CN104525235A - Nitrogen-doped graphene catalyst as well as preparation method and application thereof - Google Patents

Nitrogen-doped graphene catalyst as well as preparation method and application thereof Download PDF

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CN104525235A
CN104525235A CN201410804872.3A CN201410804872A CN104525235A CN 104525235 A CN104525235 A CN 104525235A CN 201410804872 A CN201410804872 A CN 201410804872A CN 104525235 A CN104525235 A CN 104525235A
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mfc
nitrating
catalyst
nitrogen
melamine
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朱能武
杨婷婷
黄健键
吴平霄
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South China University of Technology SCUT
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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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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a nitrogen-doped graphene catalyst as well as a preparation method and application thereof. The preparation method comprises the following steps: drying and dehydrating glucose and urea, and mixing with melamine, wherein the mass ratio of the urea to melamine is 2-4; uniformly grinding the mixture, and calcining the mixture into a muffle furnace at the temperature of 550 DEG C for 3 hours; cooling and grinding uniformly, adding the mixture into a tube furnace, introducing into nitrogen protection, calcining at the temperature of 850-1000 DEG C for an hour, thereby obtaining the nitrogen-doped graphene catalyst. According to the in-situ nitrogen-doped graphene disclosed by the invention, the used raw materials are low in price, the method is simple, the yield is high, and graphite-like nitrogen doped graphene with the highest ratio is obtained by changing the rate of the raw materials and the temperature, so that the catalyst has a good oxidation-reduction effect, and expensive Pt can be replaced to a certain degree.

Description

A kind of nitrating graphen catalyst and its preparation method and application
Technical field
The invention belongs to bioenergy Material Field, be specifically related to a kind of preparation method and application thereof of nitrating graphen catalyst.
Background technology
Microbiological fuel cell (microbial fuel cells, MFCs) is a kind of using microorganism as catalyst, organic chemical energy is become the advanced energy technology of electric energy.There is environmental pollution and the large crisis of shortage of resources two in current human world; MFCs is electrogenesis while process debirs (including organic waste water and organic solid castoff); realize refuse process and energy recovery doulbe-sides' victory, become the focus of field of Environment Protection research.
So the amplification of microbial fuel cells system is the current subject matter faced.The key of the amplification of microbiological fuel cell is direct (without the need to adding exogenous electron transmission intermediate), single chamber and cheap cathode three importances.And at present, generally adopt efficient pt catalyst as biofuel battery cathode.But the amplification of the price of costliness and easy poisoning serious obstruction biological fuel cell.Therefore the substitute that Cheap highly effective is stable must be found.
At present, the two-dimensional material that Graphene (G) arranges by hexagonal lattice as sp2 hydbridized carbon atoms, because its low-resistivity, swift electron transmission capacity and excellent chemical stability become ideal cathode catalyst material.But Graphene lacks enough avtive spots due to stable sp2 hybrid structure, and scission of link needs the energy of at substantial, so need to carry out modification to Graphene.Wherein nitrating Graphene is subject to (NGs) to extensive concern, due to the electronegativity that nitrogen is higher, can from carbon pull-up electronics when nitrogen-atoms is embedded in carbon matrix, so, the carbon atom of positively charged just more easily makes Activation of Molecular Oxygen and is also of value to the Charger transfer of adjacent carbon atom.And we know that nitrogen can cause the defect of carbon, the exposure of edge plane perhaps can be increased to promote catalytic activity.Nitrogen in carbon is netted may be designated as class pyrimidine, class pyrroles, class graphite and oxide.Wherein class graphite nitrogen is found in the role that in ORR activity, performance one is important, and the minimum obstacle to first electron transfer rate restriction can be produced in outermost graphitization nitrogen position, has efficient selective equally to four electron reduction paths.The relative electronegativies of class graphite nitrogen-atoms reduces the electron density on adjacent carbon atom core, be so just of value to the transfer of electronics from adjacent carbon atom to nitrogen, and nitrogen feeds back to the P of electronics to adjacent carbon atom ztrack, to electronics with feed back to electronic processes and not only make oxygen divide on adjacent carbon atom, is also of value to and forms a kind of strong chemical bond between oxygen and carbon.There is the report of a large amount of nitrating Graphene in the recent period, mainly contain later stage nitric acid treatment, and original position nitrating.Wherein the effect of post processing is not very desirable, and in original position nitrating, CVD method process is more conventional, but technical requirement is high, wayward, and the prices of raw and semifnished materials costly.
Summary of the invention
One of the object of the invention is to provide a kind of nitrating graphen catalyst.
Two of the object of the invention is to provide the preparation method of above-mentioned catalyst.
Three of object of the present invention is to provide the application of above-mentioned catalyst.
The inventive method improves inertia and the hydrophobicity of Graphene, by synthesis nitrating Graphene, the relatively high nitrating Graphene of class graphite nitrogen content is prepared by change proportion of raw material and temperature, form large π key, improve catalytic performance, Surface oxygen-containing groups is enriched, provides more absorption, coordination and displacement functional group; Also can provide more chemical active sites simultaneously.
The present invention is realized by following technical step:
A preparation method for nitrating graphen catalyst, step is as follows:
Mix after glucose and urea drying and dehydrating with melamine, the mass ratio of described urea and melamine is 2 ~ 4, calcines 3h by putting into 550 DEG C of Muffle furnaces after said mixture grinding evenly; Put into the logical nitrogen protection of tube furnace after cooling grinding evenly, at 850 ~ 1000 DEG C, calcine 1h, namely obtain nitrating graphen catalyst.
Preferably, the mass ratio of described glucose and melamine is between 0.2 ~ 0.5.
Preferably, the mass ratio of described glucose, urea and melamine is 0.32:3:1.
Preferably, the calcining heat in tube furnace is 950 DEG C.
Preferably, described drying and dehydrating is forced air drying 24h at 80 DEG C.
The nitrating graphen catalyst utilizing said method to prepare prepares the air cathode of microbiological fuel cell.
The preparation method of described air cathode is: first by matrix material carbon cloth graphite and the coating of 40%PTFE mixture, process 20-30min being preheating in advance in 370 DEG C of Muffle furnaces after air-dry, be then coated with PTFE layer as diffusion layer at another side; Finally coat nitrating graphen catalyst at another side.
The concrete preparation process of described diffusion layer is: shake 60%PTFE latex vessel makes suspension be uniformly dispersed as far as possible, is evenly coated on carbon cloth with brush; After air-dry 5-10min, carbon cloth is placed in the Muffle furnace heat treatment 10-15min being preheating to 370 DEG C in advance; Then take out carbon cloth and be cooled to room temperature; In triplicate, be altogether coated with, heat treatment 4 layers of PTFE coating.
The process utilizing described air cathode to run microbiological fuel cell is: after the bed mud preculture of pig farm, get supernatant as inoculum; By inoculum and 1gL -1dextrose broth according to 1:1 volume ratio mixing after be inoculated in microbiological fuel cell, be run under the condition of 30 DEG C in temperature.
Component nutrient solution used during described preculture is as follows: 1gL -1glucose, 0.08gL -1nH 4cl, 0.04gL -1kH 2pO 4, 0.48gL -1yeast extract and 5mLL -1trace element solution.
The component of described dextrose broth is as follows: 1gL -1glucose, 5mLL -1vitamin solution, 12.5mLL -1trace element and 50mmolL -1pBS solution.
The component of described PBS solution is: 0.31gL -1nH 4cl, 2.452gL -1naH 2pO 4h 2o, 0.576gL -1na 2hPO 4and 0.13gL -1kCl.
The present invention compared with prior art tool has the following advantages and beneficial effect:
(1) original position nitrating Graphene raw materials of the present invention is cheap, method is simple, output is large, and obtains the highest class graphite nitrogen-atoms of ratio by change proportion of raw material and temperature, makes it have good redox effect can substitute expensive Pt to a certain extent.
(2) the present invention has not only invented the nitrating Graphene of function admirable, simultaneously the CNt of intermediate x/y/zfor carbonitride (C 3n 4), as excellent photochemical catalyst, the preparation method of this carbonitride is cheap and simple to operate relative to additive method.
(3) the present invention has optimized optimal proportion between several raw material and best tube furnace calcining heat, the nitrating Graphene NG950 obtained 7.5/2.5/0.8catalytic performance is better than the nitrating Graphene of other proportionings and temperature, wherein the ratio of class graphite nitrogen-atoms reaches the highest, form large π key, catalytic performance is the strongest, and cyclic voltammetry curve reduction peak cutting edge of a knife or a sword intensity and area under the curve are better than Pt/C (10%), illustrate that its electric conductivity and ORR performance are all better than Pt/C (10%) catalyst.
(4) the NG catalyst in described scope is energy effectively start MFC all, realizes MFC cathodic oxygen reduction.But, NG950 7.5/2.5/0.8catalytic oxidation-reduction efficiency stronger, and effectively can shorten the starting period of MFC to the shortest 18h.
(5) electricity generation performance of MFC shows the NG950 of preparation 7.5/2.5/0.8catalyst, as MFC cathode catalysis oxygen reduction reaction, not only can reduce the internal resistance of MFC, also substantially increases the output voltage of MFC.Under same current density, MFC-NG950 7.5/2.5/0.8power density and output voltage be all better than MFC-Pt/C, this demonstrates NG950 7.5/2.5/0.8catalytic oxidation-reduction ability be better than Pt/C (10%).
Accompanying drawing explanation
Fig. 1 a, Fig. 1 b, Fig. 1 c represent NG950 in embodiment 2 respectively 7.5/2.5/1, NG950 7.5/2.5/0.8and NG950 7.5/2.5/0.6the full spectrogram of N1s.
Fig. 2 a, Fig. 2 b, Fig. 2 c represent NG950 in embodiment 2 respectively 7.5/2.5/1, NG950 7.5/2.5/0.8and NG950 7.5/2.5/0.6c1s spectrogram.
Fig. 3 represents that in embodiment 3, a represents NG900 6.7/3.3/1, NG900 7.5/2.5/1, NG900 8.0/2.0/1; B represents NG1000 7.5/2.5/1, NG950 7.5/2.5/1, NG900 7.5/2.5/1, NG850 7.5/2.5/1; C represents NG950 7.5/2.5/1.2, NG950 7.5/2.5/1, NG950 7.5/2.5/0.8, NG950 7.5/2.5/0.6xRD collection of illustrative plates.
Fig. 4 represents that in embodiment 4, a represents NG900 6.7/3.3/1, NG900 7.5/2.5/1, NG900 8.0/2.0/1; B represents NG1000 7.5/2.5/1, NG950 7.5/2.5/1, NG900 7.5/2.5/1, NG850 7.5/2.5/1; C represents NG950 7.5/2.5/1.2, NG950 7.5/2.5/1, NG950 7.5/2.5/0.8, NG950 7.5/2.5/0.6raman collection of illustrative plates.
Fig. 5 represents NG950 in embodiment 5 7.5/2.5/0.8, CN550 7.5/2.5/0.8tEM figure.Wherein a represents CN550 7.5/2.5/0.8, b represents NG950 7.5/2.5/0.8.
Fig. 6 represents that in embodiment 6, a represents NG900 6.7/3.3/1, NG900 7.5/2.5/1mFC-NG900 8.0/2.0/1; B represents NG850 7.5/2.5/1, NG900 7.5/2.5/1, NG950 7.5/2.5/1, NG1000 7.5/2.5/1; C represents NG950 7.5/2.5/1.2, NG950 7.5/2.5/1, NG950 7.5/2.5/0.8, NG950 7.5/2.5/0.6with graphene (pure Graphene) cyclic voltammogram.
