CN106000438A - Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials - Google Patents
Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials Download PDFInfo
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- CN106000438A CN106000438A CN201610391182.9A CN201610391182A CN106000438A CN 106000438 A CN106000438 A CN 106000438A CN 201610391182 A CN201610391182 A CN 201610391182A CN 106000438 A CN106000438 A CN 106000438A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 17
- 239000011574 phosphorus Substances 0.000 title claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 title abstract 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000003763 carbonization Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 238000005255 carburizing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229940059574 pentaerithrityl Drugs 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- -1 phosphate ester Chemical class 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229960002920 sorbitol Drugs 0.000 claims description 2
- 229940113165 trimethylolpropane Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract 3
- 239000003990 capacitor Substances 0.000 abstract 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 2
- 238000010306 acid treatment Methods 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 34
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 33
- 229910052697 platinum Inorganic materials 0.000 description 17
- 229910002462 C-Pt Inorganic materials 0.000 description 14
- 239000010970 precious metal Substances 0.000 description 14
- 239000003863 metallic catalyst Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000036228 toxication Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 102100031478 C-type natriuretic peptide Human genes 0.000 description 1
- 101000796277 Homo sapiens C-type natriuretic peptide Proteins 0.000 description 1
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- NAIXASFEPQPICN-UHFFFAOYSA-O p-nitrophenylphosphocholine Chemical compound C[N+](C)(C)CCOP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 NAIXASFEPQPICN-UHFFFAOYSA-O 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Abstract
The invention provides a preparation method and application of nitrogen and phosphorus co-doped porous carbon materials which are used in the aspects of electric catalysis, catalyst carriers, super capacitors, water treatment and the like. The method comprises that a carbon source, a nitrogen source, a phosphorus source and a carbonization activating agent are mixed in different proportions, ground, then subjected to high temperature carbonization treatment in nitrogen gas, and then subjected to acid treatment to obtain the porous carbon materials with different nitrogen and phosphorus compositions. The prepared carbon materials are used as non-noble metal catalysts; compared with traditional noble metal catalysts, the materials have the advantages of simpler preparation process, high activity, strong anti-poisoning ability, and good stability, and are ideal oxygen reduction catalysts for fuel cells. The prepared carbon materials are used as catalyst carriers; compared with traditional carbon powder carriers, the catalysts loaded with nanoparticles have the catalytic activity, stability, anti-poisoning ability and the like improved significantly. The carbon materials have relatively idea effects when used in the fields of super capacitors and water treatment.
Description
Technical field
The invention belongs to poroid material with carbon element preparing technical field, relate to the poroid material with carbon element processed as eelctro-catalyst, catalyst carrier, ultracapacitor or water, be specifically related to the preparation method and applications of the poroid material with carbon element of a kind of nitrogen-phosphor codoping.
Background technology
Poroid material with carbon element is because having big specific surface area, high porosity, high heat stability, good electric conductivity and heat conductivity, it is widely used at numerous areas such as fuel cell, ultracapacitor, catalyst carrier, water process, adsorbent and gas storages, has become as a big focus of current materialogy research and development.At present, the synthetic method of poroid material with carbon element mainly has the method such as soft/hard template method, catalytic activation method, by different preparation process, can obtain orderly or unordered, have the poroid material with carbon element of Different Pore Structures.The poroid material with carbon element that these structures are different can produce distinct character, thus has higher using value.So, select cost-effective method particularly important to prepare poroid material with carbon element.On the whole, although using template can obtain the poroid material with carbon element of regular appearance, but have that preparation material cost is high, synthesis technique is complicated and the problem such as last handling process is loaded down with trivial details.Prepare poroid material with carbon element by catalytic activation method, not only reduce cost prepared by poroid material with carbon element, and synthesis technique is simple, with little need for last handling process, be therefore currently to prepare the relatively effective a kind of means of poroid material with carbon element.
It is found that in recent years, due to the hetero atom such as nitrogen, phosphorus and carbon atom adjoining dimensions, can be doped in the graphite-structure of material with carbon element, utilize nitrogen or the special role of phosphorus heteroatoms of doping, such that it is able to change the chemistry of poroid material with carbon element, mechanics and electric property, therefore individually the poroid material with carbon element of nitrogen or phosphorus doping is increasingly becoming a new study hotspot.And synthesis technique is simple, can with large-scale production, there is the poroid material with carbon element of nitrogen-phosphor codoping of many-sided application prospect there is no correlation technique at present or document is reported.
Summary of the invention
It is an object of the invention to for problems of the prior art, it is provided that a kind of low cost, method are simple, the preparation method of the poroid material with carbon element of nitrogen-phosphor codoping of good stability.
The technical solution used in the present invention is: the preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope, specifically carbon source, nitrogen source, phosphorus source three are mixed in proportion with activator as carbonized precursor, after ball mill grinding, high temperature cabonization under a nitrogen, then with acid soak process, then grind, sucking filtration, wash, be vacuum dried after obtain.
Described carbon source is any one in trimethylolpropane, tetramethylolmethane, xylitol, sorbitol.
Described nitrogen source is any one in carbamide, tripolycyanamide, polyaniline, polypyrrole, polyamide.
Phosphorus source is any one in phosphoric acid, red phosphorus, sodium hypophosphite, ammonium polyphosphate, phosphate ester.
Carbon source, nitrogen source, phosphorus source ratio are 1:
Between 0.1: 0.1 ~ 1: 3: 3.
Described activator is the nitrate of ferrum, cobalt, nickel, copper, zinc, or the chlorate of ferrum, cobalt, nickel, copper, zinc, and addition is 0.01 % ~ 20 % of carbonized precursor quality.
The heating rate of described high temperature cabonization is 0.5 ~ 20 DEG C, and carburizing temperature is 300 ~ 1200 DEG C, the process time is 0.5 ~
6 hours.
Described preparation process is carbonization treatment 1 ~ 3 time under nitrogen protection.
Described acid soak process be use concentration be 0.1 ~ 5 molL-1Nitric acid, sulphuric acid or hydrochloric acid solution, at 20 ~ 100 DEG C process 2 ~ 24 hours.
Described poroid material with carbon element is applied to catalyst carrier, ultracapacitor, water processes or fuel cell oxygen reduction, the precipitation of fuel cell oxygen.
(1) sign of the poroid material with carbon element of nitrogen-phosphor codoping that prepared by the present invention:
Test material with carbon element poroid to gained nitrogen-phosphor codoping (NPPC) below by XRD and Raman to characterize:
XRD and Raman characterize: Fig. 1 be XRD and Fig. 2 of nitrogen-phosphor codoping poroid material with carbon element non-precious metal catalyst (NPPC) prepared by the present invention be nitrogen-phosphor codoping poroid material with carbon element non-precious metal catalyst (NPPC) Raman spectrogram prepared by the present invention.From Fig. 1. the XRD figure of (a) can be seen that, NPPC has the diffraction maximum of (002) and (100) crystal face of obvious carbon, and do not have obvious diffraction maximum to occur in the XRD low angle diagram of illustration, further illustrate the poroid material with carbon element of this nitrogen-phosphor codoping and there is microcellular structure.From Fig. 2 .(b) Raman spectrogram it can be seen that there is obvious D peak and G peak in NPPC, the ratio of its peak intensityI D/I GIt is 1.11, and carbon dust is correspondingI D/I GIt is 1.15, graphitization sp of this explanation NPPC2Hydbridized carbon atoms proportion is suitable with carbon dust, and has good crystallinity.
(2) performance test of the poroid material with carbon element of nitrogen-phosphor codoping that prepared by the present invention:
The poroid material with carbon element of nitrogen-phosphor codoping that the present invention provides, owing to it has the characteristic of nitrogen-phosphor codoping, also has the biggest specific surface area, can apply to the fields such as eelctro-catalyst, catalyst carrier, ultracapacitor and water process.But for better illustrating the excellent performance of the poroid material with carbon element of nitrogen-phosphor codoping prepared by the present invention, the performance being the most only used as oxygen reduction electro-catalyst illustrates.
Fig. 3 is nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC) and Fig. 4 business platinum C catalyst (C-Pt/C) cyclic voltammogram in 0.1 M KOH solution.Can be seen that from Fig. 3,4, in the cyclic voltammogram that nitrogen is saturated, C-Pt/C catalyst shows distinctive suction dehydrogenation peak and oxide reduction peak, and NPPC catalyst curve is almost without characteristic peak, by contrast, in the cyclic voltammogram that oxygen is saturated, NPPC and C-Pt/C occurs in that the response current of oxygen, illustrates that NPPC has good oxygen reduction catalytic activity.
Fig. 5 is nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC), self-control platinum C catalyst (H-Pt/C) and business platinum C catalyst (C-Pt/C) polarization curve in 0.1 M KOH solution.From figure 5 it can be seen that half current potential of NPPC is apparently higher than H-Pt/C catalyst 25.0 mV, differ 24.9 mV with half current potential of C-Pt/C catalyst.
Fig. 6 is nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC) and business platinum C catalyst (C-Pt/C) chrono-amperometric test curve in 0.1 M KOH solution.From fig. 6 it can be seen that after 28000 s, the electric current conservation rate that C-Pt/C catalyst is corresponding is 81.9 %, and NPPC electric current conservation rate is 98.2 %, shows extraordinary stability.
Fig. 7 is nitrogen-phosphor codoping poroid material with carbon element non-precious metal catalyst (NPPC) and business platinum C catalyst (C-Pt/C) anti methanol toxication test curve in 0.1 M KOH solution prepared by the present invention.From the test result of Fig. 7 it can be seen that be passed through oxygen in the solution during as 1000 s, all there is a hydrogen reduction current-responsive peak (1000 the biggest in NPPC and C-Pt/C catalyst
~ 2000 s), growth over time, and this response current is increasingly stronger, the most steady.3M methanol solution is added again during 2000 s, the hydrogen reduction response current of C-Pt/C catalyst strongly reduces, and the hydrogen reduction electric current of NPPC catalyst does not change significantly, illustrate that NPPC catalyst there's almost no the problem of methanol poisoning in Cathodic oxygen reduction, there is good anti methanol toxication ability.
In sum, the low cost of nitrogen-phosphor codoping poroid material with carbon element non-precious metal catalyst prepared by the present invention, activity poisoning capability high, anti-are strong, good stability, are the preferable catalyst of fuel battery negative pole oxygen reduction reaction.The least bit position of nitrogen-phosphor codoping poroid material with carbon element non-metallic catalyst prepared by the present invention is negative compared to business platinum C catalyst has moved 15-25
MV, illustrates the oxygen reduction activity of catalyst of gained with business platinum carbon closely.
The poroid material with carbon element of nitrogen-phosphor codoping prepared by the present invention is applied to ultracapacitor, catalyst carrier, water treatment field the most all yield good result.
Accompanying drawing explanation
Fig. 1. for the XRD figure of nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC)；
Fig. 2. for the Raman spectrogram of nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC)；
Fig. 3. for the nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC) cyclic voltammogram in 0.1 M KOH solution；
Fig. 4. for business platinum C catalyst (C-Pt/C) at 0.1 M
Cyclic voltammogram in KOH solution；
Fig. 5. for nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC), self-control platinum C catalyst (H-Pt/C) and business platinum C catalyst (C-Pt/C) polarization curve in 0.1 M KOH solution；
Fig. 6. the chrono-amperometric test curve in 0.1 M KOH solution for nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC) and business platinum C catalyst (C-Pt/C)；
Fig. 7. the anti methanol toxication test curve in 0.1 M KOH solution for nitrogen-phosphor codoping of the present invention poroid material with carbon element non-precious metal catalyst (NPPC) and business platinum C catalyst (C-Pt/C).
Detailed description of the invention
Preparation and performance below by specific embodiment material with carbon element poroid to nitrogen-phosphor codoping non-precious metal catalyst are described further.
Embodiment
1
By trimethylolpropane, carbamide and phosphoric acid are that the ratio of 1:0.1:0.1 mixes as carbonized precursor in mass ratio, after addition carbonization-activation agent anhydrous ferric trichloride (0.01 % of carbonized precursor gross mass) grinds 12 hours, carry out a carbonization treatment under a nitrogen, the process time is that (carburizing temperature was 300 DEG C in 0.5 hour, heating rate is 1 DEG C/min), then after processing 12 hours with 0.1 M nitric acid dousing, place into ball mill and be fully ground 12 hours, sucking filtration, put into vacuum drying oven after washing and be dried 10 hours, i.e. obtain nitrogen, phosphorus forms the non-metallic catalyst of poroid material with carbon element.
Add that the least bit position of the nitrogen-phosphor codoping poroid material with carbon element non-metallic catalyst that carbonization-activation dosage is 0.01 % is negative compared to business platinum C catalyst has moved 15 mV.
Embodiment
2
:
Using tetramethylolmethane, tripolycyanamide and red phosphorus be in mass ratio the ratio mixing of 1:0.5:2 as carbonized precursor, add after carbonization-activation agent cobaltous chloride (0.1 % of carbonized precursor gross mass) grinds 12 hours, carry out secondary carbonization treatment under a nitrogen.Within 1 hour, (carburizing temperature is 400 DEG C to carbonization treatment for the first time, 5 DEG C/min of heating rate), within 1 hour, (carburizing temperature is 800 DEG C to carbonization treatment for the second time, 5 DEG C/min of heating rate), then after processing 10 hours with 0.5 M soak with sulphuric acid, place into ball mill to be fully ground 12 hours, put into vacuum drying oven after sucking filtration, washing and be dried 10 hours, i.e. obtain nitrogen, the non-metallic catalyst of the phosphorus poroid material with carbon element of composition.
Add the nitrogen-phosphor codoping poroid material with carbon element non-metallic catalyst that carbonization-activation dosage is 0.1 % to bear has moved 18 mV compared to business platinum C catalyst, half current potential.
Embodiment
3
:
The ratio of xylitol, polyaniline and sodium hypophosphite 1:1:1 in mass ratio is mixed as carbonized precursor, add carbonization-activation agent Nickel dichloride. (1 % of carbonized precursor gross mass), after grinding 12 hours, carry out a carbonization treatment under a nitrogen.Within 1 hour, (carburizing temperature is 850 DEG C to carbonization treatment, 2 DEG C/min of heating rate), then after processing 14 hours with 1 M soak with hydrochloric acid, place into ball mill and be fully ground 12 hours, put into vacuum drying oven after sucking filtration, washing to be dried 10 hours, i.e. obtain nitrogen, the non-metallic catalyst of the phosphorus poroid material with carbon element of composition.
Add the nitrogen-phosphor codoping poroid material with carbon element non-metallic catalyst that carbonization-activation dosage is 1 % to bear has moved 20 mV compared to business platinum C catalyst, half current potential.
Embodiment
4
:
The ratio of sorbitol, polypyrrole and ammonium polyphosphate 1:2:1 in mass ratio is mixed as carbonized precursor, add carbonization-activation agent copper nitrate (5 % of carbonized precursor gross mass), after grinding 12 hours, carry out secondary carbonization treatment under a nitrogen.Within 1 hour, (carburizing temperature is 300 DEG C to carbonization treatment for the first time, 2 DEG C/min of heating rate), within 2 hours, (carburizing temperature is 800 DEG C to carbonization treatment for the second time, 5 DEG C/min of heating rate), then after processing 16 hours with 2 M nitric acid dousings, place into ball mill to be fully ground 12 hours, put into vacuum drying oven after sucking filtration, washing and be dried 10 hours, i.e. obtain nitrogen, the non-metallic catalyst of the phosphorus poroid material with carbon element of composition.
Add the nitrogen-phosphor codoping poroid material with carbon element non-metallic catalyst that carbonization-activation dosage is 5 % to bear has moved 24mV compared to business platinum C catalyst, half current potential.
Embodiment
5
:
The ratio of trimethylolpropane, polyamide and phosphate ester 1:2:2 in mass ratio is mixed as carbonized precursor, add carbonization-activation agent zinc chloride (10 % of carbonized precursor gross mass), after grinding 12 hours, carry out secondary carbonization treatment under a nitrogen.Within 2 hours, (carburizing temperature is 500 DEG C to carbonization treatment for the first time, 5 DEG C/min of heating rate), within 2 hours, (carburizing temperature is 950 DEG C to carbonization treatment for the second time, 5 DEG C/min of heating rate), then after processing 18 hours with 3 M soak with sulphuric acid, place into ball mill to be fully ground 12 hours, put into vacuum drying oven after sucking filtration, washing and be dried 10 hours, i.e. obtain nitrogen, the non-metallic catalyst of the phosphorus poroid material with carbon element of composition.
Add the nitrogen-phosphor codoping poroid material with carbon element non-metallic catalyst that carbonization-activation dosage is 10 % to bear has moved 22mV compared to business platinum C catalyst, half current potential.
Embodiment
6
:
Using tetramethylolmethane, carbamide and phosphoric acid be in mass ratio the ratio mixing of 1:3:3 as carbonized precursor, add carbonization-activation agent anhydrous ferric trichloride (20 % of carbonized precursor gross mass), after grinding 12 hours, carry out a carbonization treatment under a nitrogen.Within 4 hours, (carburizing temperature is 800 DEG C to carbonization treatment, 5 DEG C/min of heating rate), then after processing 24 hours with 1 M soak with hydrochloric acid, place into ball mill and be fully ground 12 hours, put into vacuum drying oven after sucking filtration, washing to be dried 10 hours, i.e. obtain nitrogen, the non-metallic catalyst of the phosphorus poroid material with carbon element of composition.
Add the nitrogen-phosphor codoping poroid material with carbon element non-metallic catalyst that carbonization-activation dosage is 20 % to bear has moved 25mV compared to business platinum C catalyst, half current potential.
Claims (10)
1. one kind nitrogenous, the preparation method of the poroid material with carbon element of P elements codope, it is characterized in that: specifically carbon source, nitrogen source, phosphorus source three are mixed in proportion with activator as carbonized precursor, after ball mill grinding, high temperature cabonization under a nitrogen, then with acid soak process, then grind, sucking filtration, wash, be vacuum dried after obtain.
The preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope the most as claimed in claim 1, it is characterised in that: described carbon source is any one in trimethylolpropane, tetramethylolmethane, xylitol, sorbitol.
The preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope the most as claimed in claim 1, it is characterised in that: described nitrogen source is any one in carbamide, tripolycyanamide, polyaniline, polypyrrole, polyamide.
The preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope the most as claimed in claim 1, it is characterised in that: phosphorus source is any one in phosphoric acid, red phosphorus, sodium hypophosphite, ammonium polyphosphate, phosphate ester.
5. the preparation method of the poroid material with carbon element of a kind of nitrogenous, the P elements codope as described in any one of claim 1-4, it is characterised in that: carbon source, nitrogen source, phosphorus source ratio are 1: 0.1: 0.1 ~ 1: between 3: 3.
The preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope the most as claimed in claim 5, it is characterized in that: described activator is the nitrate of ferrum, cobalt, nickel, copper, zinc, or the chlorate of ferrum, cobalt, nickel, copper, zinc, addition is 0.01 % ~ 20 % of carbonized precursor quality.
The preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope the most as claimed in claim 6, it is characterised in that: the heating rate of described high temperature cabonization is 0.5 ~ 20 DEG C, and carburizing temperature is 300 ~ 1200 DEG C, and the process time is 0.5 ~ 6 hour.
The preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope the most as claimed in claim 7, it is characterised in that: described preparation process is carbonization treatment 1 ~ 3 time under nitrogen protection.
The preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope the most as claimed in claim 7 or 8, it is characterised in that: it is that to use concentration be 0.1 ~ 5 mol that described acid soak processesL-1Nitric acid, sulphuric acid or hydrochloric acid solution, 20 ~
Process 2 ~ 24 hours at 100 DEG C.
The preparation method of the poroid material with carbon element of a kind of nitrogenous, P elements codope the most as claimed in claim 1, it is characterised in that: described poroid material with carbon element is applied to catalyst carrier, ultracapacitor, water processes or fuel cell oxygen reduction, fuel cell oxygen separate out.
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