CN110038634B - Oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and synthesis method thereof - Google Patents
Oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and synthesis method thereof Download PDFInfo
- Publication number
- CN110038634B CN110038634B CN201910373344.XA CN201910373344A CN110038634B CN 110038634 B CN110038634 B CN 110038634B CN 201910373344 A CN201910373344 A CN 201910373344A CN 110038634 B CN110038634 B CN 110038634B
- Authority
- CN
- China
- Prior art keywords
- mxene
- oxygen evolution
- evolution reaction
- catalyst
- mofs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 66
- 239000001301 oxygen Substances 0.000 title claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000003054 catalyst 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 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 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
- 239000002060 nanoflake Substances 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 30
- 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 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
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 238000010189 synthetic method Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-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
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000010411 electrocatalyst Substances 0.000 abstract 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000011943 nanocatalyst Substances 0.000 description 20
- 229910000510 noble metal Inorganic materials 0.000 description 12
- 239000002905 metal composite material Substances 0.000 description 9
- 239000002135 nanosheet Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 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
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy 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
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002505 iron Chemical class 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
- 239000000203 mixture Substances 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
- 229910052697 platinum Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 229910003289 NiMn Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 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
- 150000003841 chloride salts Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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
An oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and a synthesis method thereof belong to the field of nano materials, energy and catalysis. The catalyst consists of MXene two-dimensional nano flakes with MOFs nano particles uniformly loaded on the surfaces, and has a two-dimensional structure. The preparation method comprises the following steps: MXene, metal salt, organic ligand and an acid-binding agent are dissolved and mixed uniformly, and then centrifugation, washing and vacuum drying are carried out to obtain the electrocatalyst with the two-dimensional nano structure, the structure and the components of which can be finely regulated and controlled. The electrocatalyst obtained by the invention can effectively overcome the fundamental problem that the catalytic performance of the oxygen evolution reaction cannot be exerted due to poor conductivity and poor stability of MOFs; the obtained catalyst shows excellent catalytic activity and stability for oxygen evolution reaction in alkaline electrolyte, and lays a foundation for wide application of new energy technologies such as fuel cells, metal air cells, electrolyzed water and the like.
Description
Technical Field
The invention belongs to the field of nano materials, energy and catalysis, and relates to an oxygen evolution reaction catalyst based on a MXene and metal organic framework compound composite structure and a synthesis method thereof.
Background
Fuel cells, metal air cells, electrolytic water, etc. which use Oxygen Evolution Reaction (OER) as a core reaction are one of the most promising new renewable energy storage and conversion technology systems at present. The oxygen evolution reaction involves a four-electron transfer process, the reaction energy barrier is high, the process kinetic rate is slow, and a high-efficiency catalyst needs to be used to improve the energy conversion efficiency. RuO2And IrO2Etc. are the best active catalysts at present, but the scarce resources and high costs limit their scaleAnd (5) chemical application. The development of cheap, efficient and stable non-noble metal oxygen evolution reaction catalyst is one of the key bottleneck problems for promoting the new energy technologies such as fuel cells, metal air cells, water electrolysis and the like to be practically applied.
Metal-Organic Frameworks (MOFs) are a class of three-dimensional ordered network porous crystal materials formed by transition Metal ions and Organic ligands through coordination bonds, and have the advantages of high porosity, large specific surface area, adjustable pore diameter and the like. The high controllability of metal central elements and organic ligands in the MOFs structure on the chemical composition endows the MOFs structure with various unique properties, and the MOFs structure has wide application prospects in the fields of energy storage and conversion, catalysis, sensors, gas separation and the like. However, the application of MOFs in the field of electrochemical catalysis is still greatly limited by its poor electrical conductivity and structural stability, and the development of high-performance oxygen evolution reaction catalysts based on MOFs still faces a great challenge.
MXene is a new kind of two-dimensional crystal material of transition metal carbide or nitride. Having the chemical formula Mn+1XnTx(n ═ 1, 2, 3, M is a transition metal element, X is a carbon or nitrogen element, and T is a chemical group), can be obtained by selective etching of the phase of the laminar ceramic material MAX. MXene surface is rich in active chemical functional groups such as-OH, -F, -O and the like, and simultaneously has excellent conductivity of metalloid, so that MXene can be expected to be used as an ideal conductive and active matrix to comprehensively improve the conductivity and the reaction activity of MOFs materials, and the creation and controllable construction of a new structure and high-performance oxygen evolution reaction catalyst based on MOFs are realized.
