CN109012749A - Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope - Google Patents
Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 56
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 title claims abstract description 15
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 claims abstract description 22
- 229940083982 sodium phytate Drugs 0.000 claims abstract description 22
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 105
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 229960004756 ethanol Drugs 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- KETSPIPODMGOEJ-UHFFFAOYSA-B dodecasodium;(2,3,4,5,6-pentaphosphonatooxycyclohexyl) phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OC1C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C1OP([O-])([O-])=O KETSPIPODMGOEJ-UHFFFAOYSA-B 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000011031 large-scale manufacturing process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 5
- 239000013153 zeolitic imidazolate framework Substances 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003863 metallic catalyst Substances 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- -1 zeolite imidazole ester Chemical class 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B01J35/33—
-
- B01J35/618—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
A kind of nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope.The present invention is using ZIF-8 as template, respectively using sodium phytate and lauryl mercaptan as phosphorus source and sulphur source, calcining prepares the poroid nano-complex of non-metal carbon under an inert atmosphere, due to the porous skeleton structure of ZIF, carbon material inherits its porous structure after calcining, and the carbon material of the uniform codope of p and s has been made then because its low boiling point is sublimated removing in metal Zn.Gained catalyst has high specific surface area and electric conductivity, has good hydrogen reduction and analysis oxygen electro catalytic activity in alkaline medium, this is primarily due to porous carbon materials catalyst and effectively increases specific surface area and electric conductivity；Phosphorus sulphur part is instead of C-C sp2Hybridized orbit forms the connection of C-P and C-S, increases active site, be more advantageous to the conduction of electronics, greatly improve the electrocatalysis characteristic of material, have potential application in energy conversion and storage art.
Description
Technical field:
The invention belongs to novel energy resource material technology and electrochemical catalysis fields, and in particular to double-doped based on ZIF-8 phosphorus sulphur
Miscellaneous nonmetallic difunctional VPO catalysts；Further relate to the catalyst preparation method and its alkaline fuel cell cathode oxygen also
Electro-catalysis application in original reaction and anode of electrolytic water oxygen evolution reaction.
Background technique:
The energy technologys such as fuel cell, metal-air battery cause people with its efficient energy conversion, environment friendly
Extensive concern.Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the key that for various sustainable energy technology electrodes
Process, but the two processes all have a slow dynamics problem, and the catalyst currently used for ORR reaction be mainly Pt and
Its alloy, the catalyst for OER reaction is mainly IrO2And RuO2, but content is rare in nature for these noble metals, so
It develops new elctro-catalyst to play a crucial role in new energy storage and conversion art, wherein carbon-based base metal
Catalyst causes extensive concern as the catalyst for most possibly substituting above-mentioned noble metal.
ZIF, that is, zeolite imidazole ester frame structure material, is porous crystalline material, itself has high stability and high porosity
The characteristics of, ZIF is mainly used for efficient catalytic and separation process.ZIF-8 is reacted by zinc nitrate hexahydrate with 2-methylimidazole,
In view of the low boiling point of Zn, it can be used as sacrifice template and prepares nonmetallic porous carbon by high-temperature calcination removing metal Zn
Material, and introducing hetero-atoms realize that the electronic property for being doped into step section raising composite material and surface polarity and electrochemistry are urged
Change activity, doping hetero atom more commonly used at present has N, S, B, P etc., these nonmetalloids may replace the graphite wafer in material
Certain sp in lattice2The characteristic electron of carbon material can be changed, to further increase the catalytic activity of carbon material in the carbon atom of hydridization
And stability.Although achieving certain achievement by the porous carbon nanomaterial of precursor preparation of ZIF at present, yet there are no with
ZIF-8 is template and presoma, with sodium phytate for the source P, prepares the poroid nano-complex of non-metal carbon of P doping and studies it
The report of the difunctional electrocatalysis characteristic of ORR and OER.
