CN105413731B - A kind of doped carbon nanocatalyst and its preparation method and application - Google Patents
A kind of doped carbon nanocatalyst and its preparation method and application Download PDFInfo
- Publication number
- CN105413731B CN105413731B CN201510929372.7A CN201510929372A CN105413731B CN 105413731 B CN105413731 B CN 105413731B CN 201510929372 A CN201510929372 A CN 201510929372A CN 105413731 B CN105413731 B CN 105413731B
- Authority
- CN
- China
- Prior art keywords
- egc1
- doped carbon
- mfc
- nanocatalyst
- preparation
- 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
Classifications
-
- 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
- H01M4/90—Selection of catalytic material
-
- 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
Abstract
The invention discloses a kind of doped carbon nanocatalyst and its preparation method and application, step is as follows：By whole cooked egg grinding dehydration after with g C3N4Mixing, egg and g C after the dehydration3N4Mass ratio be 0.5~2, by said mixture grinding uniformly be put into tube furnace lead to nitrogen protection, 1~3h is being calcined at 800~1000 DEG C with the heating rate of 5~15 DEG C/min, that is, is obtaining doped carbon nanocatalyst.The doped carbon nanocatalyst raw materials of the present invention are cheap, method is simple, yield is big, and obtain the best doped carbon nanocatalyst of catalytic effect by varying proportion of raw material and heating rate, make it in neutral conditions, its hydrogen reduction effect can substitute the Pt/C (20%) of costliness to a certain extent.
Description
Technical field
The invention belongs to bioenergy Material Field, and in particular to a kind of preparation method of doped carbon nanocatalyst and its
Using.
Background technology
Microbiological fuel cell (microbial fuel cells, MFCs) is that a kind of be used as using electricity-producing microorganism is catalyzed
The chemical energy of organic matter, is changed into the advanced energy technology of electric energy by agent.Human world is short with resource there are environmental pollution at present
Two big crises are lacked, MFCs is produced electricity while debirs (including organic wastewater and organic solid castoff) is handled, and is realized useless
Thing processing and energy recovery two-win, as the hot spot of field of environment protection research.
Microbiological fuel cell is in laboratory stage mostly at present, so the amplification of microbial fuel cells system is to work as
The preceding main problem faced.The key of the amplification of microbiological fuel cell is directly (without adding in exogenous electron transmission
Mesosome), three importances of single-chamber and cheap cathode.And it is current, generally use efficient pt as biofuel battery cathode
Catalyst.But the serious amplification for hindering biological fuel cell of its expensive price and easily poisoning.Therefore must find cheap
The substitute of efficient stable.
New carbon, if carbon nanotubes and graphene are the research hotspots of cathod catalyst in recent years.Carbon nanotubes
Mechanical performance, chemical stability and the electric conductivity that (Carbon Nanotubes, CNTs) has, and possess high ratio surface
Product, therefore other carbon materials can be substituted, as microorganism and the excellent carrier of metallic catalyst.Graphene is and CNT structures
And kin two-dimentional carbon nanomaterial, also it is applied to the research of MFC cathodes.When graphene is as catalyst, it, which is catalyzed, lives
Property it is poor, it is more as catalyst carrier in research.It is higher yet with graphene and carbon nanotubes own cost, and mixing
The problem of in miscellaneous process there is also stablizing, can also be subject to a definite limitation applied to actual stability.Natural biomass such as chicken
Egg (Jian et al., 2014), agaric, pig blood, soybean (Guo et al., 2014), sludge, fungi, bacterium contain abundant
Nutrient can realize that auto-dope reduces complicated doping process in preparation process.Wherein iron, manganese, phosphorus, sulphur, nitrogen, halogen family
Element etc. is all proved to have positive facilitation to hydrogen reduction effect.So selection natural biomass prepares the moon for predecessor
Electrode catalyst becomes research hotspot, but most preparation method is more complicated, not easy to control, it is necessary to further study, with
Its cost and complexity are reduced, and improves its catalytic activity.
The content of the invention
One of the object of the invention is to provide a kind of doped carbon nanocatalyst.
The two of the object of the invention are to provide the preparation method of above-mentioned catalyst.
The third object of the present invention is to provide the application of above-mentioned catalyst.
The method of the present invention takes full advantage of the elements such as the iron being rich in biomass, manganese, phosphorus, sulphur, nitrogen, halogen, its
Middle nitrogen can form big pi bond, improve catalytic performance, enrich Surface oxygen-containing groups, there is provided more to adsorb, be coordinated and put
Function is changed, while is also capable of providing more chemical active sites.And other elements are also proved effectively improve catalysis
The limiting current density of agent and make starting point position move forward.And the mode of original position doping, can make catalyst have the steady of higher
It is qualitative.