Disclosure of Invention
Aiming at the defects of poor conductivity, poor structural stability and the like of MOFs, the invention provides an oxygen evolution reaction catalyst based on an MXene and MOFs composite structure and a synthesis method thereof, and the prepared catalyst consists of MXene two-dimensional nano sheets with MOFs nano particles uniformly loaded on the surfaces. The introduction of the high-conductivity MXene and the uniform loading of the MOFs nano thin layer on the MXene surface overcome the fundamental problem that the catalytic performance of the oxygen evolution reaction cannot be exerted due to poor conductivity and poor stability of the MOFs, and the obtained catalyst shows excellent catalytic activity and stability in the electrochemical oxygen evolution reaction process under the alkaline condition. The synthesis method is green and environment-friendly, low in energy consumption, easy to control and universal, and can be used for large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that:
an oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound is composed of MXene two-dimensional nano sheets with MOFs nano particles uniformly loaded on the surfaces, has a two-dimensional structure, and has the size of between 100 and 500 nm; the content of MOFs nano particles loaded on MXene is more than 75 wt%, the size of the MOFs nano particles is 10-100nm, and metal elements in the MOFs comprise at least one or more of nickel, iron, cobalt and manganese. The obtained catalyst has excellent catalytic activity and stability for oxygen evolution reaction under alkaline condition.
A synthetic method of an oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound comprises the following steps:
1) MXene was dispersed in water at normal temperature and pressure to prepare a dispersion.
The concentration of the MXene dispersion liquid is 5-15mg mL-1。
2) Dissolving metal salt and organic ligand in a mixed solvent of N, N-Dimethylformamide (DMF) and ethanol at normal temperature and pressure to form a uniform solution.
The molar ratio of the metal salt to the organic ligand is 1:1, and the concentration of the organic ligand is 0.0375-0.04 mol/L.
The organic ligand is at least one of terephthalic acid and 2-amino terephthalic acid.
In the mixed solvent, the volume ratio of DMF to ethanol is 5:1-15: 1.
The metal salt is one, any two or any three combination of nickel salt, iron salt, cobalt salt and manganese salt, wherein the nickel salt, the iron salt, the cobalt salt and the manganese salt all comprise chloride salt, nitrate and acetate. When two metal salts are used, the molar ratio of the two different cationic metal salts is from 5:1 to 1: 5; when three metal salts are used, the molar ratio of the three different cationic metal salts is 1:1: 1.
3) Uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand uniform solution prepared in the step 2) at normal temperature and normal pressure.
4) Adding triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, stirring and reacting for 2-4h, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
The volume ratio of the triethylamine to the mixed solution is as follows: 1:20-68.
Compared with the prior art, the invention solves the problems of preparation and application of the MOFs-based oxygen evolution reaction catalyst, and has the following beneficial effects:
1) MXene with excellent metalloid conductivity is introduced to remarkably improve the conductivity of MOFs, so that the catalytic activity of the MOFs on oxygen evolution reaction is fully exerted.
2) MXene chemical coupling with rich surface active chemical functional groups is introduced, MOFs is efficiently and stably stabilized, and the obtained composite nano-catalyst has excellent catalytic stability.
3) MXene with a two-dimensional nanostructure is introduced to be combined with the MOFs nanostructure, and the obtained two-dimensional nanostructure composite nano catalyst has an electrode-electrolyte-oxygen three-phase reaction interface and an electrochemical reaction active surface area which are larger than those of a block MOFs material, and exposes more catalytic reaction active sites, so that the catalytic reaction activity of the composite nano catalyst is synergistically improved.
4) The invention can realize the fine regulation and control of the microstructure, the chemical composition and the like of the oxygen evolution reaction catalyst based on the MXene and MOFs composite nano structure. The process is simple, environment-friendly and easy for large-scale production, and has wide application prospect in the fields of energy storage and conversion application such as fuel cells, full-electrolysis water, metal-air batteries and the like.
