CN110479338A - A kind of elctro-catalyst and the preparation method and application thereof - Google Patents
A kind of elctro-catalyst and the preparation method and application thereof Download PDFInfo
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- CN110479338A CN110479338A CN201910843880.1A CN201910843880A CN110479338A CN 110479338 A CN110479338 A CN 110479338A CN 201910843880 A CN201910843880 A CN 201910843880A CN 110479338 A CN110479338 A CN 110479338A
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- elctro
- catalyst
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- coal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003245 coal Substances 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 53
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 49
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- 239000011593 sulfur Substances 0.000 claims abstract description 37
- 229940095991 ferrous disulfide Drugs 0.000 claims abstract description 30
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006722 reduction reaction Methods 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 17
- 229910052960 marcasite Inorganic materials 0.000 description 14
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 14
- 229910052683 pyrite Inorganic materials 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 230000005611 electricity Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010742 number 1 fuel oil Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010117 shenhua Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- -1 iodine halogen Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of elctro-catalysts and the preparation method and application thereof, belong to solid waste resource recovery and utilize technical field.Elctro-catalyst of the invention is prepared by coal directly-liquefied residue and inorganic base are thermally treated, the elctro-catalyst is ferrous disulfide/cementite/sulfur doping carbon complex, iron content is 0.1~10wt% in the elctro-catalyst, sulfur content is 0.1~10wt%, and carbon element content is 80~95wt%.Elctro-catalyst of the invention has good catalytic performance to oxygen reduction reaction and oxygen evolution reaction.Embodiment statistics indicate that: the present invention gained elctro-catalyst have porous structure, have good electro catalytic activity, take-off potential 0.91V, limiting current density 5.35mA/cm to oxygen reduction reaction2；Moreover, having higher electro catalytic activity to oxygen evolution reaction, when current density is 10mA/cm2When, potential is 1.60~1.64V.
Description
Technical field
The present invention relates to solid waste resource recoveries to utilize technical field more particularly to a kind of elctro-catalyst and its preparation side
Method and application.
Background technique
As a kind of important technology for converting coal to liquid fuel and chemicals, DCL/Direct coal liquefaction process be may be implemented
Clean utilization to coal resources.However, a large amount of by-products, such as residue, residue can be generated during coal hydrogenation cracking reaction
Yield account for about the 30wt% of raw coal used in DCL/Direct coal liquefaction.Coal directly-liquefied residue is a kind of rich carbon, high ash, high-sulfur mixing
Object mainly contains asphalitine, ash content, DCL/Direct coal liquefaction ferrum-based catalyst, unconverted feed coal and a small amount of heavy oil.It reduces very
Environment bring is threatened to coal directly-liquefied residue is eliminated, its high value added utilization new way is developed, is DCL/Direct coal liquefaction
Industry important problem urgently to be resolved.
Due to coal directly-liquefied residue carbon rich in, using itself or its rich carbon extract as raw material
Prepare the representative manner that carbon materials are its resource utilizations.The Chinese patent of Publication No. CN105720233A discloses one
Kind is by the method that the preparation of coal liquefaction pitch is used for lithium ion battery negative pole carbon material: purified rear remove of coal liquefaction residue is deashed
Coal liquefaction pitch is obtained, polymerization and stabilization processes is carried out to it later, lithium ion battery negative pole carbon material is obtained after being carbonized.
The Chinese patent of Publication No. CN107055505A discloses a kind of porous charcoal and preparation method thereof prepared by coal liquefaction pitch:
Using coal liquefaction pitch as raw material, it is mixed in organic solvent with tetraethyl orthosilicate, hydrochloric acid, mixture is carbonized after dry
And it removes silica and obtains porous charcoal.The Chinese patent of Publication No. CN103288070A discloses a kind of residual using coal liquefaction
The method that slag heavy organic component prepares N doping porous charcoal: obtaining heavy organic component with solvent extraction coal liquefaction residue, it
It is mixed with nitrogen source afterwards, prepares the nitrogenous porous charcoal of high-specific surface area through pre-oxidation, activation or addition template.Publication No.
The Chinese patent of CN108584952A discloses a kind of spherical porous charcoal and preparation method thereof: carrying out at heating to coal liquefaction pitch
Reason obtains pitch, is spray-dried to obtain pitch microballoon later, and spherical shape is made after pre-oxidation, charing, activation processing
Porous charcoal.The Chinese patent of Publication No. CN102733008A discloses a kind of method for preparing carbon fiber: with DCL/Direct coal liquefaction
Residue base asphaltene substance is raw material, carries out high temperature to it in tube furnace or reaction kettle, HIGH PRESSURE TREATMENT obtains that centre can be spun
Phase obtains carbon fiber by melt spinning, pre-oxidation, carbonization treatment.The Chinese patent of Publication No. CN104804708A discloses
A kind of preparation method of structural absorbing mater ials: by the metal salts such as coal directly-liquefied residue and manganese, bromine or iodine halogen family simple substance, four
The organic solvents such as hydrogen furans are hybridly prepared into maceration extract, and impregnate mould material polyurethane foam with the liquid, at cured, carbonization
It manages and structural absorbing mater ials is made.The Chinese patent of Publication No. CN104058381A discloses one kind and is prepared by coal liquefaction residue
The method and nano carbon microsphere of nano carbon microsphere: the oil-solubles such as the transistion metal compounds such as coal liquefaction residue and titanium, phenol are organised
Close object mixing, after through high-temperature calcination, washing, the hollow Nano carbon ball that dry obtained diameter is 20~50nm.Publication No.
The Chinese patent of CN1807715A discloses the method for preparing carbon nano-material as raw material plasma using coal liquefied residue: will
Coal hydroliquefaction residue without any processing is placed in DC arc plasma jet, is made and is received by arc discharge reaction
Rice Carbon fibe material.
As can be seen that these are DCL/Direct coal liquefaction by the method that coal directly-liquefied residue or residue asphalitine prepare carbon material
The high value added utilization of residue provides important channel.But in these prior arts, not to coal directly-liquefied residue institute
Iron, the element sulphur contained is used, and the program for preparing carbon material is complicated, equipment is expensive, this is obviously unfavorable for straight to coal
It connects the abundant conversion of liquefied residue and utilizes.
Oxygen reduction reaction, oxygen evolution reaction are including fuel cell, metal-air battery, electro-catalysis producing hydrogen peroxide, electrolysis water
Hydrogen manufacturing etc. plays an important role in interior various new technology.Exploitation can be used for base metal Quito function electricity of the two reactions
Catalyst converts clean energy resource most important with the extensive use of green chemical production technology.Recently, Heteroatom doping
Carbon material shows application advantage in oxygen reduction reaction, oxygen evolution reaction as elctro-catalyst with containing carbon complex.
Therefore, it is very necessary to develop a kind of cheap and with excellent electrocatalysis characteristic elctro-catalyst.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of elctro-catalysts and the preparation method and application thereof.The present invention mentions
The elctro-catalyst of confession is prepared by coal directly-liquefied residue and inorganic base, at low cost, and obtained elctro-catalyst is with excellent
Electrocatalysis characteristic.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of elctro-catalyst, the elctro-catalyst is thermally treated by coal directly-liquefied residue and inorganic base
It is prepared, the elctro-catalyst is ferrous disulfide/cementite/sulfur doping carbon complex, and ferro element contains in the elctro-catalyst
Amount is 0.1~10wt%, and sulfur content is 0.1~10wt%, and carbon element content is 80~95wt%.
Preferably, the mass ratio of the coal directly-liquefied residue and inorganic base is 1:0.1~10.
Preferably, the inorganic base includes potassium hydroxide or sodium hydroxide.
Preferably, the temperature of the heat treatment is 600~1100 DEG C, and soaking time is 0.5~4h.
Preferably, the heat treatment carries out under protective atmosphere.
Preferably, the heating rate for being warming up to the temperature of the heat treatment is 1~20 DEG C/min.
The present invention also provides the preparation methods of the elctro-catalyst described in above-mentioned technical proposal, comprising the following steps:
Coal directly-liquefied residue and inorganic base are mixed, is heat-treated, obtains the elctro-catalyst.
The present invention also provides the answering in oxygen reduction reaction or oxygen evolution reaction of the elctro-catalyst described in above-mentioned technical proposal
With.
The present invention also provides the elctro-catalysts described in above-mentioned technical proposal to urge in fuel cell, metal-air battery, electricity
Change H processed2O2Or the application in electrolysis water.
Preferably, the load capacity of the elctro-catalyst is 0.1~0.8mg/cm2。
The present invention provides a kind of elctro-catalyst, the elctro-catalyst is thermally treated by coal directly-liquefied residue and inorganic base
It is prepared, the elctro-catalyst is ferrous disulfide/cementite/sulfur doping carbon complex, and ferro element contains in the elctro-catalyst
Amount is 0.1~10wt%, and sulfur content is 0.1~10wt%, and carbon element content is 80~95wt%.The present invention is direct with coal
Liquefied residue is raw material, and under the action of inorganic base, carbon contained by coal directly-liquefied residue, iron, element sulphur are made full use of, and
And the ash content reaction in inorganic base and coal directly-liquefied residue generates soluble salt and carries out pore-creating to elctro-catalyst, obtains having porous
Ferrous disulfide/cementite/sulfur doping carbon complex of structure, which has oxygen reduction reaction and oxygen evolution reaction urges well
Change performance.Embodiment statistics indicate that: elctro-catalyst provided by the invention have porous structure, have well to oxygen reduction reaction
Electro catalytic activity, take-off potential 0.91V, limiting current density 5.35mA/cm2；Moreover, thering is higher electricity to urge oxygen evolution reaction
Change activity, when current density is 10mA/cm2When, potential is 1.60~1.64V.
The present invention also provides the preparation method of the elctro-catalyst described in above-mentioned technical proposal, the preparation method is direct with coal
Liquefied residue is raw material, low in cost；Meanwhile preparation method is simple, easy to operate.
Detailed description of the invention
Fig. 1 is 1 gained ferrous disulfide of the embodiment of the present invention/cementite/sulfur doping carbon (FeS2/Fe3C/S-C) compound
Powder x-ray diffraction spectrogram；
Fig. 2 is 1 gained ferrous disulfide of the embodiment of the present invention/cementite/sulfur doping carbon (FeS2/Fe3C/S-C) the X of compound
The high-resolution S2p spectrogram of X-ray photoelectron spectroscopy X；
Fig. 3 is 1 gained ferrous disulfide of the embodiment of the present invention/cementite/sulfur doping carbon (FeS2/Fe3C/S-C) compound
Scanning electron microscope diagram piece；
Fig. 4 is 1 gained ferrous disulfide of the embodiment of the present invention/cementite/sulfur doping carbon (FeS2/Fe3C/S-C) compound
Linear sweep voltammetry (LSV) oxygen reduction reaction performance map；
Fig. 5 is 1 gained ferrous disulfide of the embodiment of the present invention/cementite/sulfur doping carbon (FeS2/Fe3C/S-C) compound
Linear sweep voltammetry (LSV) oxygen evolution reaction performance map.
Specific embodiment
The present invention provides a kind of elctro-catalyst, the elctro-catalyst is thermally treated by coal directly-liquefied residue and inorganic base
It is prepared, the elctro-catalyst is ferrous disulfide/cementite/sulfur doping carbon complex, and ferro element contains in the elctro-catalyst
Amount is 0.1~10wt%, and sulfur content is 0.1~10wt%, and carbon element content is 80~95wt%.
In the present invention, the elctro-catalyst is ferrous disulfide/cementite/sulfur doping carbon complex (FeS2/Fe3C/S-
C)；Iron content is 0.1~10wt% in the ferrous disulfide/cementite/sulfur doping carbon complex, and sulfur content is
0.1~10wt%, carbon element content are 80~95wt%.
Elctro-catalyst of the invention is prepared by coal directly-liquefied residue and inorganic base are thermally treated.
In the present invention, the inorganic base preferably includes sodium hydroxide or potassium hydroxide.In the present invention, the coal is direct
The mass ratio of liquefied residue and inorganic base is preferably 1:0.1~10, further preferably 1:0.5~8, more preferably 1:1~6.
The present invention without limitation, is using commercial product well known to those skilled in the art to the source of the coal directly-liquefied residue
Can, specifically, such as the coal directly-liquefied residue for being purchased from Shenhua Erdos coal oil company.
In the present invention, the temperature of the heat treatment is preferably 600~1100 DEG C, and further preferably 700~1000 DEG C,
More preferably 800~900 DEG C；The heating rate for being warming up to the temperature of the heat treatment is preferably 1~20 DEG C/min, further excellent
It is selected as 5~15 DEG C/min；Soaking time is preferably 0.5~4h, further preferably 1~3h.
In the present invention, the heat treatment preferably carries out under protective atmosphere；The protective atmosphere is preferably N2。
After heat treatment, the present invention obtains the electricity and urges it is also preferable to include gained heat-treated products are washed and dried
Agent.
In the present invention, the washing is preferably water with reagent；The number of the washing is preferably 3 times.In the present invention,
The washing can remove the soluble-salt (such as sodium metasilicate, potassium silicate) in heat-treated products.
In the present invention, the temperature of the drying is preferably 80 DEG C, and the time is preferably 6h；The mode of the drying is preferably
Air blast.
In the present invention, inorganic base is mixed with coal directly-liquefied residue, inorganic base can be straight with coal in heat treatment process
Asphalitine, unconverted feed coal and the reaction of a small amount of heavy oil in liquefied residue are connect, derived carbon material etch is activated；And coal
DCL/Direct coal liquefaction ferrum-based catalyst in direct liquefaction residue reacts to form ferrous disulfide/carbon with carbon during heat treatment
Change iron/sulfur doping carbon complex；Meanwhile inorganic base is reacted with the ash content in coal directly-liquefied residue, is generated soluble salt and is urged electricity
Agent carries out pore-creating, so that final elctro-catalyst has porous structure, improves its catalytic performance.
The present invention also provides the preparation methods of the elctro-catalyst described in above-mentioned technical proposal, comprising the following steps:
Coal directly-liquefied residue and inorganic base are mixed, is heat-treated, obtains the elctro-catalyst.
In the present invention, the amount ratio of the coal directly-liquefied residue and inorganic base, heat treatment parameter with above-mentioned skill
Art scheme is consistent, and details are not described herein.
The present invention also provides the answering in oxygen reduction reaction or oxygen evolution reaction of the elctro-catalyst described in above-mentioned technical proposal
With.
The present invention also provides the elctro-catalysts belonging to above-mentioned technical proposal to urge in fuel cell, metal-air battery, electricity
Change H processed2O2Or the application in electrolysis water；The fuel cell, metal-air battery, electro-catalysis H2O2Or in electrolysis water preferably
There are oxygen reduction reaction or oxygen evolution reactions.In the present invention, the load capacity of the elctro-catalyst is preferably 0.1~0.8mg/cm2。
Ferrous disulfide/cementite in elctro-catalyst provided by the invention/sulfur doping carbon complex can be used as hydrogen reduction is anti-
It should be with the electro catalytic activity site of oxygen evolution reaction；Meanwhile the porous structure of the elctro-catalyst is convenient for ion, electron-transport, makes it
Show good electrocatalysis characteristic.
Elctro-catalyst provided by the invention and the preparation method and application thereof is described in detail below with reference to embodiment,
But they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
0.5g coal directly-liquefied residue (Erdos coal oil company, Shenhua), 2.0g potassium hydroxide (KOH) are mixed, In
N2In, it is risen to 800 DEG C by room temperature with 5 DEG C/min heating rate and is kept the temperature 1h and be heat-treated, product is washed with water, at 80 DEG C
Forced air drying 6h obtains ferrous disulfide/cementite/sulfur doping carbon (FeS2/Fe3C/S-C) composite materials；Gained composite material
The content of middle element sulphur is 1.5wt%, and the content of ferro element is 3.2wt%, and the content of carbon is 95.3wt%.
Fig. 1 is ferrous disulfide/cementite/sulfur doping carbon (FeS obtained by the present embodiment2/Fe3C/S-C) the powder X-ray of compound
X ray diffraction spectrogram；As can be seen from Figure 1: corresponding to cubic phase FeS positioned at the diffraction maximum of 33.0 °, 58.9 °2(JCPDS 71-
0053) characteristic peak, be located at 35.3 °, 37.7 °, 40.7 °, 43.0 °, 43.8 °, 44.7 °, 45.1 °, 46.0 °, 48.7 °,
49.2 °, 78.8 ° of diffraction maximum correspond to orthorhombic phase Fe3The characteristic peak of C (JCPDS89-2867), i.e., in present invention gained compound
Contain FeS2、Fe3C。
Fig. 2 is ferrous disulfide/cementite/sulfur doping carbon (FeS obtained by the present embodiment2/Fe3C/S-C) the X-ray of compound
The high-resolution S2p spectrogram of photoelectron spectroscopy；As can be seen from Figure 2: occurring thiophene type S characteristic peak at 163~166eV, 167
Occur oxidized form S characteristic peak at~172eV, shows to contain sulfur doping carbon component in compound obtained by the present invention.
Fig. 3 is ferrous disulfide/cementite/sulfur doping carbon (FeS obtained by the present embodiment2/Fe3C/S-C) the scanning electricity of compound
Sub- microscope photograph；As can be seen from Figure 3: present invention gained compound has pore structure abundant.
With ferrous disulfide/cementite/sulfur doping carbon (FeS obtained by the present embodiment2/Fe3C/S-C) composite materials are as electricity
Catalyst carries out oxygen reduction reaction, oxygen evolution reaction experiment, and to evaluate its performance, test condition is as follows:
The elctro-catalyst that 5mg is prepared is weighed, (20 μ L 0.5wt%Nafion+ are dispersed in 1mL mixed solution
+ 490 μ L ethyl alcohol of 490 μ L water), ultrasonic 30min obtains uniform dispersion liquid.10 μ L dispersant liquid drops are pipetted to rotating circular disk glass carbon electricity
It on extremely, is dried at room temperature for, obtaining catalyst loadings is 0.255mg cm-2Working electrode；Using platinum filament as to electrode,
Hg/HgO electrode forms three-electrode system as reference electrode, with working electrode.Respectively in the O of 0.1M2It is molten to be saturated KOH electrolyte
In liquid and KOH electrolyte solution in in different potential ranges carry out LSV test, evaluate the electrocatalytic oxidation reproducibility of elctro-catalyst
It can and analyse oxygen performance.
Fig. 4 is ferrous disulfide/cementite/sulfur doping carbon (FeS obtained by the present embodiment2/Fe3C/S-C) the linear of compound is swept
Retouch voltammetry (LSV) oxygen reduction reaction performance map；As can be seen from Figure 4: ferrous disulfide/cementite/sulphur obtained by the present embodiment is mixed
Miscellaneous carbon (FeS2/Fe3C/S-C) compound has higher electro catalytic activity, take-off potential 0.91V, carrying current to oxygen reduction reaction
Density is 5.35mA/cm2。
Fig. 5 is ferrous disulfide/cementite/sulfur doping carbon (FeS obtained by the present embodiment2/Fe3C/S-C) the linear of compound is swept
Retouch voltammetry (LSV) oxygen evolution reaction performance map；As can be seen from Figure 5: ferrous disulfide/cementite/sulfur doping obtained by the present embodiment
Carbon (FeS2/Fe3C/S-C) compound has higher electro catalytic activity to oxygen evolution reaction, when current density is 10mA/cm2When, electricity
Gesture is 1.63V.
Embodiment 2
0.5g coal directly-liquefied residue (Erdos coal oil company, Shenhua), 0.5g potassium hydroxide (KOH) are mixed, In
N2In, it is risen to 800 DEG C by room temperature with 5 DEG C/min heating rate and is kept the temperature 1h and be heat-treated, product is washed with water, at 80 DEG C
Forced air drying 6h obtains ferrous disulfide/cementite/sulfur doping carbon (FeS2/Fe3C/S-C) composite materials；Gained composite material
The content of middle element sulphur is 3.3wt%, and the content of ferro element is 6.8wt%, and the content of carbon is 89.9wt%.
Using method same as Example 1 to ferrous disulfide/cementite/sulfur doping carbon (FeS obtained by the present embodiment2/
Fe3C/S-C) composite materials carry out oxygen reduction reaction, oxygen evolution reaction experiment, as a result are as follows: ferrous disulfide/carbon obtained by the present embodiment
Change iron/sulfur doping carbon (FeS2/Fe3C/S-C) compound has higher electro catalytic activity, take-off potential to oxygen reduction reaction
0.89V, limiting current density 5.20mA/cm2；Also there is higher electro catalytic activity to oxygen evolution reaction, when current density is
10mA/cm2When, potential 1.60V.
Embodiment 3
0.5g coal directly-liquefied residue (Erdos coal oil company, Shenhua), 3.0g potassium hydroxide (KOH) are mixed, In
N2In, it is risen to 900 DEG C by room temperature with 5 DEG C/min heating rate and is kept the temperature 1h and be heat-treated, product is washed with water, at 80 DEG C
Forced air drying 6h obtains ferrous disulfide/cementite/sulfur doping carbon (FeS2/Fe3C/S-C) composite materials；Gained composite material
The content of middle element sulphur is 4.1wt%, and the content of ferro element is 8.3wt%, and the content of carbon is 87.6wt%.
Using method same as Example 1 to ferrous disulfide/cementite/sulfur doping carbon (FeS obtained by the present embodiment2/
Fe3C/S-C) composite materials carry out oxygen reduction reaction, oxygen evolution reaction experiment, as a result are as follows: ferrous disulfide/carbon obtained by the present embodiment
Change iron/sulfur doping carbon (FeS2/Fe3C/S-C) compound has higher electro catalytic activity, take-off potential to oxygen reduction reaction
0.88V, limiting current density 5.41mA/cm2；Also there is higher electro catalytic activity to oxygen evolution reaction, when current density is
10mA/cm2When, potential 1.64V.
The present invention is directly using coal directly-liquefied residue as raw material, and the thermally treated electricity that just obtained is urged under the action of inorganic base
Change the elctro-catalyst haveing excellent performance；It is easy to operate, make full use of carbon, iron, sulphur contained by Industrial Solid Waste coal directly-liquefied residue
Element is realized and is converted to the high added value of residue, is easy to industrial mass production.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of elctro-catalyst, which is characterized in that the elctro-catalyst is by coal directly-liquefied residue and the thermally treated system of inorganic base
Standby to obtain, the elctro-catalyst is ferrous disulfide/cementite/sulfur doping carbon complex, iron content in the elctro-catalyst
For 0.1~10wt%, sulfur content is 0.1~10wt%, and carbon element content is 80~95wt%.
2. elctro-catalyst according to claim 1, which is characterized in that the quality of the coal directly-liquefied residue and inorganic base
Than for 1:0.1~10.
3. elctro-catalyst according to claim 1 or 2, which is characterized in that the inorganic base includes potassium hydroxide or hydrogen
Sodium oxide molybdena.
4. elctro-catalyst according to claim 1, which is characterized in that the temperature of the heat treatment is 600~1100 DEG C, is protected
The warm time is 0.5~4h.
5. elctro-catalyst according to claim 1 or 4, which is characterized in that the heat treatment carries out under protective atmosphere.
6. elctro-catalyst according to claim 1 or 4, which is characterized in that be warming up to the heating of the temperature of the heat treatment
Rate is 1~20 DEG C/min.
7. the preparation method of the described in any item elctro-catalysts of claim 1~6, which comprises the following steps:
Coal directly-liquefied residue and inorganic base are mixed, is heat-treated, obtains the elctro-catalyst.
8. application of the described in any item elctro-catalysts of claim 1~6 in oxygen reduction reaction or oxygen evolution reaction.
9. the described in any item elctro-catalysts of claim 1~6 are in fuel cell, metal-air battery, electro-catalysis H2O2Or
Application in electrolysis water.
10. application according to claim 9, which is characterized in that the load capacity of the elctro-catalyst is 0.1~0.8mg/
cm2。
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