CN109732918A - Gradient porous graphene oxide three-dimensional microorganism electrode of 3D printing and preparation method thereof - Google Patents
Gradient porous graphene oxide three-dimensional microorganism electrode of 3D printing and preparation method thereof Download PDFInfo
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- 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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides gradient porous graphene oxide three-dimensional microorganism electrode of 3D printing and preparation method thereof.The gradient porous graphene oxide three-dimensional microorganism electrode is to pass through Fe3+Or Ca2+With graphene oxide molecule cross-link, or Fe is further added3O4Or FeS2Etc. graphene oxide hydrogel made from conductive nano-particles be material, prepared using 3D printing technique.The present invention is based on the 3D printing principles of low temperature depositing, using graphene oxide hydrogel as printed material, manufacture the three-diemsnional electrode with gradient pore structured, good biocompatibility, electric conductivity and good interface electron transfer characteristic, to be applied among microorganism electrochemical system, its electrochemical efficiency is improved.
Description
Technical field
The invention belongs to the microorganism electrochemical system electrode manufacturing technology fields of field of renewable energy, and in particular to a kind of
With gradient pore structured three-dimensional microorganism electrode and the preparation method and application thereof.
Background technique
Microorganism electrochemical system is a kind of novel energy conversion device, is mainly characterized by using being attached to electrode table
The electro-chemical activity bacterium in face is as the catalyst to driving electrodes redox reaction.Wherein, microbiological fuel cell is by waste water
In organic matter generate electric current while degraded, microorganism electro synthesis system can lesser applied voltage (0.2V~
Under 0.8V), fuel or chemicals are produced.Microorganism electrode is to determine as the core component of microorganism electrochemical system performance
The key factor of microorganism electrochemical system performance.Microorganism electrode material mostly uses the two-dimensional structures such as carbon cloth, carbon paper at present,
Surface area is small, and adhesion amount of the microorganism on its surface is few, and the interface delivery rate between microbial catalyst and electrode is lower, electricity
Chemical activity biomass is few, and chemical property is poor.Therefore, with morphology controllable, with high-specific surface area, biofacies is constructed
Capacitive gets well and there is the three-diemsnional electrode structure of good interface electron transfer characteristic can greatly improve microorganism electrode performance.
3 D-printing (3DP) i.e. one kind of rapid prototyping technology, it is one kind based on digital model file, with powder
The adhesive materials such as last shape metal material or polymer cast the technology of object by layer-by-layer printing.It is usually used in mould
Have the fields such as manufacture, industrial design, after now introducing polymeric biomaterial, is increasingly used for manufacturing biology in clinical medicine domain
Organizer's (such as cartilage, tooth).
Material will be provided with good stickiness when graphene oxide hydrogel concentration is higher, can be prepared using it and be suitble to 3D printing
Ink.Meanwhile the overlap joint between graphene sheet layer can generate porous structure, provide sky for the attachment and growth of microorganism
Between.In addition, graphene oxide can be graphene by micro-reduction, there is good electric conductivity.
Although graphene-structured has good electric conductivity, graphene oxide hydrogel is when concentration is higher by higher viscous
Property, but more problem: (1) graphene oxide is still had during preparing three-diemsnional electrode using graphene oxide hydrogel
The Problems in forming of hydrogel: even if at higher concentrations, the viscosity of graphene oxide hydrogel is not enough to support the three of 3D printing
Tie up porous structure, the easily adhesion and integrally-built collapsing between generation silk and silk.(2) forming of graphene oxide hydrogel
Precision problem: since there are certain elasticity for graphene oxide hydrogel, in print procedure inside gel there are internal stress and
Biggish internal strain, so that the extrusion and dwell time of printing silk can not be precisely controlled, the forming essence of large effect material
Degree.(3) the electric conductivity problem of three-diemsnional electrode: graphene oxide itself is almost non-conductive, needs for graphene oxide to be reduced to
Graphene.But reduction meeting of general hydroiodic acid method is used so that electrode becomes toxic, it is not suitable for microorganism and grows.Meanwhile oxygen
Bridging arrangement between graphite alkene lamella is also unfavorable for effective relay of electronics.(4) microorganism for being attached to electrode surface is urged
Interface electron transmission problem between agent and electrode: microorganism obtains electronics (or microbiological oxidation organic matter from electrode
Electron transmission will be generated to electrode surface) ability have decisive influence to microorganism electrochemical system performance, however in mesh
In preceding microorganism electrochemical system, the interface electron transport rate between microorganism and electrode is lower.
Summary of the invention
In order to solve the above technical problems, the present invention is directed to the 3D printing principles based on low temperature depositing, with graphene oxide water
Gel has gradient pore structured, good biocompatibility, electric conductivity and good interface electron transmission as printed material, manufacture
The three-diemsnional electrode of characteristic improves its electrochemical efficiency to be applied among microorganism electrochemical system.
The present invention according to microorganism electrochemical system for the performance requirement of electrode, using graphene oxide hydrogel conduct
Printed material explores the preparation process and material property of graphene oxide；Devise threedimensional model and the 3D printing side of electrode
Case；The 3D printing equipment of graphene oxide has been transformed based on preparation technology in low temperature, has realized the extruded type 3D printing of the condition of low temperature
(extrusion-based 3D printing), while keeping the room temperature environment of syringe needle and needle tubing part；It is explored based on the equipment
Optimal printing parameter out；Microorganism electrochemical system is observed and assembled eventually by microsection come the physics for novel electrode of testing and assessing
Characteristic and electrochemical properties.
The research of the invention finds that adding appropriate Fe into graphene oxide hydrogel3+Or Ca2+, can solve graphite oxide
The Problems in forming of alkene hydrogel, can support the three-dimensional porous structure of 3D printing, and overall structure is not easy to collapse；Also improve printing
There are internal stress inside gel in the process, the extrusion of printing silk and dwell time are precisely controlled, so as to control
The forming accuracy of material；In addition, addition Fe3+Or Ca2+The electric conductivity of graphene oxide hydrogel is also improved afterwards.Further
Ground, by adding Fe3O4Or FeS2Etc. conductive nano-particles can promote the extracellular electron transmission mistake of the long-range in microorganism reticular structure
Journey, including to promote the interface electron transmission between electrode and microorganism and between different population microorganism.In addition, Fe3O4
Or FeS2Etc. conductive nano-particles also there is good biocompatibility, the characteristics such as low cost and easy processing have significant excellent
Gesture.
Specifically, the present invention provides a kind of gradient porous graphene oxide three-dimensional microorganism electrode, it is to pass through Fe3+
Or Ca2+With graphene oxide molecule cross-link, and further add conductive nano-particles, prepared by graphene oxide hydrogel be
Material, using 3D printing technique preparation.The conductive nano-particles are preferably Fe3O4Or FeS2。
Specifically, by adding Fe into graphene oxide hydrogel3+Or Ca2+, make Fe3+Or Ca2+With graphene oxide
The functional groups such as-COOH ,-OH crosslink effect in molecule, further improve the mechanical strength of hydrogel network.Meanwhile passing through
Fe is further added3O4Or FeS2Etc. conductive nano-particles, be made and meet microorganism electrode condition, and can be used for the oxygen of 3D printing
Graphite alkene hydrogel material.
The present invention also provides the preparation methods of above-mentioned gradient porous graphene oxide three-dimensional microorganism electrode, comprising: preparation
Graphene oxide hydrogel, it is interior thereto to add Fe3+Or Ca2+, make Fe3+Or Ca2+(mainly wherein with graphene oxide molecule
The functional groups such as-COOH ,-OH) crosslink effect, modified graphene oxide hydrogel is made；And Fe is further added3O4Or
FeS2Etc. conductive nano-particles, be made and meet microorganism electrode condition and the gradient porous graphene oxide three of 3D printing can be used for
Tie up microorganism electrode.
In above-mentioned preparation method, graphene oxide hydrogel can be prepared by conventional method in that art, such as be first passed through
Hummers method prepares graphene oxide dispersion, and using 18000rmp, the high speed centrifugation of 30min obtains graphene oxide water
Gel.
Further, the concentration of the graphene oxide hydrogel is 20-30mg/ml, preferably 25mg/ml.
Further, added Fe3+Or Ca2+Molar ratio with graphene oxide molecule is 10-15:16-24, preferably
For 14:20.
The Fe3+Or Ca2+It can be provided by conventional source of iron, calcium source, such as Nantong Badische Chemical Company, Weifang great mansion
Believe snow melt Products Co., Ltd etc..
Further, the Fe being added3O4Or FeS2Etc. concentration of the conductive nano-particles in graphene oxide hydrogel be
1.5-3mmol preferably 2.08mmol.
For the correlated performance for further improving above-mentioned gradient porous graphene oxide three-dimensional microorganism electrode, the present invention is also right
It is optimized using 3D printing technique relevant parameter.Process Exploration and microexamination based on early period, the study found that oxidation stone
Black alkene print performance at different temperatures is different, the 3D printing of above-mentioned modified graphene oxide hydrogel need temperature≤-
10 DEG C of the complete and circular wire section that just can guarantee structure, is preferably printed under the conditions of -25 DEG C to -15 DEG C.
On this basis, the parameters such as optimal print temperature, the print speed of graphene oxide are further explored.Specific forming
Parameter is as follows: forming room temperature: -15 DEG C；Syringe needle syringe temperature: 25 DEG C；160-300 μm of dispensing needle head internal diameter；Extruded velocity:
0.25-0.40mm/s；Shear velocity: 10-15mm/s；Layer is 100-1000 μm high.It is preferred that print parameters are dispensing needle head internal diameter 200
μm；Extruded velocity: 0.3mm/s；Shear velocity: 12mm/s；Layer is 200-400 μm high.
Further, the computer mould of design novel electrode is required for the morpheme of electrode based on microorganism electrochemical system
Type, and be layered by software, printing path is generated, realization overall dimensions are (12-21mm) × (12-21mm) × (3-
10mm), silk spacing is 1.0-3.0mm, the print structure that silk diameter is 200-400 μm；It is preferred that print structure overall dimensions are 20
× 20 × 5mm, silk spacing are 2mm, and silk diameter is 250 μm.
Further, the present invention is also optimized the treatment process of microorganism electrode made of 3D printing.Specifically,
By first cryo-conservation under the conditions of≤- 80 DEG C of microorganism electrode obtained by 3D printing, then low temperature freeze-drying is carried out, can be prepared by finished product ladder
Spend porous oxidation graphene three-dimensional microorganism electrode.Low temperature freeze-drying carries out preferably under the conditions of 0.05mbar, -50 DEG C, general 48h
It can be lyophilized.
Specifically, the preparation method of above-mentioned gradient porous graphene oxide three-dimensional microorganism electrode includes: to first pass through
Hummers method prepares graphene oxide dispersion, obtains graphene oxide hydrogel using high speed centrifugation；Addition in thereto
Fe3+Or Ca2+, make Fe3+Or Ca2+Effect is crosslinked with graphene oxide molecule；And further add Fe3O4Or FeS2Etc. conductions
Modified graphene oxide hydrogel is made in nano particle；3D printing, low-temperature frozen are drying micro- at gradient porous graphene oxide three-dimensional
Bioelectrode.
The invention also includes the gradient porous graphene oxide three-dimensional microorganism electrodes of above method preparation.
Above-mentioned gradient porous graphene oxide three-dimensional microorganism electrode, resistance are 5.0-25.3 Ω；It is seen by scanning electron microscope
Display is examined, in generally existing several microns to tens microns of horizontal surface and section not etc. mesoporous, and vertical surface and section
Then seldom exist mesoporous；By quality estimation, porosity is about 92.0%-98.7%；It, can under the relative potentials of 0V
Reaching density peak value is 15A/m2；By running (such as by prolonged electricity production bacterium culture), electric current for a long time
Density can reach 13A/m2, much higher than the 2.5A/m of carbon cloth2Highest current density, show good electrochemistry
Energy.In short, microorganism electrode of the present invention has gradient pore structured, good electric conductivity, good biocompatibility；It can show
It writes and improves microorganism electrochemical system load bacterium amount and electron transfer rate.
For the correlated performance for further improving above-mentioned gradient porous graphene oxide three-dimensional microorganism electrode, be more suitable on
The 3D printing of modified graphene oxide hydrogel is stated, the present invention is also based on preparation technology in low temperature, devises and is exclusively used in graphite oxide
The 3D printing equipment of alkene gel comprising 3D printing spray head, the 3D printing spray head include feed pipe and connect with the feed pipe
The temperature control equipment connect, the temperature control equipment are used to control the temperature of 3D printing material in the feed pipe.Further
Ground, the material of the temperature control equipment are copper.
The present invention compared with prior art the utility model has the advantages that
1) manufacture in microorganism electrochemical system with gradient pore structured three-diemsnional electrode is realized, relative to carbon cloth
The attachment and growth of microorganism are more advantageous to higher porosity and specific surface area with two-dimensional electrodes such as carbon papers.
2) preparation technology in low temperature is utilized, realizes the 3D printing of graphene oxide hydrogel under cryogenic conditions, and utilize this
One technology realizes gradient pore structured three-diemsnional electrode.Tiring out 3D printing technique using low temperature depositing may be implemented the quick of structure
Printing-forming.
3) it is based on multiple cross-linked mechanism, realizes bridging arrangement and official between lamella simultaneously in graphene oxide hydrogel
Cross-linked structure between capable of rolling into a ball, increases the viscosity of graphene oxide hydrogel, significantly improves its forming property and forming accuracy.
4) by adding Fe in graphene oxide hydrogel3O4(or FeS2) etc. conductive nano-particles, promote microorganism urge
Interface (between electrode and microorganism interface and between different population microorganism) electron transfer process between agent and electrode reduces
Charge transfer impedance optimizes microorganism electrochemical system to improve microorganism electrochemical system performance.
Detailed description of the invention
Fig. 1: 3D printing device structure schematic diagram (A) of the present invention and 3D printing nozzle structure schematic diagram (B)；
1 is 3D printing spray head, and 2 be shaped structure, and 3 be substrate, and 4 be working chamber, and 5 be temperature control equipment (Heated Copper
Column), 6 be 3D printing material, and 7 be syringe needle.
Fig. 2: the gradient porous graphene oxide three-dimensional microorganism electrode structural schematic diagram (second level meso-hole structure) of the present invention and
Partial enlarged view.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
3D printing equipment used in following embodiment is as shown in Figure 1A comprising 3D printing spray head 1.Print procedure is in working chamber
It is completed in 4, prints shaped structure 2 on the substrate 3.Figure 1B is the enlarged drawing of 3D printing spray head 1, and the 3D printing spray head 1 wraps
Feed pipe and the temperature control equipment connecting with the feed pipe 5 are included, further includes syringe needle 7, the temperature control equipment 5 is for controlling
Make the temperature of 3D printing material 6 in the feed pipe.Further, the temperature control equipment 5 is heating copper post.
Embodiment 1
Add Fe3+The gradient porous graphene oxide three-dimensional microorganism electrode of crosslinking, preparation method include the following steps:
1) graphene oxide dispersion is prepared by Hummers method, using 18000rmp, the high speed centrifugation of 30min is obtained
To 25mg/ml graphene oxide hydrogel.Into graphene oxide hydrogel, 3.11wt% adds 0.2mol/L Fe in proportion3+
Solution passes through Fe3+With the crosslinked action of the functional groups such as-COOH ,-OH in graphene oxide molecule, further improve hydrogel network
Modified graphene oxide hydrogel is made in the mechanical strength of network.
2) gradient porous graphene oxide three-dimensional microorganism electrode is made in 3D printing
The computer model of design novel electrode is required for the morpheme of electrode based on microorganism electrochemical system, and is passed through
Software is layered, and printing path is generated, and realizes 20 × 20 × 10mm, and silk spacing is the print structure of 1.5mm.
Specific forming parameter is as follows: forming room temperature: -15 DEG C；Syringe needle syringe temperature: 25 DEG C；200 μ of dispensing needle head internal diameter
m；Extruded velocity: 0.3mm/s；Shear velocity: 12mm/s；Layer is 250 μm high.
First cryo-conservation under the conditions of -80 DEG C of 3D printing resulting materials, then 0.05mbar is carried out, -50 DEG C, the freeze-drying of 48h
Processing, is made gradient porous graphene oxide three-dimensional microorganism electrode
Porous oxidation graphene three-dimensional microorganism electrode made from the embodiment is applied to microorganism electrochemical system, it can
To pass through electricity production bacterium direct-reduction.
Experiment 1
Physicochemical property test is carried out to gradient porous graphene oxide three-dimensional microorganism electrode made from embodiment 1.
1) physical property is tested and assessed
Pass through the graphite of gradient porous graphene oxide three-dimensional microorganism electrode obtained by electricity production bacterium reduction-oxidation implementation 1
Oxygen-containing functional group in alkene, to measure its resistance.It is 10 Ω by the resistance that reduction reaction measures novel electrode.
It is shown by scanning electron microscopic observation, generally existing several microns to tens microns in horizontal surface and section of novel electrode
Not equal is mesoporous, and vertical surface and section then seldom exist it is mesoporous, this is because caused by material stacking under the influence of gravity.
By quality estimation, the porosity for obtaining new electrode materials is about 97.9%.
2) electrochemical properties are tested and assessed
Complete microorganism electricity is assembled into using gradient porous graphene oxide three-dimensional microorganism electrode made from embodiment 1
Chemical system is grown up situation and chemical property by control group its microorganism of testing and assessing of carbon felt.Under the starting potential of 50mV, lead to
Cross Fe3+The graphene oxide electrode of crosslinking can reach density peak value 18A/m2, it is carbon felt density peak value (4A/m2)
4.5 times or so, show good chemical property.
Embodiment 2
Add Ca2+The gradient porous graphene oxide three-dimensional microorganism electrode of crosslinking, preparation method include the following steps:
1) graphene oxide dispersion is prepared by Hummers method, using 18000rmp, the high speed centrifugation of 30min is obtained
To 25mg/ml graphene oxide hydrogel.Into graphene oxide hydrogel, 3.11wt% adds 0.2mol/L Ca in proportion2+
Solution passes through Ca2+With the crosslinked action of the functional groups such as-COOH ,-OH in graphene oxide molecule, further improve hydrogel network
Modified graphene oxide hydrogel is made in the mechanical strength of network.
2) gradient porous graphene oxide three-dimensional microorganism electrode is made in 3D printing
The computer model of design novel electrode is required for the morpheme of electrode based on microorganism electrochemical system, and is passed through
Software is layered, and printing path is generated, and realizes 20 × 20 × 5mm, and silk spacing is the print structure of 2mm.
Specific forming parameter is as follows: forming room temperature: -15 DEG C；Syringe needle syringe temperature: 25 DEG C；200 μ of dispensing needle head internal diameter
m；Extruded velocity: 0.3mm/s；Shear velocity: 12mm/s；Layer is 250 μm high.
First cryo-conservation under the conditions of -80 DEG C of 3D printing resulting materials, then 0.05mbar is carried out, -50 DEG C, the freeze-drying of 48h
Processing, is made gradient porous graphene oxide three-dimensional microorganism electrode (as shown in Figure 2).
Porous oxidation graphene three-dimensional microorganism electrode made from the embodiment is applied to microorganism electrochemical system, it can
To pass through electricity production bacterium direct-reduction.
Experiment 2
Physicochemical property test is carried out to gradient porous graphene oxide three-dimensional microorganism electrode made from embodiment 2.
1) physical property is tested and assessed
Pass through gradient porous graphene oxide three-dimensional microorganism electrode obtained by 55% hydroiodic acid reduction-oxidation embodiment 2
Graphene in oxygen-containing functional group, to measure its resistance.It is 5 Ω by the resistance that reduction reaction measures novel electrode.
It is shown by scanning electron microscopic observation, generally existing several microns to tens microns in horizontal surface and section of novel electrode
Not equal is mesoporous, and vertical surface and section then seldom exist it is mesoporous, this is because caused by material stacking under the influence of gravity.
By quality estimation, the porosity for obtaining new electrode materials is about 98.7%.
2) electrochemical properties are tested and assessed
Complete microorganism electricity is assembled into using gradient porous graphene oxide three-dimensional microorganism electrode made from embodiment 2
Chemical system is grown up situation and chemical property by control group its microorganism of testing and assessing of carbon cloth.Under the relative potentials starting of 0V,
Novel electrode can reach density peak value 15A/m2, it is carbon cloth density peak value (3A/m2) 5 times or so.Through it is too long when
Between the culture of electricity production bacterium, the current density of novel electrode can reach 13A/m2, much higher than the 2.5A/m of carbon cloth2Highest electricity
Current density shows good chemical property.
Embodiment 3
Add Fe3+Crosslinking, and use Fe3O4The gradient porous graphene oxide three of nano particle reinforcement interface electron transmission
Microorganism electrode is tieed up, preparation method includes the following steps:
1) graphene oxide dispersion is prepared by Hummers method, using 18000rmp, the high speed centrifugation of 30min is obtained
To 25mg/ml graphene oxide hydrogel.Into graphene oxide hydrogel, 3.11wt% adds 0.2mol/L Fe in proportion3+
Solution and 2.08mmol Fe3O4After being sufficiently mixed, modified 3D printing graphene oxide ink is made in nano particle.
2) gradient porous graphene oxide three-dimensional microorganism electrode is made in 3D printing
The computer model of design novel electrode is required for the morpheme of electrode based on microorganism electrochemical system, and is passed through
Software is layered, and printing path is generated, and realizes 20 × 20 × 5mm, and silk spacing is the print structure of 2mm.
Specific forming parameter is as follows: forming room temperature: -15 DEG C；Syringe needle syringe temperature: 25 DEG C；200 μ of dispensing needle head internal diameter
m；Extruded velocity: 0.3mm/s；Shear velocity: 12mm/s；Layer is 250 μm high.
First cryo-conservation under the conditions of -80 DEG C of 3D printing resulting materials, then 0.05mbar is carried out, -50 DEG C, the freeze-drying of 48h
Processing, is made gradient porous graphene oxide three-dimensional microorganism electrode
Gradient porous graphene oxide three-dimensional microorganism electrode made from the embodiment is applied to microorganism electrochemical system
System passes through electricity production bacterium direct-reduction.
Experiment 3
Respectively by microorganism electrode made from microorganism electrode made from embodiment 3 and embodiment 1 in microorganism electrochemical
Electrochemical impedance test is carried out in system, as a result, it has been found that, the two electrochemical impedance curve shape is similar.Pass through circuit the Fitting Calculation
Obtaining microorganism electrode electron transmission impedance made from embodiment 3 is 12.6 Ω, and microorganism electrode electronics made from embodiment 1
Transfer impedance is 25.3 Ω, this shows that addition conductive nano-particles can increase the interface electron transmission between microorganism and electrode
Rate promotes the transmitting of extracellular microbial exoelectron, to reach higher power density.
Embodiment 4
Difference with embodiment 3 is only that Fe3O4Replace with FeS2Interface electron transmission is reinforced in nano particle, preparation
Gradient porous graphene oxide three-dimensional microorganism electrode.Obtained microorganism electrode electrochemical properties are approximate with embodiment 3.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of gradient porous graphene oxide three-dimensional microorganism electrode, is to pass through Fe3+Or Ca2+With graphene oxide molecule
Being crosslinked and further adding graphene oxide hydrogel prepared by conductive nano-particles is material, is prepared using 3D printing technique
's；The conductive nano-particles are preferably Fe3O4Or FeS2。
2. a kind of preparation method of gradient porous graphene oxide three-dimensional microorganism electrode characterized by comprising preparation oxidation
Graphene hydrogel, it is interior thereto to add Fe3+Or Ca2+, make Fe3+Or Ca2+Effect is crosslinked with graphene oxide molecule, and
Conductive nano-particles are further added, modified graphene oxide hydrogel is made；Gradient porous graphene oxide is made in 3D printing
Three-dimensional microorganism electrode；The conductive nano-particles are preferably Fe3O4Or FeS2。
3. preparation method according to claim 2, which is characterized in that the concentration of the graphene oxide hydrogel is 20-
30mg/ml, preferably 25mg/ml；And/or
Added Fe3+Or Ca2+Molar ratio with graphene oxide molecule is 10-15:16-24, preferably 14:20；And/or
Concentration of the conductive nano-particles being added in graphene oxide hydrogel is 1.5-3mmol, preferably 2.08mmol.
4. preparation method according to claim 2 or 3, which is characterized in that the 3D printing preferably exists in temperature≤- 10 DEG C
It is carried out under the conditions of -25 DEG C to -15 DEG C of temperature.
5. preparation method according to claim 2 or 3, which is characterized in that the 3D printing forming parameter: forming room temperature
Degree: -15 DEG C；Syringe needle syringe temperature: 25 DEG C；160-300 μm of dispensing needle head internal diameter；Extruded velocity: 0.25-0.40mm/s；Shearing
Speed: 10-15mm/s；Layer is 100-1000 μm high；It is preferred that print parameters are 200 μm of dispensing needle head internal diameter；Extruded velocity: 0.3mm/
s；Shear velocity: 12mm/s；Layer is 200-400 μm high；And/or
The 3D printing structure is (12-21mm) × (12-21mm) × (3-10mm), and silk spacing is 1.0-3.0mm, and silk diameter is
200-400μm；It is preferred that print structure is 20 × 20 × 5mm, silk spacing is 2mm, and silk diameter is 250 μm.
6. according to the described in any item preparation methods of claim 2-5, which is characterized in that further include by microorganism obtained by 3D printing
First cryo-conservation under the conditions of≤- 80 DEG C of electrode, then low temperature freeze-drying is carried out, the gradient porous graphene oxide three-dimensional of finished product is micro-
Bioelectrode；Low temperature freeze-drying carries out preferably under the conditions of 0.05mbar, -50 DEG C.
7. according to the described in any item preparation methods of claim 2-6 characterized by comprising first pass through the preparation of Hummers method
Graphene oxide dispersion obtains graphene oxide hydrogel using high speed centrifugation；Fe is added in thereto3+Or Ca2+, make
Fe3+Or Ca2+Effect is crosslinked with graphene oxide molecule, and further modified oxidized stone is made in addition conductive nano-particles
Black alkene hydrogel；3D printing, low-temperature frozen are drying at gradient porous graphene oxide three-dimensional microorganism electrode.
8. the gradient porous graphene oxide three-dimensional microorganism electrode of any one of claim 2-7 the method preparation.
9. gradient porous graphene oxide three-dimensional microorganism electrode described in claim 1 or 8, which is characterized in that its resistance
5.0-25.3Ω；Its in generally existing several microns to tens microns of horizontal surface and section not etc. mesoporous, and vertical surface and
Section then seldom exists mesoporous；Its porosity is about 92.0-98.7%；Under the relative potentials starting of 0V, electricity can be reached
Current density peak value is 15A/m2；By running for a long time, current density can reach 13A/m2。
10. a kind of 3D printing equipment, which is characterized in that including 3D printing spray head, the 3D printing spray head include feed pipe and with
The temperature control equipment of the feed pipe connection, the temperature control equipment is for controlling 3D printing material in the feed pipe
Temperature；Preferably, the material of the temperature control equipment is copper.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252754A (en) * | 2020-03-12 | 2020-06-09 | 浙江大学 | Graphene aerogel air hole regulation and control method and graphene gradient aerogel |
| CN112606391A (en) * | 2020-11-27 | 2021-04-06 | 山东第一医科大学附属省立医院(山东省立医院) | Manufacturing method of medical instrument for digestive system department |
| WO2021179232A1 (en) * | 2020-03-12 | 2021-09-16 | 浙江大学 | Method for preparing aerogel via solvent plasticization and foaming |
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| CN111252754A (en) * | 2020-03-12 | 2020-06-09 | 浙江大学 | Graphene aerogel air hole regulation and control method and graphene gradient aerogel |
| CN111252754B (en) * | 2020-03-12 | 2020-12-29 | 浙江大学 | Graphene aerogel air hole regulation and control method and graphene gradient aerogel |
| WO2021179232A1 (en) * | 2020-03-12 | 2021-09-16 | 浙江大学 | Method for preparing aerogel via solvent plasticization and foaming |
| CN112606391A (en) * | 2020-11-27 | 2021-04-06 | 山东第一医科大学附属省立医院(山东省立医院) | Manufacturing method of medical instrument for digestive system department |
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