Drawings
FIG. 1 is a scanning electron microscope photomicrograph of a non-noble metal composite nano-catalyst based on MXene and NiFe-BDC MOFs prepared in example 1 of the invention;
FIG. 2 is a TEM photograph of MXene and NiFe-BDC MOFs-based non-noble metal composite nanocatalysts prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope photomicrograph of a non-noble metal composite nanocatalyst based on MXene and NiCo-BDC MOFs prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope photomicrograph of a non-noble metal composite nanocatalyst based on MXene and NiMn-BDC MOFs prepared in example 3 of the present invention;
FIG. 5 is a scanning electron microscope photomicrograph of a non-noble metal composite nanocatalyst based on MXene and NiFeMn-BDC MOFs prepared in example 5 of the present invention;
FIG. 6 is the characterization of the catalytic activity of the non-noble metal composite nano-catalyst based on MXene and NiFe-BDC MOFs prepared in example 1 of the present invention on oxygen evolution reaction and its reaction with commercial RuO2Comparing the activity of the catalysts;
FIG. 7 is a graph of MXene and NiFe-BDC MOFs-based non-noble metal composite nanocatalysts prepared in example 1 of the present invention for stability characterization of oxygen evolution reaction and its reaction with commercial RuO2Comparison of catalyst stability.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution of the present invention, and further explains the technical solution, the implementation process and the principle, etc. as follows. It is to be understood, however, that within the scope of the present invention, each of the above-described features of the present invention and each of the features described in detail below (examples) may be combined with each other to form new or preferred embodiments.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation method of composite nanocatalyst based on MXene and NiFe-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of 10 mg/mL solution-1The dispersion of (1);
2)1.0mmol of nickel acetate, 0.2mmol of ferric nitrate and 1.2mmol of terephthalic acid are dissolved in 30mL of N, N-Dimethylformamide (DMF) and 2mL of ethanol at normal temperature and pressure to form a uniform solution;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 0.8mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 2 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 100-500nm loaded with NiFe-based MOFs nanoparticles having a size of about several nanometers with a loading of about 88.0 wt.%.
Example 2 preparation method of composite nanocatalyst based on MXene and NiCo-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of 5 mg/mL solution-1The dispersion of (1);
2) dissolving 0.6mmol of nickel chloride, 0.6mmol of cobalt chloride and 1.2mmol of terephthalic acid in 30mL of N, N-Dimethylformamide (DMF) and 2mL of ethanol at normal temperature and pressure to form a uniform solution;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 0.5mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 2 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nano-sheets with the average size of about 100-500nm and loaded with NiCo-based MOFs nanoparticles with the size of about several nanometers and the loading of about 94.0 wt.% are obtained.
Example 3 preparation method of composite nanocatalyst based on MXene and NiMn-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of solution with a concentration of 15mg mL-1The dispersion of (1);
2) dissolving 0.2mmol of nickel acetate, 1.0mmol of manganese nitrate and 1.2mmol of terephthalic acid in 28mL of N, N-Dimethylformamide (DMF) and 4mL of ethanol at normal temperature and pressure to form a uniform solution;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 1.0mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 4 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 100-500nm loaded with NiMn-based MOFs nanoparticles having a size of about several nanometers with a loading of about 80.0 wt.%.
Example 4 preparation of composite nanocatalysts based on MXene and Ni-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of solution with a concentration of 15mg mL-1The dispersion of (1);
2)1.2mmol of nickel chloride and 1.2mmol of terephthalic acid are dissolved in 28mL of N, N-Dimethylformamide (DMF) and 4mL of ethanol at normal temperature and pressure to form a uniform solution;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 1.0mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 3 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 100-500nm loaded with Ni-based MOFs nanoparticles having a size of about several nanometers with a loading of about 78.0 wt.%.
Example 5 preparation of composite nanocatalysts based on MXene and NiFeMn-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of 10 mg/mL solution-1The dispersion of (1);
2)0.4mmol of nickel acetate, 0.4mmol of ferric chloride, 0.4mmol of manganese nitrate and 1.2mmol of terephthalic acid were dissolved in 25mL of N, N-Dimethylformamide (DMF) and 5mL of ethanol at normal temperature and pressure to form a uniform solution.
3) Uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 1.5mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 4 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 150-500nm loaded with NiFeMn-based MOFs nanoparticles having a size of about several nanometers with a loading of about 92.0 wt.%.
Example 6 based on MXene and NiFe-BDC-NH2Preparation method of MOFs composite nano-catalyst
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of 10 mg/mL solution-1The dispersion of (1);
2)1.0mmol of nickel acetate, 0.2mmol of ferric nitrate and 1.2mmol of 2-amino terephthalic acid were dissolved in 30mL of N, N-Dimethylformamide (DMF) and 2mL of ethanol at room temperature under normal pressure to form a homogeneous solution.
3) Uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 1.0mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 3 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 100-500nm loaded with NiFe-based MOFs nanoparticles having a size of about several nanometers with a loading of about 89.0 wt.%.
FIG. 6 is the characterization of the catalytic activity of the non-noble metal composite nano-catalyst based on MXene and NiFe-BDC MOFs prepared in example 1 of the present invention on oxygen evolution reaction and its reaction with commercial RuO2Comparison of catalyst activity. The test is carried out in a three-electrode system, 1M KOH is used as electrolyte, and a working electrode is loadedThe composite nano catalyst based on MXene and NiFe-BDC MOFs comprises an Ag/AgCl electrode as a reference electrode, a platinum sheet as a counter electrode and a scanning rate of 10mV s-1The electrochemical workstation was CHI 760E. As can be seen, the catalyst obtained by the invention only needs 268mV overpotential to reach 10mA cm-1Current density of (2), while RuO is commercialized2The overpotential required for the catalyst to reach the same current density was 378 mV. Therefore, the catalytic activity of the catalyst obtained by the invention on oxygen evolution reaction in alkaline electrolyte is superior to that of commercial noble metal RuO2A catalyst.
FIG. 7 is a graph of MXene and NiFe-BDC MOFs-based non-noble metal composite nanocatalysts prepared in example 1 of the present invention for stability characterization of oxygen evolution reaction and its reaction with commercial RuO2Comparison of catalyst stability. The test is carried out in a three-electrode system, 1M KOH is used as electrolyte, a working electrode is loaded with a composite nano catalyst based on MXene and NiFe-BDC MOFs, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the scanning rate is 10mV s-1The electrochemical workstation was CHI 760E. As can be seen from the figure, the catalyst obtained by the invention has the current density of 10mA cm-1While the voltage can be kept stable for 23h, RuO is commercialized2The catalyst rapidly rises in voltage under the same current density, and becomes invalid after 3 hours. Therefore, the stability of the catalyst obtained by the invention on oxygen evolution reaction in alkaline electrolyte is better than that of commercial noble metal RuO2A catalyst.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A synthetic method of an oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound is characterized by comprising the following steps:
1) dispersing MXene in water at normal temperature and pressure to prepare a dispersion liquid;
2) dissolving metal salt and organic ligand in a mixed solvent of N, N-dimethylformamide DMF and ethanol at normal temperature and pressure to form a uniform solution; the molar ratio of the metal salt to the organic ligand is 1:1, and the concentration of the organic ligand is 0.0375-0.04 mol/L; the organic ligand is at least one of terephthalic acid and 2-amino terephthalic acid; the metal salt is at least one or more than two of chloride, nitrate and acetate of nickel, iron, cobalt and manganese;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand uniform solution prepared in the step 2) at normal temperature and normal pressure;
4) adding triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, stirring and reacting for 2-4h, centrifugally washing by using ethanol after the reaction is finished, and drying in vacuum to obtain a product.
2. The method for synthesizing the catalyst for oxygen evolution reaction based on the compound structure of MXene and metal organic framework compound of claim 1, wherein the concentration of MXene dispersion in step 1) is 5-15mg mL-1。
3. The method for synthesizing the catalyst for oxygen evolution reaction based on the composite structure of MXene and metal organic framework compound according to claim 1, wherein the volume ratio of DMF and ethanol in the mixed solvent of step 2) is 5:1-15: 1.
4. The method for synthesizing the catalyst for oxygen evolution reaction based on the compound structure of MXene and metal organic framework compound as claimed in claim 1, wherein in step 2), when two metal salts are used, the molar ratio of two different cationic metal salts is 5:1-1: 5; when three metal salts are used, the molar ratio of the three different cationic metal salts is 1:1: 1.
5. The method for synthesizing the catalyst for oxygen evolution reaction based on the composite structure of MXene and metal organic framework compound according to claim 1, wherein the volume ratio of the triethylamine in the step 4) to the mixed solution is as follows: 1:20-68.
6. An oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound, which is obtained by the synthesis method of any one of claims 1 to 5, wherein the catalyst consists of MXene two-dimensional nano flakes with MOFs nano particles uniformly loaded on the surface, has a two-dimensional structure, and has the size of 100-500 nm; the content of MOFs nano particles loaded on MXene is more than 75 wt%, the size of the MOFs nano particles is 10-100nm, and metal elements in the MOFs comprise at least one or more of nickel, iron, cobalt and manganese; the obtained catalyst has excellent catalytic activity and stability for oxygen evolution reaction under alkaline condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910373344.XA CN110038634B (en) | 2019-05-07 | 2019-05-07 | Oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910373344.XA CN110038634B (en) | 2019-05-07 | 2019-05-07 | Oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110038634A CN110038634A (en) | 2019-07-23 |
| CN110038634B true CN110038634B (en) | 2021-11-05 |
Family
ID=67280981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910373344.XA Active CN110038634B (en) | 2019-05-07 | 2019-05-07 | Oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110038634B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589786A (en) * | 2019-10-16 | 2019-12-20 | 大连理工大学 | Based on three-dimensional porous transition metal carbide Ti3C2MXene composite nano structure and general preparation method thereof |
| CN111151304A (en) * | 2020-02-26 | 2020-05-15 | 吴晓峰 | Preparation of three-dimensional MXene/MOF hydrogel and application thereof in water treatment |
| CN111883745B (en) * | 2020-06-15 | 2023-10-17 | 辽宁科技大学 | MOF/MXene/CF composite nano-sheet and synthesis method thereof |
| CN111872600B (en) * | 2020-07-08 | 2021-06-08 | 中国矿业大学 | MOFs carbonized product, preparation method and application in lead-free solder modification |
| CN112670524B (en) * | 2020-09-04 | 2022-09-27 | 华中科技大学 | Ultrathin flexible air battery electrode material, lithium air battery and preparation method thereof |
| CN112251193A (en) * | 2020-09-25 | 2021-01-22 | 同济大学 | Composite wave-absorbing material based on MXene and metal organic framework and preparation method and application thereof |
| CN112321858B (en) * | 2020-10-22 | 2022-07-26 | 河北工业大学 | Method for macroscopic quantity preparation of MOFs nanosheets with oxygen evolution performance |
| CN112680746B (en) * | 2020-11-26 | 2022-07-12 | 大连理工大学 | ZIF-67@ MXene composite material, and preparation method and application thereof |
| CN112635738B (en) * | 2020-12-22 | 2021-09-21 | 江西理工大学 | Preparation method of FeNiP/C @ MXene composite anode material for lithium ion battery |
| CN113130923B (en) * | 2021-04-15 | 2022-10-11 | 北京师范大学 | Preparation method and application of two-dimensional porous carbon supported catalyst |
| CN114011261B (en) * | 2021-10-28 | 2022-09-06 | 大连理工大学 | General method for enhancing stability of MXene aqueous solution |
| CN114700097B (en) * | 2022-05-17 | 2023-01-06 | 南京大学 | Fe 2 O 3 -MXenes composite catalyst and preparation method and application thereof |
| CN115400796B (en) * | 2022-08-02 | 2023-08-18 | 华南理工大学 | Two-dimensional nickel-based metal organic framework catalyst and preparation method and application thereof |
| CN115193482A (en) * | 2022-08-08 | 2022-10-18 | 江苏盛剑环境设备有限公司 | Composite catalyst, preparation method and application thereof |
| CN115895394B (en) * | 2023-01-09 | 2023-05-23 | 广东腐蚀科学与技术创新研究院 | Interface passivation type heavy-duty anticorrosive powder coating and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106513056A (en) * | 2016-11-28 | 2017-03-22 | 南京工业大学 | Preparation method of hybrid material, hybrid material and application of hybrid material |
| CN108660473A (en) * | 2018-05-17 | 2018-10-16 | 大连理工大学 | A kind of electrolytic seawater catalyst for preparing hydrogen and its synthetic method based on MXene Yu transition metal carbide composite nanostructure |