Fig. 7 represents that in embodiment 9, a represents MFC-NG900 6.7/3.3/1, MFC-NG900 7.5/2.5/1mFC-NG900 8.0/2.0/1; B represents MFC-NG800 7.5/2.5/1, MFC-NG850 7.5/2.5/1, MFC-NG900 7.5/2.5/1, MFC-NG950 7.5/2.5/1, MFC-NG1000 7.5/2.5/1; C represents NG950 7.5/2.5/1.2, MFC-NG950 7.5/2.5/1, MFC-NG950 7.5/2.5/0.8, MFC-NG950 7.5/2.5/0.6with MFC-Pt (10%); D represents MFC-NG950 7.5/2.5/0.8with the voltage-time graph of MFC-Pt (10%).
Fig. 8 represents that in embodiment 9, a represents MFC-NG900 6.7/3.3/1, MFC-NG900 7.5/2.5/1, MFC-NG900 8.0/2.0/1; B represents MFC-NG850 7.5/2.5/1, MFC-NG900 7.5/2.5/1, MFC-NG950 7.5/2.5/1, MFC-NG1000 7.5/2.5/1; C represents MFC-NG950 7.5/2.5/1.2, MFC-NG950 7.5/2.5/1, MFC-NG950 7.5/2.5/0.8, MFC-NG950 7.5/2.5/0.6with the power density curve of MFC-Pt.
Fig. 9 represents that in embodiment 9, a represents MFC-NG900 6.7/3.3/1, MFC-NG900 7.5/2.5/1, MFC-NG900 8.0/2.0/1; B represents MFC-NG850 7.5/2.5/1, MFC-NG900 7.5/2.5/1, MFC-NG950 7.5/2.5/1, MFC-NG1000 7.5/2.5/1; C represents MFC-NG950 7.5/2.5/1.2, MFC-NG950 7.5/2.5/1, MFC-NG950 7.5/2.5/0.8, MFC-NG950 7.5/2.5/0.6with the polarization curve of MFC-Pt.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited thereto, for the technological parameter do not indicated especially, can refer to routine techniques and carry out.
Embodiment 1
The preparation of nitrating Graphene
NG950 7.5/2.5/0.8preparation process be: get 7.5g urea, 2.5g melamine and 0.8g glucose, put into 80 DEG C of dry 24h of drying box respectively.By even for medicine mixed grinding in crucible, put into crucible with cover at 550 DEG C of calcining 3h.In tube furnace, 1h are calcined at 950 DEG C after grinding evenly after taking-up cooling.
(NGT x/Y/Z, wherein T is tube furnace temperature, and X is the amount of urea, and Y is the amount of melamine, and Z is the amount (wherein the temperature of Muffle furnace is defaulted as 550 DEG C) of glucose.CNt x/y/z, t is the temperature of Muffle furnace, and x is the amount of urea, and y is the amount of melamine, and z is the amount of glucose)
Wherein NG900 6.7/3.3/1, NG900 7.5/2.5/1, NG900 8.0/2.0/1, NG850 7.5/2.5/1, NG950 7.5/2.5/1, NG1000 7.5/2.5/1, NG950 7.5/2.5/1.2, NG950 7.5/2.5/0.6prepare according to upper type.
By the nitrating graphite under this example different condition, obtain 9 kinds of different nitrating Graphenes.
Embodiment 2
The XPS of nitrating Graphene characterizes
NG950 7.5/2.5/1, NG950 7.5/2.5/0.8, NG950 7.5/2.5/0.6the XPS test of three kinds of nitrating Graphenes is in the upper realization of multi-functional x-ray photoelectron spectroscopy (model is Axis Ultra DLD), and vacuum during analysis room's work is about 5 × 10 -9torr, the Al K α source (MonoAlK α) that the X source of use is monochromatization, energy is 1486.6eV, 10mA × 15KV, and bundle 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 is 1 time.Before interpretation of result, first peak-fit processing is carried out to C1s and N1s of each sample, then the C1s of most low energy end is combined and can be calibrated to 284.6eV, move according to C1s peak position and N1s element is corrected.