The present invention seeks to what is be achieved through the following technical solutions：
A kind of preparation method of doped carbon nanocatalyst, step are as follows：
By whole cooked egg grinding dehydration after with g-C3N4Mixing, egg and g-C after the dehydration3N4Mass ratio be 0.5
~2, by said mixture grinding uniformly be put into tube furnace lead to nitrogen protection, with the heating rate of 5~15 DEG C/min 800
1~3h is calcined at~1000 DEG C, that is, obtains doped carbon nanocatalyst.
The g-C3N43h preparations are calcined by being put into after urea dehydration grinding uniformly in 550 DEG C of Muffle furnaces.
The dehydration egg and g-C3N4Mass ratio be 1.
Heating rate in tube furnace is 10 DEG C/min, and calcining heat is 900 DEG C, calcination time 2h.
The drying and dehydrating is the forced air drying 24h at 80 DEG C.
The doped carbon nanocatalyst prepared using the above method prepares the air cathode of microbiological fuel cell.
The preparation method of the air cathode is：First basis material carbon cloth graphite and 40%PTFE mixtures are coated with,
20-30min is handled in prior be preheating in 370 DEG C of Muffle furnaces after air-drying, then applying PTFE layers in one side is used as diffusion layer, another
Simultaneously coat doped carbon nanocatalyst.
The specific preparation process of the diffusion layer is：Shaking 60%PTFE latex vessels makes suspension be uniformly dispersed as far as possible,
It is evenly coated in brush on carbon cloth；Carbon cloth is placed in the prior Muffle furnace for being preheating to 370 DEG C after air-dried 5-10min to be heat-treated
10-15min；Carbon cloth is then taken out to be cooled to room temperature；In triplicate, it is coated with altogether, is heat-treated 4 layers of PTFE coatings.
Microbiological fuel cell is run using the air cathode.Detailed process is：After the bed mud preculture of pig farm, take
Supernatant is as inoculum；By inoculum and 1gL-1Dextrose broth according to 1:It is inoculated in after 1 volume ratio mixing micro-
Biological fuel cell, runs under conditions of being 30 DEG C in temperature.
Nutrient solution used component is as follows during the preculture：1g·L-1Glucose, 0.08gL-1NH4Cl, 0.04g
L-1KH2PO4, 0.48gL-1Yeast extract and 5mLL-1Trace element solution.
The component of the dextrose broth is as follows：1g·L-1Glucose, 5mLL-1Vitamin solution, 12.5mLL-1
Trace element and 50mmolL-1PBS solution；The component of PBS solution is：0.31g·L-1NH4Cl, 2.452gL- 1NaH2PO4·H2O, 0.576gL-1Na2HPO4And 0.13gL-1KCl。
The present invention has the following advantages that compared with prior art and beneficial effect：
(1) doped carbon nanocatalyst raw materials in situ of the invention are cheap, and method is simple, and yield is big, and passes through
Change proportion of raw material and heating rate and calcination time obtains the highest catalyst of oxygen reduction catalytic activity, make it in certain journey
The Pt/C (20%) of costliness can be substituted on degree.
(2) the excellent optimal proportion that have selected between raw material of the present invention and optimal tube furnace heating rate and calcination time,
Obtained doped carbon nanocatalyst EGC1-10-2 catalytic performances are better than other quality proportionings, heating rate and calcination time
Doped carbon nanocatalyst, wherein the sum of graphite mould nitrogen-atoms and pyridine type nitrogen-atoms ratio reach highest, and catalytic performance is most
By force, and cyclic voltammetry curve reduction peak cutting edge of a knife or a sword intensity and area under the curve with Pt/C (20%) quite, illustrate its electric conductivity and ORR all with
Pt/C (20%) catalyst is suitable.
(3) the energy effectively start MFC of the carbon nanocatalyst in the scope, realizes MFC cathodic oxygen reductions.But
The catalytic oxidation-reduction efficiency of EGC1-10-2 is stronger, and can effectively shorten starting period of MFC to most short 18h.
(4) the EGC1-10-2 catalyst that the electricity generation performance of MFC shows to prepare is as MFC cathode catalysis oxygen reduction reactions, no
The internal resistance of MFC can only be reduced, also substantially increase the output voltage of MFC.Under same current density, MFC-EGC1-10-2
Power density and output voltage it is suitable with MFC-Pt/C, this shows the catalytic oxidation-reduction ability and Pt/C of EGC1-10-2
(20%) quite.
Brief description of the drawings
Fig. 1 a, Fig. 1 b, Fig. 1 c represent that the N1s of EGC1-5-2, EGC1-10-2 and EGC1-15-2 in embodiment 2 are composed entirely respectively
Figure.