The present invention is high under an inert atmosphere respectively using sodium phytate and lauryl mercaptan as phosphorus source and sulphur source using ZIF-8 as template
Warm calcining prepares the poroid nano-complex of non-metal carbon, and due to the porous skeleton structure of ZIF, it is more to inherit it for carbon material after calcining
Pore structure, and metal Zn, so that the carbon material of the uniform codope of PS be made, is denoted as then because its low boiling point is sublimated removing
PSpC.Gained PSpC catalyst has high electric conductivity and specific surface area, effectively reduces the overpotential of its OER and ORR, leads to
It crosses rotating disk electrode (r.d.e) (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE) shows that its ORR process is 4 electronic catalytic mechanism, be more
Ideal ORR reaction process, and the catalyst has good long-time stability and excellent methanol tolerance.This method
Mixing non-metal carbon electrochemical catalyst and energy conversion and memory device to exploitation hetero atom has important theory and practical meaning
Justice.
Summary of the invention:
In view of the deficiencies of the prior art and the demand of this field research and application, an object of the present invention are to provide one
Nonmetallic difunctional VPO catalysts of the kind based on ZIF-8 phosphorus sulphur codope；I.e. using ZIF-8 as template, respectively by itself and sodium phytate
After solution and lauryl mercaptan solution interaction, then the non-gold of phosphorus sulphur codope will be obtained after the white solid high-temperature calcination of collection
Belong to difunctional VPO catalysts, is denoted as PSpC；
The second object of the present invention is to provide a kind of nonmetallic difunctional VPO catalysts based on ZIF-8 phosphorus sulphur codope
Preparation method, specifically includes the following steps:
(a) preparation of ZIF-8
By 0.29g Zn (NO3)·6H2O and 0.66g 2-methylimidazole is dissolved in respectively in 15mL methanol, is kept the temperature at
Between 25~35 DEG C, the methanol solution of 2-methylimidazole is slowly dropped to or is quickly poured under stirring condition the methanol of zinc nitrate
In solution, continue after stirring 15min, for 24 hours, white precipitate is collected by centrifugation in aging at the same temperature, continuously washs 3 with methanol
It is secondary, last 50 DEG C of dry 12h in a vacuum drying oven；
(b) preparation of the nonmetallic difunctional VPO catalysts of PSpC
By ZIF-8 grind into powder obtained in step (a), takes 0.5g to be scattered in 10mL methanol, weigh 0.1~1.2g
Sodium phytate and 0.1~0.8g lauryl mercaptan are dissolved in respectively in 15mL dehydrated alcohol, first that the alcohol dispersion liquid of sodium phytate is slow
It is added drop-wise in ZIF-8 dispersion liquid, is stood again for 24 hours after stirring 2h；The alcohol dispersion liquid of lauryl mercaptan is added under agitation again
Enter in ZIF-8 and sodium phytate mixed dispersion liquid, stir 2h after stand again for 24 hours, centrifuge separation, white precipitate with ethanol washing 3 times,
50 DEG C of dry 12h in a vacuum drying oven, obtained white powder is put in tube furnace, under nitrogen atmosphere, with 5 DEG C/min
Heating rate be heated to 250 DEG C by room temperature, keep the temperature 2h, be heated to 700~1000 DEG C with same heating rate, heat preservation
Nonmetallic difunctional VPO catalysts PSpC is made in 4h.
Wherein the phosphorus source sodium phytate obtained by the preparation method in catalyst and sulphur source lauryl mercaptan are from a wealth of sources, cost compared with
It is low, convenient for large-scale production；P and S uniform doping in the catalyst, the average grain diameter of catalyst are 150~250nm, mesoporous carbon
Diameter between 5~7nm；Specific surface area is in 1514.6~1641.2m2/g。
The three of the object of the invention are to provide a kind of nonmetallic difunctional VPO catalysts based on ZIF-8 phosphorus sulphur codope in alkali
The catalytic applications of property fuel battery negative pole ORR and anode of electrolytic water OER.
The present invention use using ZIF-8 as template, respectively using sodium phytate and lauryl mercaptan as phosphorus source and sulphur source, in indifferent gas
High-temperature calcination prepares the poroid carbon material of phosphorus sulphur codope as nonmetallic difunctional VPO catalysts under atmosphere；Not only increase catalyst
Electric conductivity and specific surface area, and gained VPO catalysts effectively reduce the overpotential of ORR and OER, the results showed that its ORR
Process is largely 4 electronic catalytic mechanism, is ideal ORR reaction process.
Compared with prior art, the present invention have following major advantage and the utility model has the advantages that
1) difunctional VPO catalysts of the present invention are base metal composite material, raw materials used to be easy to buy and make
Standby, resourceful and price is lower, easily operated, convenient for large-scale production；
2) methanol tolerance that difunctional VPO catalysts of the present invention have had, in 0.1mol/L KOH electrolyte
3mol/L methanol is added, the catalytic activity of catalyst is almost without decaying；
3) difunctional VPO catalysts of the present invention are a kind of non-metal carbon material of phosphorus sulphur codope, are had preferable
ORR and OER catalytic activity has significant compared with the one-side ORR activity of base metal/non-metallic catalyst of current research report
Advantage；
4) compared with the Pt/C catalyst of commercialization 20wt%, stability obtains difunctional VPO catalysts of the present invention
It significantly improves, good catalytic activity can be kept in fuel cell long-time service.
Detailed description of the invention:
Fig. 1 is embodiment 1 (A), 1 institute of scanning electron microscope (SEM) photograph and embodiment of ZIF-8 obtained by embodiment 2 (B), embodiment 3 (C)
Obtain PSpC (D) transmission electron microscope picture.
Fig. 2 be embodiment 1 (left side), embodiment 4 (in) with embodiment 5 (right side) obtained by obtained by PSpC catalyst optics photograph
Piece.
Fig. 3 is that 1 gained PSpC of embodiment, 1 gained PpC of comparative example, 2 gained SpC of comparative example and 3 gained pC of comparative example distinguish
Modify the ORR linear sweep voltammetry curve graph of RDE.
Fig. 4 is the ORR dynamic curve diagram and corresponding K-L curve graph that 1 gained PSpC of embodiment modifies RDE.
The ORR dynamic curve diagram and corresponding transfer electron number and peroxide that Fig. 5 is 1 gained PSpC of embodiment modification RRDE
Change hydrogen yield figure.
Fig. 6 is that the nonmetallic VPO catalysts of 1 gained PSpC of embodiment modify the methanol tolerance linear sweep voltammetry curve that RDE is carried out
Figure.
Fig. 7 is that 1 gained PSpC of embodiment modifies I-t curve graph of the RDE under 0.8V constant voltage.
Fig. 8 is that 1 gained PSpC of embodiment, 1 gained PpC of comparative example, 2 gained SpC of comparative example and 3 gained pC of comparative example distinguish
Modify the OER linear sweep voltammetry curve graph of RDE.
Specific embodiment:
To further understand the present invention, present invention will be further explained below with reference to the attached drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1:
(a) preparation of ZIF-8
By 0.29g Zn (NO3)·6H2O and 0.66g 2-methylimidazole is dissolved in respectively in 15mL methanol, is kept the temperature at
Between 30~35 DEG C, the methanol solution of 2-methylimidazole is slowly dropped in the methanol solution of zinc nitrate under stirring condition, after
After continuous stirring 15min, for 24 hours, white precipitate is collected by centrifugation in aging at the same temperature, is continuously washed with methanol 3 times, finally true
50 DEG C of dry 12h in empty drying box；
(b) preparation of the nonmetallic difunctional VPO catalysts of PSpC
By ZIF-8 grind into powder obtained in step (a), 0.5g is taken to be scattered in 10mL methanol, weighs 0.2g phytic acid
Sodium and 0.12g lauryl mercaptan are dissolved in respectively in 15mL dehydrated alcohol, are first slowly dropped to the alcohol dispersion liquid of sodium phytate
In ZIF-8 dispersion liquid, stood again for 24 hours after stirring 2h；ZIF-8 is added in the alcohol dispersion liquid of lauryl mercaptan under agitation again
In sodium phytate mixed dispersion liquid, stood again for 24 hours after stirring 2h, centrifuge separation, white precipitate is with ethanol washing 3 times, in vacuum
50 DEG C of dry 12h, obtained white powder is put in tube furnace in drying box, under nitrogen atmosphere, with the heating of 5 DEG C/min
Rate is heated to 250 DEG C by room temperature, keeps the temperature 2h, is being heated to 900 DEG C with same heating rate, is keeping the temperature 4h, be made nonmetallic
Difunctional VPO catalysts PSpC, specific surface area 1641.2m2/g。
Embodiment 2:
(a) preparation of ZIF-8
By 0.29g Zn (NO3)·6H2O and 0.66g 2-methylimidazole is dissolved in respectively in 15mL methanol, is kept the temperature at
25 DEG C, the methanol solution of 2-methylimidazole is slowly dropped in the methanol solution of zinc nitrate under stirring condition, continues to stir
After 15min, for 24 hours, white precipitate is collected by centrifugation in aging at the same temperature, is continuously washed with methanol 3 times, is finally being dried in vacuo
50 DEG C of dry 12h in case；
(b) preparation of the nonmetallic difunctional VPO catalysts of PSpC
According to the method and condition preparation of step (b) in embodiment 1, the specific surface area of gained PSpC catalyst is
1514.6m2/g。
Embodiment 3:
(a) preparation of ZIF-8
By 0.29g Zn (NO3)·6H2O and 0.66g 2-methylimidazole is dissolved in respectively in 15mL methanol, is kept the temperature at
Between 25~35 DEG C, the methanol solution of 2-methylimidazole is quickly poured into the methanol solution of zinc nitrate under stirring condition, is continued
After stirring 15min, for 24 hours, white precipitate is collected by centrifugation in aging at the same temperature, is continuously washed with methanol 3 times, finally in vacuum
50 DEG C of dry 12h in drying box；
(b) preparation of the nonmetallic difunctional VPO catalysts of PSpC
According to the method and condition preparation of step (b) in embodiment 1, the specific surface area of gained PSpC catalyst is
1594.8m2/g。。
Embodiment 4:
(a) preparation of ZIF-8
According to the method and condition preparation of step (a) in embodiment 1.
(b) preparation of the nonmetallic difunctional VPO catalysts of PSpC
By ZIF-8 grind into powder obtained in step (a), 0.5g is taken to be scattered in 10mL methanol, weighs 0.5g phytic acid
Sodium and 0.4g lauryl mercaptan are dissolved in respectively in 15mL dehydrated alcohol, and the alcohol dispersion liquid of sodium phytate is first slowly dropped to ZIF-
In 8 dispersion liquids, stood again for 24 hours after stirring 2h；ZIF-8 and plant is added in the alcohol dispersion liquid of lauryl mercaptan under agitation again
In sour sodium mixed dispersion liquid, stood again for 24 hours after stirring 2h, centrifuge separation, white precipitate is being dried in vacuo with ethanol washing 3 times
50 DEG C of dry 12h, obtained white powder is put in tube furnace in case, under nitrogen atmosphere, with the heating rate of 5 DEG C/min
250 DEG C are heated to by room temperature, keeps the temperature 2h, 900 DEG C is being heated to same heating rate, is keeping the temperature 4h, nonmetallic double function are made
It can VPO catalysts PSpC, specific surface area 1596.2m2/g。。
Embodiment 5:
(a) preparation of ZIF-8
According to the method and condition preparation of step (a) in embodiment 1.
(b) preparation of the nonmetallic difunctional VPO catalysts of PSpC
By ZIF-8 grind into powder obtained in step (a), 0.5g is taken to be scattered in 10mL methanol, weighs 1.0g phytic acid
Sodium and 0.5g lauryl mercaptan are dissolved in respectively in 15mL dehydrated alcohol, and the alcohol dispersion liquid of sodium phytate is first slowly dropped to ZIF-
In 8 dispersion liquids, stood again for 24 hours after stirring 2h；ZIF-8 and plant is added in the alcohol dispersion liquid of lauryl mercaptan under agitation again
In sour sodium mixed dispersion liquid, stood again for 24 hours after stirring 2h, centrifuge separation, white precipitate is being dried in vacuo with ethanol washing 3 times
50 DEG C of dry 12h, obtained white powder is put in tube furnace in case, under nitrogen atmosphere, with the heating rate of 5 DEG C/min
250 DEG C are heated to by room temperature, keeps the temperature 2h, 800 DEG C is being heated to same heating rate, is keeping the temperature 4h, nonmetallic double function are made
It can VPO catalysts PSpC, specific surface area 1612.2m2/g。。
Embodiment 6:
(a) preparation of ZIF-8
According to the method and condition preparation of step (a) in embodiment 1.
(b) preparation of the nonmetallic difunctional VPO catalysts of PSpC
By ZIF-8 grind into powder obtained in step (a), 0.5g is taken to be scattered in 10mL methanol, weighs 0.2g phytic acid
Sodium and 0.12g lauryl mercaptan are dissolved in respectively in 15mL dehydrated alcohol, are first slowly dropped to the alcohol dispersion liquid of sodium phytate
In ZIF-8 dispersion liquid, stood again for 24 hours after stirring 2h；ZIF-8 is added in the alcohol dispersion liquid of lauryl mercaptan under agitation again
In sodium phytate mixed dispersion liquid, stood again for 24 hours after stirring 2h, centrifuge separation, white precipitate is with ethanol washing 3 times, in vacuum
50 DEG C of dry 12h, obtained white powder is put in tube furnace in drying box, under nitrogen atmosphere, with the heating of 5 DEG C/min
Rate is heated to 250 DEG C by room temperature, keeps the temperature 2h, is being heated to 700 DEG C with same heating rate, is keeping the temperature 4h, be made nonmetallic
Difunctional VPO catalysts PSpC, specific surface area 1608.8m2/g。。
Comparative example 1:
(a) preparation of PpC non-metallic catalyst
It weighs 0.5g ZIF-8 powder to be scattered in 10mL methanol, weighs 0.2g dissolution of sodium phytate in 15mL dehydrated alcohol
In, the alcohol dispersion liquid of sodium phytate is slowly dropped in ZIF-8 dispersion liquid, is stood again for 24 hours after stirring 2h, centrifuge separation is white
Color precipitating is used ethanol washing 3 times, and 50 DEG C of dry 12h, obtained white powder is put in tube furnace in a vacuum drying oven,
Under nitrogen atmosphere, 250 DEG C are heated to by room temperature with the heating rate of 5 DEG C/min, keeps the temperature 2h, with the heating of same heating rate
To 900 DEG C, 4h is kept the temperature, nonmetallic difunctional VPO catalysts PpC is made.
Comparative example 2:
(a) preparation of SpC non-metallic catalyst
It weighs 0.5g ZIF-8 powder to be scattered in 10mL methanol, weighs 0.12g lauryl mercaptan and be dissolved in the anhydrous second of 15mL
In alcohol, the ethanol solution of lauryl mercaptan is slowly dropped in ZIF-8 dispersion liquid, is stood again for 24 hours after stirring 2h, centrifuge separation,
White precipitate is with ethanol washing 3 times, and 50 DEG C of dry 12h, obtained white powder is put in tube furnace in a vacuum drying oven,
Under nitrogen atmosphere, 250 DEG C are heated to by room temperature with the heating rate of 5 DEG C/min, keep the temperature 2h, adds with same heating rate
Heat keeps the temperature 4h, nonmetallic difunctional VPO catalysts SpC is made to 900 DEG C.
