CN109675632A - A kind of carbon-based ZIF composite catalyst and preparation method thereof and the application in electro-catalysis reduction carbon dioxide reaction - Google Patents
A kind of carbon-based ZIF composite catalyst and preparation method thereof and the application in electro-catalysis reduction carbon dioxide reaction Download PDFInfo
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- CN109675632A CN109675632A CN201811626374.9A CN201811626374A CN109675632A CN 109675632 A CN109675632 A CN 109675632A CN 201811626374 A CN201811626374 A CN 201811626374A CN 109675632 A CN109675632 A CN 109675632A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 21
- 239000001569 carbon dioxide Substances 0.000 title claims description 18
- 230000009467 reduction Effects 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 title claims description 10
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims abstract description 67
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 38
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 24
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 24
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- -1 transition metal salt Chemical class 0.000 claims abstract description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 230000012010 growth Effects 0.000 claims abstract description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000013249 bimetallic zeolitic imidazolate framework Substances 0.000 claims abstract description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 12
- 239000011790 ferrous sulphate Substances 0.000 claims description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 8
- 239000011736 potassium bicarbonate Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006396 nitration reaction Methods 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000006911 nucleation Effects 0.000 abstract description 2
- 238000010899 nucleation Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 239000004744 fabric Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- 238000001548 drop coating Methods 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 238000004321 preservation Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000002604 ultrasonography Methods 0.000 description 12
- 229910021607 Silver chloride Inorganic materials 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229960000935 dehydrated alcohol Drugs 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 239000013049 sediment Substances 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 229920000557 Nafion® Polymers 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000000840 electrochemical analysis Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 150000002460 imidazoles Chemical class 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/33—
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- C25B11/095—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 at least one of the compounds being organic
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Abstract
The present invention provides a kind of carbon-based ZIF composite catalyst and its preparation method and application, comprising the following steps: step 1, the pretreatment of carbon material: carbon material is carried out purifying and acid is handled；Step 2, bimetallic ZIF induced growth: carbon material and binder that step 1 pretreatment finishes are added in the methanol solution of transition metal salt, zinc nitrate and 2-methylimidazole, are stirred to react to obtain presoma；Step 3, high temperature carbonization: the presoma that step 2 is obtained carries out high temperature carbonization under an inert atmosphere.The present invention uses polyvinylpyrrolidone or polyethyleneimine for binder, on the one hand can modify carbon material surface, on the other hand can uniformly capture more transition metal ions on its surface, and induce ZIF in its surface homogeneous nucleation and growth.C-base composte material performance produced by the present invention is prominent, alternative traditional rare metal catalyst, and easy to operate, and raw material is easy to get, and is easy to be promoted in electro-catalysis related fields.
Description
Technical field
The invention belongs to electro-catalysis field, specially a kind of carbon-based ZIF composite catalyst and preparation method thereof and urged in electricity
Change reduction CO2Application in reaction.
Background technique
ZIF is one kind of MOFs (metal organic framework compound) material, is that a kind of be crosslinked by organic imidazate is connected to
On transition metal, a kind of tetrahedral framework material is formed.Due to its large specific surface area, pore size is adjustable and frame can be modified
Feature, so that ZIF material has been reported that repeatly in electro-catalysis field.
Currently, electro-catalysis carbon dioxide reduction is an extremely concerned hot subject, among this, elctro-catalyst is main
Two classes can be divided into: 1) metal-based catalyzed with rare metal, transition metal, transition metal oxide or sulfide etc. for representative
Agent；It 2) is the non-metallic catalyst of representative with nitrogen, phosphorus, boron, the graphene of sulfur doping, carbon nanotube etc..
Although having been reported proves that rare metal has remarkable activity to catalysis carbon dioxide reduction, it is volatile to be limited by its
The problems such as living, expensive and be unable to get extensive use；Although non-metallic catalyst is stablized, live without enough catalysis
Property, also it is unable to satisfy application requirement.Therefore finding a kind of cheap catalyst for capableing of efficient catalytic carbon dioxide reduction is still
The target that people constantly pursue.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of carbon-based ZIF composite catalyst and preparation method thereof
And application in turn ensures the stability of catalyst material while realizing efficient catalytic carbon dioxide conversion.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of carbon-based ZIF composite catalyst, comprising the following steps:
Step 1, the pretreatment of carbon material: carbon material is subjected to purifying and acid is handled；
Step 2, transition metal bimetallic ZIF induced growth: is added in carbon material and binder that step 1 pretreatment finishes
In the methanol solution of salt, zinc nitrate and 2-methylimidazole, it is stirred to react to obtain presoma；
Step 3, high temperature carbonization: the presoma that step 2 is obtained carries out high temperature carbonization under an inert atmosphere.