By this example to NG950 7.5/2.5/1, NG950 7.5/2.5/0.8and NG950 7.5/2.5/0.6the XPS analysis of three kinds of materials, is wherein divided into four peaks, represents the nitrogen-atoms of Four types respectively, wherein NG950 by nitrogen 7.5/2.5/0.8class graphite nitrogen-atoms ratio the highest, class graphite nitrogen-atoms be nitrogen-atoms replace the position of carbon atom in hexatomic ring plane participate in into key, form large π key, reduce bond energy, add activity, more chemical active sites is provided, thus add the hydrogen reduction catalytic performance of NG.
Embodiment 3
The XRD of nitrating graphen catalyst characterizes
XRD analysis: be used for analyzing NGT x/Y/Zthe crystalline structure of catalyst, test process realizes on D8ADVANCE instrument, and test condition is copper target, incident ray λ=0.15418nm, Ni filter plate, pipe pressure 40KV, pipe stream 40mA; Scanning step 0.02 degree, sweep speed 0.1 second/step; Slit DS0.5 ° RS8mm (corresponding LynxExe detector array).
By the XRD analysis of this example to 9 kinds of catalyst, the existence of the strong diffraction maximum wherein about 2 θ=26 ° and prove the existence of carbonization structure, proves that this material is Graphene.Along with large change does not occur change 2 θ of proportion of raw material or temperature, illustrate that large change does not occur carbonization structure.But, when urea and melamine ratio change, NG900 7.5/2.5/1performance is best, but peak intensity is minimum, illustrates at the structure influence of lower nitrogen to it that rescale larger.At certain proportion of raw material, when temperature changes, NG950 7.5/2.5/1performance best, but peak intensity is the most weak, illustrates to change at temperature nitrogen comparatively large on the impact of its structure, destroys larger to its Graphene crystal formation.Fix in other condition one, change the amount of glucose, NG950 7.5/2.5/0.8performance is best, and the intensity at its peak does not have obvious difference, but NG950 7.5/2.5/0.8peak offset by the right a bit, more other two kinds little of interlamellar spacing is described.
Embodiment 4
The Raman of nitrating graphen catalyst characterizes
Raman analyzes: be used for analyzing NGT x/Y/Zthe defect of catalyst graphene-structured and degree of graphitization, test process realizes on Lab-RAM Aramis (French HORIBA JOBIN YVON company produces) instrument, and test specification is from 800 ~ 2000cm -2.
This example passes through prepared nitrating Graphene, pure Graphene and NG950 7.5/2.5/0.8middle CN550 7.5/2.5/0.8body carries out Raman and analyzes contrast.Present fault of construction and the degree of graphitization of nitrating Graphene.D-band belongs to the crystallization of the finite size of graphite, due near crystal or have on the edge of crystal symmetry reduction, so make it have activity, D line belongs in disordered graphite plane and the vibration being embedded into the carbon atom suspension key on five limits or seven limit graphite-like structures.G-band be cause due to the vibration mode of E2g and observe out by sp2 key on graphite network, G-band reflects the carbon atom peak intensity of sp2 hydridization, the intensity ratio (I that D-band is with G- d/i g) be commonly used to compare the defect level of material with carbon element or unordered degree qualitatively.As can be seen from Figure, when different urea and melamine ratio, NG900 7.5/2.5/1i d/i gvalue is minimum, illustrates that the degree of this material recovers graphene-structured is best; Identical in other conditions, when changing temperature, NG950 7.5/2.5/1i d/i gbe worth lower, at illustrating 950 DEG C, the degree that material recovers graphene-structured is best; Finally, other conditions are constant, change the amount of glucose, NG950 7.5/2.5/0.8ratio minimum, illustrate that under this condition prepared nitrating Graphene is most graphene-structured.
Embodiment 5
The TEM of nitrating graphen catalyst characterizes
The configuration of surface of nitrating graphen catalyst is observed with transmission electron microscope (transmission electronmicroscopy, TEM).
Tem analysis: the configuration of surface being used for being viewed as nitrating graphen catalyst and intermediate thereof.
By this example to CN550 7.5/2.5/08and NG950 7.5/2.5/08the tem observation of two kinds of catalyst, the intermediate product preparing nitrating Graphene is the carboritride of yarn shape is carbonitride (C 3n 4) be the photochemical catalyst that a kind of performance is fabulous, NG950 7.5/2.5/08in yarn shape tulle shape, but there is fold, similar three-dimensional structure, increase the surface area of material, improve its performance.
Embodiment 6
The chemical property of nitrating Graphene
The chemical property of catalyst, namely directly oxygen reduction activity is characterized by cyclic voltammetry (CyclicVoltammetry).Test with Shanghai occasion China CHI660d.Experiment adopts three-electrode system, and the platinized platinum of 10*10mm is to electrode, and diameter is the Ag/Agcl electrode of 3mm is reference electrode, and drip and have the glass-carbon electrode of the 3mm of catalyst to be working electrode, the PBS buffer solution of 50mM (PH=7) is electrolyte.Wherein the preparation method of working electrode is by the catalyst of 2mg in the 0.2wt%Nafion solution of 2ml, ultrasonicly makes it be evenly distributed, and gets 10ul mixing drop, drips and treats its natural drying in glass-carbon electrode.Respectively, cycle-index is 4 to the parameter arranged, and voltage is by-0.8 ~ 0.5v, and sweep speed is 0.1v/s, and it is some 0.001v that scanning is got.
This example is by finding out NG900 to the ratio of the different urea of Fig. 6 a and melamine 7.5/2.5/1the value of the most obvious peak, redox peak voltage turnover is also closest to 0, and all hydrogen reduction performances are best; Fig. 6 b finds out NG950 at different temperatures 7.5/2.5/1peak value maximum the most obvious, the flex point at peak also occurs at first, and when all 950 DEG C, hydrogen reduction is best; The amount of the different glucose of Fig. 6 c and obtained NGs catalyst carries out cyclic voltammetry test, obtains different cyclic voltammetry curves, can find out wherein NG950 7.5/2.5/0.8the turnover peakedness ratio of reduction peak comparatively keep right, higher than other NGs and pure Graphene.To sum up draw at 950 DEG C, urea is 7.5g, and melamine is 2.5g, and the catalytic oxidation-reduction effect of the nitrating Graphene obtained when glucose is 0.8g is best.
Embodiment 7
The preparation of MFC air cathode
The carbon cloth getting out 10*10cm is some; According to 1.56mg/cm 2dosage, according to electrode area 10*10cm=100cm 2take graphite 156mg (according to electrode one side geometric area cm 2calculate); According to the dosage of 12 μ L/mg graphite powders, measure 40%PTFE emulsion 12*156=1872 μ L=1.872mL with pipettor; The graphite powder taken is placed in plastic tube with cover, the 40%PTFE emulsion adding 6-8 3mm bead He measure, cover lid, stirs and evenly mixs; All C-PTFE suspension small brushes are uniformly coated on carbon cloth surfaces.Care should be used to operation during coating, in order to avoid suspension gets the other one side of carbon cloth; Be coated with and be placed on air-dry at least 2h on hardboard.Also can with hair-dryer to accelerate dry run; Muffle furnace is preheating to 370 DEG C, is then put in Muffle furnace by one piece of high temperature resistant porcelain tray, then be put on porcelain tray by the carbon cloth after air-dry, close Muffle furnace door, heat treatment continues 20-30min; Open Muffle furnace door, take out porcelain tray and carbon cloth is cooled to room temperature.Cooled carbon cloth can occur curling.
Shake 60%PTFE latex vessel makes suspension be uniformly dispersed as far as possible; The other one side (coating one deck) of carbon cloth is obtained above being evenly coated in a new small brushes; Catch up with bubble, ensure carbon cloth surfaces coating evenly; Air-dry 5-10min, being coated with ply strain after dry is white; Carbon cloth be placed in one piece of high temperature resistant porcelain tray and be put into the Muffle furnace heat treatment 10-15min (noting: use thick mitten in order to avoid scald) being preheating to 370 DEG C in advance; Open Muffle furnace door, take out porcelain tray and carbon cloth and be cooled to room temperature (noting: use thick mitten in order to avoid scald).After cooling, should become shiny black containing PTFF layer carbon cloth; Repeat step 1-6 tri-times, altogether coating, heat treatment 4 layers of PTFE coating.PTFE layer now can provide optimum thickness of diffusion layer; With the electrode size that scissors addition needs.
Finally, the NGT will prepared x/Y/Zto be scattered in Nafion and isopropyl alcohol and deionized water evenly in brush carbon based layer after the pre-treatment with Pt/C (10%) catalyst.
Embodiment 8
The Start-up and operating performance of MFC
The present invention's MFC reactor used is the air cathode reactor of single chamber without film, and dischargeable capacity is about 6.28mL, and electrode spacing is 2cm, and electrode area is 3.14cm 2, will by NGT x/Y/Xthe MFC called after MFC-NGT of assembling x/Y/Z, in addition, install one group of check experiment additional, with Pt/C (10%) as air cathode assembling MFC, called after MFC-Pt.
Get after sediment of pond preculture 3 ~ 4d as inoculum.The component of pre-culture solution is: 1gL -1glucose, 0.08gL -1nH 4cl, 0.04gL -1kH 2pO 4, 0.48gL -1yeast extract and 5mLL -1trace element solution.Nutrient solution is manual simulation's waste water (1gL -1dextrose broth), component is 1gL -1glucose, 5mLL -1vitamin solution, 12.5mLL -1trace element and 50mmolL -1(component of PBS solution is PBS solution: 0.31gL -1nH 4cl, 2.452gL -1naH 2pO 4h 2o, 0.576gL -1na 2hPO 4and 0.13gL -1kCl).Inoculum and nutrient solution are inoculated MFC according to after the volume ratio mixing of 1:1, then the external resistance in loop is adjusted to 1000 Ω.The output voltage of MFC adopts Keithley 2700 to gather.Change inoculation liquid in time when MFC output voltage continuous decrease or when dropping to about 0.05V, so circulate, until output voltage reaches more than 0.1V, be considered as starting successfully.After this only 1gL is changed -1dextrose broth.Three batteries assembled are 30 DEG C of constant temperature culture in biochemical cultivation case.
All MFC-NGT by this case verification x/Y/Zall successfully can start, and obtain the best MFC-NG950 of performance 7.5/2.5/0.8, and its battery can be better than MFC-Pt/C.
Embodiment 9
The performance test of MFC
The battery performance Keithley 2700 of the performance test of MFC: MFC gathers.Wherein output voltage U directly can monitor with collector, and every 10s gathers data, and outer meeting resistance adopts 5 variable dc resistance casees (Great Wall, sky and water electrician, ZX-21), and 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: in the output voltage of battery reach high and the most stable several hours, variable rheostat is utilized to regulate external loop extrernal resistance from 1000 Ω to 100 Ω, gather output voltage, and utilize Ohm's law calculating current density, take current density as transverse axis, cell voltage be the longitudinal axis to draw polarization curve, internal resistance is then estimated by the slope of polarization curve linear segment.The drawing process of power density curve of the present invention is as follows: power density is by formula P=U 2/ (RS) calculates, and in formula, U is output voltage, and R is external loop resistance, and S is electrode area.Take current density as transverse axis, power density is that the longitudinal axis is to draw power density curve.
NG900 can be drawn by this example 6.3/3.3/1, NG900 7.5/2.5/1and NG900 8.0/2.0/1maximum power density be respectively 416.2mWm -2, 433.2mWm -2and 303.16mWm -2, internal resistance is respectively 300 Ω, 300 Ω and 800 Ω, thus selects urea: melamine is the ratio of 7.5:2.5=3:1.And then different temperatures is selected under the condition of U:M:G=7.5:2.5:1, obtain NG850 7.5/2.5/1, NG900 7.5/2.5/1, NG950 7.5/2.5/1and NG1000 7.5/2.5/1power density be respectively 331.7mWm -2, 403.7mWm -2, 433.2mWm -2, 542.2mWm -2, 407.6mWm -2, internal resistance is respectively 600 Ω, 300 Ω, 300 Ω, 300 Ω, 200 Ω, thus it is best to obtain performance 950 DEG C time.Last at 950 DEG C and urea: when melamine is 7.5g:2.5g, to select the amount of different glucose.Obtain NG950 7.5/2.5/0.6, NG950 7.5/2.5/0.8, NG950 7.5/2.5/1and NG950 7.5/2.5/1.2power density be respectively 443.4mWm -2, 587.0mWm -2, 542.2mWm -2and 291.7mWm -2, internal resistance is respectively 400 Ω, 200 Ω, 300 Ω and 500 Ω.Thus obtain the best nitrating Graphene NG950 of performance 7.5/2.5/0.8, there is better redox efficiency than other several catalyst.And show that the power density of MFC-Pt is 153.8mWm by control group -2, internal resistance is 400 Ω.And MFC-NG950 7.5/2.5/0.8start-up time be that the start-up time of 18h, MFC-Pt is for for 60h.Namely NG950 is proved 7.5/2.5/1be applicable to being alternative Pt/C (10%) as base metal high-efficiency battery cathodic oxygen reduction catalyst material.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. a preparation method for nitrating graphen catalyst, is characterized in that, step is as follows:
Mix after glucose and urea drying and dehydrating with melamine, the mass ratio of described urea and melamine is 2 ~ 4, calcines 3h by putting into 550 DEG C of Muffle furnaces after said mixture grinding evenly; Put into the logical nitrogen protection of tube furnace after cooling grinding evenly, at 850 ~ 1000 DEG C, calcine 1h, namely obtain nitrating graphen catalyst.
2. method according to claim 1, is characterized in that, the mass ratio of described glucose and melamine is between 0.2 ~ 0.5.
3. method according to claim 1, is characterized in that, the mass ratio of described glucose, urea and melamine is 0.32:3:1.
4. the method according to claim 1 or 2 or 3, is characterized in that, the calcining heat in tube furnace is 950 DEG C.
5. the method according to claim 1 or 2 or 3, is characterized in that, described drying and dehydrating is forced air drying 24h at 80 DEG C.
6. the nitrating graphen catalyst prepared of any one method described in Claims 1 to 5.
7. the application of nitrating graphen catalyst described in claim 6, is characterized in that, utilizes the air cathode of this catalyst preparing microbiological fuel cell.
8. application according to claim 7, it is characterized in that, the preparation method of described air cathode is: first by matrix material carbon cloth graphite and the coating of 40%PTFE mixture, process 20-30min being preheating in advance in 370 DEG C of Muffle furnaces after air-dry, be then coated with PTFE layer as diffusion layer at another side; Finally coat nitrating graphen catalyst at another side.
9. application according to claim 8, is characterized in that, the concrete preparation process of described diffusion layer is: shake 60%PTFE latex vessel makes suspension be uniformly dispersed as far as possible, is evenly coated on carbon cloth with brush; After air-dry 5-10min, carbon cloth is placed in the Muffle furnace heat treatment 10-15min being preheating to 370 DEG C in advance; Then take out carbon cloth and be cooled to room temperature; In triplicate, be altogether coated with, heat treatment 4 layers of PTFE coating.
10. the application according to claim 7 or 8 or 9, is characterized in that, the process utilizing described air cathode to run microbiological fuel cell is: after the bed mud preculture of pig farm, get supernatant as inoculum; By inoculum and 1gL -1dextrose broth according to 1:1 volume ratio mixing after be inoculated in microbiological fuel cell, be run under the condition of 30 DEG C in temperature;
Component nutrient solution used during described preculture is as follows: 1gL -1glucose, 0.08gL -1nH 4cl, 0.04gL -1kH 2pO 4, 0.48gL -1yeast extract and 5mLL -1trace element solution;
The component of described dextrose broth is as follows: 1gL -1glucose, 5mLL -1vitamin solution, 12.5mLL -1trace element and 50mmolL -1pBS solution.
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