CN110248731A - The non-metal catalyst for being originated from useless biomass for oxygen reduction reaction - Google Patents
The non-metal catalyst for being originated from useless biomass for oxygen reduction reaction Download PDFInfo
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- CN110248731A CN110248731A CN201680091939.0A CN201680091939A CN110248731A CN 110248731 A CN110248731 A CN 110248731A CN 201680091939 A CN201680091939 A CN 201680091939A CN 110248731 A CN110248731 A CN 110248731A
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- biomass
- carbon
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- 239000002028 Biomass Substances 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 17
- 239000001301 oxygen Substances 0.000 title claims abstract description 16
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000000034 method Methods 0.000 claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000003763 carbonization Methods 0.000 claims abstract description 39
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 34
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 109
- 239000000047 product Substances 0.000 claims description 38
- 239000011592 zinc chloride Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 229910001510 metal chloride Inorganic materials 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000003780 insertion Methods 0.000 claims description 5
- 230000037431 insertion Effects 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003863 metallic catalyst Substances 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 239000006227 byproduct Substances 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 19
- 239000003575 carbonaceous material Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 238000001994 activation Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 230000009466 transformation Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000446 fuel Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 8
- 238000004502 linear sweep voltammetry Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 241000234295 Musa Species 0.000 description 6
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000000622 irritating effect Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 240000003826 Eichhornia crassipes Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 206010037211 Psychomotor hyperactivity Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004178 amaranth Substances 0.000 description 1
- 235000012735 amaranth Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/643—
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
The method for being used to prepare the non-metal catalyst for oxygen reduction reaction, comprising the following steps: useless biomass (solid or liquid) and catalyst are mixed together to form uniform powder or slurry；Fast catalysis carbonization is carried out by heating the uniform mixture to obtain highly porous carbonaceous mesophase object material；Carbonaceous mesophase object is blended with melamine to form carbon structure；It is modified by heating carbon structure progress nitrogen-enriched compounds；Enter in the carbon structure with by N doping.Gained catalyst has classifying porous carbon structure, with relatively high N doping and no metal.
Description
Invention field
The present invention relates to the non-metal catalysts for oxygen reduction reaction, including its manufacturing method.
Background of invention
Due in world wide use non-renewable fossil fuel, cause serious environmental pollution (such as greenhouse gases and
Global warming therewith), therefore the exploitation substituted with the sustainable energy becomes emergency task.In this background, have
High-energy density and the fuel cell of sustainable feature cause great interest.However, the transformation efficiency of this types of fuel cells
Usually limited by the overactivity energy of reaction by slow oxygen reduction reaction (ORR) in cell cathode.It can be dropped by catalyst
Low-activation energy, and currently a popular selection is the catalyst based on noble metal, is typically based on the material of platinum (Pt).Unfortunate
It is that for the catalyst based on noble metal not only under some fuel cell conditions by the stability of difference, there are also poor methanol to be resistant to
Property.In addition, noble metal is very expensive and rare.A research based on U.S. Department of Energy, the catalyst based on Pt account for fuel electricity
About the 50% of pond totle drilling cost.Therefore, exploitation has high ORR efficiency, extremely strong methanol tolerance and good ability for mass production
Cheap catalyst it is extremely important, but still maintain great challenge.
Carbonaceous material is low cost and has high-biocompatibility and electro catalytic activity, makes such no metal catalytic
Agent becomes the good candidate of material of the substitution based on platinum.In this background, carbon from useless biomass due to it almost zero
The raw material of cost and using the burden of severe environments at that time reduction and cause the interest increasingly increased.Normally, excellent ORR
Catalyst should have big specific surface area, suitable porosity (such as mesoporous-micropore of classification) and Heteroatom doping (such as N
Doping).However, because the intrinsic property (such as poor porosity, low N content) of useless biomass, such carbon is in no particular procedure
In the case where, generally lack these important features.In order to evade this challenge, propose many methods for improve biomass with
Overcome these difficulties.
Biomass is being used to be disclosed in Graglia etc. as the typical method of the disadvantage in non-metal catalyst for evading
People (ACSNano10, 2016, 4364-4371).Graglia discloses the porous carbon catalysis of the N doping for hydrogen reduction
Agent.Include four steps in synthesis: 1) by 220 DEG C hydro-thermal process 15h extract the lignin in waste wood, in THF
Dissolve and be finally dried in vacuo, 2 in solvent) pass through HNO in anhydrous acetic acid3Nitration of lignin, 3) pass through thunder Buddhist nun at 130 DEG C
Nickel is by H2By NO2Lignin is restored to NH2Lignin and 4) pass through ZnCl2The activation carbonization of-KCl fused salt.Graglia et al. report
Road introduces NH in lignin2Group and the catalytic activity for promoting final carbonaceous product is important by fused salt activation.
Zhang et al. (Small 10,2014,3371-3378) describe directly using hydrothermal carbonization (180 DEG C,
10h) to obtain the carbon based on useless grass than Pt.After hydro-thermal reaction, produced by being centrifuged 15min at 4500rmp to collect
Object.Then product is obtained by the way that solution is evaporated 6h at 70 DEG C.Zhang et al. discovery, product are the carbon nanometers of N doping
Point/nano flake aggregation.The high-content of pyridine N is necessary the high activity of material in carbon.
Liu et al. people (Nanoscale 7,2015,6136-6142) develops a step ZnCl2Carbonization technique is activated to obtain
It obtains porous N and adulterates carbonaceous catalyst.Waste water cucurbit is used as carbonaceous sources.Carbon product is mainly adulterated by pyridine N and graphite N.The source N comes from
Original chemical substance containing N in water hyacinth.ZnCl2Significant role is played in hole generates.The product has the performance than Pt.
In another experiment, Gao et al. (Energy&Environmental Science 8,2015,221-229)
Directly three-coloured amaranth waste material is carbonized to obtain high-performance without metal carbonaceous catalyst.Do not use special processing.Therefore, the mistake
Journey very simple.
However, for by useless Biomass, at excellent ORR catalyst, above four kinds of typical methods are not usually to be connect
The method received.In general, high porosity and enough N doping are two Fundamentals for determining no metal ORR catalyst performance.But
It is between variety classes, the chemical composition of useless biomass changes.Some N groups with high-content, and some do not have.No
Between same type, the porosity of useless biomass is also changed.Therefore, these four methods have not been able to the product by changing useless biomass
Kind is to obtain excellent ORR catalyst.
Have proposed NH3It activates as successfully solving the problems, such as this method (Energy & Environmental Science
7,2014,4095-4103:Journal of Power Sources 272,2014,8-15).The method is universal.
In activation process, NH3Not only etching carbon is to generate hole but also by N2Covalently it is introduced to carbon molecules structure.Although in ORR activity
It greatly improves, the method still suffers from some following significant drawbacks: a) NH3The use of gas is potential danger, especially
It is in large-scale production；B) in NH3Before activation, need the pretreatment of elapsed time/energy (such as with freeze-drying or high temperature
The water-heat process of carbonization) and c) give up biomass C transformation efficiency it is relatively low, be unsatisfactory for efficient resource recycling requirement.
Summary of the invention
The present invention not only realizes that useless biomass (solid or liquid) arrives the generally transformation of excellent ORR catalyst；But also there is height
Transformation efficiency, and be that the time is effective.
The present invention is the new side that production has high nitrogen doped graded porous carbon and the non-metal catalyst for ORR
Method.The catalyst mainly includes carbon and hetero atom (such as nitrogen) but does not have metal.Such carbonaceous catalyst has height to contain
The hierarchical porosity of micropore is measured, which prepares by being catalyzed carbonisation fastly, this is catalyzed carbonisation fastly and is given up using common
Biomass (solid or liquid) is then modified with nitrogen-enriched compounds as precursor.
Critical process of the invention has follow steps:
A) directly the insertion of the mixture (having been placed in bottle) of useless biomass and catalyst is had been warmed up to specific temperature
In the vertical heater of (DEG C).This step is referred to as " fast catalysis carbonization " and obtains highly porous carbonaceous mesophase object material.The sample quilt
Referred to as " CM Fastly- X ", whereinMIt represents the metal of catalyst and X represents the temperature of furnace.In the case where not using catalyst, pass through
The carbon of fast carbonization method synthesis is marked as " fast-X of C ", and
B) the carbonaceous mesophase object is blended with melamine, and blend is heated to specific temperature.This step is referred to as " rich nitrogen
It is compound modified ".Then nitrogen is doped into carbon structure.The sample is marked as " CM Fastly- X- melamine-Y ", wherein Y, which is represented, lives
Change temperature.In order to compare, undoped graded porous carbon is to handle in the case where no melamine and be labeled as " CM Fastly-X-
Y”。
An embodiment according to the present invention (step 1, takes the useless biomass of solid to make by so-called fast catalysis carbonization
For example) classifying porous carbonaceous material is prepared with high nitrogen doped, and it is then modified (step with ramped heating schedule
2).In step 1, (≤700 DEG C) realization carbonizations at relatively low temperatures.Directly by the mixture of raw material and catalyst
Relatively low temperature region is put into for being carbonized fastly.In this step using vertical heater and the classifying porous carbonaceous material of production.It should
Carbonaceous material is not final product, so it is referred to as intermediate product.In step 2, in the relatively high temperature for passing through temperature programming
Under degree, further use nitrogen-enriched compounds modified in horizontal chamber furnace (oven) the carbonaceous mesophase object.
The present invention can also be used in classifying porous nitrogen with excellent catalytic activity of the preparation for oxygen reduction reaction (ORR) and mix
Miscellaneous carbon promotes relevant electrochemical applications.The performance of carbon material (non-metal catalyst) reaches the level than Pt.
The present invention can also be used to prepare the porous nitrogen-doped carbon with ORR catalytic activity by following: use useless biology
Matter (solid or liquid) is used as raw material, uses ZnCl2As catalyst, and use nitrogen-enriched compounds such as nitrogen dopant.It is useless
Biomass is Common materials, including pericarp, leaf, gutter oil etc..Before carbonization, solid biomass of giving up is done at 105 DEG C
It is dry so that it becomes fragile.The useless biomass of liquid can use as former state.Compound ZnCl2It plays an important role in hole generates.In carbon
Before change, by ball milling by useless biomass and ZnCl2Equably mix.Hole in carbon shows graded features, is accounted for mainly with micropore
Status.Nitrogen-enriched compounds are used to prepare the porous carbon of N doping.Nitrogen content in the carbon is accounted for greater than 3at%, with pyridine N and pyrroles N
In the highest flight.When being used for ORR, classifying porous and nitrogen-doped carbon has high electrocatalytic active.
In addition, the present invention can be used for preparing the active porous nitrogen-doped carbon of ORR with high generality, i.e., it can be extensive kind
The mode of the biological material (solid or liquid) of class uses.Fast catalysis carbonization generates graded porous carbon, and uses nitrogen-enriched compounds
Modification hetero atom is introduced into carbon structure.Based on this process, by various types of common useless Biomass at high-performance ORR
Catalyst, without worrying very much the difference in useless biomass composition and microstructure in various applications to the shadow of its performance
It rings.
According to the present invention it is possible to very high efficiency system for porous carbon materials.In N2Under the protection of stream, by raw material and
The homogeneous mixture of catalyst is directly placed into preheated tank.It gives up biomass for solid, carbonization is usually tied in 10min
Beam, and be then 1 hour for liquid biomass of giving up.Then carbonaceous mesophase object is taken out to N2Filling tank is for being quickly cooled down
(15min).It gives up biomass for solid, whole process, which expends, is less than 30min, and is then 75min for liquid biomass of giving up.
The present invention can also be used to prepare porous carbon materials in continuous operation.Fast catalysis carbonization includes two action: insertion
With withdraw from.After fast catalysis carbonization, directly carbonaceous mesophase object is taken out and then by by the mixture of raw material and catalyst
New lot be directly inserted into tank the new lot for forming fast char-forming material.
Finally, the purpose of the present invention is provided by the way that useless biomass (solid or liquid) is transformed into valuable material
Reduce the solution of environmental pressure.The transformation of useless biomass to Functional carbon material remains carbon, it is avoided to be discharged into
In natural environment.
The present invention relates to following embodiments:
1. the method for being used to prepare the non-metal catalyst for oxygen reduction reaction, comprising the following steps:
There is provided uniform mixture by following: (i) solid is given up biomass and catalyst is mixed together to form uniformly
Powder, or (ii) liquid is given up biomass and catalyst is mixed together to form uniform slurry；
It carries out being catalyzed carbonization fastly by heating the uniform mixture in an inert atmosphere, to obtain porous carbon intermediary material
Material；
Carbonaceous mesophase object material is blended with melamine to form carbon structure；
It is modified that nitrogen-enriched compounds are carried out by heating carbon structure；With
N doping is entered in carbon structure.
2. the method for embodiment 1, wherein the catalyst is metal chloride, it include zinc chloride, iron chloride, chlorination
One of aluminium or their mixture.
3. the method for embodiment 2, wherein the catalyst is ZnCl2Powder.
4. the method for embodiment 1, wherein the mixing is carried out as ball milling.
5. the method for embodiment 1, wherein the step of hybrid solid biomass the following steps are included:
It washes with water solid and gives up biomass to remove dirt；
Solid biomass is cut into slices；
It is in an oven that piece is dry until biomass reaches constant weight；With
Dried solid biomass is equably mixed with metal chloride powder with ball mill.
6. the method for embodiment 1, wherein the step of mixing liquid biomass includes: will be without appointing with ball mill
The useless biomass of what pretreated liquid mixes directly and equably with metal chloride powder.
7. the method for embodiment 1, wherein the step of progress fast catalysis carbonization the following steps are included:
Uniform mixture is put into the vertical bottle for wherein having nitrogen；
Promptly bottle insertion is had been warmed up into the vertical heater between 300 DEG C and 700 DEG C, to form graded porous carbon；
After first time period, by bottle from vertical heater pull out and be inserted into water fill container in be used to be quickly cooled down；
After second time period, carbon is rinsed to remove and recycle metallic catalyst with acid solution and water；With
Carbon is dry until it has constant weight.
8. the method for embodiment 7, wherein the vertical bottle is formed by one of quartz and titanium.
9. the method for embodiment 7, wherein give up biomass for solid, vertical drying oven is preheated to 400 DEG C, and for
The useless biomass of liquid is then preheated to 650 DEG C.
10. the method for embodiment 7, wherein give up biomass for solid, the first time period 8 and 12 minutes it
Between, preferably 10 minutes, and biomass is given up then between 30-90min for liquid, preferably 60min.
11. the method for embodiment 7, wherein the second time period is between 12 and 18 minutes, preferably 15 minutes.
12. the method for embodiment 7, wherein between 60 DEG C and 80 DEG C, preferably at 70 DEG C that carbon is dry.
13. the method for embodiment 7, wherein the acid solution is the solution of HCl.
14. the method for embodiment 1, wherein the useless biomass is organic non-fossil material of biological source, for pair
Product or reject product.
15. the method for embodiment 14, wherein the material of the biological source is pericarp, leaf, waste oil, one in wood
Or mixtures thereof kind.
16. the method for embodiment 1 carries out in an inert atmosphere.
17. the method for embodiment 16, wherein the inert atmosphere includes N2With at least one in Ar.
18. the method for embodiment 1, wherein the step of doping nitrogen is related to urging fastly using rich nitrogen molecular will come from
The carbon for changing carbonization is modified.
19. the method for embodiment 18, wherein the richness nitrogen molecular include urea, melamine, thiocarbamide, dicyandiamide or
Their mixture.
20. the method for embodiment 1, wherein it is modified to carry out nitrogen-enriched compounds within the temperature range of 800-1100 DEG C.
21. for the catalyst of electrochemical oxygen reduction reaction, comprising with flowering structure or by following structure composition: having extremely
The classifying porous carbon structure of the N doping of few 3at%, 13-90at%, 23-80at%, 33-70at%, and the catalyst does not include gold
Belong to.
22. the catalyst of embodiment 21, wherein the carbon is less than the micropore of 2nm with the size of > 80%.
23. the catalyst of embodiment 21, wherein the carbon is adulterated by pyridine nitrogen and pyrroles's nitrogen 50-100%.
The present invention can be related in the catalyst reacted for electrochemical oxygen reduction using the above classification with N doping
Porous carbon structure.
Brief description
When in conjunction with features as discussed above to consider, aforementioned and other objects and advantages of the invention will become more
Obviously, identical label indicates identical element in each view in attached drawing, and wherein:
Fig. 1 is the schematic diagram of graded porous carbon and the manufacturing process of its N doped products；
Fig. 2A is shown at 400 DEG C through the SEM image for the carbon intermediary that catalysis carbonization obtains fastly；Fig. 2 B is shown for Fig. 2A's
Carbon intermediary, the relationship between relative pressure and adsorbance；Fig. 2 C shows that the pore-size distribution of the carbon intermediary of Fig. 2A, Fig. 2 D are to say
The SEM image of the bright nitrogen-doped carbon product after cyanurotriamide modified；Fig. 2 E shows the nitrogen-doped carbon product for Fig. 2 D, relatively
Relationship between pressure and adsorbance；And Fig. 2 F shows the pore-size distribution of the nitrogen-doped carbon product of Fig. 2 D；
Fig. 3 shows the high-resolution XPS spectrum of carbon product in the following sequence: by 400 DEG C (Fig. 3 A), 900 DEG C (Fig. 3 C),
The C1s spectrum of the carbon intermediary of catalysis carbonization preparation fastly under 1000 DEG C (Fig. 3 E) and 1100 DEG C (Fig. 3 G).Also show by
Cyanurotriamide modified nitrogen-doped carbon produces under 400 DEG C (Fig. 3 B), 900 DEG C (Fig. 3 D), 1000 DEG C (Fig. 3 F) and 1100 DEG C (Fig. 3 H)
The N1s XPS spectrum of object；
Fig. 4 A is shown through the nitrogen-doped carbon product and business Pt/C of preparation cyanurotriamide modified at 1000 DEG C in O2Saturation
Linear sweep voltammetry (LSV) curve in KOH solution under the 1600rpm speed of rotation, Fig. 4 B show various samples in O2It is full
LSV curve in the KOH of the 0.1M of sum under the speed of rotation of 1600rpm, Fig. 4 C are shown through the melamine at 1000 DEG C
The nitrogen-doped carbon product of modified preparation is under different rotary rate in O2In 5mV s in the KOH solution of the 0.1M of saturation-1Scanning
LSV curve under rate, and Fig. 4 D is derived from the nitrogen-doped carbon production by preparation cyanurotriamide modified at 1000 DEG C of Fig. 4 C
K-L figure of the object under different potentials；
Fig. 5 A and 5B show for by business Pt/C catalyst and at 1000 DEG C cyanurotriamide modified preparation nitrogen-doped carbon
Product, in no O2KOH solution, O2The KOH solution and O of saturation2In the KOH and addition MeOH of saturation, in 50mVs-1Lower ORR's
CV curve；Fig. 5 C shows for the nitrogen-doped carbon product by preparation cyanurotriamide modified at 1000 DEG C and does not use
ZnCl2As the nitrogen-doped carbon product of catalyst preparation, in O2In the KOH solution of the 0.1M of saturation, the rotation of ORR at 1600 rpm
Change disc electrode measurement result, which disk electric current (Id) it is shown in the lower half portion of figure, and circular current (Ir) it is shown in the upper half of figure
Part；Fig. 5 D is shown based on RRDE data corresponding in Fig. 5 C, under each current potential, by cyanurotriamide modified at 1000 DEG C
The nitrogen-doped carbon product (solid line) of preparation and without use ZnCl2The peroxidating of the nitrogen-doped carbon product (dotted line) of catalyst preparation
The percentage (black line) and electron transfer number (n) (blue line) of object；
Fig. 6 shows the nitrogen-doped carbon product (Fig. 6 A) and business Pt/C (Fig. 6 B) by preparation cyanurotriamide modified at 1000 DEG C
In O2In the KOH solution of the 0.1M of saturation, in 100mVs-1Sweep speed under the 1st and the 2000th CV curve；
Fig. 7 A shows CZnFastlyLSV curve of -1000 catalyst of TrPC-400- melamine compared with conventional Pt/C catalyst, and
Fig. 7 B shows CZnFastlyCV curve of -1000 catalyst of OPC-400- melamine compared with conventional Pt/C catalyst.CZnFastlyTrPC
In Tr mean leaf, CZnFastlyO in OPC means orange peel；
Fig. 8 shows LSV curve of the following each sample compared with conventional Pt/C: BP-1100-NH3-1000、CZnFastly- 400- three
Poly cyanamid -1000, BP-HT180-NH3-800,BPC-800-1h；With
Fig. 9 is shown in the supercapacitor made of active carbon according to the present invention compared with commercially available supercapacitor
The comparison of capacitor；
Figure 10 A shows the porous carbon nano-structured SEM image for being originated from the useless biomass of liquid, and Figure 10 B shows TEM image.
Detailed description of the invention
The present invention being described in detail below prepares the carbon material of catalytic activity using useless biomass (solid or liquid), for
Oxygen reduction reaction has catalytic activity, this is realized by noble metal (usually platinum (Pt)) at present.The main object of the present invention is to provide
The selection of low cost is to substitute very expensive noble metal.Another main purpose of the invention is reduced by largely generating daily
Useless biomass caused by environmental pressure.
In fact, the whole world generates ~ 1,400 hundred million tonnes of biomass every year from agricultural and many ultimately becomes waste material.It should
The common processing of biomass is only to open wide burning, leads to serious air pollution.The common attribute of useless biomass is that it includes
The carbon (C) of high relative contents, typically larger than 35wt%.This is expected to close to prototype biomass --- the carbon content of glucose, display
As suitable carbon source.The present invention is by useless Biomass at the Functional carbon with excellent oxygen reduction reaction (ORR) catalytic activity
Material.
As the candidate for substituting the elctro-catalyst based on Pt in a fuel cell, no metal carbon material due to they
High conductivity, porous structure and excellent durability in alkaline solution and the attention for causing many researchers.However, thick
Carbon material shows weak electro catalytic activity.In order to enhance the electro catalytic activity of common carbon material, it appears that destroy the electricity of graphite material
Neutrality is conducive to O to generate2The electrically charged site of absorption can be effective.Nitrogen (or P, B) atom is introduced into graphene (or one
Other a little carbon nanomaterials) in sp2The carbon skeleton of hydridization is certified as highly effective on improving electrocatalysis characteristic.N doped carbon
Material is widely studied by whole world researcher.Compared with the catalyst based on Pt, although some N doped carbon electricity are urged
Agent has comparable even preferably electro catalytic activity, and has better stability and fuel tolerance, but these materials
Material is typically based on carbon nanomaterial and itrogenous organic substance, very expensive and limited by their raw material.In addition, current
N doping method is all based on greatly NH3, a kind of irritative gas may also lead to environmental problem.When referring to large-scale application, make
Use NH3As N2The N doping method in source is improper because of gas storage and the difficulty transported.It is urged based on the ORR to high activity
The urgent need of agent, developing low-cost and efficient method from cheap raw material even waste material to obtain elctro-catalyst tool
It is significant.
A committed step of the invention is by useless biomass and ZnCl2Catalyst equably mixes.By useless biomass
During converting the process to obtain elctro-catalyst, useless biomass is completely dried in an oven.The temperature of baking oven is preferably set to
It is the boiling point of water greater than 100 DEG C.It should be noted that the direct carbonization of useless biomass retains its original microstructure, reality
The upper porosity with low content.Although the processing of useless biomass be it is required, therefore it is made of and many macromoleculars
It generally can not be dissolved in common solvents (such as water), this makes the processing relative difficulty of useless biomass.According to the present invention, lead to
Ball-milling treatment is crossed by useless biomass (solid or liquid) and ZnCl2Equably mix.Mill processes make raw material and catalyst
Between can be in close contact.It is preferred that useless biological-material-tall is worn into small powder particle before mixing with catalyst, although
It is also feasible for not having directly to mix both substances in any pretreated situation.
The method that another kind handles useless biomass is to be dispersed in ZnCl for it as powder2In solution.This makes raw material
It extraordinary can be contacted between catalyst.However, because of ZnCl in the drying process2It is strong with hydrone and useless biomass
It interacts strongly, so drying process is very long.In fact, complete drying is nearly impossible.Substantially, ball milling
Processing is optimal selection that is currently that raw material and catalyst are efficient and being uniformly mixed together.In addition, ball milling be currently at
Ripe industrial technology meets the purpose of large-scale production.It ensure that expanding the possibility of the scale of reaction mixture preparation.Separately
On the one hand, other metal chlorides (such as FeCl3、MgCl2, KCl and NaCl) formation of porous carbon can also be caused and be suitable for
The present invention.
Another committed step of the invention is that uniform mixture is promptly carbonized.By the way that mixture is directly placed into
It completes to heat rapidly in furnace, which has inert atmosphere and be preheated to specific temperature.High temperature makes reaction mixture
Set-point temperature can be very rapidly heated to.It gives up biomass typically, for solid, temperature is controlled at 300-500 DEG C
In the range of, it is then ~ 700 DEG C for liquid biomass of giving up.Too low temperature would not allow for the initiation of carbonization, and too high temperature
The part burning that can lead to useless biomass, because absolutely inert atmosphere is difficult to realize.For example, when being carbonized, by furnace
The lid of tank rises and is directly placed into the bottle for accommodating reaction mixture wherein.In this step, when covering liter, around furnace
Air inevitably enters in tank, to the inert gas in thinning tank and allow to burn.
Generally, the decomposition of the useless biomass of solid starts at 250 DEG C and when temperature is increased to greater than 400 DEG C, biomass
Weight loss tend towards stability.It gives up the decomposition of biomass for solid, this universal and similar phenomenon is because of useless biomass
Main component be it is similar, i.e., by C2、H2And O2Element composition.ZnCl2It is catalyzed the carbonization of useless biomass and ZnCl2Usually exist
~ 285 DEG C of fusings.The ZnCl of fusing2The carbonaceous mesophase object of liquid, soluble solution useless biomass and it.The microstructure of useless biomass because
This is destroyed.The carbon (such as the species being graphitized) just formed cannot be dissolved in the ZnCl of fusing2In and will precipitating.At this
In the process, ZnCl2Cause the formation of porous carbon.Based on scanning electron microscope, the aperture of porous carbon is in 15nm to 50nm's
In range.According to N2The pore-size distribution of adsorption-desorption isothermal, which has hierarchical porosity and main aperture type is micropore.
Such hole construction is beneficial to fast mass transfer.The flash carbonization of every batch of continues 10 minutes.After that, by porous material
It is promptly removed and placed in and uses N2For being quickly cooled down in the case of filling.Cooling time is only 15 minutes.Substantially, whole process
Only expend 25 minutes in total.There are three steps for conventional prior art carbonization tool: being gradually heated up, isothermal heats and cooling.This three
A usual every batch of of step needs to be greater than 5 hours.This prior art operation height is inconvenient and may not apply to actual production.Greatly
It is very fast with operation of the invention unlike having.After tank taking-up, another bottle of insertion can be used for down by carbon intermediary
A batch of carbonization.In fact, this process is nearly singular integral.This allows for the preparation of expansion scale level, and its
It cannot be realized with the prior art.In addition, give up biomass for liquid, it is porous it is carbon nano-structured can be by means of ZnCl2Easily obtain
?.It is carbon nano-structured that there is uniform micropore based on TEM image.
ZnCl2It is very easy to evaporation at relatively high temperature.In general, its evaporation will become when temperature is greater than 750 DEG C
It obtains strongly.Therefore, most of ZnCl2Environment will be escaped into from furnace and lead to serious environmental pollution.In the present invention,
Far below 600 DEG C at a temperature of very short carbonization time avoid solid give up biomass this disadvantage.Note that for liquid
Useless biomass, reaction system are sealings without ZnCl2Steam can escape.
Final key step of the invention is by N doping that porous carbon is modified.It can be used melamine as nitrogen source.
The carbon intermediary obtained in catalysis carburising step fastly has oxygen functional group (such as-COOH ,-COH ,-CO).Amino is at high temperature
It is potential nucleophile, and can be reacted with porous carbon to realize N doping.Melamine is the compound of high temperature stable.Work as temperature
When degree is greater than 345 DEG C, it will tempestuously distil, but will promptly precipitate in low-temperature space.Even if when temperature is greater than 800 DEG C,
Melamine is not also carbonized.Therefore, melamine function only as nitrogen dopant and distillation melamine can low-temperature space easily
Recycling.On the other hand, melamine is decomposed into active species containing N and realizes that N is adulterated to react with chemical inertness carbon.
The N doping method of tradition or the prior art is based on NH3Use.In this process, NH3Not only in N doping,
And it plays an important role in hole generates.However, because NH3It is that height is irritating to the mankind, so it is potential danger
, therefore this will limit the large-scale production of carbon product.On the other hand, in NH3Before activation, it is desirable that relatively long/energy
The pretreatment of consumption.For example, need the hydro-thermal process greater than 10 hours to every batch of, and also need freeze-drying in several days to avoid
The aggregation of product.In addition, the C transformation efficiency of useless biomass is relatively low, it is unsatisfactory for resource reclaim.
It prepares the detailed process of N doping porous carbon described below and is generally shown in Fig. 1.
Useless biomass (such as a large amount of banana skins) is washed with water except crude removal.Then, it is cut into slices and at 105 DEG C
It is dried in baking oven until it reaches constant weight.By dried biomass and ZnCl2Powder is equably mixed with ball grinding technique
It closes.Uniform powder, which is put into, wherein has N2Vertical quartz bottle or vertical titanium alloy bottle 10 in.Bottle is quickly inserted
(step a) in the vertical heater 12 of (such as 400 DEG C) is preheated between 300 DEG C and 500 DEG C.It is deep yellow what is interesting is noticing
The volume of color (coming from banana skin) mixture sharply expands in the carbonized.At least about after ten minutes, bottle 10 is pulled out into (step b)
And it is inserted into the container 14 with water for being quickly cooled down.Cooling time is ~ 15min.Entire carbonisation, which expends, is less than 30
Minute.Carbon is rinsed with HCl acid solution and water to remove and recycle ZnCl2(step c).By carbon between 60 DEG C to 80 DEG C, preferably
It is dry at 70 DEG C, until it has constant weight.This can expend about 6 hours.
Dried carbon is mixed into (step d) with melamine.Uniform mixture is put into porcelain boat, porcelain boat is put into
In horizontal pipe furnace 16.It heats the mixture between specific temperature, such as 800 DEG C and 1100 DEG C.Entire doping process is by N2
Atmosphere protection.After that, decline temperature naturally at ambient conditions.
As shown in the bottom in Fig. 1, fast catalysis carbonization according to the present invention causes volume expansion to graded porous carbon N
Doped products.Fig. 2 has by the SEM image (Fig. 2A) for the carbon intermediary that catalysis carbonization obtains fastly at 400 DEG C and three
The SEM image (Fig. 2 D) of the modified nitrogen-doped carbon product of poly cyanamid.The scale bar of two images is all 500nm.This is illustrated
Expansion.Fig. 2 B and 2E respectively show the N of carbon intermediary and nitrogen-doped carbon product2Adsorption-desorption isothermal.In addition, Fig. 2 C and
The particle diameter distribution of the material of 2F display difference.
Fig. 3 shows the high-resolution XPS spectrum of carbon product in the following sequence: by 400 DEG C (Fig. 3 A), 900 DEG C of (figures
3C), the carbon intermediary of catalysis carbonization preparation fastly under 1000 DEG C (Fig. 3 E) and 1100 DEG C (Fig. 3 G).It is also shown that in 400 DEG C of (figures
3B), with the XPS of cyanurotriamide modified nitrogen-doped carbon product under 900 DEG C (Fig. 3 D), 1000 DEG C (Fig. 3 F) and 1100 DEG C (Fig. 3 H)
Spectrum.Various lines in figure represent specific C or N species, i.e. C1N1, C2N2, C3N3, C4N4 and N5, and wherein C1 is sp2 hydridization
Graphitized carbon, C2 is sp3 C-C carbon, and C3 is C-O or C-N, and C4 is C=O；N1 is pyridine-N, and N2 is amine or imines, and N3 is pyrrole
N is coughed up, N4 is season N, and N5 is pyridine-N-oxides.The figure of Fig. 3 shows that the main component of final carbon product includes pyridine N and pyrrole
N is coughed up, is catalyzed active species.
Various tests are run to confirm purport of the invention.
Embodiment 1
Use banana skin as useless biomass in a test, because it is the biological material that typically gives up.Banana skin is used
Water is cleaned to remove dirt.Then it is cut into slices and is dried in an oven until it reaches constant weight at 105 DEG C.Pass through
Ball grinding technique is by dried skin and ZnCl2Powder equably mixes, and skin: ZnCl2Weight rate be set as 1:5.When milling
Between and rate of milling controlled respectively in 30min and 500rpm.Uniform powder, which is put into, wherein has N2Vertical quartz bottle 10
In.See Fig. 1.Bottle is quickly inserted in vertical heater 12, the temperature in the vertical heater has been lifted to specific value, such as
400℃.Between 8 and 12 minutes, after preferably 10 minutes periods, bottle is pulled out and is inserted into it is used to be quickly cooled down in water.It is cold
But the time is between 12 and 18 minutes, preferably ~ 15 minute.Carbon is rinsed with HCl- aqueous solution to remove and recycle ZnCl2.At 70 DEG C
Under it is in an oven that carbon is dry until it has constant weight.
Dried carbon is mixed with melamine with the weight rate of 1:10 (carbon: melamine).It will uniformly mix
Object is placed into porcelain boat, and porcelain boat is put into horizontal pipe furnace 16.With 5 DEG C of min-1Ramp rate and 2 hours isothermal times
Heat the mixture to specific temperature.Entire doping process is by N2Atmosphere protection.After that, make temperature at ambient conditions from
So reduce.
For different applications, melamine can be substituted by other chemicals or partly be substituted, for example, with 1:2 (carbon:
KOH KOH, urea, thiocarbamide, dicyandiamide and their mixture of weight rate) etc..Depending on used activating chemical
Product, the product obtained in this step can be used as electrode material and apply in supercapacitor and oxygen reduction reaction.
Linear sweep voltammetry (LSV) test is carried out on product of the invention, and uses business Pt/C as reference
Material (Fig. 4).LSV is voltammetry, wherein current potential or electricity in punctually linear scan between working electrode and reference electrode
While pressure, the electric current on working electrode is measured.In the case where species start the current potential being easily oxidized or reduced, the oxidation of species or also
Original is registered as peaks or valleys in current signal.
As shown in Figure 4 A, for ORR, CZnFastly- 400- melamine -1000 shows starting electricity similar with Pt/C
Position and reduction current, show comparable electro catalytic activity.This can be mixed by relatively good electric conductivity, hierarchical porosity and high N
The synergistic effect of miscellaneous level is explained.Other conditions are considered in systematicness experiment, are included whether using ZnCl2And it urges fastly
Change carbonization and cyanurotriamide modified temperature.These test displays CZnFastly- 400- melamine -1000 (red line in Fig. 4 B) is most
Dominance energy.On the other hand, by by CZnFastly- 400- melamine -1000 and CZnFastly- 400-1000 compares, and demonstrates N doping
Important function (Fig. 4 B) in catalytic activity.It should be noted that in addition to N is not introduced into porous carbon using melamine
In addition, use and CZnFastlyThe condition of -400- melamine -1000 (red line) equally prepares CZnFastly- 400-1000 (green line).CZnFastly-
The take-off potential of 400- melamine -1000 is 82mV, is higher than CZnFastlyThe take-off potential of -400-1000.LSV in figure 4 c is bent
Line shows that when improving the speed of rotation, current density rises appreciably, this is attributable to shorter diffused line.It is based on
Koutecky-Levich (K-L) equation exports Fig. 4 D from Fig. 4 C, and the equation is as follows:
(4)
(5)
WhereinJ k Dynamic current density is represented,J L For Limited diffusion current density, ω represents the speed of rotation (rpm) of RDE,FFor
Faraday constant is known as 96485 Cmol-1,D 0 For diffusion coefficient and O2Volumetric concentration is expressed asC 0 , υ is the dynamic of electrolyte
Power viscosity, B can be obtained from the slope of fit line.
On the basis of K-L equation, n (electron transfer number) can be calculated from B.Based on the analysis of K-L figure, hydrogen reduction process master
It will be by four electronic channel (O2+2H2O+4e-=4OH-) guide, it is consistent with analysis above.
It should be noted that noble metal catalyst is one of the ultimate challenge of fuel cells applications to the poor tolerance of methanol.It is logical
Measurement is crossed in the O for being added with 3M methanol2The CV curve operated in the KOH of saturation aoxidizes to assess catalyst of the invention to methanol
Resistivity.If shown in fig. 5, a pair of of peak (paddy) is found in 0.12V and 0.16V and can belong to Pt/C catalyst
Methanol oxidation.And in figure 5B, CZnFastly- 400- melamine -100 does not almost have in methanol condition and at typical condition
Observe any variation, this shows that there is the sample prepared compared with business Pt/C catalyst better methanol to be resistant to energy
Power.In addition, in N2And O2The CV curve tested in the KOH solution of saturation shows the O in potential range2The presence of reduction peak.
For a further understanding of passing through CZnFastlyThe electronics transfer route of the oxygen catalysis reaction of -400- melamine -100, into
Row rotating ring disk electrode (r.r.d.e) (RRDE) measurement and the HO with post analysis during hydrogen reduction2 -Generation.Measure circular current and disk electricity
Stream is to obtain HO in the reaction2 -Yield (Fig. 5 C).
CZn in the KOH of 0.1MFastly- 400- melamine -1000 and CFastly- 400- melamine -1000 is in -0.55V
The HO recorded in the potential range of -0.2V2 -Percentage be respectively lower than 20% and 50%, show it is corresponding ~ 3.7 and ~ 3.3
Electron transfer number (Fig. 5 D).CZnFastlyThe calculated result and RRDE result good agreement of the K-L figure of -400- melamine -1000,
It confirmed CZnFastlyDuring the hydrogen reduction process of -400- melamine -1000 close to four electronics transfer routes.
As shown in Figure 6A, the CZn in the 1st circulationFastlyThe CV curve of -400- melamine -1000 has been recycled with the 2000th
Beauty is coincide, and shows its excellent durability in alkaline solution.Stability of the Pt/C in the KOH of 0.1M is also evaluated with confirmation
CZnFastlyThe superiority of the potential application of -400- melamine -1000 in the fuel cell for long period of operation.In fig. 6b,
The 1st circulation of Pt/C and the CV curve of the 2000th circulation are mutually not relatively consistent, show and CZnFastly- 1000 phase of -400- melamine
Than the relatively weak durability of Pt/C.
Embodiment 2
Test of the invention also uses the typical solid in addition to banana skin to give up biomass to carry out.They include orange peel and leaf
Son.Preparation process is similar to illustrated in embodiment 1 (it uses banana skin).Here it is verified with orange peel and leaf biomass
Generality of the invention.As shown in Figure 7, corresponding carbon material shows good catalytic activity, urges with business Pt/C
The catalytic activity of agent is very close.It should be noted that the preparation condition and CZn of these carbon materialsFastly- 400- melamine -1000
It is identical.Although for both raw material optimal Carbonization Conditions due to their different compositions and microstructure pole
It is possible that mutually different, this performance evaluation, which is still strongly suggested that from conventional solid biomass of giving up, generally manufactures excellent carbon materials
The altitude validity of the method for the present invention of material.
The present invention has the extensive use to different types of solid useless biomass (including pericarp, leaf and wood).
Embodiment 3
In addition to solid gives up biomass, the method can also be used to give up liquid Biomass into porous functional carbon material.Allusion quotation
The program of type includes: by with the speed of 300rpm equably ball milling 10min, by the ZnCl of the gutter oil of 1mL and 16g2Mixing；
The mixture is put into Al2O3In crucible；Crucible is put into N2In the Ti alloy tank of protection；Tank is sealed and tank is direct
It is put into and has been warmed up into the furnace of 650 DEG C of temperature 1 hour.After that directly by tank from pulling out and be inserted into water in furnace
For being quickly cooled down.The porous form of carbonaceous product can be found in Figure 10.It is used using identical program such as in embodiment 1
Melamine is modified by this carbonaceous product and obtains the porous carbon nano-structured of N doping.
Embodiment 4
Embodiment 4 is the embodiment of control, prepares the porous carbon of N doping from useless biomass using method of the invention.
NH3As nitrogen source and hole producing agent.Program is identical with those of in Examples 1 and 2.As described in Fig. 8, with CZnFastly-
400- melamine -1000 (red curve) is compared, all these sample (i.e. BP-1100-NH3-1000、BP-HT180-NH3-
The Pt/C of 800 and BPC-800-1h and routine) show slightly poor ORR catalytic performance.This has fully showed that high in manufacture
Superiority of the performance without current method on metal ORR catalyst.
Money of the invention is studied based on compared with the C transformation efficiency for other classical ways (the following table 1) being previously reported
Source recuperability.For taking rich N molecule activation.As shown in table 1, C transformation efficiency of the invention is up to 41.9%.However, fast
That using in the case where catalyst, C transformation efficiency is not rapidly decreased to 17.2% in carbonization.Also measure the C conversion effect of prior method
Rate.The value is less than 31%.These results effectively verify excellent resource recuperability of the invention.Here, in view of manufacture
Efficiency and C transformation efficiency, for large-scale production, the present invention has substantial capability.
Table 1
The ratio of the yield of carbon product, C content and C transformation efficiency that are formed by the method for the invention with the art methods of report
Compared with
| Method | M Finally /M Raw material | C content (wt.%) | C transformation efficiency (%) |
| aZhu Jianjiare &NH3Activation | 0.033 | 55.4 | 4.2 |
| bShui Re &NH3Activation | 0.127 | 61.6 | 17.9 |
| cDirect carbonization | 0.184 | 73.1 | 30.8 |
| dCurrent method does not have to catalyst | 0.091 | 82.4 | 17.2 |
| Current method | 0.204 | 89.7 | 41.9 |
a、b、cThe preparation process of sample with it is identical in following article: (a) F. Pan, Z. Cao, Q. Zhao, H.
Liang and J. Zhang, J. Power Sources, 2014,272,8-15, (b) P. Chen, L.-K. Wang,
G. Wang, M.-R. Gao, J. Ge, W.-J. Yuan, Y.-H. Shen, A.-J. Xie and S.-H.
Yu, Energy Environ. Sci., 2014,7,4095-4103, and (c) S. Gao, K. Geng, H. Liu,
X. Wei, M. Zhang, P. Wang and J. Wang, Energy Environ. Sci., 2015,8,221-229.
Pay attention tod: in addition to being added without ZnCl in fast carburising step2In addition, using condition identical with current method and program.
Oxygen reduction reaction (ORR) can be used for by the active carbon of melamine activation preparation according to the present invention, in fuel
It is important in battery.Common materials for ORR are noble metal --- Pt, very expensive.As shown in Figure 4, of the invention
Material be better than Pt.
Supercapacitor has important application in electric vehicle.It according to the present invention can by the active carbon of KOH activation preparation
For supercapacitor.Performance is better than those of business, as shown in FIG. 9.
The present invention uses metallic catalyst (such as ZnCl2) turned with promoting the carbon obtained in the carburising step of useless biomass
Change the porosity of efficiency and carbon.The technique avoids the activation chemistry using high dose and promotes the quality of carbon product.However, not
Be same as conventional metals catalyst, current catalyst far below catalyst boiling point at a temperature of be used for fast pyrolytic technique.Therefore, it makes
The corrosion of manufacturing apparatus is low and manufacture efficiency is very high.In addition, the technique can be carried out continuously compared with traditional handicraft.
Although the present invention is specifically shown and is described by reference to its preferred embodiment, those skilled in the art will
Understand, without departing from the spirit and scope of the present invention, various changes can be carried out in form and details.
Claims (8)
1. the method for being used to prepare the non-metal catalyst for oxygen reduction reaction, comprising the following steps:
There is provided uniform mixture by following: (i) solid is given up biomass and catalyst is mixed together to form uniformly
Powder, or (ii) liquid is given up biomass and catalyst is mixed together to form uniform slurry；
It carries out being catalyzed carbonization fastly by heating the uniform mixture in an inert atmosphere, to obtain porous carbon intermediary material
Material；
The carbonaceous mesophase object material is blended with melamine to form carbon structure；
It is modified that nitrogen-enriched compounds are carried out by heating carbon structure；With
N doping is entered in carbon structure.
2. method described in claim 1, wherein the catalyst is metal chloride, including zinc chloride, iron chloride, aluminium chloride
One of or their mixture；
Wherein the catalyst is ZnCl2Powder；
Wherein the mixing is carried out as ball milling；
Wherein the step of hybrid solid biomass the following steps are included:
It washes with water solid and gives up biomass to remove dirt；
Solid biomass is cut into slices；
Piece is dried in an oven until biomass reaches constant weight；With
Dried solid biomass is equably mixed with metal chloride powder with ball mill；And/or
Wherein the step of mixing liquid biomass include: with ball mill will without any pretreated liquid give up biomass with
Metal chloride powder is direct and equably mixes.
3. method described in claim 1, wherein the step of progress fast catalysis carbonization the following steps are included:
The uniform mixture is put into the vertical bottle for wherein having nitrogen；
Rapidly this bottle insertion is had been warmed up into the vertical heater between 300 DEG C and 700 DEG C, to form graded porous carbon；
After first time period, by bottle from pulled out in vertical heater and be inserted into water fill container in be used to be quickly cooled down；
After second time period, carbon is rinsed to remove and recycle metallic catalyst with acid solution and water；With
Carbon is dry until it has constant weight.
4. method as claimed in claim 3, wherein the vertical bottle is formed by one of quartz and titanium；
It wherein gives up biomass for solid, the vertical heater is preheated to 400 DEG C, and liquid biomass of giving up then is preheated to
650℃；
It wherein gives up biomass for solid, the first time period is between 8 and 12 minutes, preferably 10 minutes, and for liquid
Useless biomass is then between 30-90min, preferably 60min；
Wherein the second time period is between 12 and 18 minutes, and preferably 15 minutes；
It is wherein between 60 DEG C and 80 DEG C, preferably at 70 DEG C that the carbon is dry；And/or
Wherein the acid solution is the solution of HCl.
5. method described in claim 1, wherein the useless biomass is organic non-fossil material of biological source, it is by-product
Product or reject product；
Wherein the material of the biological source is or mixtures thereof one of pericarp, leaf, waste oil, wood；
Wherein this method carries out in an inert atmosphere；
Wherein inert atmosphere includes N2With at least one in Ar；
Wherein the step of doping nitrogen is related to using rich nitrogen molecular to be modified the carbon from fast catalysis carbonization；
Wherein the rich nitrogen molecular includes: urea, melamine, thiocarbamide, dicyandiamide or their mixture, and/or
It is modified that nitrogen-enriched compounds are wherein carried out within the temperature range of 800-1100 DEG C.
6. for the catalyst of electrochemical oxygen reduction reaction, comprising with flowering structure or by following structure composition: having at least 3at%
N doping classifying porous carbon structure, and the catalyst do not include metal.
7. catalyst as claimed in claim 6, wherein the carbon is less than with the size of 50-100%, 60-90% or 70-80%
The micropore of 2nm.
8. catalyst as claimed in claim 6, wherein the carbon is by pyridine nitrogen and pyrroles's nitrogen 50-100%, 60-90% or 70-
80% doping.
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