Comparative example 3:
(a) preparation of pC non-metallic catalyst
It weighs 0.5g ZIF-8 powder to be put in tube furnace, under nitrogen atmosphere, with the heating rate of 5 DEG C/min by room temperature
250 DEG C are heated to, 2h is kept the temperature, 900 DEG C is being heated to same heating rate, is keeping the temperature 4h, nonmetallic difunctional oxygen is made and urges
Agent pC, specific surface area 1150.6m2/g。
Fig. 1 is embodiment 1 (A), 1 institute of scanning electron microscope (SEM) photograph and embodiment of ZIF-8 obtained by embodiment 2 (B), embodiment 3 (C)
Obtain PSpC (D) transmission electron microscope picture.As can be seen that the regular dodecahedron of standard, explanation is presented in the crystal grain of ZIF-8 from figure A
ZIF-8 crystalline form is preferable, and crystal successfully synthesizes.In contrast, ZIF-8 crystal morphology obtained by figure B and figure C is not presented just well
Dodecahedron illustrates that preparation method and condition described in embodiment 1 can realize the controllable preparation of ZIF-8 pattern.Figure D shows PS
After codope, ZIF-8 crystal has lost the regular dodecahedron pattern of its rule, is converted into poroid carbon material.
Fig. 2 be embodiment 1 (left side), embodiment 4 (in) with embodiment 5 (right side) gained PSpC catalyst optical photograph.By
Figure observes that 1 gained PSpC catalyst color of embodiment is carbonarius, illustrates that material is largely made of C, and embodiment 4 (in)
Canescence is presented with two kinds of PSpC catalyst obtained by embodiment 5 (right side), this is because during doping, due to sodium phytate and ten
The amount of two mercaptan significantly increases, and sulfur-bearing and phosphorus amount are excessively high in product, is unfavorable for catalyst and plays its electrochemical catalysis performance.
Above-mentioned electrocatalysis characteristic test is to be saturated Ag/AgCl electrode as reference electrode, and Pt electrode is to electrode, and sweeping speed is
10mV/s, electrolyte are 0.1M KOH, need to carry out O before ORR catalytic performance test2Saturated process, electricity before OER catalytic performance test
Solution liquid need to carry out N2Saturated process.RDE test result is after Koutecky-Levich formula manipulation, by the K-L slope of curve
(B) electron transfer number (n) can be calculated.
J-1=Jk -1+(Bω1/2)-1
B=0.62nF C0D0 2/3v1/6
Wherein F=96485C/mol, C0=1.2 × 10-3Mol/L, D0=1.9 × 10-5cm2/ s, v=0.01cm2/s。
RRDE test result can obtain electron transfer number (n) and H by following formula manipulation2O2Content:
N=4Id·(Id+Ir/N)
HO- 2%=200Id/N·(Id+Ir/ N),
Wherein N=0.43.
Fig. 3 is that 1 gained PSpC of embodiment, 1 gained PpC of comparative example, 2 gained SpC of comparative example and 3 gained pC of comparative example distinguish
Modify the ORR linear sweep voltammetry curve graph of RDE.As seen from Figure 3, the PSpC of P, S codope has highest take-off potential
And current density, show that hetero atom P and S plays facilitation to the ORR performance of catalyst jointly, due to P, in electricity between S
Synergistic effect in chemical catalysis further improves the specific surface area of carbon material, increases active site, improves catalyst
The property on surface, so that the electro-chemical activity of PSpC is more preferable than the PpC and SpC that singly adulterate and undoped pC.
Fig. 4 is the resulting kinetic parameter of ORR research that 1 gained PSpC of embodiment modifies that RDE is carried out.The results show that should
Electronics transfer number is about 3.91 in ORR catalytic process, close to no HO2 -4 electronic transfer process of product, to illustrate that PSpC is repaired
The ORR process for adoring electrode catalyst is 4 ideal electron reaction mechanism.
The ORR dynamic curve diagram and corresponding transfer electron number and peroxide that Fig. 5 is 1 gained PSpC of embodiment modification RRDE
Change hydrogen yield figure.The results show that electronics transfer number is about 3.9 in the ORR catalytic process, it is consistent with RDE test result, and
And 2 electron reaction course HO2 -Product maintains always 7% hereinafter, further illustrating the ORR process is close to 4 electronics
The reaction mechanism mechanism of reaction, PSpC catalyst have good ORR catalytic activity.
Fig. 6 is that the nonmetallic VPO catalysts of 1 gained PSpC of embodiment modify the methanol tolerance linear sweep voltammetry curve that RDE is carried out
3mL methanol is added as seen from the figure in figure in KOH electrolyte, and it is excellent to illustrate that PSpC has there is no substantially changeing for curve
Methanol tolerance poisons effect, this also has benefited from the good meso-hole structure of PSpC and adulterates uniform point of hetero atom P and S on the carbon material
Cloth.
Fig. 7 is that the nonmetallic VPO catalysts of 1 gained PSpC of embodiment modify constant voltage I-t test chart of RDE when 0.8V.By
For figure it is found that in the test of 30000s, the performance of PSpC has only decayed 13.64%, shows good long-time stability,
Be much better than decayed 47.26% business 20%Pt/C catalyst, in terms of Future New Energy Source application have important meaning
Justice has potential application value in the decorative material field of pluralities of fuel cell cathode.
Fig. 8 is the 1 nonmetallic VPO catalysts of gained PSpC of embodiment and 1 gained PpC of comparative example, 2 gained SpC of comparative example and right
The OER linear sweep voltammetry curve comparison figure of 3 gained pC of ratio.PSpC as shown in the figure has optimal take-off potential and electric current close
Degree.Meanwhile when current density is 10mA/cm2When, PSpC has minimum overpotential, hence it is evident that is better than PpC, SpC and pC.Knot
Fruit shows that ZIF-8 by the codope of progress P and S, significantly reduces its overpotential.This is primarily due to the carbon material after carbonization
ZIF-8 cavernous structure is inherited, the specific surface area and electric conductivity of carbon material are effectively increased；P and S portion are instead of C-C sp2
Hybridized orbit forms the connection of C-P and C-S, increases electro-chemical activity site, be more advantageous to the conduction of electronics, greatly mention
The high electrocatalysis characteristic of material, so showing minimum overpotential.
Claims (3)
1. a kind of nonmetallic difunctional VPO catalysts based on ZIF-8 phosphorus sulphur codope, it is characterised in that the catalyst be with
ZIF-8 is template, respectively by its with after sodium phytate solution and lauryl mercaptan solution interaction, then it is the white solid of collection is high
The nonmetallic difunctional VPO catalysts of phosphorus sulphur codope are obtained after temperature calcining, are denoted as PSpC；
The preparation method of the nonmetallic difunctional VPO catalysts based on ZIF-8 phosphorus sulphur codope, it is characterised in that including with
Lower specific steps:
(a) preparation of ZIF-8
By 0.29g Zn (NO3)·6H2O and 0.66g 2-methylimidazole is dissolved in respectively in 15mL methanol, keep the temperature at 25~
Between 35 DEG C, the methanol solution of 2-methylimidazole is slowly dropped to or is quickly poured under stirring condition the methanol solution of zinc nitrate
In, continue after stirring 15min, for 24 hours, white precipitate is collected by centrifugation in aging at the same temperature, continuously washs 3 times with methanol, most
50 DEG C of dry 12h in a vacuum drying oven afterwards；
(b) preparation of the nonmetallic difunctional VPO catalysts of PSpC
By ZIF-8 grind into powder obtained in step (a), 0.5g is taken to be scattered in 10mL methanol, weighs 0.1~1.2g phytic acid
Sodium and 0.1~0.8g lauryl mercaptan are dissolved in respectively in 15mL dehydrated alcohol, and first the alcohol dispersion liquid of sodium phytate is slowly added dropwise
Into ZIF-8 dispersion liquid, stood again for 24 hours after stirring 2h；The alcohol dispersion liquid of lauryl mercaptan is added under agitation again
In ZIF-8 and sodium phytate mixed dispersion liquid, stir 2h after stand again for 24 hours, centrifuge separation, white precipitate with ethanol washing 3 times,
50 DEG C of dry 12h, obtained white powder is put in tube furnace in vacuum oven, under nitrogen atmosphere, with 5 DEG C/min's
Heating rate is heated to 250 DEG C by room temperature, keeps the temperature 2h, is being heated to 700~1000 DEG C with same heating rate, is keeping the temperature 4h,
Nonmetallic difunctional VPO catalysts PSpC is made.
2. a kind of nonmetallic difunctional VPO catalysts based on ZIF-8 phosphorus sulphur codope according to claim 1, feature
It is that phosphorus source sodium phytate in the catalyst and sulphur source lauryl mercaptan are from a wealth of sources, cost is relatively low, convenient for large-scale production；This is urged
The average grain diameter of P and S uniform doping in agent, catalyst is 150~250nm, and the diameter of mesoporous carbon is between 5~7nm；Compare table
Area is in 1514.6~1641.2m2/g。
3. a kind of nonmetallic difunctional VPO catalysts based on ZIF-8 phosphorus sulphur codope according to claim 1 or 2,
It is characterized in that the catalyst for alkaline fuel cell cathode oxygen reduction reaction and anode of electrolytic water oxygen evolution reaction.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109742413A (en) * | 2018-12-28 | 2019-05-10 | 上海电力学院 | A kind of preparation method of hexagonal nano-sheet fuel cell oxygen reduction catalyst |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006599A (en) * | 2016-05-11 | 2016-10-12 | 浙江工业大学 | Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material |
| CN106887607A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of Pt bases elctro-catalyst of chemical molecular modification and its preparation and application |
| CN107661772A (en) * | 2017-10-20 | 2018-02-06 | 中国科学院化学研究所 | A kind of Nonmetal oxygen reduction catalyst and preparation method and application |
| CN107999109A (en) * | 2017-12-25 | 2018-05-08 | 西北师范大学 | The preparation and application of a kind of nitrogen, sulphur, phosphor codoping carbon material |
-
2018
- 2018-08-14 CN CN201810922744.7A patent/CN109012749A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106887607A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of Pt bases elctro-catalyst of chemical molecular modification and its preparation and application |
| CN106006599A (en) * | 2016-05-11 | 2016-10-12 | 浙江工业大学 | Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material |
| CN107661772A (en) * | 2017-10-20 | 2018-02-06 | 中国科学院化学研究所 | A kind of Nonmetal oxygen reduction catalyst and preparation method and application |
| CN107999109A (en) * | 2017-12-25 | 2018-05-08 | 西北师范大学 | The preparation and application of a kind of nitrogen, sulphur, phosphor codoping carbon material |
Non-Patent Citations (2)
| Title |
|---|
| PEIMIN HUANG等: "Multiheteroatom-Doped Porous Carbon Catalyst for Oxygen Reduction Reaction Prepared using 3D Network of ZIF-8/Polymeric Nanofiber as a Facile-Doping Template", 《ACS APPL. MATER. INTERFACES》 * |
| 潘泽宇: "基于介孔碳材料的氧还原电催化剂研究 ", 《化工管理》 * |
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