CN1960042A - Non noble metal catalyst for cathode of direct methanol fuel cell, and preparation method - Google Patents
Non noble metal catalyst for cathode of direct methanol fuel cell, and preparation method Download PDFInfo
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- CN1960042A CN1960042A CNA2006101136926A CN200610113692A CN1960042A CN 1960042 A CN1960042 A CN 1960042A CN A2006101136926 A CNA2006101136926 A CN A2006101136926A CN 200610113692 A CN200610113692 A CN 200610113692A CN 1960042 A CN1960042 A CN 1960042A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 75
- 239000000446 fuel Substances 0.000 title claims description 17
- 229910000510 noble metal Inorganic materials 0.000 title abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- -1 transition metal nitride Chemical class 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 150000004032 porphyrins Chemical class 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000010970 precious metal Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- HCIIFBHDBOCSAF-UHFFFAOYSA-N octaethylporphyrin Chemical compound N1C(C=C2C(=C(CC)C(C=C3C(=C(CC)C(=C4)N3)CC)=N2)CC)=C(CC)C(CC)=C1C=C1C(CC)=C(CC)C4=N1 HCIIFBHDBOCSAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 150000004767 nitrides Chemical class 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 150000002678 macrocyclic compounds Chemical class 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 10
- 230000009467 reduction Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- CVKFXBUVLBFHGO-UHFFFAOYSA-N cobalt 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Co].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 CVKFXBUVLBFHGO-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000036228 toxication Effects 0.000 description 2
- YYEWJWCGUVZBPQ-UHFFFAOYSA-N C(C)C1=C(C=2C=C3C(=C(C(=CC=4C(=C(C(=CC5=C(C(=C(N5)C=C1N2)CC)CC)N4)CC)CC)N3)CC)CC)CC.[Mo] Chemical compound C(C)C1=C(C=2C=C3C(=C(C(=CC=4C(=C(C(=CC5=C(C(=C(N5)C=C1N2)CC)CC)N4)CC)CC)N3)CC)CC)CC.[Mo] YYEWJWCGUVZBPQ-UHFFFAOYSA-N 0.000 description 1
- MNSFATSRSQVCJF-UHFFFAOYSA-N C1(=CC=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=CC=CC=C5)N4)C4=CC=CC=C4)N3)C3=CC=CC=C3)=N2.[Mo] Chemical compound C1(=CC=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=CC=CC=C5)N4)C4=CC=CC=C4)N3)C3=CC=CC=C3)=N2.[Mo] MNSFATSRSQVCJF-UHFFFAOYSA-N 0.000 description 1
- JTRFAZCZWWBOFZ-UHFFFAOYSA-N COC1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)OC)N4)OC)N3)OC)=N2.[Mo] Chemical compound COC1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)OC)N4)OC)N3)OC)=N2.[Mo] JTRFAZCZWWBOFZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- 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
Existing catalysts are noble metals generally, which are costly and easy poisoning. Active component of the disclosed catalyst is transition metal nitride. Carrier is activated carbon powder Vulcan XC-72. Percentage content of mass of transition metal nitride in active component is 1-6%. The preparation method includes steps: dissolving macrocyclic compound of transition metal, Vulcan XC-72 into organic solvent, and carrying out ultrasonic action for 30-60 minutes; stirring up and drying out the said solution under normal temperature, and obtaining powder after drying; loading the powder to closed container and letting ammonia into the container; controlling temperature of heat treatment at 600-1000 deg.C, and time as 0.5-10h so as to obtain the catalyst after natural cooling. Area ratio activity of carbon carried platinum catalyst is 1.5mA/cm2, and the disclosed carbon carried nitride catalyst reaches to 3.1 mA/cm2. Features are: simple flow and easy controlled procedure.
Description
Technical field
The invention belongs to the fuel-cell catalyst field.
Background technology
Direct methanol fuel cell is a kind of of Proton Exchange Membrane Fuel Cells, is electrolyte with the solid polymer membrane, uses liquid or gas methyl alcohol to act as a fuel.It is a kind of of fuel cell, has the plurality of advantages of fuel cell: do not pollute, quiet efficient, help environmental protection.Also having does not in addition need middle the reformation or reforming unit, and volume in light weight is little, battery design and simple to operateization.Owing to above-mentioned plurality of advantages, be particularly suitable for the removable power supply of various uses, as mobile phone, notebook computer and electric vehicle power sources etc.
In direct methanol fuel cell, the Pt/C catalyst is often used as the cathodic oxygen reduction eelctro-catalyst, is that people study maximum a kind of fuel-cell catalysts.Because precious metals pt is less relatively, price comparison is expensive, has limited its practical application and commercialization fully, must develop a kind of oxygen reduction electro-catalyst that on a small quantity or does not contain noble metal that contains.Wherein the heat treatment of carbon-supported metal porphyrin compound in this respect application obtain bigger progress, have good catalytic activity and stability, and the methanol tolerance performance arranged, promise to be the catalyst that replaces noble metal.Performance and commercialization in direct methanol fuel cell at present requires to have the problem of big gap to also have one to be exactly the methyl alcohol penetrate proton exchange membrane arrival negative electrode of anode, and can carry at carbon commonly used oxidation takes place on the platinum cathode, make catalyst poisoning, this not only makes methyl alcohol can not get sufficient application, and has a strong impact on the performance of battery.
Just have been found that transition metal macrocyclic compound can be used for the catalyst of hydrogen reduction the sixties in 20th century, but these transition metal huge legendary turtle compounds are unsettled eelctro-catalysts when directly using.At this phenomenon, [Faubert G, Lalande G, Cote R, et al.Electrochimica Acta[J], 1996,41 (10): 1689-1701.] etc. the people is adsorbed on iron, cobalt tetraphenylporphyrin on the carbon black respectively, heat-treats under argon gas is saturated, and heat treated temperature is at 100-1000 ℃. can improve activity of such catalysts and stability by heat treatment, up to now, people's research mostly is under inert atmosphere fuel-cell catalyst to be heat-treated.Existing catalyst is generally noble metal, the expensive and easy poisoning of price comparison.
Summary of the invention
The invention provides a kind of cathode in direct methanol fuel cells non-precious metal catalyst, it is characterized in that, active component is a transition metal nitride, and carrier is a Vulcan XC-72 activated carbon powder, and wherein the quality percentage composition of transition metal nitride is 1-6% in the active component.
Have extremely similar character because nickel, iron, manganese all belong to transition metal, its porphyrin also has similar character, so also have similar hydrogen reduction character after the heat treatment in ammonia.
The present invention also provides a kind of preparation method of cathode in direct methanol fuel cells non-precious metal catalyst, it is characterized in that, may further comprise the steps:
1) transition metal macrocyclic compound, Vulcan XC-72 activated carbon powder are dissolved in the organic solvent ultrasonic 30-60 minute; Wherein transition metal macrocyclic compound is for being one of the monokaryon porphyrin of central metal ion and derivative thereof with molybdenum, cobalt, nickel, iron, manganese; Organic solvent is one of oxolane, ethanol, acetone, isopropyl alcohol, N-N dimethyl formamide, N-N dimethylacetylamide, methyl-sulfoxide, n-hexane, carrene, chloroform, tetrachloromethane, pyridine or ether; The mass ratio of transition metal macrocyclic compound and Vulcan XC-72 activated carbon powder is 1 in solvent: 9-1: 1;
2) above-mentioned solution is stirred evaporate to dryness at normal temperatures, 60-80 ℃ of drying obtains powder;
3) with above-mentioned steps 2) powder that the obtains closed container of packing into, feed ammonia, the flow of ammonia is 0.5-31/min, and controlling heat treated temperature is 600-1000 ℃, and heat treatment time is 0.5-10h, and lowering the temperature naturally obtains catalyst.
Described monokaryon derivatives of porphyrin is the tetramethoxy porphyrin, tetrasulfonic acid base porphyrin, tetraphenylporphyrin, one of octaethylporphyrin.
In the step 1) in organic solvent the content of activated carbon be 0.02-9g/L, the content of transition metal macrocyclic compound is 0.02-1g/L.
This method technological process is simple, and process is easy to control.By the direct methanol fuel cell catalyst of this method preparation, X-ray diffraction analysis is the result show, resulting activity of such catalysts component is a nitride.The model of transmission electron microscope is JEM-2010F, and the lens analysis result shows that resultant catalyst granules particle diameter is little, is 4-6nm substantially, is uniformly dispersed.All raw materials that the present invention uses are not noble metals, thereby have realized the base metalization of catalyst.The carbon of preparation is carried nitride catalyst and normally used carbon supported platinum catalyst, be prepared into electrode, adopt the monocell three-electrode system to carry out electro-chemical test, the cathodic polarization curve test result shows, under identical test condition, the area specific activity of carbon supported platinum catalyst is 1.5mA/cm
2Carbon of the present invention carries nitride catalyst, has then reached 3.1mA/cm
2Quite and the former 2 times.In the direct methanol fuel cell noble metal catalyst, cathod catalyst is poisoned and has been had a strong impact on the performance of battery, cathodic polarization curve test shows as a result has or not the curve of methyl alcohol front and back not have substantially to change, and illustrates that this catalyst has anti methanol toxication ability preferably.Carry out electro-chemical test equally under the monocell three-electrode system, the timing current curve shows that this catalyst oxidation current attenuation ratio in acid solution is slower, has stability preferably.
Prepared catalyst adopts the monocell three-electrode system to carry out electro-chemical test.To electrode is smooth platinized platinum electrode, and reference electrode is the mereurous sulfate electrode, and all for this electrode, electrolyte is 0.5mol/l H to current potential as described below
2SO
4Solution and 0.5mol/l H
2SO
4+ 0.5mol/lCH
3OH, logical 30 minutes N before the experiment
2Or O
2Gas, sweep speed are 10mV/s.The electro-chemical test instrument is U.S. EG﹠amp; The Model 273A type constant potential/electric current instrument of G company.
Description of drawings:
Accompanying drawing 1 is the X ray diffracting spectrum of the catalyst that provided of the embodiment of the invention 4.
Accompanying drawing 2 is that the catalyst that provided of the embodiment of the invention 1 is at 0.5MH
2Cathodic polarization curve in the SO4 solution.
Accompanying drawing 3 is lens photos of the catalyst that provided of the embodiment of the invention 2.
Accompanying drawing 4 is stability curves of the catalyst that provided in the embodiment of the invention 1.
Accompanying drawing 5 is that the catalyst that provided in the embodiment of the invention 4 is at 0.5MH
2SO
4And 0.5MH
2SO
4+ 0.5CH
3Linear scan curve among the OH.
Embodiment:
Also in conjunction with the accompanying drawings the present invention is explained in detail below by embodiment.
Embodiment 1
Is to be dissolved in oxolane ultrasonic 60 minute at 1: 9 with molybdenum tetraphenylporphyrin and Vulcan XC-72 activated carbon powder by mass ratio; Above-mentioned solution stirring at normal temperature evaporate to dryness, 80 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 11/min, and controlling heat treated temperature is 700 ℃, reacts 3h under this temperature, stops heating then, is chilled to room temperature, obtains the MoN/C catalyst.The lens photo shows that the particle diameter of MoN is that 5-6nm. is obtained by cathodic polarization curve accompanying drawing 2, and the reduction take-off potential of oxygen on catalyst is-0.1V that the area specific activity is 3.1mA/cm
2, and carbon supported platinum catalyst area specific activity is 1.5mA/cm under the relative rotation speed situation consistent with sweep speed
2, having increased by 1 times, catalytic activity is better than carbon supported platinum catalyst.When having methyl alcohol to exist, the polarization curve of catalyst does not have significant change, and methanol tolerance character has been described.Accompanying drawing 4 is the timing current curve of catalyst, and this curve shows that oxidation current is undamped substantially, catalyst stable relatively good.
Embodiment 2.
Is to be dissolved in acetone ultrasonic 50 minute at 1: 1 with molybdenum octaethylporphyrin and Vulcan XC-72 activated carbon powder by mass ratio; Above-mentioned solution stirring at normal temperature evaporate to dryness, 60 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 0.51/min, and controlling heat treated temperature is 700 ℃, reacts 4h under this temperature, stops heating then, is chilled to room temperature, obtains the MoN catalyst.Accompanying drawing 2 lens photos show that the particle diameter of catalyst is that 5-6nm. shows that by electrochemistry cathodic polarization curve and timing current curve this catalyst performance is better than the carbon platinum-carrying electrocatalyst.
Embodiment 3
Is to be dissolved in N-N dimethylacetylamide ultrasonic 50 minute at 2: 3 with molybdenum tetramethoxy porphyrin and Vulcan XC-72 activated carbon powder by mass ratio; Above-mentioned solution stirring at normal temperature evaporate to dryness, 70 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 21/min, and controlling heat treated temperature is 600 ℃, reacts 5h under this temperature, stops heating then, is chilled to room temperature, obtains the MoN catalyst.The lens photo shows that the particle diameter of catalyst is that 5-6nm. shows that by electrochemistry cathodic polarization curve and timing current curve this catalyst performance is better than the carbon platinum-carrying electrocatalyst.
Embodiment 4
Is to be dissolved in ethanol ultrasonic 40 minute at 2: 3 with molybdenum tetrasulfonic acid base porphyrin and Vulcan XC-72 activated carbon powder by mass ratio; Above-mentioned solution stirring at normal temperature evaporate to dryness, 80 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 31/min, and controlling heat treated temperature is 1000 ℃, reacts 4h under this temperature, stops heating then, is chilled to room temperature, obtains the MoN catalyst.Accompanying drawing 1XRD collection of illustrative plates show the component of gained catalyst be MoN and standard diagram coincide relatively good. the lens photo shows that the particle diameter of catalyst is that 5-6nm. accompanying drawing 5 is this catalyst 0.5MH
2SO
4And 0.5MH
2SO
4+ 0.5CH
3The OH cathodic polarization curve shows, the peak of methanol oxidation does not appear in catalyst when methyl alcohol exists, and the take-off potential of oxygen reduction cathode electric current is approaching in two kinds of solution, the significantly not negative phenomenon of moving, reduction current just reduces a little when methyl alcohol exists, this catalyst that illustrates that we prepare has good anti methanol toxication performance. show that by electrochemistry cathodic polarization curve and timing current curve the catalytic performance of this catalyst has reached the catalytic performance of carbon platinum-carrying electrocatalyst.
Embodiment 5
Is to be dissolved in tetrachloromethane ultrasonic 30 minute at 1: 9 with cobalt tetraphenylporphyrin and Vulcan XC-72 activated carbon powder by mass ratio; Above-mentioned solution stirring at normal temperature evaporate to dryness, 80 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 11/min, and controlling heat treated temperature is 900 ℃, reacts 3h under this temperature, stops heating then, is chilled to room temperature, obtains the CoN catalyst.The lens photo shows that the particle diameter of catalyst is that 5-6nm. shows that by electrochemistry cathodic polarization curve and timing current curve this catalyst performance is better than the carbon platinum-carrying electrocatalyst.
Claims (4)
1. a cathode in direct methanol fuel cells non-precious metal catalyst is characterized in that, active component is a transition metal nitride, and carrier is a Vulcan XC-72 activated carbon powder, and wherein the quality percentage composition of transition metal nitride is 1-6% in the active component.
2. the preparation method of a cathode in direct methanol fuel cells non-precious metal catalyst is characterized in that, may further comprise the steps:
1) transition metal macrocyclic compound, Vulcan XC-72 activated carbon powder are dissolved in the organic solvent ultrasonic 30-60 minute; Wherein transition metal macrocyclic compound is for being one of the monokaryon porphyrin of central metal ion and derivative thereof with molybdenum, cobalt, nickel, iron, manganese; Organic solvent is one of oxolane, ethanol, acetone, isopropyl alcohol, N-N dimethyl formamide, N-N dimethylacetylamide, methyl-sulfoxide, n-hexane, carrene, chloroform, tetrachloromethane, pyridine or ether; The mass ratio of transition metal macrocyclic compound and Vulcan XC-72 activated carbon powder is 1 in solvent: 9-1: 1;
2) above-mentioned solution is stirred evaporate to dryness at normal temperatures, 60-80 ℃ of drying obtains powder;
3) with above-mentioned steps 2) powder that the obtains closed container of packing into, feed ammonia, the flow of ammonia is 0.5-3l/min, and controlling heat treated temperature is 600-1000 ℃, and heat treatment time is 0.5-10h, and lowering the temperature naturally obtains catalyst.
3, the preparation method of a kind of cathode in direct methanol fuel cells non-precious metal catalyst according to claim 2 is characterized in that described monokaryon derivatives of porphyrin is the tetramethoxy porphyrin, tetrasulfonic acid base porphyrin, tetraphenylporphyrin, one of octaethylporphyrin.
4, a kind of cathode in direct methanol fuel cells non-precious metal catalyst according to claim 2 is characterized in that in the step 1) that the content of activated carbon is 0.02-9g/L in organic solvent, and the content of transition metal macrocyclic compound is 0.02-1g/L.
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Cited By (12)
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