CN110252421A - A kind of conductive catalytic Netowrk tape and preparation method thereof - Google Patents
A kind of conductive catalytic Netowrk tape and preparation method thereof Download PDFInfo
- Publication number
- CN110252421A CN110252421A CN201910618760.1A CN201910618760A CN110252421A CN 110252421 A CN110252421 A CN 110252421A CN 201910618760 A CN201910618760 A CN 201910618760A CN 110252421 A CN110252421 A CN 110252421A
- Authority
- CN
- China
- Prior art keywords
- preparation
- modified graphene
- conductive catalytic
- netowrk tape
- slurry
- Prior art date
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- Pending
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 155
- 239000002002 slurry Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 47
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 43
- 239000010439 graphite Substances 0.000 claims abstract description 43
- 230000007547 defect Effects 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000013067 intermediate product Substances 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000006260 foam Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 82
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 125000005842 heteroatom Chemical group 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 7
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 7
- 125000006413 ring segment Chemical group 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 150000002085 enols Chemical class 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000004332 deodorization Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 229910021389 graphene Inorganic materials 0.000 description 30
- 239000000243 solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 11
- 239000002019 doping agent Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- POVXOWVFLAAVBH-UHFFFAOYSA-N n-formamidoformamide Chemical compound O=CNNC=O POVXOWVFLAAVBH-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052755 nonmetal Inorganic materials 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000005518 electrochemistry Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000003911 water pollution Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 241000446313 Lamella Species 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229960003180 glutathione Drugs 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 108010024636 Glutathione Proteins 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 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 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000003292 glue 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
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229940023462 paste product Drugs 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000010148 water-pollination Effects 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/33—
-
- B01J35/56—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/638—
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
Abstract
The present invention provides a kind of conductive catalytic Netowrk tapes and preparation method thereof.The preparation method carries out slurry, drying comprising steps of substrate is drawn in catalysis slurry, obtain the first intermediate product；Rolling formation is carried out to the first intermediate product, obtains the second intermediate product；By the second intermediate product cut-parts, conductive catalytic piece is obtained；Conductive catalytic piece is subjected to redrying, obtains conductive catalytic Netowrk tape；Wherein, substrate includes foam metal or foamy graphite；The defects of catalysis slurry includes modified graphene, binder and solvent, and modified graphene is rich in edge, pore structure, catalytic activity is high.The conductive catalytic Netowrk tape includes the material prepared using the above method.The beneficial effect comprise that preparation method is easy, easy to operate, lot stability is high, production cost is low；Conductive catalytic Netowrk tape can be recycled, and can decompose the organic matter in water body, to water body deodorization, and can directly dock, save money laborsaving quick with other water body treating technologies.
Description
Technical field
The present invention relates to water body process fields, are a kind of conductive catalytic Netowrk tapes and preparation method thereof particularly.
Background technique
With rapid economic development, how efficiently water pollution becomes the huge problem that present society faces,
Cheap solution water pollution problem has become research hotspot.
Traditional water correction method has control source to cut dirt, desilt and dredge, power water transfer, artificial oxygenation, clear water supply, plantation
Emergent aquactic plant etc., recently as the rapid growth of national economy, the investment of traditional water correction method is increasing, and takes
Visible progress was obtained, but water environment severe situation does not obtain fundamental reversal generally, water pollution improvement is faced with
Expending huge manpower and financial resources, still effect is but difficult to the problem of embodying at once.It is administered in recent years using photocatalysis, electro-catalysis dirty
Dye water body is concerned by people, but there are high production cost, and need high to illumination condition requirement for water by photocatalysis body technique
The problems such as occupying a large amount of water surface space is unfavorable for the sustainable development of ecological environment.Traditional electro-catalysis mainly uses gold
Category or metal oxide, can bring the consumption of metal ion secondary pollution and metal/metal oxide itself in governance process,
Catalytic effect cannot be stablized for a long time, so that treatment cost is higher.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to solve above-mentioned one existing in the prior art
Or multiple problems.For example, one of the objects of the present invention is to provide a kind of conductive catalytic Netowrk tapes that can be improved and purify water
And preparation method thereof.
To achieve the goals above, one aspect of the present invention provides a kind of preparation method of conductive catalytic Netowrk tape.
The preparation method of the conductive catalytic Netowrk tape can comprise the following steps that draw substrate in catalysis slurry and carry out
Slurry, drying obtain the first intermediate product；Rolling formation is carried out to the first intermediate product, obtains the second intermediate product；To second
Intermediate product is dried, and obtains conductive catalytic Netowrk tape；Wherein, substrate includes foam metal or foamy graphite；It is catalyzed slurry
In contain modified graphene, the modified graphene can rich in edge, pore structure, five-membered ring, heptatomic ring and hetero atom at least
A kind of defect.
Another aspect of the present invention also provides a kind of preparation method of conductive catalytic Netowrk tape.
The preparation method of the conductive catalytic Netowrk tape can comprise the following steps that draw substrate in catalysis slurry and carry out
Slurry, drying obtain the first intermediate product；Rolling formation is carried out to the first intermediate product, obtains the second intermediate product；By second
Intermediate product cut-parts obtain conductive catalytic piece；Conductive catalytic piece is dried, conductive catalytic Netowrk tape is obtained；Wherein, substrate
It may include foam metal or foamy graphite；Contain modified graphene in the catalysis slurry, the modified graphene can be rich in side
At least one of edge, pore structure, five-membered ring, heptatomic ring and hetero atom defect.
One or more exemplary embodiment according to the present invention, the BET specific surface area of the modified graphene can be 200
~1100m2/ g, pore volume can be 1.6~2.0cm3/ g, aperture can be 3~30nm, and granularity can be 0.5~5 μm.
One or more exemplary embodiment according to the present invention, in the catalysis slurry can containing mass ratio for 1000~
Modified graphene, binder and the solvent of 3000:500~3000:40000~90000, wherein the solvent may include water, two
At least one of methylformamide, N-Methyl pyrrolidone, dimethyl acetamide；The binder may include carboxymethyl cellulose
At least one of plain sodium, hydroxypropyl methyl cellulose, polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol and butadiene-styrene rubber.
One or more exemplary embodiment according to the present invention, can also contain dispersing agent in the catalysis slurry, described
Dispersing agent may include the dispersing agent include in polyvinylpyrrolidone, dodecyl sodium sulfate and polyvinyl alcohol at least one
Kind；The mass ratio of the dispersing agent and modified graphene can be 20~200:1000~3000.
One or more exemplary embodiment according to the present invention, the catalysis slurry may also include additive, described to add
Add the quality of agent that can be no more than the one third of the modified graphene quality.
One or more exemplary embodiment according to the present invention, the catalysis slurry can by mass ratio for 40000~
90000,20~200,500~3000,0~1000 and 1000~3000 solvent, dispersing agent, binder, additive and modification
Graphene composition.
One or more exemplary embodiment according to the present invention, the surface density of the substrate can be 300~350g/m3。
One or more exemplary embodiment according to the present invention, before substrate is drawn catalysis slurry, the side
The preparation method, which may further comprise the step of:, is ultrasonically treated catalysis slurry.
One or more exemplary embodiment according to the present invention, the drying carried out to conductive catalytic piece may include true
Sky is dry, and vacuum drying temperature can be 100 DEG C~120 DEG C, and the time can be 6~12 hours, vacuum degree can for -0.9~-
0.1MPa。
One or more exemplary embodiment according to the present invention, before the slurry step, the preparation method is also
May include the preparation step for being catalyzed slurry:
By the solvent of 40000~90000 parts by weight, the dispersing agent of 20~200 parts by weight, 500~3000 parts by weight it is viscous
The modified graphene mixing for tying agent, the additive of 0~1000 parts by weight and 1000~3000 parts by weight, stirs evenly, is changed
Property graphene be catalyzed slurry, wherein the solvent may include water, dimethylformamide, N-Methyl pyrrolidone, dimethylacetamide
At least one of amine；The dispersing agent may include in polyvinylpyrrolidone, dodecyl sodium sulfate and polyvinyl alcohol extremely
Few one kind；The binder may include sodium carboxymethylcellulose, hydroxypropyl methyl cellulose, polytetrafluoroethylene (PTFE), Kynoar,
At least one of polyvinyl alcohol and butadiene-styrene rubber；The additive may include BET specific surface area not less than 1200m2The work of/g
Property absorption carbon material.
One or more exemplary embodiment according to the present invention, before preparing the catalysis slurry, the preparation side
Method may also include the preparation step of modified graphene: graphite oxide being mixed with water according to mass ratio 1:30~50, stirs, obtains
Starchiness product；Starchiness product is freeze-dried under low temperature, low humidity and vacuum condition, obtains cold dry product；By institute
It states cold dry product to be made annealing treatment, obtains the modified graphene of high catalytic activity.
One or more exemplary embodiment according to the present invention can also be used first in the preparation step of modified graphene
Cleaning solution cleans graphite oxide, the i.e. preparation step of modified graphene can include: cleans graphite oxide with cleaning solution to go to clean
Matter, filtering, obtains filter cake, wherein cleaning solution includes weak polar solvent；Filter cake is mixed with water according to mass ratio 1:30~50,
Stirring, obtains starchiness product；Starchiness product is freeze-dried under low temperature, low humidity and vacuum condition, is obtained cold dry
Product；The cold dry product is made annealing treatment, the modified graphene of high catalytic activity is obtained.
One or more exemplary embodiment according to the present invention, before preparing the catalysis slurry, the preparation side
Method further includes the preparation step of modified graphene: graphite oxide being mixed with water according to mass ratio 1:30~50, stirs, is starched
Paste product；Starchiness product is doped, doped products are obtained；By doped products under low temperature, low humidity and vacuum condition
It is freeze-dried, obtains cold dry product；The cold dry product is made annealing treatment, modified graphene is obtained.
One or more exemplary embodiment according to the present invention can also be used first in the preparation step of modified graphene
Cleaning solution cleans graphite oxide, the i.e. preparation step of modified graphene can include: cleans graphite oxide with cleaning solution to go to clean
Matter, filtering, obtains filter cake, wherein cleaning solution includes weak polar solvent；Filter cake is mixed with water according to mass ratio 1:30~50,
Stirring, obtains starchiness product；Starchiness product is doped, doped products are obtained；By doped products low temperature, low humidity and
It is freeze-dried under vacuum condition, obtains cold dry product；The cold dry product is made annealing treatment, modified graphite is obtained
Alkene.
The step of one or more exemplary embodiment according to the present invention, the annealing can include: in indifferent gas
Under atmosphere, the cold dry product is heated to 300~400 DEG C and keeps the temperature 1~3h, is then again heated to 500~600 DEG C and keep the temperature 1
~3h, it is cooling.
Further aspect of the present invention provides a kind of conductive catalytic Netowrk tape.The conductive catalytic Netowrk tape may include substrate,
And the modified graphene of coating on the substrate, wherein the substrate may include foam metal or foamy graphite；It is described to change
Property graphene rich at least one of edge, pore structure, five-membered ring, heptatomic ring and hetero atom defect.
One or more exemplary embodiment according to the present invention, modified graphene BET specific surface area can for 200~
1100m2/ g, pore volume can be 1.6~2.0cm3/ g, aperture can be 3~30nm, and granularity can be 0.5~5 μm.
One or more exemplary embodiment according to the present invention, the number of plies of the modified graphene can be 5~7.
One or more exemplary embodiment according to the present invention, the surface density of the substrate can be 300~350g/m3,
The surface density of the conductive catalytic Netowrk tape can be 370~400g/m3。
One or more exemplary embodiment according to the present invention, the porosity of the substrate can be 0.25~0.36, institute
The conductivity for stating conductive catalytic Netowrk tape can be 15~60m Ω/m3。
Compared with prior art, beneficial effects of the present invention can include: preparation method is easy, easy to operate, lot stability
High, lower production costs；Conductive catalytic Netowrk tape can be recycled, and can reach and be decomposed to the organic matter in water body, is right
Water body carries out deodorization, increases the effect of oxygen content of water, and can directly dock with other water body treating technologies, saves money laborsaving
It is quick.
Detailed description of the invention
By the description carried out with reference to the accompanying drawing, above and other purpose of the invention and feature will become more clear
Chu, in which:
Fig. 1 shows the flow diagram that conduction of the invention urges the preparation method of Netowrk tape；
Fig. 2 shows a scanning electron microscope (SEM) photographs of modified graphene in an illustrative embodiment of the invention；
Fig. 3 shows another scanning electron microscope (SEM) photograph of modified graphene in an illustrative embodiment of the invention；
Fig. 4 shows a scanning electron microscope (SEM) photograph of the modified graphene material of nonmetal doping；
Fig. 5 shows another scanning electron microscope (SEM) photograph of the modified graphene material of nonmetal doping；
Fig. 6 shows a scanning electron microscope (SEM) photograph of metal-doped modified graphene material；
Fig. 7 shows another scanning electron microscope (SEM) photograph of metal-doped modified graphene material；
Fig. 8 shows a scanning electron microscope (SEM) photograph of conductive catalytic Netowrk tape；
Fig. 9 shows another scanning electron microscope (SEM) photograph of conductive catalytic Netowrk tape；
Figure 10 shows an electrochemistry CV curve graph of conductive catalytic Netowrk tape；
Figure 11 shows another electrochemistry CV curve graph of conductive catalytic Netowrk tape.
Specific embodiment
Hereinafter, by conjunction with attached drawing and exemplary embodiment describe in detail conductive catalytic Netowrk tape of the invention and its
Preparation method, what is occurred in the present invention first, second does not indicate sequencing, is only used for being mutually distinguishable.
Conductive catalytic Netowrk tape of the invention includes the modified graphene of high catalytic performance.Completely graphene itself is
Without any catalytic performance, but the meeting being difficult to avoid that in actual production introduces various lack in nano-graphene lamella
It falls into, and edge, five-membered ring heptatomic ring, hetero atom (can be doped) in these defects etc. is the catalytic for realizing graphene
Possibility can be brought.The present invention can increase defect by increasing the method for oxidation depth (O/C ratio) on graphene sheet layer
Density, and a large amount of edge defects are being formed after annealing.Therefore key to the invention is that appropriateness improves the side of graphene
Edge defect, typical method be exactly to improve the oxidizability of graphite oxide, is obtained after annealing rich in edge, pore structure
Defect increases the active site of material.The present invention can also increase the foreign atom in graphene by adulterating simultaneously, adjust
The distribution of graphene surface/edge electronics is controlled, new electronics transfer/migration site is constructed, forms the activity for being easy to excite electronics
Site or O2,-OH adsorption site to be to further increase catalytic activity.
One aspect of the present invention provides a kind of preparation method of conductive catalytic Netowrk tape.
Fig. 1 shows the flow diagram that conduction of the invention urges the preparation method of Netowrk tape.
In an exemplary embodiment of conductive catalytic Netowrk tape of the invention, as shown in Figure 1, the preparation method can
The following steps are included:
S01: substrate is drawn into progress slurry, drying in catalysis slurry, obtains the first intermediate product.Wherein, the base
Material may include foam metal or foamy graphite.Modified graphene, binder, dispersing agent and the activity that the catalysis slurry may include
Adsorb carbon material.Wherein, the modified graphene is rich at least one of edge, pore structure, five-membered ring, heptatomic ring and hetero atom
Defect further can be rich in edge, pore structure and hetero atom defect.The BET specific surface area of modified graphene can for 200~
1100m2/ g, pore volume can be 1.6~2.0cm3/ g, aperture can be 3~30nm, and the number of plies can be 5~7, and granularity can be 0.5~5 μ
m.Drying temperature in the step can determine according to specific solvent, such as 100~125 DEG C.
S02: first intermediate product is carried out to roll film (rolling mold forming), obtains the second intermediate product.The step can
It is carried out by strength roll forming machine, such as LDHY600-N60 strength roll forming machine, mill rolling force can be 8~12T, such as 10T, milling train
Power of motor can be 380V, 11KW, and efficiency can be 2~3m/min.Rolling film can make the conductive network to be formed smooth (in i.e. second
Between product), eliminate surface spikes.
S03: by the second intermediate product cut-parts, conductive catalytic piece is obtained.The size of conductive catalytic piece can be according to client
It is required that cut, such as 300 × 400~600mm etc..Wherein, step S03 is the step of a selectivity, i.e. conductive catalytic network
The preparation method of band may include having the step, also may not include the step.In the case where preparation method does not include step S03,
Dry object correspondingly becomes the second intermediate product in step S04.Further, preparation method may include the step, because
Cut-parts can carry out post-processing convenient for client.Slice can be carried out by slitter, and precision can be 0~0.1mm.
S04: the conductive catalytic piece is dried, conductive catalytic Netowrk tape is obtained.Wherein, drying can remove conduction
Residual solvent in network makes conductive network form secured, stable catalysis network.Drying mode is preferably vacuum drying,
The vacuum drying time is short, effect is good；If drying effect is very slow under non-vacuum condition, time consumption is long, energy waste compared with
Greatly.Vacuum drying vacuum degree (i.e. relative degree of vacuum) can be -0.9~-0.1MPa, drying temperature can for 100~120 DEG C, when
Between can be 6~12h, by vacuum drying state modulator in above range first is that can greater efficiency obtain product, second is that this
The cementability of the conductive network obtained under the conditions of temperature, structural stability are best；If drying temperature is lower, the time is shorter, glue
Relay is bad, easily loses powder；If temperature is excessively high, overlong time, it is existing that conductive network will form excess shrinkage, catalysis network collapsing etc.
As.
In the present embodiment, foam metal may include nickel foam, copper etc..Substrate select foamed material (i.e. foam metal or
Foamy graphite) one processing of the subsequent clients to Netowrk tape is contributed to, second is that these substrates itself have good conductive property,
Internal resistance is smaller, and a large amount of electric energy will not be consumed in water treatment procedure.
The width dimensions of institute's substrate can be 100mm~1000mm, can easily meet different clients demand in this way.The substrate
Porosity can be 0.25~0.36, such as 0.3 ± 0.03, can make to be catalyzed slurry in this way can smoothly enter into hole and forms three-dimensional knot
Structure.The surface density of the substrate can be 300~350g/m3, such as 310,330,345g/m3Deng, can control in this way product entirety
Weight helps to improve the designability of product entirety.
In the present embodiment, the slurry may include mass ratio are as follows: 40000~90000:20~200:500~3000:
1000~3000 solvent, dispersing agent, binder and modified graphene.
Wherein, solvent may include one of water, dimethylformamide, N-Methyl pyrrolidone, dimethyl acetamide or
It is a variety of；Further, it may include one or both of water, dimethylformamide, NMP, dimethyl acetamide mixture.
Dispersing agent may include at least one of PVP (polyvinylpyrrolidone), dodecyl sodium sulfate and polyvinyl alcohol.
Powder body material can be evenly dispersed into solvent substrate by dispersing agent, form uniform and stable dispersion.
Binder may include CMC (sodium carboxymethylcellulose), HPMC (hydroxypropyl methyl cellulose), PTFE (polytetrafluoroethyl-ne
Alkene), PVDF (Kynoar), at least one of PVA (polyvinyl alcohol) and SBR (butadiene-styrene rubber).The effect of binder is
Connect powder body material, and the drying that powder is connected on substrate and is occurred in application process during slurry application
More closely knit accumulation body is formed in link.
The graphene catalysis material (i.e. modified graphene) contains a large amount of defect, and active site is more.It is described
Defect may include at least one of edge, pore structure, five-membered ring, heptatomic ring, hetero atom, such as pore structure, edge defect etc..
In the realization generation for existing for graphene catalytic activity of the defect, has carried out possibility.The grapheme material is the cotton-shaped powder of black
Or black powder, density can be 1~8g/L, BET specific surface area can be 200~1100m2/ g, pore volume can be 1.6~2.0cm3/
G, aperture can be 3~30nm.
In the present embodiment, the catalysis slurry may also include additive, and the mass ratio of additive and modified graphene can
The one third of modified graphene quality can be no more than for the additional amount of 0.001~1000:1000~3000, and additive.
Additive may include high-specific surface area activated adoption carbon material, such as carbon nanotube, active carbon etc..Activated adoption carbon
Material BET specific surface area can be not less than 1200m2/ g, such as 1300,1400m2/ g, partial size can be 3~8 μm, such as 5um (D95).
Within the above range by the specific surface area of activated adoption Carbon Materials and size controlling, advantageous as two-dimensional nano piece catalyst
The support carrier of (i.e. modified graphene) is conducive to improve catalytic efficiency.
In the present embodiment, the viscosity for being catalyzed slurry can be for 3500~6500mPas, such as 5000 ± 500mPas,
With the better preparation for realizing catalysis Netowrk tape.
In the present embodiment, in pulling phase, modified graphene is able to enter in the hole of foamed material and covers
On the surface of foamed material.Modified graphene can be firmly combined together by the binder in slurry with foamed material.
In the present embodiment, slurry, drying process can be carried out by tensile pulp machine.Tensile pulp machine can according in slurry solvent it is dry
The different temperature section of dry condition setting, such as 100,110,120,125,120,110 DEG C of 6 temperature sections, the slurry speed of tensile pulp machine
Degree can be 1~2m/min.
In the present embodiment, foamed material (such as foam metal) surface density can be 300~350g/m3, such as 310,
325、345g/m3Deng；Product (the i.e. catalysis Netowrk tape) 370~400g/m of surface density processed3, such as 375,385,394g/m3
Deng.
In the present embodiment, the preparation method may further comprise the step of: before substrate is drawn catalysis slurry, to urging
Slurrying material is ultrasonically treated, and can be accelerated catalysis slurry in this way and be entered inside foam metal, facilitate slurry in foam metal
Inside is evenly distributed.
It is described to lead on the basis of a upper exemplary embodiment in another exemplary embodiment of the invention
The preparation method of electro-catalysis Netowrk tape may also include the preparation link of catalysis slurry.
The preparation of the catalysis slurry is comprising steps of by the solvent of 40000~90000 parts by weight, 20~200 parts by weight
The modification of dispersing agent, the binder of 500~3000 parts by weight, the additive of 0~5000 parts by weight and 1000~3000 parts by weight
Graphene mixing, stirs evenly, and obtains modified graphene catalysis slurry.Wherein, solvent, dispersing agent, binder, additive and change
Property graphene can be identical as in a upper exemplary embodiment.
In the present embodiment, in the case where the solvent is water, the step of the mixing can include:
By the water of 70000~90000 parts by weight, the first binder of 150~250 parts by weight and 20~100 parts by weight
PVP is mixed and stirred for uniformly, obtaining the first intermediate product.Wherein, first deionized water can be mixed with CMC, is stirred evenly, then
PVP is added to stir evenly；Alternatively, can first mix deionized water with PVP, stir evenly, it is equal then to add CMC stirring
It is even.First binder may include sodium carboxymethylcellulose or hydroxypropyl methyl cellulose.
The modified graphene of first intermediate product and 2500~3000 parts by weight is mixed and stirred for uniformly, obtaining in second
Between product.
Second binder of the second intermediate product, 1700~2200 parts by weight is mixed and stirred for uniformly, to obtain modified stone
Black alkene is catalyzed slurry.Second binder may include in polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol and butadiene-styrene rubber at least
It is a kind of.
In the present embodiment, in the case where the solvent is dimethylformamide, the step of the mixing can include: will
The dispersant of the dimethylformamide of 40000~60000 parts by weight and 80~120 parts by weight simultaneously stirs evenly, and obtains
One product；The binder of first product and 1200~1300 parts by weight is mixed and stirred for uniformly, to obtain the second product；By second
Product and the modified graphene of 1300~1700 parts by weight are mixed and stirred for uniformly, obtaining modified graphene catalysis slurry.
In the present embodiment, the stirring vacuum-pumping in mixing step, vacuum degree (relative degree of vacuum) can for -0.95~-
0.1MPa (relative degree of vacuum), such as -0.98Mpa.On the one hand vacuumizing facilitates dispersion effect under the conditions of high-speed stirred, and two
It is that can remove the bubble generated in high-speed stirred, it is very useful for the stability and uniformity of slurry.
In the present embodiment, in the preparation process of slurry, additive, which can add, to be not added.The case where additive is added
Under, the additional amount of additive can be no more than the one third of modified graphene, and its addition opportunity is that modified graphene is being added
After material.Further, additive can be contained by being catalyzed in slurry, first is that can increase the adsorption capacity of catalyst system, be helped
In raising catalytic efficiency；Second is that the hydrophily of the middle carbon material of slurry can be increased, it is easily formed stable dispersion；Third is that
Due to high-specific surface area, biggish particle size and three dimensional particles shape structure, two-dimensional nano sheet catalyst support load can be used as
Body；Fourth is that the interaction of the carbon material and binder of different dimensions, is easily formed interconnected three-dimensional channel, help to inhale
Product diffusion after attached pollutant and decomposition.
In third exemplary embodiment of the invention, on the basis of second exemplary embodiment, in slurry
Before preparation, the preparation method of the conductive catalytic network may also include the preparation link of modified graphene.
The meeting being difficult to avoid that in actual production introduces various defects in nano-graphene lamella, and these defects are real
The catalytic performance of existing graphene brings possibility.The present invention can be by increasing the method for oxidation depth (O/C ratio) in graphene
Increase defect concentration on lamella, and forms a large amount of edge defects after annealing.Therefore the modification that the present invention obtains
Defect of the graphene rich in edge, pore structure, has a large amount of active site.The present invention can also be increased by adulterating simultaneously
Add the foreign atom (i.e. hetero atom) in graphene to further increase catalytic activity.In other words, the present invention prepares slurry
" modification " in modified graphene can come together to realize by " increasing defect " or by " increasing defect " and " doping ".
The preparation link of the modified graphene can include:
(A): cleaning graphite oxide with cleaning solution, filter, obtain filter cake.Wherein, in the purpose removal graphite oxide of cleaning
At least one of remaining impurity, such as K, Mn, Na, S and P impurity.The cleaning solution may include weak polar solvent, such as first
One of alcohol, ethyl alcohol and acetone.Wherein, the washable PH to graphite oxide dispersion (being formed by graphite oxide and cleaning solution)
The impurity in graphite oxide can be effectively removed in the range for 3~5, PH control.Wherein, step (A) can be a choosing
The step of selecting property, the preparation of modified graphene may include the step, can also not include, in the case where not including, in step (B)
Filter cake become graphite oxide accordingly.
(B): filter cake being mixed with water, stirs, obtains starchiness product.Wherein, the mass ratio of filter cake and water can be 1:30
~50, the mass ratio of the two is readily able to disperse in the range；Further, the mass ratio of filter cake and water can be 1:35~45.
Preferably, deionized water is selected, can be conducive to be formed uniform and stable paste intermediate or dispersed liquid crystal liquid in this way (i.e. in liquid crystal
State).Starchiness, which is made, in filter cake can make reaction system uniform and stable.
(C): the starchiness product being freeze-dried under low temperature, low humidity and vacuum condition, obtains cold dry product.
Wherein, the low temperature, low humidity and vacuum condition can include: temperature -60~-45 DEG C, humidity (i.e. relative humidity) less than 0.5%,
Vacuum degree -0.95~-0.1MPa, cold dry condition control can make hydrone become ice molecule within the above range, to pass through body
The lamellar structure etc. of graphite is further widened in product expansion；Further, temperature can be -55 DEG C, vacuum degree is -0.97MPa.Into
The time of row freeze-drying can be 48~72h, facilitate to obtain airsetting gum-like product (i.e. cold dry product) in this way.Through above-mentioned cold dry
The product for aeroge state that treated has three-dimensional interconnection channel, and interconnected structure is varied, in process, is in
The gelatinous cold dry product of airsetting keeps the high-specific surface area of product and three-dimensional porous structure particularly significant subsequent heat treatment.It is cold
The number of plies of dry product can have and significantly decrease compared to the number of plies of raw material graphite oxide, for example, its number of plies can be 10 layers hereinafter, this
It is to further increase interlamellar spacing because the hydrone of interlayer becomes ice crystal in refrigerating process, accelerate the removing of graphite oxide,
Further oxidized graphite flake layer is prevented to reunite.The cold dry product can be gluey for glassy yellow airsetting, density can for 0.010~
0.015g/cm3, such as 0.012g/cm3, the size of cold dry product can be 10~120 μm, such as 20,70,80,90 μm etc..
(D): the cold dry product being made annealing treatment, the modified graphene material of high catalytic activity is obtained.Wherein, it moves back
Fire processing can be in inert atmosphere or air atmosphere；It preferably, is inert atmosphere, the inert atmosphere may include nitrogen or inertia
The atmosphere that gas (such as Ar gas etc.) is constituted, the burning that inert atmosphere can reduce product lose ratio, improve yield.To cold dry product into
Row annealing can make graphene form a large amount of defect sturcture, and then form the active site of efficient stable.Specifically
Ground, annealing can include: the cold dry product is heated to 300~400 DEG C and keeps the temperature 1~3h, then it is again heated to 500~
It 600 DEG C and 1~3h of heat preservation, cools down, obtains the modified graphene material with high catalytic activity.It further, can be by cold dry production
Object is heated to 350 DEG C and keeps the temperature 2h, is then again heated to 550 DEG C and keeps the temperature 2h.Wherein, the heating rate in heating process can be
5~10 DEG C/min, it can guarantee that material thermal expansion is uniform in this way.The type of cooling may include cooling with furnace temperature.Modified graphene
The number of plies is less, such as 5~7 layers.
In the present embodiment, the raw material graphite oxide in step A, O/C can be 2~7, such as 3,5,6 etc. than high.Oxygen
Functional group's type of graphite includes carbonyl and/or carboxyl, and the number of plies can be ten several layers to tens of layers, such as 20~30 layers；Interlayer
Away from can beSuch as 7 or
In the present embodiment, the graphite oxide in step (A) can be using graphite oxide as raw material, and pass through low-temperature oxidation
Graft process obtains.Low-temperature oxidation intercalation method can be improved the oxidizability of graphite oxide, can lead on oxidized graphite flake layer
Increasing degree of oxidation is crossed to increase defect concentration, so that graphene is formed a large amount of edge, hole in subsequent annealing with this
The defects of structure, and then increase the active site of modified graphene material.
Specifically, low-temperature oxidation intercalation method prepares graphite oxide and can comprise the following steps that
Graphite, potassium nitrate and potassium permanganate are uniformly mixed, the concentrated sulfuric acid is added, obtains the first mixture.The graphite, nitre
The mass ratio of sour potassium and potassium permanganate can be 0.8~1.2:0.4~0.6:2~4, can be 0.86~1.08 further:
0.45~0.55:2.1~2.9, such as 1:0.5:2.5.The graphite of 5g~150g can correspond to the concentrated sulfuric acid of 115~3450mL of addition
(98%).Graphite can be expanded graphite or crystalline flake graphite.
First mixture is successively subjected to oxidation processes under 0~4 DEG C, 35~45 DEG C and 80~100 DEG C three temperature sections,
Obtain the second mixture.3~40h, 2~6h and 5~15min can be followed successively by from the reaction time down to high three temperature sections.It is described
Oxidant can be hydrogen peroxide.
Oxidant is added in the second mixture to be aoxidized, pickling, washing is obtained containing functional group and containing impurity
Graphite oxide.Oxidant can be hydrogen peroxide.
In the present embodiment, Fig. 2, Fig. 3 respectively illustrate the modified stone of high catalytic activity that the present exemplary embodiment is prepared
Two scanning electron microscope (SEM) photographs of black alkene, wherein length scales in Fig. 2 are that scale in 1 μm and figure has carried out ten equal parts, in Fig. 3
Length scales be 1 μm；It can be seen from the figure that constituting reticular structure between each layer of grapheme material, and there is a large amount of hole
Gap structure.
In the present embodiment, undoped graphene is mainly based on mesoporous absorption, BET specific surface area can for 200~
300m2/g。
In the 4th exemplary embodiment of the invention, on the basis of the preparation step of third exemplary embodiment
On, the preparation of the modified graphene may also include the step of being doped to starchiness product.
Compared with the preparation method in third exemplary embodiment, what the preparation method in the present exemplary embodiment had more
Step (i.e. step (C)) are as follows: starchiness product is doped, doped products are obtained；The object phase being freeze-dried in step (D)
That answers becomes doped products.
Step (A), (B), (D), (E) in the present exemplary embodiment in second exemplary embodiment step (A),
(B), (C), (D) can be corresponded identical.
In the present embodiment, the doping may include nonmetal doping.Wherein, the scalar quantity and dopant of starchiness product
The ratio of quality can be 1:0.1~1, such as 1:0.2~0.9.The scalar quantity of starchiness product include starchiness product low temperature,
Quality after being freeze-dried under low humidity and vacuum condition, wherein low temperature, low humidity and vacuum condition can be with above-mentioned freeze-drying steps
In it is consistent.During doping, can by mass ratio of the measurement starchiness product before and after freeze-drying, then in conjunction with
The mass ratio of the scalar quantity of starchiness product and dopant determines the mass ratio between starchiness product and dopant.
The dopant may include more hydrazide kind compounds.More hydrazide kind compounds may include benzoyl hydrazine, to benzene
At least one of diformylhydrazine, ammonia triacetyl hydrazine and oxalic acid diformylhydrazine.
Illustrate only as an example, doping may include nonmetal doping (N): first by GO-0 (i.e. starchiness product) into
Row concentration calibration, scaling method are to take the direct low temperature and low humidity vacuum freeze drying of 10ml starchiness GO-0, then weigh weight, really
Determine the content in GO-0.According to GO-0 (content of calibration): dopant=1:0.1~1 is doped.Wherein, dopant is optional
With: more hydrazide kind compounds such as benzoyl hydrazine, terephthalhydrazide, ammonia triacetyl hydrazine, oxalic acid diformylhydrazine, this kind of hydrazides doping
Agent is white flock, can large scale be dissolved in aqueous solution, preparation method can be all made of conventional method, and yield can reach
90% or more.GO-0 is mixed, mechanical stirring 30min under normal temperature conditions with more hydrazides solution, obtains brown shape precipitating
(brown pureed product can be obtained when concentration is higher)；Then it is filtered using industrial centrifugal or accurate press drier carries out at dehydration
Reason, obtained filter cake (i.e. doped products).
In the present embodiment, it is described be doped to nonmetal doping in the case where, the graphene being prepared scanning electricity
Mirror figure is as shown in Figure 4,5, wherein the length scales in Fig. 4 are 5 μm and have carried out 10 equal parts, and the length scales in Fig. 5 are 50 μm
And 10 equal parts are carried out.In conjunction with attached drawing it is found that the modified graphene after carrying out nonmetal doping has a large amount of defect, such as hole
Structure, marginal texture etc..The grapheme material being prepared can be black powder, and density can be 2~3g/L, such as 2.5 ±
0.2g/L；The BET specific surface area of grapheme material can be 300~750m2/ g can be further 300~400m2/ g, such as
330、340m2/ g etc.；Pore volume can be 0.8~1.0cm3/ g, such as 0.85,0.95cm3/ g etc.；Aperture can be 4~10nm, example
Such as 5,7,9nm.It may occur in which macroporous absorption on the nonmetallic grapheme material mixed, compared with undoped situation, specific surface
Product increases.
In the present embodiment, the doping may also include metal-doped.Wherein, the scalar quantity and dopant of starchiness product
The ratio of quality can be 1:0.5~1, such as 1:0.6~0.9.The scalar quantity of starchiness product include starchiness product low temperature,
Quality after being freeze-dried under low humidity and vacuum condition, wherein low temperature, low humidity and vacuum condition can be with above-mentioned freeze-drying steps
In it is consistent.The dopant may include ferrocene analog derivative.
Further, the dopant may include ferrocene diformylhydrazine.The process of the doping can include:
Ferrocene diformylhydrazine is dissolved in ethanol solution and glacial acetic acid is added as catalyst, obtains ferrocene diformylhydrazine
Solution.Wherein, ethyl alcohol accounting can be 0.4~0.6 in ethanol solution, and further, the ratio of second alcohol and water can be 1:1.Ice second
The additional amount of acid can be 0.5~1% (i.e. the 0.5~1% of ethanol solution quality) of overall reaction liquid solvent, and the catalysis of glacial acetic acid is made
With including activated carbonyl and/or-NH2。
The starchiness product is mixed with ferrocene diformylhydrazine solution, temperature rising reflux is simultaneously stirred, and is adulterated
Product.
Illustrate only as an example, dopant can be ferrocene analog derivative, first synthesis two hydrazides chemical combination of ferrocene
Object, preparation route are by ferrocene to obtain diacetyl ferrocene, obtain ferrocene dicarboxylic acid using redox, then with methanol
Esterification obtains ferrocene dicarboxylic acid methyl esters, finally obtains ferrocene diformylhydrazine with hydration hydrazine reaction, and color is red powder, is produced
Rate is greater than 80%.
Specific doping step can are as follows: 1) demarcates GO-0 (i.e. starchiness product) concentration；2) according to scalar quantity and mass ratio 1:
0.5~1 weighs ferrocene diformylhydrazine, ferrocene diformylhydrazine is dissolved in 1:1 water/alcohol mixeding liquid, and appropriate ice second is added
Acid is used as catalyst；3) it will be mixed under GO-0 and ferrocene diformylhydrazine solution normal temperature condition, increase temperature reflux and stir 1h, obtain
To black precipitate (i.e. doped products).
In the present embodiment, it is described be doped to metal-doped in the case where, the scanning electron microscope for the graphene being prepared
Figure is as shown in figs. 6-7.In conjunction with attached drawing it is found that the modified graphene after progress is metal-doped has a large amount of defect, such as edge
Defect, doped structure etc..The grapheme material being prepared can be the cotton-shaped powder of black, and density can be 5~8g/L, such as 7
±0.5g/L；The BET specific surface area of grapheme material can be 700~1100m2/ g, for example, 800,900,1000,1050,
1070m2/ g etc.；Pore volume can be 0.4~0.9cm3/ g, such as 0.41,0.8cm3/ g etc.；Aperture can be 3~8nm, such as 4,6,
7nm etc..；Metal-doped grapheme material is based on middle micro-porous adsorption, and compared with undoped situation, specific surface area substantially increases
Add.
In the present embodiment, in step (B), the mass ratio of filter cake and water is controlled in 1:30~50, can not only be easy to
Disperse, also help subsequent doping process.
Starchiness, which is made, in filter cake can not only make reaction system uniform and stable, and will not cause because of layering subsequent
Obtain being unevenly distributed for doping component in product.
In the present embodiment, in step (E), making annealing treatment to cold dry product can not only be such that graphene is formed greatly
The defect sturcture of amount, and doping component can be made to thermally decompose under high temperature environment, thus further in graphene nano lamella
Functional group or defect sturcture on introduce doping component, form the active site of efficient stable.
Heating rate in annealing process step in heating process can be 5~10 DEG C/min, for example, 6,8,9 DEG C etc., in this way
It can not only guarantee that material thermal expansion is uniform, additionally it is possible to which doping component thermal decomposition sufficiently, is unlikely to form excessive aggregate.
Another aspect of the present invention provides a kind of conductive catalytic Netowrk tape.The catalysis Netowrk tape may include above method system
Standby material out.
In an exemplary embodiment of conductive catalytic Netowrk tape of the invention, the conductive catalytic Netowrk tape may include
The modified graphene of substrate and coating on the substrate.Two SEM that Fig. 8, Fig. 9 show conductive catalytic Netowrk tape are micro-
See shape appearance figure.Wherein, the scale of length is 500 μm in Fig. 8, and the length scales in Fig. 9 are 2 μm.Figure 10 and Figure 11 are shown respectively
Electrochemistry CV curve graph of the conductive catalytic Netowrk tape in the organic pollutants such as phenol, phosphoric acid.Composite conducting catalysis network exists
Have the characteristics that significant electrochemical response in the organic pollutants such as phenol, phosphoric acid, occurs apparent oxidation in electrochemistry CV curve
Peak illustrates that the conductive catalytic network has excellent catalysis oxidation ability.
The surface density of the conductive catalytic Netowrk tape can be 370~400g/m3, such as 380g/m3, conductivity can for 15~
60mΩ/m3, for example, 15,20,35m Ω/m3Deng.
Wherein, the substrate may include above-mentioned substrate, such as foam metal or foamy graphite.Foam metal may include bubble
Foam nickel, copper etc..The porosity of the substrate can be 0.25~0.36, and catalysis slurry can be made to can smoothly enter into hole in this way and form three
Tie up structure.The surface density of the substrate can be 300~350g/m3, product overall weight can be controlled in this way, help to improve production
The designability of product entirety.
The modified graphene may include above-mentioned modified graphene, may include a large amount of defect, active site
It is more.Defect on modified graphene may include at least one of edge, pore structure, five-membered ring, heptatomic ring, hetero atom, such as
Pore structure, edge defect etc..In the realization generation for existing for graphene catalytic activity of the defect, has carried out possibility.The graphene
Density of material can be 1~8g/L, and BET specific surface area can be 200~1100m2/ g, pore volume can be 1.6~2.0cm3/ g, aperture
It can be 3~30nm, granularity is 0.5~5 μm.
Modified graphene on conductive catalytic Netowrk tape of the invention, which can be killed effectively, to be removed, contains bacterium, specifically: (1)
The cell of bacterium is adsorbed in the remaining functional group of graphene surface, and the cell membrane for causing film pressure to make cell is destroyed, cytoplasm
In endoplasm outflow, cause bacterium to lose activity；Because of the good electronic conductivity matter of graphene, the anti-oxidant base of thallus is destroyed
Matter causes oxidative pressure, and bacterium is caused to lose activity.Glutathione (GSH) is total hinge of cell antioxidant radical system, when
When it is with graphite alkene reaction, glutathione (GSH) is oxidized the efficiency of failure up to 95%, with hydrogen peroxide (H2O2) effect phase
Closely.(2) modified graphene on conductive catalytic Netowrk tape with high catalytic activity can also prevent bacterium, microorganism in water from existing
The surface of conductive catalytic Netowrk tape deposits, and influences catalytic performance, modified graphene also will form OOH*, O* etc. under power on condition
High chemically active intermediate, these intermediates can also eliminate bacterium, microorganism near catalysis network；And modified graphite
The number of drawbacks effect and nanometer size effect of alkene can effectively puncture bacteria wall and generate charge effect between cell
It answers, contains the growth of bacterium, and modified graphene contains more oxygen-containing functional group (- COOH ,-COOR) and can be recycled.
Conductive catalytic Netowrk tape of the invention can be effectively applied to controlling for the processing of water pollution, especially river water
Reason, such as effectively can reduce bad V class index COD, ammonia nitrogen, total phosphorus content in river water by Electrocatalysis Degradation, increase black
Smelly index dissolved oxygen content reduces suspension content, can be realized double eliminations of bad V class and black and odorous water.For example, disconnected to certain river
The bad V class index COD in face, ammonia nitrogen, total phosphorus respectively by 99mg/L, 4.72mg/L, 0.42mg/L, drop to 37mg/L,
1mg/L, 0.14mg/L, black smelly index dissolved oxygen by 5.37mg/L, increase to 9.43mg/L, suspended matter by 8.89mg/L, be down to
3.42mg/L tentatively realizes bad V class and black and odorous water " double eliminations ".
Conductive catalytic Netowrk tape of the invention has significant electrochemical response special in the organic pollutants such as phenol, phosphoric acid
There is apparent oxidation peak in electrochemistry CV curve, illustrates that the conductive catalytic network has excellent catalysis oxidation ability in point.
In conclusion conductive catalytic Netowrk tape and preparation method thereof of the invention can have the advantage that
(1) preparation method is easy, easy to operate, at low cost.
(2) modified graphene on conductive catalytic Netowrk tape has a large amount of defects and active site, and catalytic activity is high.
(3) graphene electro-catalysis Netowrk tape is to be set up directly on the creek water surface, is not necessarily to aeration oxygen replenishing, can improve river rapidly
Flowing water dissolved oxygen, verified, oxygen in water improves 30-50% or more, rapidly promotes the flourish of organism in water, improves river
Water ecology is gushed, creek biology habitat is restored.Since the modified graphene in catalysis Netowrk tape has more oxygen-containing function
Group [- COOH ,-COOR] can be recycled, and is decomposed to toxic organic compound in water body, deodorization, increases oxygen content of water, with it
He can directly dock Treatment process, save money laborsaving quick.
(4) conductive catalytic Netowrk tape can be effectively applied to the processing of water pollution, and energy conservation and environmental protection can be realized bad V
Double eliminations of class and black and odorous water.
Although those skilled in the art should be clear above by combining exemplary embodiment to describe the present invention
Chu can carry out exemplary embodiment of the present invention each without departing from the spirit and scope defined by the claims
Kind modifications and changes.
Claims (10)
1. a kind of preparation method of conductive catalytic Netowrk tape, which is characterized in that the preparation method comprising steps of
Substrate is drawn into progress slurry, drying in catalysis slurry, obtains the first intermediate product；
Rolling formation is carried out to the first intermediate product, obtains the second intermediate product；
Second intermediate product is dried, conductive catalytic Netowrk tape is obtained；Wherein,
Substrate includes foam metal or foamy graphite；
Contain modified graphene in catalysis slurry, modified graphene is rich in edge, pore structure, five-membered ring, heptatomic ring and hetero atom
At least one of defect.
2. a kind of preparation method of conductive catalytic Netowrk tape, which is characterized in that the preparation method comprising steps of
Substrate is drawn into progress slurry, drying in catalysis slurry, obtains the first intermediate product；
Rolling formation is carried out to the first intermediate product, obtains the second intermediate product；
By the second intermediate product cut-parts, conductive catalytic piece is obtained；
Conductive catalytic piece is dried, conductive catalytic Netowrk tape is obtained；Wherein,
Substrate includes foam metal or foamy graphite；
Contain modified graphene in catalysis slurry, modified graphene is rich in edge, pore structure, five-membered ring, heptatomic ring and hetero atom
At least one of defect.
3. the preparation method of conductive catalytic Netowrk tape according to claim 1 or 2, which is characterized in that the catalysis slurry
In containing mass ratio be 1000~3000:500~3000:40000~90000 modified graphene, binder and solvent,
In,
The solvent includes at least one of water, dimethylformamide, N-Methyl pyrrolidone, dimethyl acetamide；
The binder includes sodium carboxymethylcellulose, hydroxypropyl methyl cellulose, polytetrafluoroethylene (PTFE), Kynoar, poly- second
At least one of enol and butadiene-styrene rubber.
4. the preparation method of conductive catalytic Netowrk tape according to claim 1 or 2, which is characterized in that the catalysis slurry
It further include additive, the quality of the additive is no more than the one third of the modified graphene quality.
5. the preparation method of conductive catalytic Netowrk tape according to claim 1 or 2, which is characterized in that described to urge conduction
Changing the drying that piece carries out includes vacuum drying, and vacuum drying temperature is 100 DEG C~120 DEG C, and the time is 6~12 hours, vacuum
Degree is -0.9~-0.1MPa.
6. the preparation method of conductive catalytic Netowrk tape according to claim 1 or 2, which is characterized in that walked in the slurry
Before rapid, the preparation method further includes being catalyzed the preparation step of slurry:
By the solvent of 40000~90000 parts by weight, the dispersing agent of 20~200 parts by weight, 500~3000 parts by weight binder,
The additive of 0~1000 parts by weight and the mixing of the modified graphene of 1000~3000 parts by weight, stir evenly, obtain modified graphite
Alkene is catalyzed slurry, wherein
The solvent includes at least one of water, dimethylformamide, N-Methyl pyrrolidone, dimethyl acetamide；
The dispersing agent includes at least one of polyvinylpyrrolidone, dodecyl sodium sulfate and polyvinyl alcohol；
The binder includes sodium carboxymethylcellulose, hydroxypropyl methyl cellulose, polytetrafluoroethylene (PTFE), Kynoar, poly- second
At least one of enol and butadiene-styrene rubber；
The additive includes BET specific surface area not less than 1200m2The activated adoption carbon material of/g.
7. the preparation method of conductive catalytic Netowrk tape according to claim 6, which is characterized in that preparing the catalysis slurry
Before material, the preparation method further includes the preparation step of modified graphene:
Graphite oxide is mixed with water according to mass ratio 1:30~50, stirs, obtains starchiness product；
Starchiness product is freeze-dried under low temperature, low humidity and vacuum condition, obtains cold dry product；
Cold dry product is made annealing treatment, the modified graphene of high catalytic activity is obtained.
8. the preparation method of conductive catalytic Netowrk tape according to claim 6, which is characterized in that preparing the catalysis slurry
Before material, the preparation method further includes the preparation step of modified graphene:
Graphite oxide is mixed with water according to mass ratio 1:30~50, stirs, obtains starchiness product；
Starchiness product is doped, doped products are obtained；
Doped products are freeze-dried under low temperature, low humidity and vacuum condition, obtain cold dry product；
Cold dry product is made annealing treatment, modified graphene is obtained.
9. a kind of conductive catalytic Netowrk tape, which is characterized in that the conductive catalytic Netowrk tape includes substrate and is coated in described
Modified graphene on substrate, wherein
Substrate includes foam metal or foamy graphite；
Modified graphene is rich at least one of edge, pore structure, five-membered ring, heptatomic ring and hetero atom defect.
10. conductive catalytic Netowrk tape according to claim 9, which is characterized in that the surface density of the substrate be 300~
350g/m3, the surface density of the conductive catalytic Netowrk tape is 370~400g/m3。
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