Preferably, in step 1, carbon material is graphene oxide, carbon nanotube or conductive black；Pretreatment is for aoxidizing stone
Black alkene is chlorohydric acid pickling, is that nitration mixture flows back for carbon nanotube and conductive black, the pretreated carbon material of process spend from
Son is washed to weakly acidic pH.
Preferably, in step 2, binder is polyvinylpyrrolidone or polyethyleneimine.
Preferably, in step 2, transition metal salt is ferrous sulfate, nickel nitrate, cobalt nitrate.
Preferably, in step 2, the molar ratio of transition metal salt and zinc nitrate is 1:(10-30).
Preferably, in step 2, stirring carries out at 25-35 DEG C, continues 12-24h.
Preferably, in step 3, carbonization temperature is 850 DEG C -1050 DEG C, time 1-2h.
The carbon-based ZIF composite catalyst that the preparation method is prepared.
Application of the carbon-based ZIF composite catalyst in electro-catalysis reduction carbon dioxide reaction.
Preferably, the electrolyte that electro-catalysis uses is potassium bicarbonate solution, concentration 0.1-0.5M.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention uses polyvinylpyrrolidone or polyethyleneimine for binder, on the one hand can modify carbon material table
On the other hand face can uniformly capture more transition metal ions on its surface, and induce ZIF (zeolite imidazole ester skeleton knot
Structure) in its surface homogeneous nucleation and growth；Then abundant and uniform point of active catalyst sites is obtained by carbonization again
Scattered carbon-supported catalysts avoid the appearance of metal agglomeration or metal bulky grain.C-base composte material performance produced by the present invention
Prominent, alternative traditional rare metal catalyst, and easy to operate, raw material is easy to get, be easy to electro-catalysis related fields into
Row is promoted.
Further, by changing binder, to adjust the surface texture of composite material, ZIF when using PVP as binder
It is compound more uniform in carbon material surface.
Further, by selecting different transition metal salts, such as ferrous sulfate, nickel nitrate and cobalt nitrate, and adjusting
The amount of different metal salt solutions, by comparison, it was found that, when using ferrous sulfate and guaranteeing molar ratio as 1:20, have optimal
Catalytic effect, faradic efficiency is reachable~and 98%.
Carbon-based ZIF composite catalyst prepared by the present invention, ZIF are evenly distributed on carbon material surface, ensure that catalytic activity
Position is uniformly distributed, and so as to show the performance of excellent electro-catalysis reduction carbon dioxide, and catalyst stability is good.This
Invention can realize that the faradic efficiency of carbon dioxide is higher than 80% under wider work potential, and in the long-time by 8h
After work, faradic efficiency is not decayed, and while illustrating to realize efficient catalytic carbon dioxide conversion, is in turn ensured
The stability of catalyst material.
Further, various concentration concentration of electrolyte is selected, will lead to the change of the current value in conversion process, thus shadow
The variation of faradic efficiency is rung, thus carries out the optimization of the catalytic performance of carbon dioxide reduction by adjusting concentration of electrolyte.
Detailed description of the invention
Fig. 1 is the phenogram of graphene-based ZIF composite material, and (a) is embodiment one using PVP as the graphene-based of binder
SEM figure of the ZIF composite material before charing；It (b) is that embodiment one exists by the graphene-based ZIF composite material of binder of PVP
SEM figure after charing；It (c) is embodiment one using PVP as the FTIR spectrum of the graphene-based ZIF composite material of binder
Figure；It (d) is embodiment two using PEI as the FTIR spectrum figure of the graphene-based ZIF composite material of binder；
Fig. 2 is the performance test figure of different materials；It (a) is that embodiment one is compound as the graphene-based ZIF of binder using PVP
CV figure of the material when different atmosphere is saturated；(b) the graphene-based ZIF for embodiment one and the different binders of embodiment two is compound
Material is in CO2CV figure when saturation；It (c) is that embodiment one is surveyed by the graphene-based ZIF composite material FE performance of binder of PVP
Attempt and electric current trend graph.It (d) is embodiment one using PVP as the graphene-based ZIF composite material stability test of binder
Figure.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The present invention selects ZIF for presoma, using the method for induced growth that it is compound with carbon material, using pyrocarbon
Change, form mesopore orbit structure abundant, and constructed the activated centre of Fe-N-C, can be an oxygen by carbon dioxide conversion
Change carbon.The present invention is main by selecting different transition metal salt, no in order to realize catalyst efficient catalytic carbon dioxide reduction
Same binder and different carbon materials, the optimization of the catalytic performance of Lai Jinhang carbon dioxide reduction.The present invention will have rich
The ZIF and carbon material of rich cellular structure are compound, realize efficient catalytic carbon dioxide conversion, the preparation method of carbon-based compound ZIF
Comprising the following three steps: (1) carbon material purifying and pretreatment；(2) precursor for ZIF being added in carbon material and binder is molten
In liquid, induce ZIF in carbon material surface nucleating growth by way of stirring；(3) compound is subjected to height under an inert atmosphere
Temperature charing.
The preparation method of carbon-based ZIF composite catalyst of the present invention, follows the steps below:
(1) pre-treatment step of carbon material:
The purifying of carbon material, and carried out acid processing appropriate；
(2) bimetallic ZIF induced growth step:
The carbon material that pretreatment is finished and the methanol that transition metal salt, zinc nitrate and 2-methylimidazole is added in binder are molten
In liquid, it is stirred to obtain presoma；
(3) high temperature carbonization step:
The presoma obtained after step (2) is subjected to high temperature carbonization under an inert atmosphere.
In step (1), the carbon material includes graphene oxide (GO), carbon nanotube (CNT) and conductive black
(Carbon Black)；Preprocessing process is chlorohydric acid pickling for graphene oxide, is mixed for carbon nanotube and conductive black
Acid reflux；It is washed with deionized water by pretreated carbon material to weakly acidic pH；
In step (2), the binder is polyvinylpyrrolidone (PVP) or polyethyleneimine (PEI)；Described
Transition metal salt is ferrous sulfate, nickel nitrate, cobalt nitrate；The molar ratio of the transition metal salt and zinc nitrate is 1:(10-
30)；The whipping process carries out at 25-35 DEG C, continues 12-24h；After completion of stirring, it before high temperature carbonization, should carry out
Separating-purifying process: supernatant liquor is outwelled after the completion of stirring, sediment is cleaned three times with methanol, is transferred in vacuum oven, 70
It DEG C is dried in vacuum overnight.
In step (3), the inert atmosphere is argon gas or nitrogen；The carbonization temperature is 850 DEG C -1050 DEG C, when
Between be 1-2h；
Application the present invention also provides above-mentioned catalyst material in electro-catalysis carbon dioxide reduction field, the electro-catalysis
Carbon dioxide reduction process includes the following steps:
(1) electrode preparation step:
Catalyst material obtained is ground, ultrasound 1h is carried out after mixing with Nafion membrane solution, dehydrated alcohol, is uniformly dripped
It is applied to carbon cloth two sides；The amount of drop coating is 200 μ L on carbon cloth；
(2) catalytic performance test step
There is the carbon cloth of catalyst material to be as working electrode, platinum electrode as to electrode, silver/silver chloride electrode drop coating
Reference electrode, three constitute three-electrode system, are tested in -1.6~-0.6V vs Ag/AgCl potential range；Institute's electricity consumption
Solution liquid is potassium bicarbonate solution, concentration 0.1-0.5M；Electrolytic cell used is H-type electrolytic cell, and uses gas chromatographic detection gas
Body product.
Below by embodiment, the present invention is further described, reagent used in example and device information such as Tables 1 and 2
It is shown
Agents useful for same information table in 1 embodiment of table
Instrument information table in 2 embodiment of table
Embodiment one
1. graphene oxide pre-processes: graphene oxide obtained is cleaned with the dilute hydrochloric acid of a large amount of 0.1M, to remove wherein
The impurity for being included, then it is cleaned with a large amount of water to weakly acidic pH；
2. the preparation of graphene-based ZIF composite catalyst: the graphene oxide that pretreatment is completed is dispersed to deionized water
In (concentration about 7mg/mL)；7.3g zinc nitrate, 0.34g ferrous sulfate are weighed, is dissolved in 800mL methanol and stirs evenly, then plus
Enter 0.5g poly-methyl pyrrole alkanone (PVP) and 10mL carbon material dispersion liquid, after being again stirring for uniformly, 8.5g 2- first is added
Base imidazoles is kept stirring for 24 hours at 25 DEG C.Supernatant liquor is centrifugated out after the completion of stirring, again with methanol cleans sediment three times,
It then continues in vacuum oven, 70 DEG C are dried in vacuum overnight.After the completion of drying, high temperature carbonization is carried out in argon atmosphere, point
Not in 150 DEG C of heat preservations 5h, 950 DEG C of heat preservation 2h, then cooled to room temperature.
3. graphene-based ZIF composite catalyst performance test: the catalyst after above-mentioned charing is ground to uniform powder,
It weighs 5mg to be added in 1mL dehydrated alcohol, adds 20 μ L Nafion membrane solution, then ultrasound 1h, ultrasonic uniform ink liquid is equal
Even drop coating is in pretreated 1cm2On carbon cloth.There is the carbon cloth of catalyst material as working electrode using drop coating, platinum electrode is to electricity
Pole, silver silver chloride electrode are reference electrode, with 0.1M KHCO3Solution is electrolyte, constitutes three-electrode system, and -1.6~-
Relevant electro-chemical test is carried out in the potential range of 0.6V vs Ag/AgCl.
As shown in Fig. 1 (a) and Fig. 1 (b), graphene-based ZIF composite material has the pattern of graphene and ZIF particle special
Sign, ZIF granular size is close, and uniform fold is in surface of graphene oxide, the generation that do not reunite, and illustrates the ZIF in the case where PVP is assisted
It is compound with the success of GO.And after charing, graphene sheet layer fold and the skeleton structure of ZIF are more highlighted, after illustrating carbonization
Material perfect can keep excellent structure.
As shown in Fig. 1 (c), graphene-based ZIF composite material has the stretching vibration different from graphene oxide, represents oxygen
The stretching vibration relative intensity of graphite alkene oxygen-containing functional group reduces, and shows that carbonization process is thorough, graphene oxide sufficiently restores
As graphene.
As shown in Fig. 2 (a), CV figure of the graphene-based ZIF composite material under different saturation atmosphere shows different electricity
Stream response, and in CO2Current-responsive value when saturation is bigger, shows there is higher catalytic activity.The more significant body of Fig. 2 (c)
Revealing using PVP as the excellent properties of the graphene-based ZIF composite material of binder, faradic efficiency is reachable~and 98%.Fig. 2
(d) show that the present invention can realize that the faradic efficiency of carbon dioxide is higher than 80% under wider work potential, and passing through
After the working long hours of 8h, faradic efficiency is not decayed, and says that the stability of catalyst material is fine.
Embodiment two
1. graphene oxide pre-processes: graphene oxide obtained is cleaned with the dilute hydrochloric acid of a large amount of 0.1M, to remove wherein
The impurity for being included, then it is cleaned with a large amount of water to weakly acidic pH.
2. the preparation of graphene-based ZIF composite catalyst: the graphene oxide that pretreatment is completed is dispersed to deionized water
In (concentration about 7mg/mL)；7.3g zinc nitrate, 0.34g ferrous sulfate are weighed, is dissolved in 800mL methanol and stirs evenly, then plus
Enter 0.5g polyethyleneimine (PEI) and 10mL carbon material dispersion liquid, after being again stirring for uniformly, 8.5g 2- methyl miaow is added
Azoles is kept stirring for 24 hours at 25 DEG C.Supernatant liquor is centrifugated out after the completion of stirring, again with methanol cleans sediment three times, then
It is transferred in vacuum oven, 70 DEG C are dried in vacuum overnight.After the completion of drying, high temperature carbonization is carried out in argon atmosphere, is existed respectively
150 DEG C of heat preservations 5h, 950 DEG C of heat preservation 2h, then cooled to room temperature.
3. graphene-based ZIF composite catalyst performance test: the catalyst after above-mentioned charing is ground to uniform powder,
It weighs 5mg to be added in 1mL dehydrated alcohol, adds 20 μ L Nafion membrane solution, then ultrasound 1h, ultrasonic uniform ink liquid is equal
Even drop coating is in pretreated 1cm2On carbon cloth.There is the carbon cloth of catalyst material as working electrode using drop coating, platinum electrode is to electricity
Pole, silver silver chloride electrode are reference electrode, using 0.1M solution as electrolyte, constitute three-electrode system, and in -1.6~-0.6V
Relevant electro-chemical test is carried out in the potential range of vs Ag/AgCl.
Fig. 1 (d) is similar to the variation of the front and back of Fig. 1 (c) stretching vibration, and showing different binders and carbonizing again all no longer influences
The functional group of material is distributed.
It is the graphene-based ZIF composite material of binder in CO using PEI as shown in Fig. 2 (b)2The CV figure being saturated under atmosphere,
It can be seen that its current-responsive value is greater than the response of pure carbon cloth, less than using PVP as the graphene ZIF composite material of binder, this is
It is excessively weak because inducing too strong easy reunion caused by the ability difference of different binder induction ZIF nucleating growths, it can give birth to
It is long not exclusively, to affect catalytic performance.
Embodiment three
1. graphene oxide pre-processes: graphene oxide obtained is cleaned with the dilute hydrochloric acid of a large amount of 0.1M, to remove wherein
The impurity for being included, then it is cleaned with a large amount of water to weakly acidic pH.
2. the preparation of graphene-based ZIF composite catalyst: the graphene oxide that pretreatment is completed is dispersed to deionized water
In (concentration about 7mg/mL)；7.3g zinc nitrate, 0.71g nickel nitrate are weighed, is dissolved in 800mL methanol and stirs evenly, add
8.5g 2- methyl is added after being again stirring for uniformly in 0.5g poly-methyl pyrrole alkanone (PVP) and 10mL carbon material dispersion liquid
Imidazoles is kept stirring for 24 hours at 25 DEG C.Supernatant liquor is centrifugated out after the completion of stirring, again with methanol cleans sediment three times, with
After be transferred in vacuum oven, 70 DEG C are dried in vacuum overnight.After the completion of drying, high temperature carbonization is carried out in argon atmosphere, respectively
In 150 DEG C of heat preservations 5h, 950 DEG C of heat preservation 2h, then cooled to room temperature.
3. graphene-based ZIF composite catalyst performance test: the catalyst after above-mentioned charing is ground to uniform powder,
It weighs 5mg to be added in 1mL dehydrated alcohol, adds 20 μ L Nafion membrane solution, then ultrasound 1h, ultrasonic uniform ink liquid is equal
Even drop coating is in pretreated 1cm2On carbon cloth.There is the carbon cloth of catalyst material as working electrode using drop coating, platinum electrode is to electricity
Pole, silver silver chloride electrode are reference electrode, with 0.1M KHCO3Solution is electrolyte, constitutes three-electrode system, and -1.6~-
Relevant electro-chemical test is carried out in the potential range of 0.6V vs Ag/AgCl.
Example IV
1. graphene oxide pre-processes: graphene oxide obtained is cleaned with the dilute hydrochloric acid of a large amount of 0.1M, to remove wherein
The impurity for being included, then it is cleaned with a large amount of water to weakly acidic pH.
2. the preparation of graphene-based ZIF composite catalyst: the graphene oxide that pretreatment is completed is dispersed to deionized water
In (concentration about 7mg/mL)；7.3g zinc nitrate, 0.71g cobalt nitrate are weighed, is dissolved in 800mL methanol and stirs evenly, add
8.5g 2- methyl is added after being again stirring for uniformly in 0.5g poly-methyl pyrrole alkanone (PVP) and 10mL carbon material dispersion liquid
Imidazoles is kept stirring for 24 hours at 25 DEG C.Supernatant liquor is centrifugated out after the completion of stirring, again with methanol cleans sediment three times, with
After be transferred in vacuum oven, 70 DEG C are dried in vacuum overnight.After the completion of drying, high temperature carbonization is carried out in argon atmosphere, respectively
In 150 DEG C of heat preservations 5h, 950 DEG C of heat preservation 2h, then cooled to room temperature.
3. graphene-based ZIF composite catalyst performance test: the catalyst after above-mentioned charing is ground to uniform powder,
It weighs 5mg to be added in 1mL dehydrated alcohol, adds 20 μ L Nafion membrane solution, then ultrasound 1h, ultrasonic uniform ink liquid is equal
Even drop coating is in pretreated 1cm2On carbon cloth.There is the carbon cloth of catalyst material as working electrode using drop coating, platinum electrode is to electricity
Pole, silver silver chloride electrode are reference electrode, with 0.1M KHCO3Solution is electrolyte, constitutes three-electrode system, and -1.6~-
Relevant electro-chemical test is carried out in the potential range of 0.6V vs Ag/AgCl.
Embodiment five
1. carbon nanotube pre-processes: weighing appropriate carbon nanotube and be added in nitration mixture, 80 DEG C are heated at reflux 6h, after reflux
It is cleaned with a large amount of deionized waters to weakly acidic pH.
2. the preparation of carbon nanotube base ZIF composite catalyst: the carbon nanotube that pretreatment is completed is dispersed to deionized water
In (concentration about 7mg/mL)；7.3g zinc nitrate, 0.34g ferrous sulfate are weighed, is dissolved in 800mL methanol and stirs evenly, then plus
Enter 0.5g poly-methyl pyrrole alkanone (PVP) and 10mL carbon material dispersion liquid, after being again stirring for uniformly, 8.5g 2- first is added
Base imidazoles is kept stirring for 24 hours at 25 DEG C.Supernatant liquor is centrifugated out after the completion of stirring, again with methanol cleans sediment three times,
It then continues in vacuum oven, 70 DEG C are dried in vacuum overnight.After the completion of drying, high temperature carbonization is carried out in argon atmosphere, point
Not in 150 DEG C of heat preservations 5h, 950 DEG C of heat preservation 2h, then cooled to room temperature.
3. carbon nanotube base ZIF composite catalyst performance test: the catalyst after above-mentioned charing is ground to uniform powder
End weighs 5mg and is added in 1mL dehydrated alcohol, adds 20 μ L Nafion membrane solution, then ultrasound 1h, by the uniform ink of ultrasound
The uniform drop coating of liquid is in pretreated 1cm2On carbon cloth.There is the carbon cloth of catalyst material as working electrode using drop coating, platinum electrode is
To electrode, silver silver chloride electrode is reference electrode, with 0.5M KHCO3Solution is electrolyte, composition three-electrode system, and-
Relevant electro-chemical test is carried out in the potential range of 1.6~-0.6V vs Ag/AgCl.
Embodiment six
1. conductive black pre-processes: weighing amount of conductive carbon black and be added in nitration mixture, 80 DEG C are heated at reflux 6h, after reflux
It is cleaned with a large amount of deionized waters to weakly acidic pH.
2. the preparation of conductive black base ZIF composite catalyst: the conductive black that pretreatment is completed is dispersed to deionized water
In (concentration about 7mg/mL)；7.3g zinc nitrate, 0.34g ferrous sulfate are weighed, is dissolved in 800mL methanol and stirs evenly, then plus
Enter 0.5g poly-methyl pyrrole alkanone (PVP) and 10mL carbon material dispersion liquid, after being again stirring for uniformly, 8.5g 2- first is added
Base imidazoles is kept stirring for 24 hours at 25 DEG C.Supernatant liquor is centrifugated out after the completion of stirring, again with methanol cleans sediment three times,
It then continues in vacuum oven, 70 DEG C are dried in vacuum overnight.After the completion of drying, high temperature carbonization is carried out in argon atmosphere, point
Not in 150 DEG C of heat preservations 5h, 950 DEG C of heat preservation 2h, then cooled to room temperature.
3. conductive black base ZIF composite catalyst performance test: the catalyst after above-mentioned charing is ground to uniform powder
End weighs 5mg and is added in 1mL dehydrated alcohol, adds 20 μ LNafion coating solutions, then ultrasound 1h, by ultrasonic uniform ink liquid
Uniform drop coating is in pretreated 1cm2On carbon cloth.There is the carbon cloth of catalyst material as working electrode using drop coating, platinum electrode is pair
Electrode, silver silver chloride electrode is reference electrode, with 0.5MKHCO3Solution is electrolyte, constitutes three-electrode system, and -1.6
Relevant electro-chemical test is carried out in the potential range of~-0.6V vs Ag/AgCl.
Embodiment seven
1. conductive black pre-processes: weighing amount of conductive carbon black and be added in nitration mixture, 80 DEG C are heated at reflux 6h, after reflux
It is cleaned with a large amount of deionized waters to weakly acidic pH.
2. the preparation of conductive black base ZIF composite catalyst: the conductive black that pretreatment is completed is dispersed to deionized water
In (concentration about 7mg/mL)；7.3g zinc nitrate, 0.51g ferrous sulfate are weighed, is dissolved in 800mL methanol and stirs evenly, then plus
Enter 0.5g poly-methyl pyrrole alkanone (PVP) and 10mL carbon material dispersion liquid, after being again stirring for uniformly, 8.5g 2- first is added
Base imidazoles is kept stirring for 24 hours at 30 DEG C.Supernatant liquor is centrifugated out after the completion of stirring, again with methanol cleans sediment three times,
It then continues in vacuum oven, 70 DEG C are dried in vacuum overnight.After the completion of drying, high temperature carbonization is carried out in argon atmosphere, point
Not in 150 DEG C of heat preservations 5h, 850 DEG C of heat preservation 2h, then cooled to room temperature.
3. conductive black base ZIF composite catalyst performance test: the catalyst after above-mentioned charing is ground to uniform powder
End weighs 5mg and is added in 1mL dehydrated alcohol, adds 20 μ L Nafion membrane solution, then ultrasound 1h, by the uniform ink of ultrasound
The uniform drop coating of liquid is in pretreated 1cm2On carbon cloth.There is the carbon cloth of catalyst material as working electrode using drop coating, platinum electrode is
To electrode, silver silver chloride electrode is reference electrode, with 0.5MKHCO3Solution is electrolyte, constitutes three-electrode system, and -1.6
Relevant electro-chemical test is carried out in the potential range of~-0.6V vs Ag/AgCl.
Embodiment eight
1. conductive black pre-processes: weighing amount of conductive carbon black and be added in nitration mixture, 80 DEG C are heated at reflux 6h, after reflux
It is cleaned with a large amount of deionized waters to weakly acidic pH.
2. the preparation of conductive black base ZIF composite catalyst: the conductive black that pretreatment is completed is dispersed to deionized water
In (concentration about 7mg/mL)；7.3g zinc nitrate, 0.17g ferrous sulfate are weighed, is dissolved in 800mL methanol and stirs evenly, then plus
Enter 0.5g poly-methyl pyrrole alkanone (PVP) and 10mL carbon material dispersion liquid, after being again stirring for uniformly, 8.5g 2- first is added
Base imidazoles is kept stirring for 24 hours at 35 DEG C.Supernatant liquor is centrifugated out after the completion of stirring, again with methanol cleans sediment three times,
It then continues in vacuum oven, 70 DEG C are dried in vacuum overnight.After the completion of drying, high temperature carbonization is carried out in argon atmosphere, point
Not in 150 DEG C of heat preservations 5h, 1050 DEG C of heat preservation 2h, then cooled to room temperature.
3. conductive black base ZIF composite catalyst performance test: the catalyst after above-mentioned charing is ground to uniform powder
End weighs 5mg and is added in 1mL dehydrated alcohol, adds 20 μ L Nafion membrane solution, then ultrasound 1h, by the uniform ink of ultrasound
The uniform drop coating of liquid is in pretreated 1cm2On carbon cloth.There is the carbon cloth of catalyst material as working electrode using drop coating, platinum electrode is
To electrode, silver silver chloride electrode is reference electrode, with 0.3M KHCO3Solution is electrolyte, composition three-electrode system, and-
Relevant electro-chemical test is carried out in the potential range of 1.6~-0.6V vs Ag/AgCl.
The present invention is by changing the step the binder in 2, to adjust the surface texture of composite material, when with PVP be bonding
ZIF is compound more uniform in carbon material surface when agent, avoids the appearance of reunion.By selecting different transition metal salts, such as
Ferrous sulfate, nickel nitrate and cobalt nitrate, and the amount of different metal salt solutions is adjusted, by comparison, it was found that, using sulfuric acid Asia
Iron and when guaranteeing that molar ratio is 1:20, has optimal catalytic effect, and faradic efficiency is reachable~and 98%.It is different by selecting
ZIF successfully can be compounded in its surface by carbon material, to have more preferred composite materials.
Claims (10)
1. a kind of preparation method of carbon-based ZIF composite catalyst, which comprises the following steps:
Step 1, the pretreatment of carbon material: carbon material is subjected to purifying and acid is handled；
Step 2, bimetallic ZIF induced growth: by step 1 carbon material that finishes of pretreatment and binder be added transition metal salt,
In the methanol solution of zinc nitrate and 2-methylimidazole, it is stirred to react to obtain presoma；
Step 3, high temperature carbonization: the presoma that step 2 is obtained carries out high temperature carbonization under an inert atmosphere.
2. the preparation method of carbon-based ZIF composite catalyst according to claim 1, which is characterized in that in step 1, carbon materials
Material is graphene oxide, carbon nanotube or conductive black；Pretreatment is chlorohydric acid pickling for graphene oxide, for carbon nanotube
It is nitration mixture reflux with conductive black, is washed with deionized water by pretreated carbon material to weakly acidic pH.
3. the preparation method of carbon-based ZIF composite catalyst according to claim 1, which is characterized in that in step 2, bonding
Agent is polyvinylpyrrolidone or polyethyleneimine.
4. the preparation method of carbon-based ZIF composite catalyst according to claim 1, which is characterized in that in step 2, transition
Metal salt is ferrous sulfate, nickel nitrate, cobalt nitrate.
5. the preparation method of carbon-based ZIF composite catalyst according to claim 1, which is characterized in that in step 2, transition
The molar ratio of metal salt and zinc nitrate is 1:(10-30).
6. the preparation method of carbon-based ZIF composite catalyst according to claim 1, which is characterized in that in step 2, stirring
It is carried out at 25-35 DEG C, continues 12-24h.
7. the preparation method of carbon-based ZIF composite catalyst according to claim 1, which is characterized in that in step 3, charing
Temperature is 850 DEG C -1050 DEG C, time 1-2h.
8. the carbon-based ZIF composite catalyst that the described in any item preparation methods of claim 1-7 are prepared.
9. application of the carbon-based ZIF composite catalyst according to any one of claims 8 in electro-catalysis reduction carbon dioxide reaction.
10. application according to claim 9, which is characterized in that the electrolyte that electro-catalysis uses is dense for potassium bicarbonate solution
Degree is 0.1-0.5M.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110380062A (en) * | 2019-07-16 | 2019-10-25 | 运城学院 | The preparation method of the difunctional VPO catalysts of sulfur doping based on ZIF-67 and conductive graphene |
| CN111001428A (en) * | 2019-12-24 | 2020-04-14 | 山西大学 | Metal-free carbon-based electrocatalyst, preparation method and application |
| CN111430733A (en) * | 2020-03-17 | 2020-07-17 | 上海电气集团股份有限公司 | Non-noble metal oxygen reduction catalyst for fuel cell and preparation method thereof |
| CN112316981A (en) * | 2019-07-19 | 2021-02-05 | 天津师范大学 | Composite material based on nano porous gold and zeolite imidazole framework and preparation method and application thereof |
| CN112354552A (en) * | 2019-07-24 | 2021-02-12 | 南京理工大学 | Preparation method of cheap transition metal and nitrogen co-doped porous carbon material |
| CN113699554A (en) * | 2021-09-17 | 2021-11-26 | 中国矿业大学 | Preparation method and application of rare earth metal and transition metal co-doped carbon-based material |
| WO2023200401A3 (en) * | 2022-04-11 | 2023-11-23 | Nanyang Technological University | Anti-bacterial and anti-ammonia beads |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020745A2 (en) * | 2007-07-17 | 2009-02-12 | The Regents Of The University Of California | Preparation of functionalized zeolitic frameworks |
| CN103537322A (en) * | 2013-09-27 | 2014-01-29 | 北京大学 | Method for realizing large-scale synthesis of oxygen gas reduction reaction electrocatalyst |
| CN104016328A (en) * | 2013-02-28 | 2014-09-03 | 中国科学院大连化学物理研究所 | Method for preparing nitrogen-containing carbon nano tube |
| CN107175125A (en) * | 2017-05-31 | 2017-09-19 | 中山大学 | A kind of activation method of MOFs bases oxygen reduction electro-catalyst |
| CN107497377A (en) * | 2017-10-19 | 2017-12-22 | 山东大学 | A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere |
| CN108063056A (en) * | 2017-12-08 | 2018-05-22 | 中北大学 | A kind of porous nitrogen-doped carbon/carbon nano tube compound material and its preparation method and application |
-
2018
- 2018-12-28 CN CN201811626374.9A patent/CN109675632A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020745A2 (en) * | 2007-07-17 | 2009-02-12 | The Regents Of The University Of California | Preparation of functionalized zeolitic frameworks |
| CN104016328A (en) * | 2013-02-28 | 2014-09-03 | 中国科学院大连化学物理研究所 | Method for preparing nitrogen-containing carbon nano tube |
| CN103537322A (en) * | 2013-09-27 | 2014-01-29 | 北京大学 | Method for realizing large-scale synthesis of oxygen gas reduction reaction electrocatalyst |
| CN107175125A (en) * | 2017-05-31 | 2017-09-19 | 中山大学 | A kind of activation method of MOFs bases oxygen reduction electro-catalyst |
| CN107497377A (en) * | 2017-10-19 | 2017-12-22 | 山东大学 | A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere |
| CN108063056A (en) * | 2017-12-08 | 2018-05-22 | 中北大学 | A kind of porous nitrogen-doped carbon/carbon nano tube compound material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| PANPAN SU 等: "Nitrogen-doped carbon nanotubes derived from Zn–Fe-ZIF nanospheres and their application as efficient oxygen reduction electrocatalysts with in situ generated iron species", 《CHEMICAL SCIENCE》 * |
| RUQIANG ZOU 等: "A metal–organic framework route to in situ encapsulation of Co@Co3O4@C core@bishell nanoparticles into a highly ordered porous carbon matrix for oxygen reduction", 《ENERGY & ENVIRONMENTAL SCIENCE》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110380062A (en) * | 2019-07-16 | 2019-10-25 | 运城学院 | The preparation method of the difunctional VPO catalysts of sulfur doping based on ZIF-67 and conductive graphene |
| CN112316981A (en) * | 2019-07-19 | 2021-02-05 | 天津师范大学 | Composite material based on nano porous gold and zeolite imidazole framework and preparation method and application thereof |
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| CN112354552A (en) * | 2019-07-24 | 2021-02-12 | 南京理工大学 | Preparation method of cheap transition metal and nitrogen co-doped porous carbon material |
| CN111001428A (en) * | 2019-12-24 | 2020-04-14 | 山西大学 | Metal-free carbon-based electrocatalyst, preparation method and application |
| CN111430733A (en) * | 2020-03-17 | 2020-07-17 | 上海电气集团股份有限公司 | Non-noble metal oxygen reduction catalyst for fuel cell and preparation method thereof |
| CN111430733B (en) * | 2020-03-17 | 2022-09-20 | 上海电气集团股份有限公司 | Non-noble metal oxygen reduction catalyst for fuel cell and preparation method thereof |
| CN113699554A (en) * | 2021-09-17 | 2021-11-26 | 中国矿业大学 | Preparation method and application of rare earth metal and transition metal co-doped carbon-based material |
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Application publication date: 20190426 |