Fig. 2 represents the XRD spectrum of EC, EGC1-5-2, EGC1-10-2, EGC1-15-2 in embodiment 3.
Fig. 3 represents the Raman collection of illustrative plates of EC, EGC1-5-2, EGC1-10-2, EGC1-15-2 in embodiment 4.
Fig. 4 represents the TEM figures of EC, EGC1-10-2 in embodiment 5.Wherein a, b represent the low power of EC, EGC1-10-2 respectively
Transmission electron microscope picture, wherein the amplification factor of (1) (2) is different；C represents the high power transmission electron microscope picture of EGC1-10-2.
Fig. 5 represents to scheme the cyclic voltammogram that a represents EGC1-10-1, EGC1-10-2 and EGC1-10-3, b tables in embodiment 6
Show the electron transfer number that EGC1-10-1, EGC1-10-2 and EGC1-10-3 are calculated under electrode disk-circular current formula, c is represented
EGC1-5-2, EGC1-10-2, EGC1-15-2 and Pt/C (20%) cyclic voltammogram；D expressions EGC1-5-2, EGC1-10-2,
The lsv curves of EGC1-15-2 and Pt/C (20%) catalyst at 1600 rpm, e represent EGC1-5-2, EGC1-10-2, EGC1-
The electron transfer number that 15-2 and Pt/C (20%) are calculated under electrode disk-circular current formula.
Fig. 6 represents MFC-EGC0.5-5-2, MFC-EGC1-5-2, MFC-EGC2-5-2, MFC-EGC1-10- in embodiment 9
2nd, the power density curve and polarization curve of MFC-EGC1-15-2 and MFC-Pt/C (20%).
Fig. 7 represent embodiment 9MFC-EGC0.5-5-2, MFC-EGC1-5-2, MFC-EGC2-5-2, MFC-EGC1-10-2,
The anode and cathode polarization curve of MFC-EGC1-15-2 and MFC-Pt/C (20%).
Fig. 8 shows MFC-EGC0.5-5-2, MFC-EGC1-5-2, MFC-EGC2-5-2, MFC-EGC1-10- in embodiment 9
2nd, the voltage-time graph of MFC-EGC1-15-2 and MFC-Pt/C (20%).
Embodiment
The present invention is more specifically described in detail with reference to specific embodiment, but embodiments of the present invention are unlimited
In this, for especially not dated technological parameter, routine techniques progress can refer to.
Embodiment 1
The preparation of biomass doped carbon nanocatalyst
The preparation process of EGC1-10-2 is：It is respectively put into after urea and egg are entirely cooked grinding in 80 DEG C of drying boxes
Dry 24h, and urea is put into crucible with cover and prepares g-C in 550 DEG C of calcining 3h3N4, and the grinding of dried egg
Uniformly, dry egg and g-C are taken3N41:1, calcined after grinding uniformly in tube furnace with the heating rate of 10 DEG C/min at 900 DEG C
2h。
(EGCx-y-z, wherein X are dry egg and g-C3N4Mass ratio, Y is tube furnace heating rate, Z for heating when
Between, EC is prepared for pure egg)
Wherein EGC0.5-5-2, EGC1-5-2, EGC1-10-1, EGC1-10-3, EGC2-5-2, EGC1-10-2, EGC1-
15-2 is prepared in the above manner.
By the doped carbon nanocatalyst under this example different condition, 7 kinds of different doped carbon nano-catalytics have been obtained
Agent.
Embodiment 2
The XPS characterizations of biomass doped carbon nanocatalyst
The XPS tests of tri- kinds of doped carbon nanocatalysts of EGC1-5-2, EGC1-10-2, EGC1-15-2 are in multi-functional X-
Realized on X-ray photoelectron spectroscopy X instrument (model Axis Ultra DLD), vacuum when analysis room works is about 5 × 10- 9Torr, the X source used be monochromatization Al K α sources (Mono AlK α), energy 1486.6eV, 10mA × 15KV, beam spot
Size is 700 × 300 μm；Complete the logical of spectrum scanning can be 160eV, and narrow the logical of spectrum scanning can be 40eV, and scanning times are 1 time.
Before interpretation of result, peak-fit processing first is carried out to the C1s and N1s of each sample, then can calibrate the C1s combinations at most low energy end
To 284.6eV, N1s elements are corrected according to the movement of C1s peak positions.