-
2019
- 2019-05-07 CN CN201910373344.XA patent/CN110038634B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106513056A (en) * | 2016-11-28 | 2017-03-22 | 南京工业大学 | Preparation method of hybrid material, hybrid material and application of hybrid material |
| CN108660473A (en) * | 2018-05-17 | 2018-10-16 | 大连理工大学 | A kind of electrolytic seawater catalyst for preparing hydrogen and its synthetic method based on MXene Yu transition metal carbide composite nanostructure |
Non-Patent Citations (2)
| Title |
|---|
| Interdiffusion Reaction-Assisted Hybridization of Two-Dimensional Metal-Organic Frameworks and Ti3C2Tx Nanosheets for Electrocatalytic Oxygen Evolution;Li Zhao等;《ACS Nano》;20170517;第11卷;第5800-5807页 * |
| Metal-Organic Framework-Derived Nickel-Cobalt Sulfide on Ultrathin Mxene Nanosheets for Electrocatalytic Oxygen Evolution;Haiyuan Zou等;《ACS Appl. Mater. Interfaces》;20180611;第10卷;第22311-22319页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110038634A (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110038634B (en) | Oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and synthesis method thereof | |
| Siwal et al. | Electrocatalysts for electrooxidation of direct alcohol fuel cell: chemistry and applications | |
| Zhan et al. | Synthesis of mesoporous NiCo2O4 fibers and their electrocatalytic activity on direct oxidation of ethanol in alkaline media | |
| Cui et al. | Efficient multifunctional electrocatalyst based on 2D semiconductive bimetallic metal-organic framework toward non-Pt methanol oxidation and overall water splitting | |
| CN105514450B (en) | Nitrogen-doped graphene/difunctional VPO catalysts of ferronickel houghite and its preparation method and application | |
| CN108899558B (en) | PtCo/C electrocatalyst and preparation method thereof | |
| Kakaei et al. | Fabrication of Pt–CeO2 nanoparticles supported sulfonated reduced graphene oxide as an efficient electrocatalyst for ethanol oxidation | |
| CN100445207C (en) | Flower structure nano cerium oxide base composite material and its preparing method and use | |
| El-Deeb et al. | Effect of pore geometry on the electrocatalytic performance of nickel cobaltite/carbon xerogel nanocomposite for methanol oxidation | |
| Shi et al. | FeNi-functionalized 3D N, P doped graphene foam as a noble metal-free bifunctional electrocatalyst for direct methanol fuel cells | |
| CN102723504B (en) | Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method | |
| CN105618060A (en) | Bi-functional oxygen catalyst for graphene/nickel iron type hydrotalcite as well as preparation method and application thereof | |
| CN109201103A (en) | A kind of full electrolysis water catalyst of monolithic porous economic benefits and social benefits base metal and synthetic method | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN103495432A (en) | Method for preparing efficient stable fuel cell catalyst | |
| CN110767914B (en) | Co-N doped porous carbon-coated carbon nanotube core-shell structure catalyst and preparation method and application thereof | |
| CN112349921B (en) | Nitrogen-doped graphene hollow sphere catalyst, preparation method and application | |
| CN111744519A (en) | Preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst | |
| CN105977501B (en) | A kind of high-performance hydrogen reduction MnO2-Mn3O4/ carbon nano tube composite catalyst and its preparation method and application | |
| CN107829107A (en) | A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application | |
| CN114522706A (en) | Carbide-supported noble metal monatomic catalyst, and preparation and application thereof | |
| CN104607186B (en) | Multiwalled carbon nanotube-loaded PdSn catalyst based on deep eutectic solvent, and preparation method and application of catalyst | |
| CN103143348A (en) | Preparation method of Pd(alpha)Pt fuel cell catalyst for direct formic acid fuel cell | |
| CN110189922A (en) | Honeycomb nano-chip arrays cobalt acid nickel/rGO/ nickel foam and preparation method | |
| CN113638002A (en) | FeCo LDH/Ti3C2MXene/NF composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |