CN112345611B - Preparation method of electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method of composite material - Google Patents
Preparation method of electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method of composite material Download PDFInfo
- Publication number
- CN112345611B CN112345611B CN202011286746.5A CN202011286746A CN112345611B CN 112345611 B CN112345611 B CN 112345611B CN 202011286746 A CN202011286746 A CN 202011286746A CN 112345611 B CN112345611 B CN 112345611B
- Authority
- CN
- China
- Prior art keywords
- loofah sponge
- composite material
- biomass carbon
- electrochemical sensor
- powder
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/38—Cleaning of electrodes
Abstract
The invention relates to the technical field of electrochemical sensors, in particular to a preparation method of an electrochemical sensor based on loofah sponge biomass charcoal composite material, which comprises the following steps: pre-carbonizing loofah; activating loofah sponge powder by potassium hydroxide; preparing a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material; preparing an electrochemical sensor; the preparation method is simple, the used loofah sponge raw materials are wide in source and low in cost, the prepared composite material has a large specific surface area, high conductivity and a porous structure, and the prepared electrochemical sensor has good conductivity and excellent electrocatalytic performance; the invention also provides a preparation method of the composite material and application of the composite material modified electrode in an electrochemical sensor, and the invention not only promotes the development of the field of the electrochemical sensor, but also has wide application prospect in the fields of food, medicine, environmental detection and the like.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to a loofah sponge biomass charcoal composite material-based preparation method of an electrochemical sensor and a preparation method of the composite material.
Background
At present, electrochemical sensors with electrodes modified by carbon materials such as graphene and carbon nanotubes have been developed at a high speed. The graphene and the carbon nano tube have good conductivity, higher specific surface area and excellent electrocatalysis capability, the sensitivity of the modified electrode is improved, and the graphene and the carbon nano tube are widely applied to the detection fields of food, medicine, environment and the like. However, the disadvantages of complex preparation process, high cost, easy generation of environmental pollutants and the like of graphene and carbon nanotubes limit the commercial application of graphene and carbon nanotubes in electrochemical sensors.
In recent years, researchers find that porous carbon with different shapes can be prepared by using biomass resources as precursors and controlling a synthesis process, and the prepared porous carbon composite material modified electrode has excellent conductivity and electrocatalysis performance. The loofah sponge is a carbon material with wide distribution and low price, and has a unique natural fiber bundle structure. In the carbonization process, by controlling conditions, the pore-forming in the fiber bundle structure can improve the loading capacity and the specific surface area of the biomass carbon. The poly 3, 4-ethylenedioxythiophene and gold nanoparticles are loaded on the loofah sponge carbon by a convenient and efficient one-pot method, so that the composite material has a large specific surface area, strong conductivity and a porous structure, and the prepared electrochemical sensor has good conductivity and excellent electrocatalysis performance. The composite material has great feasibility and practicability in the field of electrochemical sensors, and provides new approaches and breakthrough points for the commercial application of the biochar material in the field of electrochemical sensors.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an electrochemical sensor based on a loofah sponge biomass charcoal composite material.
The invention also provides a preparation method of the composite material and application of the composite material modified electrode in an electrochemical sensor.
The invention adopts the following technical scheme:
a preparation method of an electrochemical sensor based on loofah sponge biomass charcoal composite material comprises the following steps:
pre-carbonizing loofah sponge: firstly, the loofah sponge is alternately soaked by deionized water and ethanol, dust and dirt impurities on the surface of the loofah sponge are removed by ultrasonic washing, and then the loofah sponge is placed in a drying box for drying; placing the dried retinervus Luffae fructus in a porcelain boat, transferring into a high temperature tube furnace, introducing argon, uniformly heating to a certain temperature at a constant speed, calcining, naturally cooling to room temperature, and pulverizing to obtain retinervus Luffae fructus powder;
potassium hydroxide-activated loofah sponge powder: weighing the loofah sponge powder prepared in the step of pre-carbonizing loofah sponge, mixing the loofah sponge powder with potassium hydroxide powder, adding a certain amount of water, performing ultrasonic dispersion, and drying in a drying oven until the solution is completely evaporated; moving the mixture into a high-temperature tubular furnace for activation, introducing argon, heating to a certain temperature at a constant speed for calcination, cooling to room temperature, treating the mixture with dilute hydrochloric acid and deionized water for repeated soaking, washing, filtering and washing until the pH of the filtrate is neutral, detecting the filtrate by using a silver nitrate solution until no white precipitate exists, and then placing the filtrate in a vacuum drying oven for drying to obtain the porous biomass carbon material;
preparing a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material: weighing the porous biomass carbon material in the step of activating the loofah sponge powder by the potassium hydroxide at room temperature, adding the porous biomass carbon material into a chloroauric acid aqueous solution, slowly dropwise adding a 3, 4-ethylenedioxythiophene monomer solution after ultrasonic dispersion, and then placing the suspension in magnetic stirring for reaction; after the reaction is finished, performing centrifugal treatment on the suspension to obtain the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material; dispersing the composite material in 30mL of distilled water, and performing ultrasonic dispersion for 30min for later use;
preparing an electrochemical sensor: firstly, polishing a glassy carbon electrode with the diameter of 3mm by using alumina powder with the diameter of 0.3 mu m and 0.05 mu m in sequence, polishing the electrode into a mirror surface, and then carrying out ultrasonic cleaning in absolute ethyl alcohol and secondary distilled water; and (3) dropwise coating a certain amount of the composite material dispersion liquid in the step of preparing the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material on the surface of an electrode, and airing under an infrared lamp to obtain the electrochemical sensor.
The technical proposal is further improved in that in the step of pre-carbonizing the loofah sponge, the drying temperature of the drying oven is 100 ℃; the constant heating rate is 5 ℃/min in the high-temperature tubular furnace calcination, the heating temperature is 400-600 ℃, and the calcination time is 1-3 h.
In the step of activating the loofah sponge powder by the potassium hydroxide, the mass ratio of the loofah sponge powder to the potassium hydroxide powder is 1; the constant heating rate is 5 ℃/min in the calcination of the high-temperature tube furnace, the heating temperature is 600-800 ℃, and the calcination time is 1-3 h; the pH is 7; the drying temperature of the vacuum drying oven is 60 ℃.
The technical scheme is further improved in that in the step of preparing the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material, the weighing amount of the porous biomass carbon material is 5-15 mg; the concentration of the chloroauric acid aqueous solution is 1mmol/L, and the added volume is 50mL; the concentration of the 3, 4-ethylene dioxythiophene monomer solution is 20mmol/L, and the added volume is 5mL; the reaction time of the magnetic stirring is 4-8 h.
The technical scheme is further improved in that in the step of preparing the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material, the step of centrifugal treatment comprises the following steps: washing and centrifuging the product by using ethanol and deionized water, wherein the centrifuging speed is 6000r/min, and the centrifuging time is 10min.
In the step of preparing the electrochemical sensor, the dropping amount of the composite material dispersion liquid is 8 muL.
A preparation method of a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material comprises the following steps:
pre-carbonizing loofah sponge: firstly, the loofah sponge is alternately soaked by deionized water and ethanol, dust and dirt impurities on the surface of the loofah sponge are removed by ultrasonic washing, and then the loofah sponge is placed in a drying box for drying; then placing the dried loofah sponge into a porcelain boat, moving the porcelain boat into a high-temperature tube furnace, introducing argon, uniformly heating the porcelain boat to a certain temperature at a constant speed, calcining the porcelain boat, naturally cooling the porcelain boat to room temperature, and crushing the porcelain boat to obtain loofah sponge powder for later use;
potassium hydroxide-activated loofah sponge powder: weighing the loofah sponge powder prepared in the step of pre-carbonizing loofah sponge, mixing the loofah sponge powder with potassium hydroxide powder, adding a certain amount of water, performing ultrasonic dispersion, and drying in a drying oven until the solution is completely evaporated; moving the biomass carbon material into a high-temperature tubular furnace for activation, introducing argon, raising the temperature to a certain temperature at a constant speed for calcination, cooling to room temperature, treating the biomass carbon material with dilute hydrochloric acid, repeatedly soaking, washing, filtering and washing with deionized water until the pH of the filtrate is neutral, detecting the filtrate with a silver nitrate solution to obtain no white precipitate, and drying the filtrate in a vacuum drying oven to obtain the porous biomass carbon material;
preparing a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material: weighing the porous biomass carbon material in the step of activating the loofah sponge powder by the potassium hydroxide, adding the porous biomass carbon material into a chloroauric acid aqueous solution, slowly dropwise adding a 3, 4-ethylene dioxythiophene monomer solution after ultrasonic dispersion, and then placing the suspension into magnetic stirring for reaction; after the reaction is finished, performing centrifugal treatment on the suspension to obtain the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material.
The technical proposal is further improved in that the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material is applied to an electrode material of an electrochemical sensor.
The invention has the beneficial effects that:
1. the loofah sponge has low price, wide source and simple carbonization process, provides new practical value for the loofah sponge, and widens the source of a precursor for modifying an electrode material in an electrochemical sensor.
2. The method for preparing the novel biomass porous material is provided by using a natural fiber structure of the loofah sponge as a substrate to load poly 3, 4-ethylenedioxythiophene-gold nanoparticles.
3. The electrochemical sensor has the advantages of simple preparation method, high efficiency, environmental protection, low consumption, good stability, high sensitivity for detecting substances, and strong practicability, and is expected to be applied in large-scale commercialization.
Drawings
Fig. 1 is a scanning electron microscope image of a loofah sponge prepared by the method for preparing an electrochemical sensor based on a loofah sponge biomass charcoal composite material according to the present invention after pre-carbonization;
fig. 2 is a scanning electron microscope image of the loofah sponge after being activated by potassium hydroxide to form pores in the preparation method of the electrochemical sensor based on the loofah sponge biomass charcoal composite material;
FIG. 3 is a scanning electron microscope image of the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material of the method for preparing the electrochemical sensor based on the loofah sponge biomass carbon composite material of the present invention;
fig. 4 is a raman diffraction spectrogram of a loofah sponge pre-carbonized and a loofah sponge activated by potassium hydroxide to form a hole according to the preparation method of the electrochemical sensor based on the loofah sponge biomass charcoal composite material;
fig. 5 shows a: a bare glassy carbon electrode; b: a porous biomass carbon/glassy carbon electrode sensor; c: poly 3, 4-ethylenedioxythiophene-gold/glassy carbon electrode sensors; d: cyclic voltammograms of porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold/glassy carbon electrode sensors at 5 μmol dm-3 luteolin in BR buffer solution (pH = 2), respectively.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the present invention.
Example 1:
pre-carbonizing loofah sponge: the loofah sponge is alternately soaked by deionized water and ethanol, the surface of the loofah sponge is cleaned by ultrasonic waves to remove dust and dirt impurities, and then the loofah sponge is placed in a drying oven at 100 ℃ for drying. Then placing the dried loofah sponge into a porcelain boat, moving the porcelain boat into a high-temperature tube furnace, introducing argon, uniformly heating to 400 ℃ at a speed of 5 ℃/min for calcining, preserving heat for 1 hour, naturally cooling to room temperature, and crushing to obtain loofah sponge powder for later use;
potassium hydroxide-activated loofah sponge powder: weighing the loofah sponge powder prepared in the pre-carbonization loofah sponge step and potassium hydroxide powder, mixing according to a mass ratio of 1; activating in a high-temperature tubular furnace, introducing argon, uniformly heating to 600 ℃ at a speed of 5 ℃/min, calcining for 1h, cooling to room temperature, repeatedly soaking, washing, filtering and washing with dilute hydrochloric acid and deionized water until the pH of the filtrate is 7, detecting the filtrate by a silver nitrate solution to obtain no white precipitate, and drying in a vacuum drying oven at 60 ℃ to obtain the porous biomass carbon material;
preparing a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material: weighing 5mg of the porous biomass carbon material in the step of activating the loofah sponge powder by the potassium hydroxide, adding the porous biomass carbon material into 50mL of 1mmol/L chloroauric acid aqueous solution, slowly dropwise adding 5mL of 20 mmol/L3, 4-ethylenedioxythiophene monomer solution after ultrasonic dispersion, and then placing the suspension in magnetic stirring for reaction for 4 hours; and after the reaction is finished, centrifuging the suspension at the speed of 6000r/min for 10min to obtain the porous biomass carbon/poly (3, 4-ethylenedioxythiophene) -gold composite material. Dispersing the composite material in 30mL of distilled water, and performing ultrasonic dispersion for 30min for later use;
preparing an electrochemical sensor: firstly, polishing a glassy carbon electrode with the diameter of 3mm by using alumina powder with the diameter of 0.3 mu m and the diameter of 0.05 mu m in sequence, polishing the electrode into a mirror surface, and then carrying out ultrasonic cleaning in absolute ethyl alcohol and secondary distilled water. And (3) dripping 8 mu L of the composite material dispersion liquid in the step of preparing the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material on the surface of an electrode, and airing under an infrared lamp to obtain the electrochemical sensor.
Example 2:
pre-carbonizing loofah sponge: the loofah sponge is alternately soaked by deionized water and ethanol, dust and dirt impurities on the surface of the loofah sponge are removed by ultrasonic washing, and then the loofah sponge is placed in a drying oven at 100 ℃ for drying. Then placing the dried loofah sponge into a porcelain boat, moving the porcelain boat into a high-temperature tube furnace, introducing argon, uniformly heating to 500 ℃ at a speed of 5 ℃/min for calcining, preserving heat for 2 hours, naturally cooling to room temperature, and crushing to obtain loofah sponge powder for later use;
potassium hydroxide-activated loofah sponge powder: weighing the loofah sponge powder prepared in the step of pre-carbonizing loofah sponge, mixing the loofah sponge powder with potassium hydroxide powder according to the mass ratio of 1; moving the mixture into a high-temperature tubular furnace for activation, introducing argon, uniformly heating to 700 ℃ at a speed of 5 ℃/min for calcining for 2h, treating the mixture with dilute hydrochloric acid after cooling to room temperature, repeatedly soaking, washing, filtering and washing the mixture with deionized water until the pH of the filtrate is 7, detecting the filtrate by using a silver nitrate solution until no white precipitate exists, and then placing the filtrate in a vacuum drying oven at 60 ℃ for drying to obtain the porous biomass carbon material;
preparing a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material: weighing 10mg of the porous biomass carbon material in the step of activating the loofah sponge powder by the potassium hydroxide, adding the porous biomass carbon material into 50mL of 1mmol/L chloroauric acid aqueous solution, slowly dropwise adding 5mL of 20 mmol/L3, 4-ethylenedioxythiophene monomer solution after ultrasonic dispersion, and then placing the suspension in magnetic stirring to react for 6 hours; and after the reaction is finished, centrifuging the suspension at the speed of 6000r/min for 10min to obtain the porous biomass carbon/poly (3, 4-ethylenedioxythiophene) -gold composite material. Dispersing the composite material in 30mL of distilled water, and performing ultrasonic dispersion for 30min for later use;
preparing an electrochemical sensor: firstly, polishing a glassy carbon electrode with the diameter of 3mm by using alumina powder with the diameter of 0.3 mu m and 0.05 mu m in sequence, polishing the electrode into a mirror surface, and then carrying out ultrasonic cleaning in absolute ethyl alcohol and secondary distilled water. And (3) dripping 8 mu L of the composite material dispersion liquid in the step of preparing the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material on the surface of an electrode, and airing under an infrared lamp to obtain the electrochemical sensor.
Example 3:
pre-carbonizing loofah sponge: the loofah sponge is alternately soaked by deionized water and ethanol, dust and dirt impurities on the surface of the loofah sponge are removed by ultrasonic washing, and then the loofah sponge is placed in a drying oven at 100 ℃ for drying. Then placing the dried loofah sponge into a porcelain boat, moving the porcelain boat into a high-temperature tube furnace, introducing argon, uniformly heating to 600 ℃ at a speed of 5 ℃/min for calcining, preserving heat for 3 hours, naturally cooling to room temperature, and crushing to obtain loofah sponge powder for later use;
potassium hydroxide-activated loofah sponge powder: weighing the loofah sponge powder prepared in the step of pre-carbonizing loofah sponge, mixing the loofah sponge powder with potassium hydroxide powder according to the mass ratio of 1; moving the mixture into a high-temperature tubular furnace for activation, introducing argon, uniformly heating to 800 ℃ at a speed of 5 ℃/min, calcining for 3h, cooling to room temperature, treating with dilute hydrochloric acid, repeatedly soaking, washing, filtering and washing with deionized water until the pH of the filtrate is 7, detecting the filtrate by a silver nitrate solution until no white precipitate exists, and drying in a vacuum drying oven at 60 ℃ to obtain the porous biomass carbon material;
preparing a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material: weighing 15mg of the porous biomass carbon material in the step of activating the loofah sponge powder by potassium hydroxide, adding the porous biomass carbon material into 50mL of 1mmol/L chloroauric acid aqueous solution, slowly dropwise adding 5mL of 20 mmol/L3, 4-ethylenedioxythiophene monomer solution after ultrasonic dispersion, and then placing the suspension in magnetic stirring for reaction for 8 hours; and after the reaction is finished, centrifuging the suspension at the speed of 6000r/min for 10min to obtain the porous biomass carbon/poly (3, 4-ethylenedioxythiophene) -gold composite material. Dispersing the composite material in 30mL of distilled water, and performing ultrasonic dispersion for 30min for later use;
preparing an electrochemical sensor: firstly, polishing a glassy carbon electrode with the diameter of 3mm by using alumina powder with the diameter of 0.3 mu m and the diameter of 0.05 mu m in sequence, polishing the electrode into a mirror surface, and then carrying out ultrasonic cleaning in absolute ethyl alcohol and secondary distilled water. And (3) dripping 8 mu L of the composite material dispersion liquid obtained in the step of preparing the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material on the surface of an electrode, and airing under an infrared lamp to obtain the electrochemical sensor.
As shown in fig. 1, fig. 1 is a scanning electron microscope image of the loofah prepared by the present invention after pre-carbonization; as can be seen from fig. 1, the surface of the loofah sponge is wrinkled, and the cross section of the loofah sponge is observed, each fiber consists of a plurality of densely arranged pore channels, the pore channels are polygonal and straight-through hollow, the pore channels are tightly combined and piled into a tubular bundle structure, and the cross section of the tubular bundle structure is similar to a honeycomb shape.
As shown in fig. 2, fig. 2 is a scanning electron microscope image of loofah sponge after pore formation by potassium hydroxide activation; as can be seen from FIG. 2, the carbon surface is collapsed due to the etching of the potassium hydroxide to form clear and obvious and uniformly distributed porous structures, the porous structures are favorable for transporting the electrolyte in the fibers, the contact area between the material and the electrolyte is increased, and the utilization rate of the material is greatly improved.
As shown in fig. 3, fig. 3 is a scanning electron microscope image of the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material.
As shown in fig. 4, fig. 4 is a raman diffraction spectrogram of the loofah sponge after being pre-carbonized and after being activated by potassium hydroxide to form pores; LSC is pre-carbonized loofah sponge, and LSAC is loofah sponge activated by potassium hydroxide to form pores; as can be seen from FIG. 4, the material has two obvious characteristic peaks at 1335cm -1 And 1589cm -1 Bands appearing nearby represent a D band and a G band of the graphene respectively; wherein, the D band represents the vibration of defect carbon and disordered carbon, and represents the lattice defect condition of carbon atoms; the G band represents stretching vibration caused by sp3 hybridization and sp2 hybridization of carbon atoms and characterizes the graphitization degree of the porous material. The strength ratio (ID/IG) of the two represents the degree of graphitization of the carbon material. After the pores are formed by potassium hydroxide activation, the strength of ID/IG is increased, which shows that the lattice defect of the loofah sponge carbon material is increased, more oxygen vacancies are caused, the electrons are captured, and the activity of the material is improved.
As shown in fig. 5, fig. 5 is a: a bare glassy carbon electrode; b: a porous biomass carbon/glassy carbon electrode sensor; c: poly 3, 4-ethylenedioxythiophene-gold/glassy carbon electrode sensors; d: cyclic voltammograms of porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold/glassy carbon electrode sensors at 5 μmol dm-3 luteolin in BR buffer solution (pH = 2), respectively; as can be seen from FIG. 5, a pair of weaker redox peaks appear at a potential of about 0.605V on the bare glassy carbon electrode, and both the porous biomass carbon/glassy carbon electrode sensor and the poly 3, 4-ethylenedioxythiophene-gold/glassy carbon electrode sensor have obvious enhancement effect on the electrochemical signal. Wherein the electrochemical signal of luteolin on the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold/glassy carbon electrode sensor is strongest; the enhancement of the current of the oxidation peak and the reduction peak is attributed to the large specific surface area of the activity and the strong electronic reduction capability of the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material.
The preparation method is simple, the loofah sponge is used as a raw material, the porous biomass carbon material (LSAC) is synthesized by two steps of pre-carbonization and potassium hydroxide activation, the poly-3, 4-ethylenedioxythiophene (PEDT) and gold nanoparticles (Au) are further loaded by a one-pot method, finally the composite material is dispersed in an aqueous solution, the porous biomass carbon/poly-3, 4-ethylenedioxythiophene-gold composite material (LSAC/PEDT-Au) is dripped and coated on the surface of a glassy carbon electrode by a dripping coating method, and the modified electrode can be prepared after solidification; taking luteolin as a research object, researching the performance of the electrochemical sensor by adopting a cyclic voltammetry method and a differential pulse voltammetry method, and detecting the content of the luteolin in the Maishu capsule by adopting a standard addition method; the loofah sponge has wide raw material sources and low price, the prepared composite material has large specific surface area, strong conductivity and a porous structure, and the prepared electrochemical sensor has good conductivity and excellent electrocatalytic performance.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A preparation method of an electrochemical sensor based on loofah sponge biomass charcoal composite material is characterized by comprising the following steps:
pre-carbonizing loofah sponge: the loofah sponge is alternately soaked by deionized water and ethanol, dust and dirt impurities on the surface of the loofah sponge are removed by ultrasonic washing, and then the loofah sponge is placed in a drying box to be dried, wherein the drying temperature is 100 ℃; then placing the dried loofah sponge into a porcelain boat, moving the porcelain boat into a high-temperature tube furnace, introducing argon, uniformly heating to a certain temperature at a constant speed for calcination, wherein the constant heating rate is 5 ℃/min in the high-temperature tube furnace calcination, the heating temperature is 400-600 ℃, the calcination time is 1-3 h, then naturally cooling to room temperature, and crushing to obtain loofah sponge powder for later use;
potassium hydroxide-activated loofah sponge powder: weighing the loofah sponge powder prepared in the step of pre-carbonizing loofah sponge, mixing the loofah sponge powder with potassium hydroxide powder, adding a certain amount of water, performing ultrasonic dispersion, and drying in a drying oven until the solution is completely evaporated; moving the mixture into a high-temperature tubular furnace for activation, introducing argon, heating to a certain temperature at a constant speed for calcination, cooling to room temperature, treating the mixture with dilute hydrochloric acid and deionized water for repeated soaking, washing, filtering and washing until the pH of the filtrate is neutral, detecting the filtrate by using a silver nitrate solution until no white precipitate exists, and then placing the filtrate in a vacuum drying oven for drying to obtain the porous biomass carbon material; the mass ratio of the loofah sponge powder to the potassium hydroxide powder is 1; the constant heating rate is 5 ℃/min in the high-temperature tubular furnace calcination, the heating temperature is 600-800 ℃, and the calcination time is 1-3 h;
preparing a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material: weighing the porous biomass carbon material in the step of activating the loofah sponge powder by the potassium hydroxide, adding the porous biomass carbon material into a chloroauric acid aqueous solution, slowly dropwise adding a 3, 4-ethylene dioxythiophene monomer solution after ultrasonic dispersion, and then placing the suspension into magnetic stirring for reaction; after the reaction is finished, performing centrifugal treatment on the suspension to obtain the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material; dispersing the composite material in 30mL of distilled water, and performing ultrasonic dispersion for 30min for later use;
preparing an electrochemical sensor: firstly, polishing a glassy carbon electrode with the diameter of 3mm by using alumina powder with the diameter of 0.3 mu m and 0.05 mu m in sequence, polishing the electrode into a mirror surface, and then carrying out ultrasonic cleaning in absolute ethyl alcohol and secondary distilled water; and (3) dropwise coating a certain amount of the composite material dispersion liquid in the step of preparing the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material on the surface of an electrode, and airing under an infrared lamp to obtain the electrochemical sensor.
2. The method for preparing the loofah sponge biomass charcoal composite-based electrochemical sensor according to claim 1, wherein in the step of activating loofah sponge powder with potassium hydroxide, the addition amount of deionized water is 20mL; the pH is 7; the drying temperature of the vacuum drying oven is 60 ℃.
3. The method for preparing the loofah sponge biomass charcoal composite-based electrochemical sensor according to claim 1, wherein in the step of preparing the porous biomass carbon/poly-3, 4-ethylenedioxythiophene-gold composite material, the porous biomass carbon material is weighed by 5-15 mg; the concentration of the chloroauric acid aqueous solution is 1mmol/L, and the added volume is 50mL; the concentration of the 3, 4-ethylene dioxythiophene monomer solution is 20mmol/L, and the added volume is 5mL; the reaction time of the magnetic stirring is 4-8 h.
4. The method for preparing an electrochemical sensor based on loofah sponge biomass charcoal composite material according to claim 1, wherein in the step of preparing the porous biomass charcoal/poly 3, 4-ethylenedioxythiophene-gold composite material, the step of centrifuging is: washing and centrifuging the product by using ethanol and deionized water, wherein the centrifugation speed is 6000r/min, and the centrifugation time is 10min.
5. The method for preparing an electrochemical sensor based on loofah sponge biomass charcoal composite material according to claim 1, wherein in the step of preparing the electrochemical sensor, the dropping amount of the composite material dispersion liquid is 8 μ L.
6. A preparation method of a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material is characterized by comprising the following steps:
pre-carbonizing loofah sponge: the loofah sponge is alternately soaked by deionized water and ethanol, dust and dirt impurities on the surface of the loofah sponge are removed by ultrasonic washing, and then the loofah sponge is placed in a drying box for drying; placing the dried retinervus Luffae fructus in a porcelain boat, transferring into a high temperature tube furnace, introducing argon, uniformly heating to a certain temperature at a constant speed, calcining, naturally cooling to room temperature, and pulverizing to obtain retinervus Luffae fructus powder;
potassium hydroxide-activated loofah sponge powder: weighing the loofah sponge powder prepared in the step of pre-carbonizing loofah sponge, mixing the loofah sponge powder with potassium hydroxide powder, adding a certain amount of water, performing ultrasonic dispersion, and then placing the mixture in a drying oven for drying until the solution is completely evaporated; moving the biomass carbon material into a high-temperature tubular furnace for activation, introducing argon, raising the temperature to a certain temperature at a constant speed for calcination, cooling to room temperature, treating the biomass carbon material with dilute hydrochloric acid, repeatedly soaking, washing, filtering and washing with deionized water until the pH of the filtrate is neutral, detecting the filtrate with a silver nitrate solution to obtain no white precipitate, and drying the filtrate in a vacuum drying oven to obtain the porous biomass carbon material;
preparing a porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material: weighing the porous biomass carbon material in the step of activating the loofah sponge powder by the potassium hydroxide, adding the porous biomass carbon material into a chloroauric acid aqueous solution, slowly dropwise adding a 3, 4-ethylene dioxythiophene monomer solution after ultrasonic dispersion, and then placing the suspension into magnetic stirring for reaction; after the reaction is finished, performing centrifugal treatment on the suspension to obtain the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material.
7. The preparation method of the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material according to claim 6, wherein the porous biomass carbon/poly 3, 4-ethylenedioxythiophene-gold composite material is applied to an electrode material of an electrochemical sensor.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011286746.5A CN112345611B (en) | 2020-11-17 | 2020-11-17 | Preparation method of electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method of composite material |
| PCT/CN2021/116759 WO2022105370A1 (en) | 2020-11-17 | 2021-09-06 | Preparation method for electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method for composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011286746.5A CN112345611B (en) | 2020-11-17 | 2020-11-17 | Preparation method of electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method of composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112345611A CN112345611A (en) | 2021-02-09 |
| CN112345611B true CN112345611B (en) | 2022-10-28 |
Family
ID=74364059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011286746.5A Active CN112345611B (en) | 2020-11-17 | 2020-11-17 | Preparation method of electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method of composite material |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112345611B (en) |
| WO (1) | WO2022105370A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112345611B (en) * | 2020-11-17 | 2022-10-28 | 东莞理工学院 | Preparation method of electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method of composite material |
| CN113257990B (en) * | 2021-04-23 | 2024-02-09 | 苏州攀特电陶科技股份有限公司 | Base metal inner electrode material for multilayer piezoelectric ceramic actuator and preparation method thereof |
| CN113831686A (en) * | 2021-09-18 | 2021-12-24 | 安徽农业大学 | Preparation method of porous network composite material with shielding and sound absorption functions |
| CN113880083B (en) * | 2021-10-27 | 2023-06-16 | 中冶集团武汉勘察研究院有限公司 | Method for preparing biomass activated carbon by using loofah sponge |
| CN114794625A (en) * | 2022-04-14 | 2022-07-29 | 浙江理工大学 | Manufacturing method of intelligent waistband based on loofah sponge sensor |
| CN115000432B (en) * | 2022-06-06 | 2023-09-08 | 广东工业大学 | Cobalt oxide-luffa derivative nitrogen-doped carbon composite material and preparation method and application thereof |
| CN115078498B (en) * | 2022-06-13 | 2023-07-18 | 山西大学 | Biomass carbon material supported metal nanoparticle catalyst and preparation method thereof |
| CN115069215A (en) * | 2022-07-04 | 2022-09-20 | 辽宁大学 | Novel functionalized magnetic porous biochar material and preparation method and application thereof |
| CN115178238A (en) * | 2022-07-15 | 2022-10-14 | 辽宁大学 | Application of magnetic adsorbent material in adsorption of heavy metal ions |
| CN115116756A (en) * | 2022-07-15 | 2022-09-27 | 东华理工大学 | Preparation method of honeycomb porous carbon based on high-temperature activation method |
| CN116239385A (en) * | 2023-02-10 | 2023-06-09 | 中国科学院金属研究所 | 3D printing silicon carbide slurry suitable for ink direct writing technology and preparation thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103149267B (en) * | 2013-02-06 | 2015-02-18 | 河南省科学院高新技术研究中心 | Electrochemical biosensor for detecting dopamine and its preparation method |
| CN103149258B (en) * | 2013-02-26 | 2015-09-23 | 山东大学 | A kind of preparation method of the bioelectrode based on nano-porous gold-conducting polymer |
| EP3480595A1 (en) * | 2017-11-02 | 2019-05-08 | Elisha Systems Ltd. | Biosensor manufacture |
| CN108226253B (en) * | 2018-01-19 | 2020-07-03 | 牡丹江师范学院 | Electrochemical sensor based on biomass carbon, preparation method and electrocatalysis application thereof |
| WO2019161049A1 (en) * | 2018-02-14 | 2019-08-22 | Wisys Technology Foundation, Inc. | FABRICATION OF NON-ENZYMATIC SENSOR BASED ON Pt/PVF OR Au/PVF OR Ir/ PVF ON A MODIFIED Pt ELECTRODE FOR DETERMINATION OF GLUCOSE |
| CN108535339B (en) * | 2018-03-28 | 2019-10-22 | 海南师范大学 | Nanogold-biomass carbon composite material modified electrode and its application in luteolin detection |
| CN109107612A (en) * | 2018-09-19 | 2019-01-01 | 平顶山学院 | A kind of poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO2-xThe preparation method of nanocomposite |
| CN109473288B (en) * | 2018-10-22 | 2020-12-18 | 江苏大学 | Method for preparing three-dimensional graphene/foamed nickel composite material |
| CN109822107B (en) * | 2019-02-27 | 2022-06-28 | 齐鲁工业大学 | Preparation method of gold nanoparticle composite biomass carbon material |
| CN109884147B (en) * | 2019-03-22 | 2021-07-02 | 石河子大学 | Electrochemical method for detecting trace heavy metals by using walnut shell-based carbon material modified glassy carbon electrode |
| CN110161096A (en) * | 2019-04-30 | 2019-08-23 | 海南师范大学 | A kind of application of preparation based on platinum-biomass carbon nanocomposite electrochemical sensor and luteolin detection |
| CN110196270A (en) * | 2019-06-20 | 2019-09-03 | 海南师范大学 | A kind of construction method based on biomass carbon-nanogold electrochemica biological sensor and analysis are applied |
| CN111346642B (en) * | 2020-02-05 | 2023-02-28 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN112345611B (en) * | 2020-11-17 | 2022-10-28 | 东莞理工学院 | Preparation method of electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method of composite material |
-
2020
- 2020-11-17 CN CN202011286746.5A patent/CN112345611B/en active Active
-
2021
- 2021-09-06 WO PCT/CN2021/116759 patent/WO2022105370A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN112345611A (en) | 2021-02-09 |
| WO2022105370A1 (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112345611B (en) | Preparation method of electrochemical sensor based on loofah sponge biomass charcoal composite material and preparation method of composite material | |
| Li et al. | Nitrogen doped and hierarchically porous carbons derived from chitosan hydrogel via rapid microwave carbonization for high-performance supercapacitors | |
| CN105271217B (en) | A kind of preparation method of the three-dimensional grapheme of N doping | |
| Wang et al. | Dual functional application of pomelo peel-derived bio-based carbon with controllable morphologies: An efficient catalyst for triiodide reduction and accelerant for anaerobic digestion | |
| CN104600238B (en) | Method for preparing directly soaking reaction type foamed nickel-graphene three-dimensional porous electrode | |
| CN105642326B (en) | A kind of porous carbon carried metal composite material and preparation method and application | |
| CN105780364B (en) | A kind of method for preparing ultramicropore flexibility carbon cloth and products thereof and application | |
| CN108579788A (en) | A kind of compound cobalt vanadium nitride nanowires elctro-catalyst and its preparation method and application | |
| CN105363483A (en) | Preparation method of titanium dioxide nanowire/two-dimensional layered titanium carbide composite material | |
| CN104477887A (en) | Method for preparing graphene from microcrystalline graphite | |
| CN106784706B (en) | A kind of carbon microspheres are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof | |
| CN109675595B (en) | Tungsten carbide/porous carbon composite material, preparation method thereof and application thereof in electrochemical hydrogen production | |
| CN110212194A (en) | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure | |
| CN109449448B (en) | Fuel cell cathode catalyst and preparation method and application thereof | |
| Askari et al. | Reduced graphene oxide supported Co3O4–Ni3S4 ternary nanohybrid for electrochemical energy storage | |
| Elanthamilan et al. | Effective conversion of Cassia fistula dry fruits biomass into porous activated carbon for supercapacitors | |
| CN109467082B (en) | Preparation method of graphitized porous corncob derived carbon electrode material | |
| CN106803461A (en) | Directly soak the three-dimensional porous electrode preparation method of nickel foam-Graphene of reaction equation | |
| Yu et al. | Large-scale synthesis of flexible TiO2/N-doped carbon nanofibres: A highly efficient all-day-active photocatalyst with electron storage capacity | |
| CN113881965A (en) | Metal nanoparticle-loaded catalyst taking biomass carbon source as template and preparation method and application thereof | |
| Deng et al. | Superior performance of flexible solid-state supercapacitors enabled by ultrafine graphene quantum dot-decorated porous carbon spheres | |
| CN113851664B (en) | Method for preparing hollow sphere electrocatalyst containing sp-nitrogen doped graphite alkyne, prepared material and application | |
| CN109821559B (en) | Preparation method and application of core-shell structure composite photoelectric material | |
| CN110732338A (en) | Carbon nanowire/g-C3N4Composite visible light catalyst and preparation method thereof | |
| CN110993359B (en) | Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |