CN110038634A - A kind of oxygen evolution reaction catalysts and its synthetic method based on MXene Yu metal organic framework compound composite construction - Google Patents
A kind of oxygen evolution reaction catalysts and its synthetic method based on MXene Yu metal organic framework compound composite construction Download PDFInfo
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- CN110038634A CN110038634A CN201910373344.XA CN201910373344A CN110038634A CN 110038634 A CN110038634 A CN 110038634A CN 201910373344 A CN201910373344 A CN 201910373344A CN 110038634 A CN110038634 A CN 110038634A
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- mxene
- oxygen evolution
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- evolution reaction
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 68
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000001301 oxygen Substances 0.000 title claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000010276 construction Methods 0.000 title claims abstract description 13
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 title claims abstract description 12
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000013110 organic ligand Substances 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000001291 vacuum drying Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000003643 water by type Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 13
- 239000010953 base metal Substances 0.000 description 10
- 239000011943 nanocatalyst Substances 0.000 description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 229910003289 NiMn Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Chemical group 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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—
-
- B01J35/33—
-
- B01J35/40—
-
- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- 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
A kind of oxygen evolution reaction catalysts and its synthetic method based on MXene Yu metal organic framework compound composite construction, belong to nano material, the energy and catalytic field.The catalyst is made of the MXene two-dimensional nano thin slice of surface uniform load MOFs nano particle, has two-dimensional structure.Preparation method: by MXene, metal salt, organic ligand and acid binding agent dissolution after mixing, centrifugation, washing, vacuum drying, obtain structure, ingredient can finely regulating two-dimensional nanostructure elctro-catalyst.The elctro-catalyst that the present invention obtains can effectively overcome MOFs poorly conductive, stability difference and the basic problem that causes oxygen evolution reaction catalytic performance that can not play；Gained catalyst shows excellent catalytic activity and stability in alkaline electrolyte to oxygen evolution reaction, and the extensive use for new energy technologies such as fuel cell, metal-air battery, electrolysis waters lays the foundation.
Description
Technical field
The invention belongs to nano material, the energy and catalytic fields, are related to one kind based on MXene and metal organic framework chemical combination
The oxygen evolution reaction catalysts and its synthetic method of object composite construction.
Background technique
It is empty for fuel cell, the metal of core reaction with oxygen evolution reaction (oxygen evolution reaction, OER)
Pneumoelectric pond, electrolysis water etc. are one of novel renewable energy storage and transformation technology system of current most prospect.Oxygen evolution reaction
It is related to four electronic transfer process, reaction energy barrier is high, and process kinetic rate is slow, needs using efficient catalyst to improve it
Energy conversion efficiency.RuO2And IrO2Etc. being the best catalyst of current activity, but rare resource and high cost limit
Its scale application.Developing cheap, efficient, stable base metal oxygen evolution reaction catalysts is to push fuel cell, metal empty
The new energy technologies such as pneumoelectric pond, electrolysis water move towards one of critical bottleneck problem of practical application.
Metal organic framework compound (Metal-Organic Frameworks, MOFs) is one kind by transition metal ions
The steric order network porous crystalline material formed with organic ligand by coordinate bond has porosity height, large specific surface area, hole
The advantages that diameter is adjustable.The height Modulatory character of metal center element and organic ligand in chemical composition assigns it in MOFs structure
The peculiar property of multiplicity, energy storage separated with conversion, catalysis, sensor and gas etc. fields present it is wide before
Scape.But application of the MOFs in electrochemical catalysis field is still heavily constrained by its poor electric conductivity and structural stability, is based on it
The exploitations of high-performance oxygen evolution reaction catalysts still face huge challenge.
MXene is a kind of novel transition metal carbide or nitride two dimensional crystal material.Its chemical formula is Mn+1XnTx(n
=1,2,3, M be transition metal element, X is carbon or nitrogen, and T is chemical group), the ceramic layered material of selective etch can be passed through
Material MAX phase obtains.The surface MXene is rich in-OH ,-F ,-O isoreactivity chemical functional group, while having both the excellent conduction of metalloid
Property, thus be expected to realize as ideal conductive and active matrix with the electric conductivity and reactivity of General Promotion MOFs material
The initiative of new construction, high-performance oxygen evolution reaction catalysts based on MOFs with controllably construct.
Summary of the invention
For MOFs poorly conductive, structural stability is poor the disadvantages of, it is multiple based on MXene and MOFs that the present invention provides one kind
The oxygen evolution reaction catalysts and its synthetic method of structure are closed, the catalyst being prepared is by surface uniform load MOFs nano particle
MXene two-dimensional nano thin slice composition.Wherein the introducing of high conductivity MXene is with MOFs nano thin-layer in the equal of the surface MXene
Even load overcomes MOFs poorly conductive, stability difference and the basic problem that causes oxygen evolution reaction catalytic performance that can not play,
Gained catalyst is under alkaline condition to showing excellent catalytic activity and stability in Electrochemical oxygen evolution reaction process.The conjunction
It is environmentally protective at method, low energy consumption, it is easy to control and have versatility, can be used for large-scale production.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of oxygen evolution reaction catalysts based on MXene Yu metal organic framework compound composite construction, the catalyst by
The MXene two-dimensional nano thin slice of surface uniform load MOFs nano particle forms, and has two-dimensional structure, size is in 100-500nm
Between；The MOFs nano-particle content loaded on MXene is in 75wt.% or more, gold of the size between 10-100nm, in MOFs
Belonging to element includes at least one of nickel, iron, cobalt, manganese or two or more.Gained catalyst is under alkaline condition to oxygen evolution reaction
With excellent catalytic activity and stability.
A kind of synthetic method based on MXene Yu the oxygen evolution reaction catalysts of metal organic framework compound composite construction,
Include the following steps:
1) MXene is dispersed in water under normal temperature and pressure conditions and prepares dispersion liquid.
The MXene dispersion liquid concentration is 5-15mg mL-1。
2) metal salt and organic ligand are dissolved in N,N-dimethylformamide (DMF) and ethyl alcohol under normal temperature and pressure conditions
In the mixed solvent formed uniform solution.
The metal salt and organic ligand molar ratio is 1:1, and the concentration of organic ligand is 0.0375-0.04mol/L.
The organic ligand is at least one of terephthalic acid (TPA) and 2- amino terephthalic acid (TPA).
The volume ratio of the in the mixed solvent, DMF and ethyl alcohol is 5:1-15:1.
The metal salt be one of nickel salt, molysite, cobalt salt, manganese salt, it is any two kinds or it is any three kinds combination,
In, nickel salt, molysite, cobalt salt, manganese salt include chlorate, nitrate, acetate form.When using two kinds of metal salts, two kinds
The molar ratio of different cationic metal salt is 5:1-1:5；When using three kinds of metal salts, three kinds of different cationic metal salt rub
You are than being 1:1:1.
3) under normal temperature and pressure conditions by step 1) prepare MXene dispersion liquid prepared with step 2) metal salt/it is organic
Ligand uniform solution uniformly mixes.
4) after acid binding agent triethylamine being added into the mixed solution that step 3) is prepared under normal temperature and pressure conditions, stirring
2-4h is reacted, ethyl alcohol centrifuge washing is used after reaction, is then dried in vacuo.
The triethylamine and mixed liquor volume ratio are as follows: 1:20-68.
Compared with prior art, the present invention solves the difficulty that the oxygen evolution reaction catalysts preparation and application based on MOFs face
Topic, it has the advantage that:
1) introducing, there is the MXene of metalloid superior electrical conductivity to significantly improve the electric conductivity of MOFs, so that MOFs is to analysis
The catalytic activity of oxygen reaction is given full play to.
2) the MXene chemical Coupling and efficient stable MOFs with abundant chemically active surface functional group are introduced, institute is assigned
It obtains composite Nano and is catalyzed excellent catalytic stability.
3) introducing, there is the MXene of two-dimensional nanostructure to combine with MOFs nanostructure, the two-dimensional nanostructure of acquisition
Composite nano-catalyst has the electrode-electric solution liquid-oxygen three-phase reaction interface and electrochemistry bigger than block MOFs material anti-
Active surface area, the more catalytic reaction activity sites of exposure are answered, so that the catalysis reaction for promoting composite nano-catalyst be cooperateed with to live
Property.
4) present invention may be implemented to the microcosmic knot of oxygen evolution reaction catalysts based on MXene Yu MOFs composite nanostructure
The finely regulating of structure, chemical composition etc..Process is simple, environmentally protective, is easy to large-scale production, in fuel cell, full electricity
The energy storages such as Xie Shui, metal-air battery and Transformation Application field have broad prospect of application.
Detailed description of the invention
Fig. 1 is that the base metal composite Nano based on MXene and NiFe-BDC MOFs prepared by present example 1 is catalyzed
The electron scanning micrograph of agent；
Fig. 2 is that the base metal composite Nano based on MXene and NiFe-BDC MOFs prepared by present example 1 is catalyzed
The transmission electron microscope photo of agent；
Fig. 3 is that the base metal composite Nano based on MXene and NiCo-BDC MOFs prepared by present example 2 is catalyzed
The electron scanning micrograph of agent；
Fig. 4 is that the base metal composite Nano based on MXene and NiMn-BDC MOFs prepared by present example 3 is catalyzed
The electron scanning micrograph of agent；
Fig. 5 is that the base metal composite Nano based on MXene and NiFeMn-BDC MOFs prepared by present example 5 is urged
The electron scanning micrograph of agent；
Fig. 6 is that the base metal composite Nano based on MXene and NiFe-BDC MOFs prepared by present example 1 is catalyzed
Agent to the catalytic activity of oxygen evolution reaction characterization and its with commercialization RuO2The comparison of catalyst activity；
Fig. 7 is that the base metal composite Nano based on MXene and NiFe-BDC MOFs prepared by present example 1 is catalyzed
Agent to the stability of oxygen evolution reaction characterization and its with commercialization RuO2The comparison of catalyst stability.
Specific embodiment
For many defects of the prior art, inventor is studied for a long period of time and is largely practiced, and proposes skill of the invention
Art scheme as follows will be further explained the technical solution, its implementation process and principle etc..It is understood, however, that
Within the scope of the present invention, above-mentioned each technical characteristic of the invention and each technical characteristic specifically described in (embodiment) below it
Between can be combined with each other, to constitute new or preferred technical side's scheme.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Preparation method of the embodiment 1 based on MXene Yu the composite nano-catalyst of NiFe-BDC MOFs
1) it is 10mg mL that MXene is dispersed in water to preparation 2mL concentration under normal temperature and pressure conditions-1Dispersion liquid；
2) 1.0mmol nickel acetate, 0.2mmol ferric nitrate and 1.2mmol terephthalic acid (TPA) dissolve under normal temperature and pressure conditions
Uniform solution is formed in 30mL N,N-dimethylformamide (DMF) and 2mL ethyl alcohol；
3) under normal temperature and pressure conditions by step 1) prepare MXene dispersion liquid prepared with step 2) metal salt/it is organic
Ligand solution uniformly mixes；
4) 0.8mL acid binding agent triethylamine is added into the mixed solution that step 3) is prepared under normal temperature and pressure conditions
Afterwards, 2h is reacted under agitation, is used ethyl alcohol centrifuge washing after reaction, is then dried in vacuo.
Acquisition product is average-size about 100-500nm, loads the two-dimensional nano piece of NiFe base MOFs nano particle, NiFe
The size approximate number nanometer of base MOFs nano particle, load capacity is about 88.0wt.%.
Preparation method of the embodiment 2 based on MXene Yu the composite nano-catalyst of NiCo-BDC MOFs
1) it is 5mg mL that MXene is dispersed in water to preparation 2mL concentration under normal temperature and pressure conditions-1Dispersion liquid；
2) 0.6mmol nickel chloride, 0.6mmol cobalt chloride and 1.2mmol terephthalic acid (TPA) dissolve under normal temperature and pressure conditions
Uniform solution is formed in 30mL N,N-dimethylformamide (DMF) and 2mL ethyl alcohol；
3) under normal temperature and pressure conditions by step 1) prepare MXene dispersion liquid prepared with step 2) metal salt/it is organic
Ligand solution uniformly mixes；
4) 0.5mL acid binding agent triethylamine is added into the mixed solution that step 3) is prepared under normal temperature and pressure conditions
Afterwards, 2h is reacted under agitation, is used ethyl alcohol centrifuge washing after reaction, is then dried in vacuo.
Acquisition product is average-size about 100-500nm, loads the two-dimensional nano piece of NiCo base MOFs nano particle, NiCo
The size approximate number nanometer of base MOFs nano particle, load capacity is about 94.0wt.%.
Preparation method of the embodiment 3 based on MXene Yu the composite nano-catalyst of NiMn-BDC MOFs
1) it is 15mg mL that MXene is dispersed in water to preparation 2mL concentration under normal temperature and pressure conditions-1Dispersion liquid；
2) 0.2mmol nickel acetate, 1.0mmol manganese nitrate and 1.2mmol terephthalic acid (TPA) dissolve under normal temperature and pressure conditions
Uniform solution is formed in 28mL N,N-dimethylformamide (DMF) and 4mL ethyl alcohol；
3) under normal temperature and pressure conditions by step 1) prepare MXene dispersion liquid prepared with step 2) metal salt/it is organic
Ligand solution uniformly mixes；
4) 1.0mL acid binding agent triethylamine is added into the mixed solution that step 3) is prepared under normal temperature and pressure conditions
Afterwards, 4h is reacted under agitation, is used ethyl alcohol centrifuge washing after reaction, is then dried in vacuo.
Acquisition product is average-size about 100-500nm, loads the two-dimensional nano piece of NiMn base MOFs nano particle, NiMn
The size approximate number nanometer of base MOFs nano particle, load capacity is about 80.0wt.%.
Preparation method of the embodiment 4 based on MXene Yu the composite nano-catalyst of Ni-BDC MOFs
1) it is 15mg mL that MXene is dispersed in water to preparation 2mL concentration under normal temperature and pressure conditions-1Dispersion liquid；
2) 1.2mmol nickel chloride and 1.2mmol terephthalic acid (TPA) are dissolved in 28mL N, N- diformazan under normal temperature and pressure conditions
Uniform solution is formed in base formamide (DMF) and 4mL ethyl alcohol；
3) under normal temperature and pressure conditions by step 1) prepare MXene dispersion liquid prepared with step 2) metal salt/it is organic
Ligand solution uniformly mixes；
4) 1.0mL acid binding agent triethylamine is added into the mixed solution that step 3) is prepared under normal temperature and pressure conditions
Afterwards, 3h is reacted under agitation, is used ethyl alcohol centrifuge washing after reaction, is then dried in vacuo.
Acquisition product is average-size about 100-500nm, loads the two-dimensional nano piece of Ni base MOFs nano particle, Ni base
The size approximate number nanometer of MOFs nano particle, load capacity is about 78.0wt.%.
Preparation method of the embodiment 5 based on MXene Yu the composite nano-catalyst of NiFeMn-BDC MOFs
1) it is 10mg mL that MXene is dispersed in water to preparation 2mL concentration under normal temperature and pressure conditions-1Dispersion liquid；
2) 0.4mmol nickel acetate, 0.4mmol iron chloride, 0.4mmol manganese nitrate and 1.2mmol terephthalic acid (TPA) are in room temperature
It is dissolved under condition of normal pressure in 25mL N,N-dimethylformamide (DMF) and 5mL ethyl alcohol and forms uniform solution.
3) under normal temperature and pressure conditions by step 1) prepare MXene dispersion liquid prepared with step 2) metal salt/it is organic
Ligand solution uniformly mixes；
4) 1.5mL acid binding agent triethylamine is added into the mixed solution that step 3) is prepared under normal temperature and pressure conditions
Afterwards, 4h is reacted under agitation, is used ethyl alcohol centrifuge washing after reaction, is then dried in vacuo.
Acquisition product is average-size about 150-500nm, loads the two-dimensional nano piece of NiFeMn base MOFs nano particle,
The size approximate number nanometer of NiFeMn base MOFs nano particle, load capacity is about 92.0wt.%.
Embodiment 6 is based on MXene and NiFe-BDC-NH2The preparation method of the composite nano-catalyst of MOFs
1) it is 10mg mL that MXene is dispersed in water to preparation 2mL concentration under normal temperature and pressure conditions-1Dispersion liquid；
2) 1.0mmol nickel acetate, 0.2mmol ferric nitrate and 1.2mmol 2- amino terephthalic acid (TPA) are in normal temperature and pressure conditions
Under be dissolved in 30mL N,N-dimethylformamide (DMF) and 2mL ethyl alcohol and form uniform solution.
3) under normal temperature and pressure conditions by step 1) prepare MXene dispersion liquid prepared with step 2) metal salt/it is organic
Ligand solution uniformly mixes；
4) 1.0mL acid binding agent triethylamine is added into the mixed solution that step 3) is prepared under normal temperature and pressure conditions
Afterwards, 3h is reacted under agitation, is used ethyl alcohol centrifuge washing after reaction, is then dried in vacuo.
Acquisition product is average-size about 100-500nm, loads the two-dimensional nano piece of NiFe base MOFs nano particle, NiFe
The size approximate number nanometer of base MOFs nano particle, load capacity is about 89.0wt.%.
Fig. 6 is that the base metal composite Nano based on MXene and NiFe-BDC MOFs prepared by present example 1 is catalyzed
Agent to the catalytic activity of oxygen evolution reaction characterization and its with commercialization RuO2The comparison of catalyst activity.Test is in three-electrode system
It carries out, using 1M KOH as electrolyte, working electrode loads the composite nano-catalyst based on MXene Yu NiFe-BDC MOFs,
Ag/AgCl electrode is reference electrode, and platinized platinum is to electrode, and sweep speed is 10mV s-1, electrochemical workstation CHI760E.By
Figure is as it can be seen that the catalyst that the present invention obtains, which only needs 268mV overpotential i.e., can reach 10mA cm-1Current density, and be commercialized
RuO2Overpotential needed for catalyst reaches same current density is 378mV.It can be seen that the catalyst that the present invention obtains is in alkali
Property electrolyte in the catalytic activity of oxygen evolution reaction better than commercialization noble metal RuO2Catalyst.
Fig. 7 is that the base metal composite Nano based on MXene and NiFe-BDC MOFs prepared by present example 1 is catalyzed
Agent to the stability of oxygen evolution reaction characterization and its with commercialization RuO2The comparison of catalyst stability.Test is in three-electrode system
It carries out, using 1M KOH as electrolyte, working electrode loads the composite nano-catalyst based on MXene Yu NiFe-BDC MOFs,
Ag/AgCl electrode is reference electrode, and platinized platinum is to electrode, and sweep speed is 10mV s-1, electrochemical workstation CHI760E.By
Figure is as it can be seen that the catalyst that obtains of the present invention in current density is 10mA cm-1When, voltage can keep stablizing 23h, and be commercialized
RuO2Catalyst voltage under same current density quickly increases, and lapses after 3h.It can be seen that the catalysis that the present invention obtains
Agent is in alkaline electrolyte to the stability of oxygen evolution reaction better than commercialization noble metal RuO2Catalyst.
It should be understood that the technical concepts and features of above-described embodiment only to illustrate the invention, ripe its object is to allow
The personage for knowing technique cans understand the content of the present invention and implement it accordingly, and protection model of the invention can not be limited with this
It encloses.Any equivalent change or modification in accordance with the spirit of the invention should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of oxygen evolution reaction catalysts based on MXene Yu metal organic framework compound composite construction, which is characterized in that should
Catalyst is made of the MXene two-dimensional nano thin slice of surface uniform load MOFs nano particle, has two-dimensional structure, and size exists
Between 100-500nm；The MOFs nano-particle content loaded on MXene in 75wt.% or more, size between 10-100nm,
Metallic element in MOFs includes at least one of nickel, iron, cobalt, manganese or two or more；Gained catalyst is under alkaline condition
There is excellent catalytic activity and stability to oxygen evolution reaction.
2. a kind of oxygen evolution reaction based on MXene and metal organic framework compound composite construction described in claim 1 is catalyzed
The synthetic method of agent, which comprises the steps of:
1) MXene is dispersed in water under normal temperature and pressure conditions and prepares dispersion liquid；
2) metal salt and organic ligand are dissolved in the mixing of N,N-dimethylformamide DMF and ethyl alcohol under normal temperature and pressure conditions
Uniform solution is formed in solvent；The metal salt and organic ligand molar ratio is 1:1, and the concentration of organic ligand is 0.0375-
0.04mol/L；The organic ligand is at least one of terephthalic acid (TPA) and 2- amino terephthalic acid (TPA)；The metal salt
For at least one of nickel, iron, cobalt, the chlorate of manganese, nitrate, acetate or two or more；
3) by metal salt/organic ligand of the MXene dispersion liquid of step 1) preparation and step 2) preparation under normal temperature and pressure conditions
Uniform solution uniformly mixes；
4) it after acid binding agent triethylamine being added into the mixed solution that step 3) is prepared under normal temperature and pressure conditions, is stirred to react
2-4h, uses ethyl alcohol centrifuge washing after reaction, and vacuum drying obtains product.
3. a kind of oxygen evolution reaction based on MXene Yu metal organic framework compound composite construction according to claim 2
The synthetic method of catalyst, which is characterized in that MXene dispersion liquid concentration described in step 1) is 5-15mg mL-1。
4. a kind of oxygen evolution reaction based on MXene Yu metal organic framework compound composite construction according to claim 2
The synthetic method of catalyst, which is characterized in that the volume ratio of in the mixed solvent described in step 2), DMF and ethyl alcohol is 5:1-15:
1。
5. a kind of oxygen evolution reaction based on MXene Yu metal organic framework compound composite construction according to claim 2
The synthetic method of catalyst, which is characterized in that in step 2), when using two kinds of metal salts, two kinds of different cationic metal salt
Molar ratio be 5:1-1:5；When using three kinds of metal salts, the molar ratio of three kinds of different cationic metal salt is 1:1:1.
6. a kind of oxygen evolution reaction based on MXene Yu metal organic framework compound composite construction according to claim 2
The synthetic method of catalyst, which is characterized in that triethylamine described in step 4) and mixed liquor volume ratio are as follows: 1:20-68.
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