XPS analysis by this example to tri- kinds of materials of EGC1-5-2, EGC1-10-2, EGC1-15-2, wherein nitrogen is divided
For four peaks, the nitrogen-atoms of four types, graphite mould nitrogen-atoms and the pyridine type nitrogen-atoms ratio of wherein EGC1-10-2 are represented respectively
The sum of example highest 0.59, wherein graphite mould nitrogen-atoms be nitrogen-atoms replace position of the carbon atom in hexa-atomic plane of a loop participate in into
Key, forms big pi bond, reduces bond energy, add activity, there is provided more chemical active sites, so as to add EGC1-10-2
Hydrogen reduction catalytic performance, pyridine type nitrogen-atoms is also proved to play ORR certain facilitation.In addition in EGC1-10-2
B, the content of S, P, Fe are all higher than the content of EGC1-5-2, EGC1-15-2, limiting current density of these elements all to material or
The reach of person's take-off potential all has a certain upgrade effect, therefore the ORR performances of EGC1-10-2 are better than EGC1-5-2, EGC1-15-
2。
Table 1 is the XPS element accountings of catalyst
| Atomic | C | N | O | S | P | B | Fe |
| EGC1-5-2 | 88.89 | 3.34 | 4.53 | 0.29 | 0.74 | 1.86 | 0.37 |
| EGC1-10-2 | 88.6 | 3.39 | 4.24 | 0.34 | 0.91 | 2.05 | 0.46 |
| EGC1-15-2 | 89.46 | 3.96 | 3.9 | 0.31 | 0.58 | 1.49 | 0.29 |
Table 2 is the ratio shared by the nitrogen-atoms of four types in catalyst
| Atomic | Nitrogen oxide | Pyrroles's nitrogen | Graphite nitrogen | Pyridine nitrogen |
| EGC1-5-2 | 0.31 | 0.17 | 0.29 | 0.23 |
| EGC1-10-2 | 0.24 | 0.17 | 0.27 | 0.32 |
| EGC1-15-2 | 0.27 | 0.19 | 0.31 | 0.23 |
Embodiment 3
The XRD characterization of biomass doped carbon nanocatalyst
XRD analysis：For analyzing the crystalline structure of EGCx-y-z catalyst, test process is on D8ADVANCE instruments
Realize, test condition is copper target, incident ray λ=0.15418nm, Ni filter plate, pipe pressure 40KV, pipe stream 40mA；Scanning step
0.02 degree, 0.1 second/step of sweep speed；DS0.5 ° of RS8mm of slit (corresponding LynxExe detector arrays).
XRD analysis by this example to 3 kinds of catalyst and EC, wherein the presence of the strong diffraction maximum of 2 θ=26 ° or so is
The characteristic peak of graphite-structure.The layer for being up to 23.6 °, illustrating the material that wherein C of EGC1-10-2 (002) peak deviates to the left
Gap ratio other materials it is big and bigger than the interlamellar spacing of graphite microcrystal more.Illustrate that the structure of the material is most open, most have ready conditions
With more avtive spots.Wherein the C of EC (002) peak is most kept right, and illustrates that its structure is most compacted, active under unit mass
The ratio in site is minimum.Contrast finds to add g-C in raw material3N4Obtained catalyst has looser structure, bigger
Interlamellar spacing, illustrates g-C3N4Leavening agent can be used as, and the interlamellar spacing of EGC1-10-2 is maximum, more likely obtains more active sites
Point, oxygen reduction catalytic activity are best.
Embodiment 4
The Raman characterizations of biomass doped carbon nanocatalyst
Raman is analyzed：The defects of for analyzing EGCx-y-z catalyst carbon nano materials and degree of graphitization, test process
Realized on Lab-RAM Aramis (French HORIBA JOBIN YVON companies production) instrument, test scope is from 800
~2000cm-2。
This example is by carrying out prepared EC, EGC1-5-2, EGC1-10-2, EGC1-15-2 Raman analysis contrasts.
Present the fault of construction and degree of graphitization of biomass doped carbon nanocatalyst.D- bands belong to the finite size of graphite
Crystallization, due to having symmetry reduction close to crystal or on the edge of crystal, so making it have activity, D lines belong to
Disordered graphite plane and be embedded into five while or carbon atom suspension key when seven on graphite-like structure vibration.G- bands are due to
The vibration mode of E2g is caused and can pass through the sp on graphite network2Key observes what is come, and G- bands reflect sp2The carbon of hydridization
Atom peak intensity, the intensity ratio (I of D- bands and G- bandsD/IG) commonly used to the defects of qualitatively comparing carbon material degree or unordered
Degree.As can be seen from Figure, under different ramp rate conditions EGC1-10-2 ID/IGValue is highest, illustrates the catalysis
The ratio that the carbon crystal structure of agent destroys is more serious, and contained defect is most, provides more contact sites for oxygen so that EGC1-
The direct oxygen reduction activity of 10-2 is the most prominent.
Embodiment 5
The TEM characterizations of biomass doped carbon nanocatalyst
Configuration of surface transmission electron microscope (the transmission of biomass doped carbon nanocatalyst
Electron microscopy, TEM) observed.
Tem analysis：For being viewed as the configuration of surface of EC and EGC1-10-2.
Tem observation by this example to two kinds of catalyst of EC and EGC1-10-2, adds g-C3N4The carbon materials of mixed calcining
Material is looser than pure egg calcining EC, and pure egg calcining illustrates g-C in caking shape3N4There is fluffy powder.EGC1-10-2 is in
Yarn shape gauze-like, but have fold, similar three-dimensional structure, increases the surface area of material, improves its performance.And transmitted by high power
Electronic Speculum, which is found out, has mixed some metallicses in EGC1-10-2, directly adulterated by biomass, is also beneficial to improve catalyst
Performance.
Embodiment 6
The chemical property of biomass doped carbon nanocatalyst
The chemical property of catalyst, i.e., direct oxygen reduction activity pass through cyclic voltammetry (Cyclic Voltammetry)
Carry out and rotating disk electrode (r.d.e) method is characterized.Tested with Shanghai Chen Hua CHI660d.Experiment uses three-electrode system, 10*
The platinized platinum of 10mm is that the Ag/Agcl electrodes of a diameter of 3mm are reference electrode to electrode, and drop has the glass-carbon electrode of the 3mm of catalyst
For working electrode, the PBS buffer of 50mM (PH=7) is electrolyte.Wherein the preparation method of working electrode is by the catalysis of 2mg
In the 0.2wt%Nafion solution of 1ml, ultrasound makes it be evenly distributed for agent, and takes 10ul mixing drops, drips and is treated in glass-carbon electrode
It is spontaneously dried.The parameter of setting is cycle-index 4 respectively, and by -0.8~0.5v, sweep speed 0.1v/s, sweeps voltage
Retouch that to take be a little 0.001v, rotating disk electrode (r.d.e) voltage is taken 20ul mixing drops, dripped in disk-ring electrode by -0.9~0.5v.
This example is schemed by the CV represented Fig. 5 a under different annealing times, it can be seen that the capacitance of EGC1-10-2
More than EGC1-10-1 and EGC1-10-3, and the hydrogen reduction peak of EGC1-10-3 and EGC1-10-2 is suitable.Can be with by Fig. 5 b
Find out that the electron transfer number of EGC1-10-2 is better than EGC1-5-3 and EGC1-10-1, the catalytic performance of the 2h that illustrates to anneal better than 1h and
3h's.By the CV figures of Fig. 5 c difference heating rate catalyst it can be seen that the redox of EGC1-10-2 is with Pt/C's (20%)
Registration highest, illustrates that its catalytic oxidation-reduction performance is suitable with the performance of Pt/C (20%)；Fig. 5 d catalyst is at 1600 rpm
Lsv curves can be seen that EGC1-10-2 half wave potentials and carrying current is better than Pt/C (20%) and other catalyst, Fig. 5 c electricity
The electron transfer number figure that pole disk-circular current formula calculates can obtain the electron transfer number 3.84~3.92 and Pt/C of EGC1-10-2
(20%) 3.84~3.95 are suitable and are better than other catalyst, to sum up draw in egg and g-C3N4Mass ratio is 1, heating speed
Rate is 10 DEG C/min, annealing time be 2h in the case of when obtained biomass doped carbon nano-catalytic and catalytic oxidation-reduction effect
It is best.
Embodiment 7
The preparation of MFC air cathodes
The carbon cloth for getting out 10*10cm is some；According to 1.56mg/cm2Dosage, according to electrode area 10*10cm=100cm2
Graphite 156mg is weighed (according to electrode single side geometric area cm2Calculate)；According to the dosage of 12 μ L/mg graphite powders, with liquid relief tolerance
Take 40%PTFE lotion 12*156=1872 μ L=1.872mL；The graphite powder weighed is placed in plastic tube with cover, adds 6-8
3mm beades and the 40%PTFE lotions measured, close the lid, stir and evenly mix；All C-PTFE suspensions small brushes are equal
It is even to be coated on carbon cloth surfaces.Careful operation is answered during coating, in case suspension gets the other one side of carbon cloth；Coating completion is placed on
At least 2h is air-dried on hardboard.Also drying process can be accelerated with hair-dryer；Muffle furnace is preheating to 370 DEG C, then by one piece
High temperature resistant porcelain tray is put into Muffle furnace, then the carbon cloth after air-drying is put on porcelain tray, closes Muffle fire door, and heat treatment continues
20-30min；Muffle fire door is opened, porcelain tray is taken out and carbon cloth is cooled to room temperature.Carbon cloth after cooling can crimp.
Shaking 60%PTFE latex vessels makes suspension be uniformly dispersed as far as possible；It is evenly coated in a new small brushes
The other one side (one layer of coating) of carbon cloth is obtained above；Catch up with bubble, ensure that carbon cloth surfaces coating is uniform；5-10min is air-dried, is done
Ply strain is applied after dry as white；Carbon cloth is placed in one piece of high temperature resistant porcelain tray and is put into the prior Muffle furnace heat for being preheating to 370 DEG C
10-15min is handled (to pay attention to：Using thick mitten in order to avoid scalding)；Muffle fire door is opened, porcelain tray is taken out and carbon cloth is cooled to room
Temperature (pays attention to：Using thick mitten in order to avoid scalding).After cooling, it should become shiny black containing PTFF layers of carbon cloth；Repeat step 1-6 three times,
It is coated with altogether, is heat-treated 4 layers of PTFE coatings.PTFE layers at this time can provide optimal thickness of diffusion layer；Needed with scissors addition
Electrode size.
Finally, the EGCx-y-z prepared and Pt/C (20%) catalyst are scattered in Nafion and isopropanol and deionization
In water uniformly in the carbon based layer of brush after the pre-treatment.
Embodiment 8
The startup and operation of MFC
MFC reactors used in the present invention are air cathode reactor of the single chamber without film, and dischargeable capacity is about
18.25mL, electrode spacing are 3cm, and electrode area is 3.14cm2, the MFC assembled by EGCx-y-z is named as MFC-
EGCx-y-z, in addition, installing one group of check experiment additional, assembles MFC by the use of Pt/C (20%) as air cathode, is named as MFC-Pt/C
(20%).
Inoculum is used as after taking 3~4d of sediment of pond preculture.The component of pre-culture solution is：1g·L-1Glucose,
0.08g·L-1NH4Cl, 0.04gL-1KH2PO4, 0.48gL-1Yeast extract and 5mLL-1Trace element solution.Nutrient solution is
Manual simulation's waste water (1gL-1Dextrose broth), component 1gL-1Glucose, 5mLL-1Vitamin solution,
12.5mL·L-1Trace element and 50mmolL-1(component of PBS solution is PBS solution：0.31g·L-1NH4Cl,
2.452g·L-1NaH2PO4·H2O, 0.576gL-1Na2HPO4And 0.13gL-1KCl).By inoculum and nutrient solution according to 1:
MFC is inoculated with after 1 volume ratio mixing, the external resistance in circuit is then adjusted to 1000 Ω.The output voltage of MFC uses Keithley
2700 collections.Inoculation liquid is replaced in time when MFC output voltages continue to decline or drop to 0.05V or so, so circulation, directly
Reach more than 0.1V to output voltage, be considered as and start successfully.Hereafter 1gL is only replaced-1Dextrose broth.Three assembled
A battery is 30 DEG C of constant temperature incubations in biochemical cultivation case.
By this case verification, all MFC-EGCx-y-z can successfully start, and it is best to have obtained performance
MFC-EGC1-10-2, and its battery can be better than MFC-Pt/C (20%).
Embodiment 9
The performance test of MFC
The performance test of MFC：The battery performance of MFC is acquired with Keithley 2700.Wherein output voltage U
It can directly be monitored with collector, a data gathered per 10s, outer connecting resistance uses 5 variable dc resistance case (sky and water Great Wall
Electrician, ZX-21), electric current is calculated by formula I=U/R.Wherein I is electric current, and U is output voltage, and R is external loop resistance.
The drawing process of polarization curve is as follows：Reach in the output voltage of battery in several hours of highest and stabilization, profit
External loop extrernal resistance is adjusted from 1000 Ω to 100 Ω with variable rheostat, gathers output voltage, and it is close using Ohm's law calculating current
Degree, using current density as transverse axis, cell voltage draws polarization curve for the longitudinal axis, and internal resistance is then by the oblique of polarization curve linear segment
Rate is estimated.The drawing process of the power density curve of the present invention is as follows：Power density is by formula P=U2/ (RS) is calculated, U in formula
For output voltage, R is external loop resistance, and S is electrode area.Using current density as transverse axis, power density draws work(for the longitudinal axis
Rate density curve.
The maximum power density that can draw MFC-EGC1-10-2 and MFC-Pt/C (20%) by this example is respectively
737.1mW·m-2And 704.0mWm-2, internal resistance is 300 Ω, and open-circuit voltage is respectively 0.755V and 0.758V.It can see
It is suitable to go out all electricity productions of MFC-EGC1-10-2 and MFC-Pt/C (20%), and is better than MFC-EGC2-5-2, MFC-EGC1-
15-2、MFC-EGC1-5-2、MFC-EGC0.5-5-2.So as to select egg：g-C3N41 ratio, heating rate for 10 DEG C/
Catalyst effect is best in the case of min.All cathode material electricity generation performances are good and bad as seen from Figure 7, and contrast draws catalyst
By good to poor order EGC1-10-2, Pt/C (20%), EGC1-15-2, EGC1-5-2, EGC0.5-5-2, EGC2-5-2.Fig. 7
It is also seen that the performance difference of anode is little, illustrate that anode will not influence the performance of battery too much.There is Fig. 8 to can be seen that MFC-
The burning voltage of EGC1-10-2 and MFC-Pt/C (20%) are that highest is also suitable, and startup time of MFC-EGC1-10-2
The startup time than MFC-Pt/C (20%) is fast 50h.Prove that EGC1-10-2 is adapted to be replacement Pt/C (20%) is used as your non-gold
Belong to high-efficiency battery cathodic oxygen reduction catalyst material.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of doped carbon nanocatalyst, it is characterised in that step is as follows：
By whole cooked egg grinding dehydration after with g-C3N4Mixing, the dewatered cooked egg and g-C3N4Mass ratio be 0.5
~2, by said mixture grinding uniformly be put into tube furnace lead to nitrogen protection, with the heating rate of 5~15 DEG C/min 800
1~3h is calcined at~1000 DEG C, that is, obtains doped carbon nanocatalyst.
2. the according to the method described in claim 1, it is characterized in that, g-C3N4By being put into after urea dehydration grinding uniformly
3h is calcined in 550 DEG C of Muffle furnaces to prepare.
3. according to the method described in claim 2, it is characterized in that, the dewatered cooked egg and g-C3N4Mass ratio be
1。
4. according to the method described in claim 1 or 2 or 3, it is characterised in that the heating rate in tube furnace is 10 DEG C/min,
Calcining heat is 900 DEG C, calcination time 2h.
5. according to the method described in claim 1 or 2 or 3, it is characterised in that the dehydration in the whole cooked egg grinding dehydration
It is the forced air drying 24h at 80 DEG C.
6. doped carbon nanocatalyst prepared by any one method described in Claims 1 to 5.
7. the application of doped carbon nanocatalyst described in claim 6, it is characterised in that fired using the catalyst preparation microorganism
Expect the air cathode of battery.
8. application according to claim 7, it is characterised in that the preparation method of the air cathode is：First by matrix material
Expect carbon cloth graphite and the coating of 40%PTFE mixtures, 20-30min handled in prior be preheating in 370 DEG C of Muffle furnaces after air-drying,
Then PTFE layers are applied in one side and is used as diffusion layer, doped carbon nanocatalyst is coated in another side.
9. application according to claim 8, it is characterised in that the specific preparation process of the diffusion layer is：Shake 60%
PTFE emulsion pipe makes suspension be uniformly dispersed as far as possible, is evenly coated in brush on carbon cloth；By carbon cloth after air-dried 5-10min
It is placed in the prior Muffle furnace heat treatment 10-15min for being preheating to 370 DEG C；Carbon cloth is then taken out to be cooled to room temperature；In triplicate, always
4 layers of coating, heat treatment PTFE coatings altogether.
10. according to the application described in claim 7 or 8 or 9, it is characterised in that utilize air cathode operation microorganism combustion
Expect battery, its process is：After the bed mud preculture of pig farm, supernatant is taken as inoculum；By inoculum and 1gL-1Portugal
Grape sugar nutrient solution is according to 1:Microbiological fuel cell is inoculated in after 1 volume ratio mixing, is run under conditions of being 30 DEG C in temperature；
Nutrient solution used component is as follows during the preculture：1g·L-1Glucose, 0.08gL-1NH4Cl, 0.04gL- 1KH2PO4, 0.48gL-1Yeast extract and 5mLL-1Trace element solution；
The component of the dextrose broth is as follows：1g·L-1Glucose, 5mLL-1Vitamin solution, 12.5mLL-1It is micro
Element and 50mmolL-1PBS solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510929372.7A CN105413731B (en) | 2015-12-14 | 2015-12-14 | A kind of doped carbon nanocatalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510929372.7A CN105413731B (en) | 2015-12-14 | 2015-12-14 | A kind of doped carbon nanocatalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105413731A CN105413731A (en) | 2016-03-23 |
| CN105413731B true CN105413731B (en) | 2018-04-13 |
Family
ID=55492531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510929372.7A Active CN105413731B (en) | 2015-12-14 | 2015-12-14 | A kind of doped carbon nanocatalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105413731B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252672B (en) * | 2016-08-19 | 2019-06-18 | 华南理工大学 | A method of doped carbon catalysis material is prepared using microorganism and iron ore |
| CN106590840B (en) * | 2016-12-06 | 2019-10-11 | 重庆中领环保产业技术研究院有限公司 | A kind of doped carbon nanometer class graphene lube oil additive and preparation method thereof |
| CN106532068A (en) * | 2016-12-10 | 2017-03-22 | 南京理工大学 | Modified graphite felt electrode used for microbial fuel cell |
| CN109560291A (en) * | 2017-09-25 | 2019-04-02 | 中国科学院化学研究所 | A kind of monatomic Fe-N-C oxygen reduction catalyst and the preparation method and application thereof |
| CN109279691A (en) * | 2018-10-18 | 2019-01-29 | 哈尔滨工业大学 | A kind of electrochemical appliance preparing hydrogen peroxide and application |
| CN113363508B (en) * | 2021-02-02 | 2022-10-28 | 井冈山大学 | Electrocatalyst for fuel cell and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872895A (en) * | 2012-10-23 | 2013-01-16 | 江西师范大学 | Natural plant based preparation method for low-cost high-efficiency catalyst for oxygen reduction reaction |
| CN103985884B (en) * | 2014-05-21 | 2017-02-01 | 华中科技大学 | Nitrogen-doped carbon nano-material as well as preparation method and application thereof |
| CN104525234A (en) * | 2014-12-17 | 2015-04-22 | 上海交通大学 | Preparation method for graphite-phase carbon nitride photocatalytic material |
| CN104525235A (en) * | 2014-12-18 | 2015-04-22 | 华南理工大学 | Nitrogen-doped graphene catalyst as well as preparation method and application thereof |
-
2015
- 2015-12-14 CN CN201510929372.7A patent/CN105413731B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105413731A (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105413731B (en) | A kind of doped carbon nanocatalyst and its preparation method and application | |
| Sonawane et al. | Low-cost stainless-steel wool anodes modified with polyaniline and polypyrrole for high-performance microbial fuel cells | |
| Zheng et al. | Nitrogen and phosphorus co-doped carbon networks derived from shrimp shells as an efficient oxygen reduction catalyst for microbial fuel cells | |
| Song et al. | Cobalt oxide/nanocarbon hybrid materials as alternative cathode catalyst for oxygen reduction in microbial fuel cell | |
| CN104525235A (en) | Nitrogen-doped graphene catalyst as well as preparation method and application thereof | |
| Stoll et al. | Sacrificing power for more cost-effective treatment: A techno-economic approach for engineering microbial fuel cells | |
| CN103191787B (en) | Application of carboxylated carbon nanotube catalyst carrier | |
| CN101656314B (en) | Application of molybdenum carbide in preparing anode of microbial fuel cell | |
| Cao et al. | Modification based on MoO3 as electrocatalysts for high power density vanadium redox flow batteries | |
| Mohamed et al. | Graphite sheets as high‐performance low‐cost anodes for microbial fuel cells using real food wastewater | |
| Li et al. | Tailoring spatial structure of electroactive biofilm for enhanced activity and direct electron transfer on iron phthalocyanine modified anode in microbial fuel cells | |
| CN106058269B (en) | A kind of air cathode and preparation method thereof for microbiological fuel cell | |
| CN110075872A (en) | Utilize electrochemical activation molybdenum disulfide/carbon composite electrocatalytic hydrogen evolution method | |
| CN106915829B (en) | Carbon fiber electrode, preparation method thereof and bipolar chamber bioelectrochemical device | |
| CN108172852A (en) | A kind of anode of microbial fuel cell, preparation method and microbiological fuel cell | |
| CN110354878A (en) | A kind of molybdenum carbide catalyst and preparation method thereof | |
| Geetanjali et al. | Enhanced performance of a single chamber microbial fuel cell using NiWO4/reduced graphene oxide coated carbon cloth anode | |
| CN107973282A (en) | A kind of carbon material and preparation method and application produces hydrogen peroxide in electro-catalysis | |
| CN109772382A (en) | A method of preparing phosphating sludge/graphitized carbon composite material | |
| Cetinkaya et al. | The development of catalytic performance by coating Pt–Ni on CMI7000 membrane as a cathode of a microbial fuel cell | |
| CN109666949B (en) | Preparation method of multi-element doped activated carbon electrode, characterization of activated carbon catalyst and oxygen reduction electrocatalysis test method | |
| CN105552391A (en) | Modified cobalt-manganese-oxide-doped carbon nanotube catalyst as well as preparation method and application thereof | |
| Jiang et al. | Sulfuration of Fe–N/C porous nanosheets as bifunctional catalyst with remarkable biocompatibility for high-efficient microbial fuel cells | |
| Luo et al. | Electrochemical surface modification of carbon mesh anode to improve the performance of air-cathode microbial fuel cells | |
| Sarma et al. | Development and comprehensive characterization of low-cost hybrid clay based ceramic membrane for power enhancement in plant based microbial fuel cells (PMFCs) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |