CN110745811A - Hydroxyapatite/graphene aerogel anode and preparation method thereof - Google Patents
Hydroxyapatite/graphene aerogel anode and preparation method thereof Download PDFInfo
- Publication number
- CN110745811A CN110745811A CN201910961505.7A CN201910961505A CN110745811A CN 110745811 A CN110745811 A CN 110745811A CN 201910961505 A CN201910961505 A CN 201910961505A CN 110745811 A CN110745811 A CN 110745811A
- Authority
- CN
- China
- Prior art keywords
- hydroxyapatite
- graphene
- anode
- preparing
- chamber
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/327—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Energy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Geology (AREA)
- Sustainable Development (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inert Electrodes (AREA)
- Carbon And Carbon Compounds (AREA)
- Fuel Cell (AREA)
Abstract
The invention belongs to the technical field of anode materials of microbial fuel cells, and particularly relates to a hydroxyapatite/graphene aerogel anode for a microbial fuel cell and a preparation method thereof, wherein the hydroxyapatite/graphene aerogel anode is prepared from graphene oxide and hydroxyapatite, high-purity single-layer graphene oxide and hydroxyapatite are respectively dispersed in ultrapure water and ultrasonically treated to obtain uniformly dispersed graphite oxide dilute aqueous solution and hydroxyapatite suspension, the hydroxyapatite suspension is added into the graphite oxide dilute aqueous solution to form mixed solution, a reducing agent is added into the mixed solution and ultrasonically treated with hydrothermal reaction to form hydroxyapatite/graphene hydrogel and graphene hydrogel, the hydroxyapatite/graphene hydrogel and the graphene hydrogel are placed in ethanol solution for dialysis for 48 hours, and a vacuum refrigerator is used for freeze drying to obtain the hydroxyapatite/graphene aerogel anode with larger specific surface area, superior biocompatibility and electrical conductivity, the high performance aerogel anodes allow for start-up time of microbial fuel cells.
Description
The technical field is as follows:
the invention belongs to the technical field of anode materials of microbial fuel cells, and particularly relates to a hydroxyapatite/graphene aerogel anode for a microbial fuel cell and a preparation method thereof.
Background art:
microbial Fuel Cells (MFCs) are a battery device that converts chemical energy into electrical energy using electricity-producing microorganisms. Taking a typical two-chamber microbial fuel cell as an example, the fuel cell is composed of a cathode region and an anode region, and the electricity generation mechanism is as follows: the electrogenic microorganisms at the anode metabolically degrade the substrate to produce electrons, protons and carbon dioxide, wherein the electrons can be transferred to the anode via extracellular membrane chromoproteins (OMCs), nanowires or by secreted electron mediators, and reach the cathode via an external circuit. At the cathode, protons transferred from the anode undergo an oxygen reduction reaction with oxygen in the cathode region to produce water.
The microbial fuel cell has the characteristics of mild reaction conditions, high safety, cleanness, high efficiency and the like, and has wide application prospects in the fields of organic wastewater treatment, metal ion removal, bioremediation, biosensors, electrolytic hydrogen production and the like. For example: the system for synchronously repairing heavy metals in soil by treating organic wastewater with a fuel cell disclosed in Chinese patent 201820083136.7 comprises a microbial fuel cell, a data acquisition regulation and control device and a soil electrodynamics repairing device; the microbial fuel cell is provided with an anode chamber and a cathode chamber, an anode unit and a cathode unit are respectively arranged in the anode chamber and the cathode chamber, activated sludge is arranged in the anode chamber, electrolyte is arranged in the cathode chamber, the anode chamber and the cathode chamber are separated by a proton exchange membrane, the outer ends of the anode unit and the cathode unit are connected with an external resistor through a lead, the anode chamber is provided with a wastewater inlet and a wastewater outlet, and the cathode chamber is provided with a vent hole and a water outlet; the soil isThe electrodynamics repairing device is provided with a cathode treating area and an anode treating area, the cathode treating area and the anode treating area are polluted soil to be repaired, a cathode electrode and an anode electrode are respectively arranged in the cathode treating area and the anode treating area, and the cathode treating area and the anode treating area are separated by a cation selective permeation membrane; one end of the data acquisition regulation and control device is respectively connected with the anode unit and the cathode unit through leads, and the other end of the data acquisition regulation and control device is respectively connected with the cathode electrode and the anode electrode through leads, and the data acquisition regulation and control device is used for acquiring voltage signals generated by the microbial fuel cell and regulating and controlling the current received by the soil electrodynamics repair device; the microbial fuel cell is used for treating organic wastewater, and meanwhile, electric energy is generated for removing heavy metals in soil, so that the structure of the soil is not damaged, and the content of organic matters in the soil is not influenced; in addition, the chinese patent 201811608208.6 discloses a method for the synergistic treatment of organic and desulfurized wastewater by microbial fuel cells, which comprises the steps of: step 1, preparing a double-chamber microbial fuel cell, which comprises the steps of maintaining an anaerobic environment in an anode chamber and a cathode chamber, inoculating an electrogenesis microorganism in the anode chamber, wherein the electrogenesis microorganism is any one of Shewanella and Rhodospirillum, and inoculating a sulfate reducing bacterium in the cathode chamber; step 2, introducing the wastewater into a double-chamber microbial fuel cell for treatment, wherein the treatment comprises introducing organic wastewater into an anode chamber, introducing desulfurization wastewater into a cathode chamber, and allowing the organic wastewater and the desulfurization wastewater to simultaneously participate in reaction in the double-chamber microbial fuel cell; step 3, discharging the treated organic wastewater from the anode chamber, and discharging the treated desulfurization wastewater from the cathode chamber; the method uses a double-chamber microbial fuel cell to cooperatively treat organic wastewater and desulfurization wastewater, uses organic wastewater such as domestic sewage with high organic matter content as an anode substrate of the microbial fuel cell to provide nutrition for anode electrogenesis microorganisms, and converts organic matters in the organic wastewater into CO in an anode chamber by adopting anaerobic electrogenesis microorganisms2And release electrons and protons; the high oxidation reduction potential desulfurization wastewater is used as an electron acceptor for microbial fuel cell catholyte, sulfate reducing bacteria are inoculated in the cathode chamber, sulfate ions in the desulfurization wastewater are reduced, two kinds of wastewater are synchronously treated, and the treatment efficiency is highThe method has the advantages of high yield, full resource utilization and dual purposes of capacity and environmental purification; the electricity and hydrogen production system of the microbial fuel cell disclosed in the Chinese patent 201820145658.5 comprises a microbial fuel cell, a data acquisition device, an electrolytic cell and a hydrogen storage tank; the microbial fuel cell comprises an anode chamber and a cathode chamber, wherein an anode electrode and a cathode electrode are respectively arranged in the anode chamber and the cathode chamber, the anode chamber and the cathode chamber are separated by a proton exchange membrane, the outer ends of the anode electrode and the cathode electrode are connected with an external resistor through a lead, constant temperature layers are respectively arranged outside the anode chamber and the cathode chamber, each constant temperature layer is provided with a constant temperature water inlet and a constant temperature water outlet, the anode chamber and the cathode chamber are provided with sampling holes, the sampling holes penetrate through the constant temperature layers, activated sludge and organic wastewater are arranged in the anode chamber, and a heavy metal solution is arranged in the cathode chamber; the data acquisition device comprises a data acquisition card and a controller, the controller is connected with the data acquisition card through a lead, and the data acquisition card is respectively connected with the anode electrode and the cathode electrode through leads; the electrolytic cell is internally provided with electrolyte, a positive electrode and a negative electrode, the positive electrode and the negative electrode are respectively connected with a negative electrode and a positive electrode through leads, the negative electrode is externally provided with a hydrogen storage cover, the hydrogen storage cover is connected with a hydrogen storage tank through a pipeline, Mg-Ti hydrogen storage alloy is arranged in the hydrogen storage tank, and the bottom of the hydrogen storage tank is provided with a heating plate; the microbial fuel cell is combined with the electrolytic cell, and the electric energy generated by the microbial fuel cell is directly applied to the electrolytic cell to electrolyze water to produce hydrogen while treating sewage and recovering heavy metals, so that the economic, efficient and sustainable production of hydrogen production by electrolyzing water is realized. However, the low output of the above microbial fuel cells limits the practical application of MFCs. The anode is used as a carrier for catalyzing and oxidizing organic matters by the microorganisms, and the improvement of the attachment amount and the conductivity of the microorganisms on the surface of the anode is very important. Therefore, the development of high performance anodes is the key to increasing the output power of microbial fuel cells.
Hydroxyapatite (HA) HAs excellent biocompatibility, cell adsorption, and superior interfacial bioactivity compared to other biomaterials, and HAs been widely used in the biomedical field, based on which it is expected to enhance adhesion between electrogenic bacteria and electrodes while increasing the load of anodic bacteria, thereby improving the extracellular electron transfer efficiency of bacteria on the anode. The graphene has a large specific surface area and good conductivity, can provide a high bacterial load for the anode, and develops the anode with the large specific surface area, the good biocompatibility and the high conductivity based on the hydroxyapatite and the graphene, so that the adhesion capability of bacteria on the anode can be enhanced, the interfacial bioactivity of the anode can be improved, and the graphene has social and economic values for the practical application of MFCs.
The invention content is as follows:
the invention aims to overcome the defects of long starting time and low output power of Microbial Fuel Cells (MFCs) in the prior art, and designs a hydroxyapatite/graphene aerogel anode for the microbial fuel cells and a preparation method thereof.
In order to achieve the purpose, the hydroxyapatite/graphene aerogel anode is prepared from graphene oxide and hydroxyapatite.
The preparation method of the hydroxyapatite/graphene aerogel anode comprises the following four steps of preparing a graphene oxide aqueous solution, preparing a hydroxyapatite suspension, preparing hydroxyapatite/graphene hydrogel and preparing the hydroxyapatite/graphene aerogel anode:
(1) preparing a graphene oxide aqueous solution: dispersing 30-120mg of graphene oxide in 30ml of ultrapure water, and carrying out ultrasonic treatment for 15-30 minutes to obtain a uniformly dispersed 1-4mg/ml graphene oxide aqueous solution;
(2) preparation of hydroxyapatite suspension: dispersing 20-50mg of hydroxyapatite in 10ml of ultrapure water, and carrying out ultrasonic treatment for 15-30 minutes to obtain a uniformly dispersed hydroxyapatite suspension liquid with the concentration of 2-5 mg/ml;
(3) preparing hydroxyapatite/graphene hydrogel: adding 1-4ml of the hydroxyapatite suspension prepared in the step (2) into 20ml of the graphene oxide aqueous solution prepared in the step (1), performing ultrasonic treatment at the frequency of 40kHz for 1-3 minutes, adding 100-;
(4) preparing a hydroxyapatite/graphene aerogel anode: and (3) putting the hydroxyapatite/graphene hydrogel prepared in the step (3) into 500mL of ethanol water solution with the volume ratio of 10-20%, dialyzing for 48 hours, and putting the ethanol water solution into a vacuum refrigerator for freeze drying to obtain the hydroxyapatite/graphene aerogel anode.
The invention relates to a hydroxyapatite/graphene aerogel anode which adopts a graphene aerogel anode as a control group when being used for performance test, and the technical process of the preparation method of the graphene aerogel anode comprises three steps of preparing a graphene oxide aqueous solution, preparing a graphene hydrogel and preparing the graphene aerogel anode:
(1) preparing a graphene oxide aqueous solution: dispersing 30-120mg of graphene oxide in 30ml of ultrapure water, and carrying out ultrasonic treatment for 15-30 minutes to obtain a uniformly dispersed 1-4mg/ml graphene oxide aqueous solution;
(2) preparing a graphene hydrogel: adding 1-4ml of ultrapure water into 20ml of the graphene oxide aqueous solution prepared in the step (1), carrying out ultrasonic treatment for 1-3 minutes at the frequency of 40kHz, adding 100-1000 mu l of reducing agent, carrying out ultrasonic treatment for 15-30 minutes, and then heating for 8-12 hours at the temperature of 120-180 ℃ to obtain graphene hydrogel;
(3) preparing a graphene aerogel anode: and (3) putting the graphene hydrogel prepared in the step (2) into 500mL of ethanol water solution with the volume ratio of 10-20%, dialyzing for 48 hours, and putting the solution into a vacuum refrigerator for freeze drying to obtain the graphene aerogel anode.
The graphene oxide related by the invention is a monolayer graphene oxide with the purity of 98%; the hydroxyapatite is nano hydroxyapatite; the reducing agent is ammonia water or ethylenediamine or hydrazine hydrate.
The process for preparing the microbial fuel cell by the hydroxyapatite/graphene aerogel anode comprises the following steps: respectively placing a hydroxyapatite/graphene aerogel anode and a cathode in an anode chamber and a cathode chamber with the volume of 100ml, wherein an anolyte is arranged in the anode chamber, a catholyte is arranged in the cathode chamber, and the anode chamber and the cathode chamber are connected by using a proton membrane to obtain a double-chamber microbial fuel cell; wherein the cathode is carbon plate, carbon felt, carbon paper or carbon fiber brush, and the anolyte is prepared from electrolyte containing 18mMSaturated N of lactate and Shewanella putrefaction suspensions2M9 buffer solution (ph7.2), the catholyte consisting of a solution containing 50 mk3Fe(CN)60.1M phosphate buffer solution (pH 7.2).
Compared with the prior art, the invention respectively disperses high-purity monolayer graphene oxide and hydroxyapatite in ultrapure water to obtain uniformly dispersed graphite oxide dilute aqueous solution and hydroxyapatite suspension by ultrasonic treatment, adds the hydroxyapatite suspension into the graphite oxide dilute aqueous solution to form mixed solution, adds reducing agent into the mixed solution by ultrasonic treatment to carry out hydrothermal reaction to form hydroxyapatite/graphene hydrogel and graphene hydrogel, places the hydroxyapatite/graphene hydrogel and graphene hydrogel in ethanol solution for dialysis for 48 hours, freezes and dries in a vacuum freezer to obtain the hydroxyapatite/graphene aerogel anode with larger specific surface area, better biocompatibility and conductivity, the high-performance aerogel anode enables the starting time of the microbial fuel cell to be shortened by 95% compared with the prior art, and the output power of the microbial fuel cell is greatly improved by high bacterial load and superior interfacial bioactivity, can reach 1800mW/m2The power output of the microbial fuel cell is 20 times of that of the traditional anode microbial fuel cell, the microbial fuel cell can drive small electrical appliances to normally work, the starting time is short, the output power is high, a foundation is laid for the practical application and the commercialization of the microbial fuel cell, and the possibility is provided.
Description of the drawings:
fig. 1 is a scanning electron microscope image of a hydroxyapatite/graphene aerogel anode according to the present invention.
Fig. 2 is an XRD (X-ray diffraction) schematic diagram of a hydroxyapatite/reduced graphene (HA/GO) anode, a reduced graphene oxide (GA) anode and a Graphene Oxide (GO) anode according to the present invention.
FIG. 3 is a graph comparing the long-term discharge curves of the HA/GA microbial fuel cell, CC microbial fuel cell and GA microbial fuel cell according to the present invention.
FIG. 4 is a graph comparing power density versus polarization curves for HA/GA microbial fuel cells, CC microbial fuel cells, and GA microbial fuel cells according to the present invention.
The specific implementation mode is as follows:
the following is a further description by way of example and with reference to the accompanying drawings.
Example 1:
the technical process of the hydroxyapatite/graphene aerogel anode preparation method related to the embodiment includes four steps of preparing a graphene oxide aqueous solution, preparing a hydroxyapatite suspension, preparing a hydroxyapatite/graphene hydrogel and preparing a hydroxyapatite/graphene aerogel anode:
(1) preparing a graphene oxide aqueous solution: dispersing 30mg of graphene oxide in 30ml of ultrapure water, and carrying out ultrasonic treatment for 15 minutes to obtain a uniformly dispersed 1mg/ml graphene oxide aqueous solution;
(2) preparation of hydroxyapatite suspension: dispersing 20mg of hydroxyapatite in 10ml of ultrapure water, and carrying out ultrasonic treatment for 15 minutes to obtain a uniformly dispersed hydroxyapatite suspension liquid with the concentration of 2 mg/ml;
(3) preparing hydroxyapatite/graphene hydrogel: adding 2ml of the hydroxyapatite suspension prepared in the step (2) into 20ml of the graphene oxide aqueous solution prepared in the step (1), performing ultrasonic treatment for 1-3 minutes at the frequency of 40kHz, adding 100 mu l of reducing agent, performing ultrasonic treatment for 15 minutes, and heating for 8 hours at the temperature of 120 ℃ to obtain hydroxyapatite/graphene hydrogel;
(4) preparing a hydroxyapatite/graphene aerogel anode: and (3) putting the hydroxyapatite/graphene hydrogel prepared in the step (3) into 500mL of ethanol water solution with the volume ratio of 10% for dialysis for 48 hours, and putting the ethanol water solution into a vacuum refrigerator for freeze drying to obtain the hydroxyapatite/graphene aerogel anode.
The embodiment relates to a performance test of hydroxyapatite/graphene aerogel anode, at first, make the control sample: adding 2mL of ultrapure water into 20mL of graphene oxide aqueous solution, carrying out ultrasonic treatment for 1-3 minutes at the frequency of 40kHz, adding 100 mu l of reducing agent, carrying out ultrasonic treatment for 15 minutes, heating for 8 hours at the temperature of 120 ℃ to obtain graphene hydrogel, dialyzing the graphene hydrogel in 500mL of ethanol aqueous solution with the volume ratio of 10% for 48 hours, and freeze-drying the graphene hydrogel in a vacuum refrigerator to obtain a graphene aerogel anode; then, respectively adopting hydroxyapatitePreparing a hydroxyapatite/graphene aerogel (HA/GA) microbial fuel cell, a Graphene Aerogel (GA) microbial fuel cell and a Carbon Cloth (CC) microbial fuel cell by using a graphene aerogel anode, a graphene aerogel anode and a carbon cloth anode; finally, open-circuit voltages of the HA/GA microbial fuel cell, the CC microbial fuel cell and the GA microbial fuel cell are acquired by using a data acquisition system, and a long-term discharge curve comparison graph shown in figure 3 is drawn, so that the starting time of the HA/GA microbial fuel cell is respectively shortened by 50% and 95% compared with the starting time of the CC microbial fuel cell and the starting time of the GA microbial fuel cell, and when a 1000-ohm resistor is externally connected, the stable voltage of the HA/GA microbial fuel cell is 3.7 times that of the CC microbial fuel cell; measuring and drawing a power density curve and a polarization curve of the hydroxyapatite/graphene aerogel microbial fuel cell and the graphene aerogel microbial fuel cell by adopting a constant resistance value discharge method: after the external resistances of the HA/GA microbial fuel cell, the CC microbial fuel cell, and the GA microbial fuel cell were adjusted and stabilized at the resistance values, the voltage and current values were recorded, the voltage-current (or current density) curve was plotted, and the power density and polarization curve was plotted by using P ═ U × I, as shown in fig. 4, it was found that the current density of the HA/GA microbial fuel cell was 4A/m2Maximum power density of 1800mW/m2The current density of the GA microbial fuel cell is 3A/m2Maximum power density of 900mW/m2The current density of the CC microbial fuel cell is 0.75A/m2Maximum power density of 90mW/m2The maximum power density of the HA/GA microbial fuel cell is 20 times the maximum power density of the CC microbial fuel cell.
Example 2:
the technical process of the hydroxyapatite/graphene aerogel anode preparation method related to the embodiment includes four steps of preparing a graphene oxide aqueous solution, preparing a hydroxyapatite suspension, preparing a hydroxyapatite/graphene hydrogel and preparing a hydroxyapatite/graphene aerogel anode:
(1) preparing a graphene oxide aqueous solution: dispersing 60mg of graphene oxide in 30ml of ultrapure water, and carrying out ultrasonic treatment for 15 minutes to obtain a uniformly dispersed 2mg/ml graphene oxide aqueous solution;
(2) preparation of hydroxyapatite suspension: dispersing 30mg of hydroxyapatite in 10ml of ultrapure water, and carrying out ultrasonic treatment for 15 minutes to obtain a uniformly dispersed hydroxyapatite suspension liquid with the concentration of 3 mg/ml;
(3) preparing hydroxyapatite/graphene hydrogel: adding 2ml of the hydroxyapatite suspension prepared in the step (2) into 20ml of the graphene oxide aqueous solution prepared in the step (1), performing ultrasonic treatment for 1-3 minutes at the frequency of 40kHz, adding 200 mul of reducing agent, performing ultrasonic treatment for 15 minutes, and heating for 10 hours at the temperature of 160 ℃ to obtain hydroxyapatite/graphene hydrogel;
(4) preparing a hydroxyapatite/graphene aerogel anode: and (3) putting the hydroxyapatite/graphene hydrogel prepared in the step (3) into 500mL of ethanol water solution with the volume ratio of 10% for dialysis for 48 hours, and putting the ethanol water solution into a vacuum refrigerator for freeze drying to obtain the hydroxyapatite/graphene aerogel anode.
Example 3:
the technical process of the hydroxyapatite/graphene aerogel anode preparation method related to the embodiment includes four steps of preparing a graphene oxide aqueous solution, preparing a hydroxyapatite suspension, preparing a hydroxyapatite/graphene hydrogel and preparing a hydroxyapatite/graphene aerogel anode:
(1) preparing a graphene oxide aqueous solution: dispersing 120mg of graphene oxide in 30ml of ultrapure water, and carrying out ultrasonic treatment for 15 minutes to obtain a uniformly dispersed 4mg/ml graphene oxide aqueous solution;
(2) preparation of hydroxyapatite suspension: dispersing 50mg of hydroxyapatite in 10ml of ultrapure water, and carrying out ultrasonic treatment for 15 minutes to obtain a uniformly dispersed hydroxyapatite suspension liquid with the concentration of 5 mg/ml;
(3) preparing hydroxyapatite/graphene hydrogel: adding 2ml of the hydroxyapatite suspension prepared in the step (2) into 20ml of the graphene oxide aqueous solution prepared in the step (1), performing ultrasonic treatment for 1-3 minutes at the frequency of 40kHz, adding 400 mu l of reducing agent, performing ultrasonic treatment for 30 minutes, and heating for 12 hours at 180 ℃ to obtain hydroxyapatite/graphene hydrogel;
(4) preparing a hydroxyapatite/graphene aerogel anode: and (3) putting the hydroxyapatite/graphene hydrogel prepared in the step (3) into 500mL of ethanol water solution with the volume ratio of 10% for dialysis for 48 hours, and putting the ethanol water solution into a vacuum refrigerator for freeze drying to obtain the hydroxyapatite/graphene aerogel anode.
Claims (6)
1. A hydroxyapatite/graphene aerogel anode is characterized by being prepared from graphene oxide and hydroxyapatite.
2. The hydroxyapatite/graphene aerogel anode according to claim 1, wherein the graphene oxide is a single layer of graphene oxide with a purity of 98%; the hydroxyapatite is nano hydroxyapatite.
3. The hydroxyapatite/graphene aerogel anode according to claims 1 to 2, characterized in that the process of preparing a microbial fuel cell is as follows: respectively placing a hydroxyapatite/graphene aerogel anode and a cathode in an anode chamber and a cathode chamber with the volume of 100ml, wherein an anolyte is arranged in the anode chamber, a catholyte is arranged in the cathode chamber, and the anode chamber and the cathode chamber are connected by using a proton membrane to obtain a double-chamber microbial fuel cell; wherein the cathode is carbon plate, carbon felt, carbon paper or carbon fiber brush, and the anolyte is saturated N containing 18mM lactate and Shewanella putrefying bacteria suspension2M9 buffer solution, the catholyte consisting of a solution containing 50mM K3Fe(CN)60.1M phosphate buffer solution.
4. A preparation method of a hydroxyapatite/graphene aerogel anode is characterized in that the technological process comprises four steps of preparing a graphene oxide aqueous solution, preparing a hydroxyapatite suspension, preparing a hydroxyapatite/graphene hydrogel and preparing a hydroxyapatite/graphene aerogel anode:
(1) preparing a graphene oxide aqueous solution: dispersing 30-120mg of graphene oxide in 30ml of ultrapure water, and carrying out ultrasonic treatment for 15-30 minutes to obtain a uniformly dispersed 1-4mg/ml graphene oxide aqueous solution;
(2) preparation of hydroxyapatite suspension: dispersing 20-50mg of hydroxyapatite in 10ml of ultrapure water, and carrying out ultrasonic treatment for 15-30 minutes to obtain a uniformly dispersed hydroxyapatite suspension liquid with the concentration of 2-5 mg/ml;
(3) preparing hydroxyapatite/graphene hydrogel: adding 1-4ml of the hydroxyapatite suspension prepared in the step (2) into 20ml of the graphene oxide aqueous solution prepared in the step (1), performing ultrasonic treatment at the frequency of 40kHz for 1-3 minutes, adding 100-;
(4) preparing a hydroxyapatite/graphene aerogel anode: and (3) putting the hydroxyapatite/graphene hydrogel prepared in the step (3) into 500mL of ethanol water solution with the volume ratio of 10-20%, dialyzing for 48 hours, and putting the ethanol water solution into a vacuum refrigerator for freeze drying to obtain the hydroxyapatite/graphene aerogel anode.
5. The method for preparing the hydroxyapatite/graphene aerogel anode according to claim 4, wherein the graphene oxide is a single-layer graphene oxide with a purity of 98%; the hydroxyapatite is nano hydroxyapatite; the reducing agent is ammonia water or ethylenediamine or hydrazine hydrate.
6. The method for preparing the hydroxyapatite/graphene aerogel anode according to claims 4 to 5, wherein the process for preparing the microbial fuel cell by using the hydroxyapatite/graphene aerogel anode comprises the following steps: respectively placing a hydroxyapatite/graphene aerogel anode and a cathode in an anode chamber and a cathode chamber with the volume of 100ml, wherein an anolyte is arranged in the anode chamber, a catholyte is arranged in the cathode chamber, and the anode chamber and the cathode chamber are connected by using a proton membrane to obtain a double-chamber microbial fuel cell; wherein the cathode is carbon plate, carbon felt, carbon paper or carbon fiber brush, and the anolyte is saturated N containing 18mM lactate and Shewanella putrefying bacteria suspension2M9 buffer solution, the catholyte consisting of a solution containing 50mM K3Fe(CN)60.1M phosphate buffer solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910961505.7A CN110745811B (en) | 2019-11-26 | 2019-11-26 | Hydroxyapatite/graphene aerogel anode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910961505.7A CN110745811B (en) | 2019-11-26 | 2019-11-26 | Hydroxyapatite/graphene aerogel anode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110745811A true CN110745811A (en) | 2020-02-04 |
| CN110745811B CN110745811B (en) | 2022-08-16 |
Family
ID=69277948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910961505.7A Active CN110745811B (en) | 2019-11-26 | 2019-11-26 | Hydroxyapatite/graphene aerogel anode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110745811B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423095A (en) * | 2020-03-05 | 2020-07-17 | 厦门大学 | Method for treating residual activated sludge |
| CN114573201A (en) * | 2022-04-20 | 2022-06-03 | 吉林大学 | Device for removing heavy metals in sludge in situ by electrically coupling graphene hydrogel |
| CN114889175A (en) * | 2022-05-25 | 2022-08-12 | 福州大学 | Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103083729A (en) * | 2013-01-28 | 2013-05-08 | 西南科技大学 | Production method of three-dimensional porous composite bar |
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
| CN105536050A (en) * | 2016-02-05 | 2016-05-04 | 山东明德生物医学工程有限公司 | Graphene oxide modified bone cement as well as preparation method and application thereof |
| CN106075590A (en) * | 2016-07-29 | 2016-11-09 | 福州大学 | A kind of composite of organic/inorganic heterogeneous induction nanometer hydroxyapatite |
| US20170088969A1 (en) * | 2015-09-25 | 2017-03-30 | Jackson State University | Method for obtaining a composite coating on titanium implants for tissue engineering |
| CN108553684A (en) * | 2018-05-15 | 2018-09-21 | 四川大学 | A kind of composite aerogel microballoon and preparation method thereof |
-
2019
- 2019-11-26 CN CN201910961505.7A patent/CN110745811B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103083729A (en) * | 2013-01-28 | 2013-05-08 | 西南科技大学 | Production method of three-dimensional porous composite bar |
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
| US20170088969A1 (en) * | 2015-09-25 | 2017-03-30 | Jackson State University | Method for obtaining a composite coating on titanium implants for tissue engineering |
| CN105536050A (en) * | 2016-02-05 | 2016-05-04 | 山东明德生物医学工程有限公司 | Graphene oxide modified bone cement as well as preparation method and application thereof |
| CN106075590A (en) * | 2016-07-29 | 2016-11-09 | 福州大学 | A kind of composite of organic/inorganic heterogeneous induction nanometer hydroxyapatite |
| CN108553684A (en) * | 2018-05-15 | 2018-09-21 | 四川大学 | A kind of composite aerogel microballoon and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423095A (en) * | 2020-03-05 | 2020-07-17 | 厦门大学 | Method for treating residual activated sludge |
| CN111423095B (en) * | 2020-03-05 | 2022-04-08 | 厦门大学 | Method for treating residual activated sludge |
| CN114573201A (en) * | 2022-04-20 | 2022-06-03 | 吉林大学 | Device for removing heavy metals in sludge in situ by electrically coupling graphene hydrogel |
| CN114573201B (en) * | 2022-04-20 | 2024-05-03 | 吉林大学 | Device for removing heavy metals in sludge through electric coupling graphene hydrogel in situ |
| CN114889175A (en) * | 2022-05-25 | 2022-08-12 | 福州大学 | Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110745811B (en) | 2022-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Feng et al. | Continuous electricity generation by a graphite granule baffled air–cathode microbial fuel cell | |
| CN110745811B (en) | Hydroxyapatite/graphene aerogel anode and preparation method thereof | |
| Zhuwei et al. | Electricity generation using membrane-less microbial fuel cell during wastewater treatment | |
| CN107342428B (en) | Method for enhancing microbial extracellular electron transfer in microbial electrochemical system | |
| Huang et al. | Long-term electricity generation and denitrification performance of MFCs with different exchange membranes and electrode materials | |
| Mehdinia et al. | Nanostructured polyaniline-coated anode for improving microbial fuel cell power output | |
| Li et al. | Response of anodic biofilm and the performance of microbial fuel cells to different discharging current densities | |
| US20110135966A1 (en) | Novel cow-dung based microbial fuel cell | |
| CN111689571A (en) | Microbial electrochemical system and method for controlling hydrogen peroxide generation and elimination | |
| Wang et al. | Enhancement of electrical properties by a composite FePc/CNT/C cathode in a bio-electro-fenton microbial fuel cell system | |
| CN107046135A (en) | Improve the method that microbiological fuel cell handles Polyester wastewater electricity production | |
| CN108217915A (en) | Microbial electrochemical biological rotating disk for sewage treatment | |
| Páez et al. | Electric power production in a microbial fuel cell using Escherichia coli and Pseudomonas aeruginosa, synthetic wastewater as substrate, carbon cloth and graphite as electrodes, and methylene blue as mediator. Laboratory scale. | |
| CN204424374U (en) | A kind of photoelectricity-microbe composite anode microbiological fuel cell | |
| CN103864201A (en) | Method for microbial electrolytic preparation of hydrogen by use of source separated urine | |
| US10396387B2 (en) | Carbon nanotube based microbial fuel cells and methods for generating an electric current | |
| CN212571061U (en) | Microbial fuel cell and equipment | |
| CN108878941B (en) | Microbial fuel cell | |
| Kim | Application of bioelectrochemical process (BES) for electricity generation and sustainable wastewater treatment | |
| Włodarczyk et al. | Single chamber microbial fuel cell with Ni-Co cathode | |
| Vineetha et al. | Electricity production coupled with wastewater treatment using microbial fuel cell | |
| Tardast et al. | Bioelectrical power generation in a membrane less microbial fuel cell | |
| Lianhua et al. | Performance of microbial fuel cell in different anode and cathode electrode sizes | |
| CN113061927B (en) | From Na 2 S 2 O 3 Preparation of carbon-loaded nano MnO by medium 2 Oxygen reduction cathode and MFC | |
| Madhavan et al. | Optimization of microbial fuel cell (MFC) operated with waste water as substrate |
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 |