极上,制备氧化铜/碳纳米管/氮化碳修饰电极,即为检测对乙酰氨基酚电化学传感器。First, the obtained copper oxide / carbon nanotube / carbon nitride composite material is washed with water, dried, and dispersed into a dispersion liquid with a concentration of 0.5 to 1.5 mg / ml with water: secondly, the base electrode is first polished with aluminum powder, Separately use ethanol and water for ultrasonic cleaning. After blowing dry with nitrogen, apply the dispersed droplets to the electrode to prepare a copper oxide / carbon nanotube / carbon nitride modified electrode, which is an electrochemical sensor for detecting acetaminophen .
在本公开的第六个典型的实施方式中,提供所述电化学传感器在检测对乙酰氨基酚中的应用。In a sixth exemplary embodiment of the present disclosure, the application of the electrochemical sensor in detecting acetaminophen is provided.
在本公开的第七个典型的实施方式中,提供一种非诊断目的的对乙酰氨基酚的检测方法,该方法包括以下步骤:In a seventh exemplary embodiment of the present disclosure, a method for detecting acetaminophen for non-diagnostic purposes is provided. The method includes the following steps:
(1)标准溶液的配制:配制一组不同浓度的对乙酰氨基酚标准溶液;(1) Preparation of standard solution: prepare a set of acetaminophen standard solutions with different concentrations;
(2)工作曲线的绘制:将所述电化学传感器置于所述不同浓度的对乙酰氨基酚标准溶液中进行方波伏安测试,得到不同浓度的乙酰氨基酚标准溶液的响应峰电流,再根据对乙酰氨基酚标准溶液的浓度以及响应峰电流,绘制线性关系曲线;(2) Drawing of the working curve: place the electrochemical sensor in the acetaminophen standard solution of different concentrations and perform square wave voltammetry to obtain the response peak current of the acetaminophen standard solution of different concentrations, and then According to the concentration of acetaminophen standard solution and the response peak current, draw a linear relationship curve;
(3)样品的检测:将所述电化学传感器置于待测样品中进行方波伏安测试,得到该待测样品的响应峰电流,再根据所述线性关系曲线,得到待测样品中对乙酰氨基酚的浓度。(3) Detection of the sample: place the electrochemical sensor in the sample to be tested for square wave voltammetry to obtain the response peak current of the sample to be tested, and then obtain the response of the sample to be tested according to the linear relationship curve The concentration of acetaminophen.
进一步的,所述线性关系曲线为I(μA)=0.5024c APAP(μM)+10.1169,相关系数为0.9985,C CAP为对乙酰氨基酚的浓度,浓度范围为1至120μM。 Further, the linear relationship curve is I (μA) = 0.5024c APAP (μM) +10.1169, the correlation coefficient is 0.9985, C CAP is the concentration of acetaminophen, and the concentration range is 1 to 120 μM.
为了使得本领域技术人员能够更加清楚地了解本公开的技术方案,以下将结合具体的实施例详细说明本公开的技术方案。In order to enable those skilled in the art to understand the technical solutions of the present disclosure more clearly, the technical solutions of the present disclosure will be described in detail below in conjunction with specific embodiments.
实施例1氮化碳(g-C 3N 4)的制备 Example 1 Preparation of carbon nitride (gC 3 N 4 )
称取3g三聚氰胺,在氩气的气氛中,以3℃/min的升温速率加热至550℃,并保持5小时。结束后,使其自然冷却至室温取出,得到浅黄色的块状氮化碳固体。将上述得到的氮化碳固体放于研钵中研磨成粉末,然后上述合成条件相同的环境中再次煅烧2小时后,待其自然冷却至室温后,得到深黄色的氮化碳粉末。取50mg氮化碳,分散于二次水中,分散浓度为2mg/mL。Weigh 3g of melamine and heat to 550 ° C at a temperature increase rate of 3 ° C / min in an argon atmosphere and hold it for 5 hours. After the end, it was naturally cooled to room temperature and taken out to obtain a light yellow solid carbon nitride solid. The carbon nitride solid obtained above was put into a mortar and ground into a powder, and then calcined again in the same environment under the above synthesis conditions for 2 hours, and after it was naturally cooled to room temperature, a deep yellow carbon nitride powder was obtained. Take 50 mg of carbon nitride and disperse it in secondary water with a dispersion concentration of 2 mg / mL.
实施例2羧基化碳纳米管(CNT)Example 2 Carboxylated Carbon Nanotubes (CNT)
称取40mg碳纳米管于烧杯中,加入20mL浓硝酸(98w/w%),超声六小时后取出, 用二次水清洗至中性,将清洗好的碳纳米管转移至真空干燥箱中,在60℃下干燥24小时,取出后得到干燥的羧基化碳纳米管,将其分散在水溶液中,浓度为2mg/mL。Weigh 40mg carbon nanotubes in a beaker, add 20mL concentrated nitric acid (98w / w%), take out after 6 hours of ultrasound, wash with secondary water until neutral, transfer the cleaned carbon nanotubes to a vacuum drying oven, It was dried at 60 ° C for 24 hours, and after taking out, dried carboxylated carbon nanotubes were obtained, which were dispersed in an aqueous solution at a concentration of 2 mg / mL.
实施例3 CNT/g-C 3N 4复合材料的制备 Example 3 Preparation of CNT / gC 3 N 4 composite material
取10mL实施例2中的碳纳米管水溶液(2mg/mL),加入5mL实施例1中的氮化碳水溶液(2mg/mL),超声5小时后取出,在真空干燥试验箱60℃真空干燥后转移至管式炉中,以4℃/min的升温速率加热至520℃,并保持三个小时,在此过程中须通入氩气保护。Take 10 mL of the carbon nanotube aqueous solution in Example 2 (2 mg / mL), add 5 mL of the carbon nitride aqueous solution in Example 1 (2 mg / mL), take out after 5 hours of ultrasound, and vacuum-dry in a vacuum drying test box at 60 ° Transfer to a tube furnace, heat to 520 ° C at a heating rate of 4 ° C / min, and hold for three hours. During this process, argon gas must be passed to protect.
实施例4 CuO/CNT/g-C 3N 4复合材料的制备 Example 4 Preparation of CuO / CNT / gC 3 N 4 composite material
取10mL实施例2中的碳纳米管水溶液(2mg/mL),加入5mL实施例1中的氮化碳水溶液(2mg/mL),超声2小时后,加入0.0053g醋酸铜粉末,继续超声震荡3小时。超声结束后,在真空干燥试验箱60℃真空干燥后转移至管式炉中,以4℃/min的升温速率加热至520℃,并保持三个小时,在此过程中须通入氩气保护。Take 10 mL of the carbon nanotube aqueous solution in Example 2 (2 mg / mL), add 5 mL of the carbon nitride aqueous solution in Example 1 (2 mg / mL), after sonication for 2 hours, add 0.0053 g of copper acetate powder, and continue ultrasonic vibration 3 hour. After the ultrasound is completed, it is vacuum-dried in a vacuum drying test box at 60 ° C and then transferred to a tube furnace, heated to 520 ° C at a heating rate of 4 ° C / min, and maintained for three hours. During this process, it must be protected by argon gas. .
经过二次煅烧以后的氮化碳纳米片(实施例1中)呈现出薄薄的片层状结构,其透射电镜图显示在图3A中。将实施例2中的CNT加入后,超声一段时间后得到了图3B所显示的结果,从图中可以看出,碳纳米管是成功的掺入到氮化碳表面的。图3C显示的是实施例4中氧化铜/碳纳米管/氮化碳复合材料的透射电镜图,从图中可以看出,当加入醋酸铜超声搅拌并煅烧后,在氮化碳的表面有氧化铜颗粒出现,其尺寸介于20-40nm之间。After the second calcination, the carbon nitride nanosheet (in Example 1) exhibits a thin sheet-like structure, and its transmission electron microscope image is shown in FIG. 3A. After the CNT in Example 2 was added, the results shown in FIG. 3B were obtained after sonication for a period of time. It can be seen from the figure that the carbon nanotubes were successfully incorporated into the surface of carbon nitride. Figure 3C shows the transmission electron micrograph of the copper oxide / carbon nanotube / carbon nitride composite material in Example 4. As can be seen from the figure, when copper acetate is added to the ultrasonic stirring and calcination, there are Copper oxide particles appear, whose size is between 20-40nm.
实施例5Example 5
检测对乙酰氨基酚电化学传感器的制备Preparation of electrochemical sensor for detecting acetaminophen
首先,将得到的氧化铜/碳纳米管/氮化碳复合材料用二次水洗涤之后,在真空干燥箱中烘干,用二次水分散成浓度为1mg/ml的分散液:其次,将基底电极先用铝粉进行打磨,分别采用乙醇和二次水进行超声清洗,用氮气吹干后,取6微升上述分散液滴涂到电极上,制备氧化铜/碳纳米管/氮化碳修饰电极,即为检测对乙酰氨基酚电化学传感器。First, after washing the obtained copper oxide / carbon nanotube / carbon nitride composite material with secondary water, it is dried in a vacuum drying oven and dispersed into a dispersion liquid with a concentration of 1 mg / ml with secondary water: secondly, the The base electrode was first polished with aluminum powder, ultrasonically cleaned with ethanol and secondary water, and dried with nitrogen, and then 6 microliters of the above dispersed droplets were applied to the electrode to prepare copper oxide / carbon nanotube / carbon nitride The modified electrode is an electrochemical sensor for detecting acetaminophen.
实施例6电化学测试Example 6 Electrochemical test
本测试使用循环伏安法(CV)和方波伏安法检测(SWV)。具体操作是:将已制备好的修饰电极与参比电极(银/氯化银电极)及对电极一起构建三电极体系,然后将此三电极体系置于浓度为0.2mM乙酰氨基酚的PBS缓冲溶液(pH=7.0)中,最后进行电化学检测。循环伏安法(CV)中其扫速设置为100mV/s。This test uses cyclic voltammetry (CV) and square wave voltammetry (SWV). The specific operation is to construct the three-electrode system with the prepared modified electrode, the reference electrode (silver / silver chloride electrode) and the counter electrode, and then place the three-electrode system in PBS buffer with a concentration of 0.2mM acetaminophen In the solution (pH = 7.0), the electrochemical detection is finally carried out. In cyclic voltammetry (CV), the sweep speed is set to 100mV / s.
图1显示了不同修饰电极在对乙酰氨基酚浓度为200μM的PBS缓冲溶液(pH=7.00)中的CV曲线。由图可以看出CuO/CNT/g-C 3N 4修饰电极的双电层面积较裸电极大,这说明CuO/CNT/g-C 3N 4修饰电极的CV曲线的面积与裸电极的CV曲线的面积相比是增加的。在对乙酰氨基酚存在下,在大约+0.45V的裸电极(a)中出现宽峰,这由对乙酰氨基酚的电 化学氧化引起的。然而,还原峰不显著,表明由于不可逆的氧化过程在裸电极处发生的电子转移速率缓慢。而对于CuO/CNT/g-C 3N 4修饰电极,在+0.3V到+0.4V之间出现了一对明显的可逆氧化还原峰,同时,CuO/CNT/g-C 3N 4修饰电极的对乙酰氨基酚的氧化峰与裸电极的氧化峰相比,其峰电流值约是裸电极的6倍。此外,CuO/CNT/g-C 3N 4修饰电极的氧化还原峰电位相对于裸电极都发生了偏移,这也说明CuO/CNT/g-C 3N 4修饰电极能够有效的促进对乙酰氨基酚的氧化。CV曲线中氧化还原峰的位置和强度表明制备的CuO/CNT/g-C 3N 4修饰电极对对乙酰氨基酚具有良好的催化作用。 Figure 1 shows the CV curve of different modified electrodes in PBS buffer solution (pH = 7.00) with a paracetamol concentration of 200 μM. It can be seen from the figure that the electric double layer area of the CuO / CNT / gC 3 N 4 modified electrode is larger than that of the bare electrode, which shows that the area of the CV curve of the CuO / CNT / gC 3 N 4 modified electrode and the area of the CV curve of the bare electrode The comparison is increased. In the presence of acetaminophen, a broad peak appeared in the bare electrode (a) of approximately + 0.45V, which was caused by the electrochemical oxidation of acetaminophen. However, the reduction peak is not significant, indicating that the electron transfer rate occurring at the bare electrode due to the irreversible oxidation process is slow. For the CuO / CNT / gC 3 N 4 modified electrode, a pair of reversible redox peaks appeared between + 0.3V and + 0.4V. At the same time, the acetamido group of the CuO / CNT / gC 3 N 4 modified electrode Compared with the oxidation peak of the bare electrode, the peak current value of phenol is about 6 times that of the bare electrode. In addition, the redox peak potential of the CuO / CNT / gC 3 N 4 modified electrode is shifted relative to the bare electrode, which also shows that the CuO / CNT / gC 3 N 4 modified electrode can effectively promote the oxidation of acetaminophen . The position and intensity of the redox peak in the CV curve indicate that the prepared CuO / CNT / gC 3 N 4 modified electrode has a good catalytic effect on acetaminophen.
实施例7一种检测对乙酰氨基酚的方法Example 7 A method for detecting acetaminophen
(1)标准溶液的配制:配制一组不同浓度的对乙酰氨基酚标准溶液;(1) Preparation of standard solution: prepare a set of acetaminophen standard solutions with different concentrations;
(2)工作曲线的绘制:将实施例5的电化学传感器置于所述不同浓度的对乙酰氨基酚标准溶液中进行方波伏安测试,得到不同浓度的乙酰氨基酚标准溶液的响应峰电流,再根据对乙酰氨基酚标准溶液的浓度以及响应峰电流,绘制线性关系曲线;(2) Drawing of working curve: place the electrochemical sensor of Example 5 in the acetaminophen standard solutions of different concentrations and perform square wave voltammetry to obtain the response peak current of acetaminophen standard solutions of different concentrations , And then draw a linear relationship curve according to the concentration of acetaminophen standard solution and the response peak current;
(3)样品的检测:将实施例5的电化学传感器置于待测样品中进行方波伏安测试,得到该待测样品的响应峰电流,再根据所述线性关系曲线,得到待测样品中对乙酰氨基酚的浓度。(3) Detection of the sample: place the electrochemical sensor of Example 5 in the sample to be tested for square wave voltammetry to obtain the response peak current of the sample to be tested, and then obtain the sample to be tested according to the linear relationship curve The concentration of acetaminophen in the medium.
图2是在最优条件下(0.1M pH为7的磷酸盐缓冲溶液),使用实施例5的电化学传感器通过方波伏安法检测不同浓度的对乙酰氨基酚。如图所示,随着对乙酰氨基酚浓度的增加,氧化峰值电流逐渐增强。从图2A和图2B可以看出,氧化峰电流与对乙酰氨基酚浓度之间呈线性关系,其线性方程为:I(μA)=51c APAP(μM)+0.394,相关系数为0.9959,浓度范围为0.02至0.1μM;从图2C和图2D可以看出,氧化峰电流与对乙酰氨基酚浓度之间呈线性关系,其线性方程为:I(μA)=0.5024c APAP(μM)+10.1169,相关系数为0.9985,浓度范围为1至120μM;最低检测线为0.00609μM(S/N=3)。 Fig. 2 shows that under the optimal conditions (0.1M phosphate buffer solution with pH 7), the electrochemical sensor of Example 5 was used to detect different concentrations of acetaminophen by square wave voltammetry. As shown in the figure, as the concentration of acetaminophen increases, the peak oxidation current gradually increases. It can be seen from Figures 2A and 2B that the peak current of oxidation is linearly related to the concentration of acetaminophen. The linear equation is: I (μA) = 51c APAP (μM) + 0.394, the correlation coefficient is 0.9959, the concentration range It is 0.02 to 0.1μM; as can be seen from Figure 2C and Figure 2D, the oxidation peak current is linearly related to the acetaminophen concentration, the linear equation is: I (μA) = 0.5024c APAP (μM) + 10.11169, The correlation coefficient is 0.9985 and the concentration range is 1 to 120 μM; the lowest detection line is 0.00609 μM (S / N = 3).
上述实施例为本公开较佳的实施方式,但本公开的实施方式并不受上述实施例的限制,其他的任何未背离本公开的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本公开的保护范围之内。The above embodiments are preferred embodiments of the present disclosure, but the embodiments of the present disclosure are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, changes, modifications, substitutions, combinations, The simplifications should all be equivalent replacement methods, which are all included in the protection scope of the present disclosure.

Claims (10)

  1. 一种氧化铜/碳纳米管/氮化碳复合材料的制备方法,其特征是,该方法包括以下步骤:将羧基化碳纳米管、氮化碳和水混合均匀,进行超声处理;然后加入醋酸铜,混匀,进行超声处理;超声处理后进行干燥,再在惰性气体氛围下进行煅烧,煅烧后得到氧化铜/碳纳米管/氮化碳复合材料。A method for preparing a copper oxide / carbon nanotube / carbon nitride composite material, characterized in that the method includes the following steps: mixing the carboxylated carbon nanotube, carbon nitride and water uniformly, and performing ultrasonic treatment; then adding acetic acid Copper, mix well, and perform ultrasonic treatment; after ultrasonic treatment, dry, and then calcinate in an inert gas atmosphere, and then obtain a copper oxide / carbon nanotube / carbon nitride composite material after calcination.
  2. 如权利要求1所述的制备方法,其特征是,羧基化碳纳米管、氮化碳、水和醋酸铜的比例为(10~30)mg:(5~15)mg:(5~20)mL(5~6)mg;The preparation method according to claim 1, wherein the ratio of carboxylated carbon nanotubes, carbon nitride, water and copper acetate is (10-30) mg: (5-15) mg: (5-20) mL (5 ~ 6) mg;
    进一步的,将羧基化碳纳米管、氮化碳和水混合均匀,超声处理时间为1~2.5h;Further, the carboxylated carbon nanotubes, carbon nitride and water are mixed evenly, and the ultrasonic treatment time is 1 to 2.5 hours;
    进一步的,加入醋酸铜,混匀,超声处理时间为3~4h;Further, add copper acetate, mix well, ultrasonic treatment time is 3 ~ 4h;
    进一步的,煅烧温度为500~600℃,煅烧时间为2~4h;Further, the calcination temperature is 500 to 600 ° C, and the calcination time is 2 to 4 hours;
    进一步的,所述惰性气体为氩气或氦气。Further, the inert gas is argon or helium.
  3. 如权利要求1所述的制备方法,其特征是,羧基化碳纳米管的制备方法,该方法包括:将碳纳米管和浓硝酸混合,然后进行超声处理,再用水清洗至中性,最后将清洗好的碳纳米管干燥,取出后得到干燥的羧基化碳纳米管;The preparation method according to claim 1, characterized in that the preparation method of the carboxylated carbon nanotubes includes: mixing the carbon nanotubes and concentrated nitric acid, then performing ultrasonic treatment, and then cleaning with water until neutral, and finally The cleaned carbon nanotubes are dried, and after taking out, dried carboxylated carbon nanotubes are obtained;
    进一步的,所述碳纳米管的直径为40-60nm,长度大于5μm;Further, the diameter of the carbon nanotube is 40-60 nm, and the length is greater than 5 μm;
    进一步的,所述碳纳米管与浓硝酸的添加比例为(30~50)mg:(15~25)mL;所述浓硝酸的质量分数为95~98%;或者,Further, the addition ratio of the carbon nanotubes and concentrated nitric acid is (30-50) mg: (15-25) mL; the mass fraction of the concentrated nitric acid is 95-98%; or,
    氮化碳的制备方法,该方法包括以下步骤:The preparation method of carbon nitride, the method includes the following steps:
    以二氰二胺、尿素或三聚氰胺为原料,在惰性气体的气氛下进行一次煅烧得到浅黄色块状固体g-C 3N 4,然后制成粉末,再在惰性气体的气氛下进行二次煅烧得到深黄色粉末g-C 3N 4Using dicyandiamine, urea or melamine as raw materials, primary calcination under an inert gas atmosphere yields a pale yellow solid gC 3 N 4 , which is then powdered, followed by secondary calcination under an inert gas atmosphere. Yellow powder gC 3 N 4 ;
    进一步的,一次煅烧或二次煅烧中,煅烧温度为500~600℃,升温速率为2.5~3.5℃/min;Further, in the primary calcination or secondary calcination, the calcination temperature is 500-600 ° C, and the heating rate is 2.5-3.5 ° C / min;
    进一步的,一次煅烧中,煅烧时间为4.5~5.5h;Further, in one calcination, the calcination time is 4.5-5.5h;
    进一步的,二次煅烧中,煅烧时间为1.5~2.5h。Further, in the secondary calcination, the calcination time is 1.5 to 2.5 hours.
  4. 采用权利要求1~3中任一项所述的方法制备得到的氧化铜/碳纳米管/氮化碳复合材料。The copper oxide / carbon nanotube / carbon nitride composite material prepared by the method according to any one of claims 1 to 3.
  5. 权利要求4所述的氧化铜/碳纳米管/氮化碳复合材料在制备检测对乙酰氨基酚电化学传感器中的应用。The application of the copper oxide / carbon nanotube / carbon nitride composite material according to claim 4 in the preparation and detection of an acetaminophen electrochemical sensor.
  6. 一种检测对乙酰氨基酚电化学传感器,其特征是,该电化学传感器包括基底电极;以及,An electrochemical sensor for detecting paracetamol, characterized in that the electrochemical sensor includes a base electrode; and,
    权利要求4所述氧化铜/碳纳米管/氮化碳复合材料,该复合材料附着在所述基底电极上;The copper oxide / carbon nanotube / carbon nitride composite material according to claim 4, which is attached to the base electrode;
    进一步的,所述基底电极为玻碳电极。Further, the base electrode is a glassy carbon electrode.
  7. 权利要求6所述的检测对乙酰氨基酚电化学传感器的制备方法,其特征是,该方法包括:The preparation method of the electrochemical sensor for detecting acetaminophen according to claim 6, wherein the method comprises:
    首先,将氧化铜/碳纳米管/氮化碳复合材料用水洗涤之后,干燥,用水分散成浓度为0.5~1.5mg/ml的分散液:其次,将基底电极先用铝粉进行打磨,分别采用乙醇和水进行超声清洗,用氮气吹干后,取所述分散液滴涂到电极上,制备氧化铜/碳纳米管/氮化碳修饰电极,即为检测对乙酰氨基酚电化学传感器。First, the copper oxide / carbon nanotube / carbon nitride composite material is washed with water, dried, and dispersed into a dispersion liquid with a concentration of 0.5 to 1.5 mg / ml with water: secondly, the base electrode is first polished with aluminum powder, respectively Ethanol and water are ultrasonically cleaned, dried with nitrogen, and the dispersed droplets are coated on the electrode to prepare a copper oxide / carbon nanotube / carbon nitride modified electrode, which is an electrochemical sensor for detecting acetaminophen.
  8. 权利要求6所述电化学传感器在检测对乙酰氨基酚中的应用。The use of the electrochemical sensor according to claim 6 in detecting acetaminophen.
  9. 一种检测对乙酰氨基酚的检测方法,其特征是,该方法包括采用权利要求6所述的电化学传感器进行检测步骤。A detection method for detecting acetaminophen, characterized in that the method includes the detection step using the electrochemical sensor according to claim 6.
  10. 如权利要求9所述的方法,其特征是:(1)标准溶液的配制:配制一组不同浓度的对乙酰氨基酚标准溶液;The method according to claim 9, characterized in that: (1) the preparation of a standard solution: preparing a set of acetaminophen standard solutions with different concentrations;
    (2)工作曲线的绘制:将权利要求6所述电化学传感器置于所述不同浓度的对乙酰氨基酚标准溶液中进行方波伏安测试,得到不同浓度的乙酰氨基酚标准溶液的响应峰电流,再根据对乙酰氨基酚标准溶液的浓度以及响应峰电流,绘制线性关系曲线;(2) Drawing of working curve: place the electrochemical sensor of claim 6 in the acetaminophen standard solution of different concentrations to perform square wave voltammetry to obtain the response peaks of the acetaminophen standard solution of different concentrations Current, and then draw a linear relationship curve according to the concentration of acetaminophen standard solution and the response peak current;
    (3)样品的检测:将权利要求6所述电化学传感器置于待测样品中进行方波伏安测试,得到该待测样品的响应峰电流,再根据所述线性关系曲线,得到待测样品中对乙酰氨基酚的浓度。(3) Detection of the sample: place the electrochemical sensor according to claim 6 in the sample to be tested for square wave voltammetry to obtain the response peak current of the sample to be tested, and then obtain the test to be tested according to the linear relationship curve The concentration of acetaminophen in the sample.
PCT/CN2019/111754 2018-11-22 2019-10-17 Copper oxide/carbon nanotube/carbon nitride electrochemical sensor for detecting acetaminophen, preparation method therefor and application thereof WO2020103616A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811399052.5 2018-11-22
CN201811399052.5A CN109298049B (en) 2018-11-22 2018-11-22 Copper oxide/carbon nano tube/carbon nitride electrochemical sensor for detecting acetaminophen and preparation method and application thereof

Publications (1)

Publication Number Publication Date
WO2020103616A1 true WO2020103616A1 (en) 2020-05-28

Family

ID=65144505

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/111754 WO2020103616A1 (en) 2018-11-22 2019-10-17 Copper oxide/carbon nanotube/carbon nitride electrochemical sensor for detecting acetaminophen, preparation method therefor and application thereof

Country Status (2)

Country Link
CN (1) CN109298049B (en)
WO (1) WO2020103616A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113466314A (en) * 2021-07-05 2021-10-01 西安交通大学 Electrochemical biosensor based on functionalized carbon-nitrogen polymer, and preparation method and application thereof
CN113559905A (en) * 2021-07-19 2021-10-29 陕西科技大学 g-C3N4/CuO photocatalytic film material grown in situ by flexible copper mesh and preparation method thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113118451B (en) * 2021-03-26 2022-01-21 中南大学 Preparation method of magnesium monoatomic catalyst applied to efficient carbon dioxide reduction reaction for generating carbon monoxide
CN114452998B (en) * 2022-01-26 2023-05-09 大连理工大学 Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material
CN115254174A (en) * 2022-09-27 2022-11-01 中国环境科学研究院 Preparation method and application of carbon nitride-based copper catalytic material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103901087A (en) * 2014-04-24 2014-07-02 青岛大学 Modified electrode for detecting pyrocatechol and hydroquinone and preparation method thereof
CN104907087A (en) * 2015-04-17 2015-09-16 浙江理工大学 Synthesis method and application of porous carbonitride/copper oxide nanorod composite material with visible light response
CN106602012A (en) * 2016-12-13 2017-04-26 上海交通大学 Flexible thin-film electrode and preparation method and application thereof
CN108195908A (en) * 2017-11-17 2018-06-22 宁夏医科大学 A kind of palladium-class graphite phase carbon nitride-carbon nano-tube combination electrode and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103901087A (en) * 2014-04-24 2014-07-02 青岛大学 Modified electrode for detecting pyrocatechol and hydroquinone and preparation method thereof
CN104907087A (en) * 2015-04-17 2015-09-16 浙江理工大学 Synthesis method and application of porous carbonitride/copper oxide nanorod composite material with visible light response
CN106602012A (en) * 2016-12-13 2017-04-26 上海交通大学 Flexible thin-film electrode and preparation method and application thereof
CN108195908A (en) * 2017-11-17 2018-06-22 宁夏医科大学 A kind of palladium-class graphite phase carbon nitride-carbon nano-tube combination electrode and its preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KARIMI-MALEH, HASSAN ET AL.: "Amplified Electrochemical Sensor Employing CuO/SWCNTs and 1-butyl-3-Methylimidazolium Hexafluorophosphate for Selective Analysis of Sulfisoxazole in the Presence of Folic Acid", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 495, 1 June 2017 (2017-06-01), pages 61 - 67, XP055709562 *
Z. MONSEF KHOSHHESAB: "Simultaneous Electrochemical Determination of Acetaminophen, Caffeine and Ascorbic Acid Using a New Electrochemical Sensor Based on CuO-graphene Nanocomposite", RSC ADVANCES, vol. 5, no. 115, 30 October 2015 (2015-10-30), pages 95140 - 95148, XP055709559 *
ZOU, JING ET AL.: "An Ultra-sensitive Electrochemical Sensor Based on 2D g-C3N4/CuO Nanocomposites for Dopamine Detection", CARBON, vol. 130, 5 January 2018 (2018-01-05), XP085346241 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113466314A (en) * 2021-07-05 2021-10-01 西安交通大学 Electrochemical biosensor based on functionalized carbon-nitrogen polymer, and preparation method and application thereof
CN113559905A (en) * 2021-07-19 2021-10-29 陕西科技大学 g-C3N4/CuO photocatalytic film material grown in situ by flexible copper mesh and preparation method thereof

Also Published As

Publication number Publication date
CN109298049A (en) 2019-02-01
CN109298049B (en) 2020-06-26

Similar Documents

Publication Publication Date Title
WO2020103616A1 (en) Copper oxide/carbon nanotube/carbon nitride electrochemical sensor for detecting acetaminophen, preparation method therefor and application thereof
Balasubramanian et al. Sonochemical synthesis of molybdenum oxide (MoO3) microspheres anchored graphitic carbon nitride (g-C3N4) ultrathin sheets for enhanced electrochemical sensing of Furazolidone
Khan et al. Glucose-assisted synthesis of Cu2O shuriken-like nanostructures and their application as nonenzymatic glucose biosensors
Lv et al. A novel electrochemical sensor for uric acid detection based on PCN/MWCNT
Fang et al. An enhanced sensitive electrochemical immunosensor based on efficient encapsulation of enzyme in silica matrix for the detection of human immunodeficiency virus p24
CN107039660B (en) The porous carbon microsphere of Fe-NPS codope preparation and its as ORR catalyst application
CN105758909A (en) Gold nanotube based flexible stretchable electrode and preparation method and application thereof
Xu et al. Cascade amplification strategy based on ultra-thin graphdiyne and CRISPR/Cas for real-time detection of tumor biomarker
Liu et al. Mesoporous ZnO-NiO architectures for use in a high-performance nonenzymatic glucose sensor
CN106442689B (en) The preparation and application of Dopamine Sensor based on nickel oxide CNT
Wu et al. Simultaneous voltammetric determination of epinephrine and acetaminophen using a highly sensitive CoAl-OOH/reduced graphene oxide sensor in pharmaceutical samples and biological fluids
CN107643331B (en) A kind of electrode face finish material and its preparation method and application
CN104555985B (en) The preparation method that a kind of boron phosphate is carbon nano-tube modified
Kang et al. Preparation of Pt nanoparticles embedded on ordered mesoporous carbon hybrids for sensitive detection of acetaminophen
CN109046429A (en) Mat gold nano particle/graphite phase carbon nitride composite material electrochemical sensor is detected for chloramphenicol
Hasanzadeh et al. Non-enzymatic determination of L-Proline amino acid in unprocessed human plasma sample using hybrid of graphene quantum dots decorated with gold nanoparticles and poly cysteine: a novel signal amplification strategy
Fu et al. Surfactant-assisted carbon black for the electrochemical detection of endocrine disruptors
Zhao et al. Label-free amperometric immunosensor based on graphene oxide and ferrocene-chitosan nanocomposites for detection of hepatis B virus antigen
Guo et al. Electrochemical recognition of tryptophan enantiomers using self-assembled diphenylalanine structures induced by graphene quantum dots, chitosan and CTAB
Fan et al. Synthesis of mesoporous CuO microspheres with core-in-hollow-shell structure and its application for non-enzymatic sensing of glucose
CN108061748A (en) For detecting the preparation method of the nanometer bismuth oxide graphene composite film electrode of lead ion and cadmium ion
CN113155933A (en) Graphene-molybdenum trioxide-based all-solid-state potassium ion selective electrode and preparation method and application thereof
CN107167502A (en) The construction method of non-enzymatic electrochemical sensor based on CNT fullerene complex and application
Shahrokhian et al. Modification of carbon paste with congo red supported on multi-walled carbon nanotube for voltammetric determination of uric acid in the presence of ascorbic acid
CN111793393B (en) Nanocomposite material, glassy carbon composite electrode, manufacturing methods of nanocomposite material and glassy carbon composite electrode, and electrochemical sensor

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19886789

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19886789

Country of ref document: EP

Kind code of ref document: A1