CN110368992A - A kind of preparation method of metal-organic framework elctro-catalyst - Google Patents
A kind of preparation method of metal-organic framework elctro-catalyst Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 12
- 238000011978 dissolution method Methods 0.000 claims abstract description 3
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical class [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 150000003639 trimesic acids Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims 1
- 239000013384 organic framework Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000006258 conductive agent Substances 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 238000004070 electrodeposition Methods 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of metal-organic framework elctro-catalyst, it is characterized by: first on conductive substrates using one layer of metal nanoparticle layer of flexible conductive substrates that obtain that treated, metal-organic framework material layer is directly grown in conductive substrates by Anodic dissolution method again, obtain the elctro-catalyst, wherein, the metal nanoparticle layer with a thickness of the nm of 100 nm~500.The present invention is grown directly upon MOFs material in any conductive substrates as elctro-catalyst, avoids the use of binder and conductive agent, can improve its catalytic performance to a certain extent by using two-step electrochemical sedimentation.
Description
Technical field
The present invention relates to a kind of preparation methods of thin-film material, and in particular to a kind of system of metal organic frame thin-film material
Preparation Method.
Background technique
Hydrogen energy source one of as most promising fossil fuel alternative energy source, with its cleaning, lightweight and it is renewable and by
To more and more concerns.Evolving hydrogen reaction (HER) is a kind of method of cheap, environmental protection water crack solution production High Purity Hydrogen, is mesh
The hot spot of preceding research.How the overpotential of reaction is reduced, and a large amount of hydrogen of continuous production is two keys of present facing mankind
Problem, and this needs efficient elctro-catalyst.Pt base catalyst is most effective HER elctro-catalyst generally acknowledged in the prior art,
But available platinum based catalyst is not only expensive currently on the market, but also is easy inactivation.Therefore, exploitation catalytic activity it is high, at
This low non-noble metal-based catalysts is the task of top priority for mass production hydrogen.
Metal organic framework (MOFs) sill has the characteristics that high porosity, high surface area and single dispersion metal unit,
Be widely used in gas storage with separate, energy storage and the fields such as conversion system and elctro-catalyst.Chinese invention patent
CN105289733A discloses a kind of preparation method based on metal organic framework compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent, and copper acetate is molten
Ultrasound after liquid is mixed with trimesic acid solution, product obtain Cu-MOF@Nafion liberation of hydrogen after mixing in proportion with organic solvent
Catalyst.However, the catalyst that the program obtains is the liquid containing organic solvent, it is only used for addition in the electrolytic solution, and
It cannot be used for preparing cathode catalysis material.
MOFs is to be coordinated the crystalline, porous material formed by organic ligand and metal ion or cluster.Organic ligand makes MOFs
It is easy to modify, but also makes the intrinsic conductivity of most of MOF materials poor, seriously hinders MOF material and urged directly as liberation of hydrogen
Agent uses.It can be effective by the way that MOF material is converted into the methods of transition metal oxide, phosphide, sulfide, selenides
The chemical property of ground improvement material.But in calcination process, the high-specific surface area of material and the active site of high dispersive can
It can lose.Overcome MOFs poorly conductive without another available strategy of calcining be added conductive material, as acetylene black, carbon are received
Mitron, graphene/graphene oxide or metal nanoparticle.However, due to size exclusion effect and binder or conductive agent
Addition, the partial charge transfer in MOFs nevertheless suffers from limitation.
To solve the above problems, a kind of consider to be directly to prepare metal-organic framework materials film in conductive material surface,
But will form different interface resistances for different conductive materials, between MOFs and conductive substrates, in the prior art, need
To select specific conductive material as conductive substrates through a large number of experiments, could obtain the material compared with low interfacial resistance with
In cathode electrode.
Summary of the invention
Goal of the invention of the invention is to provide a kind of preparation method of metal-organic framework elctro-catalyst, realizes in office
Metal-organic framework electrocatalyst materials are prepared in meaning conductive substrates.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of metal-organic framework electro-catalysis
It is conductive first using one layer of metal nanoparticle layer of flexible to obtain that treated on conductive substrates for the preparation method of agent
Substrate, then metal-organic framework material layer is directly grown in conductive substrates by Anodic dissolution method, obtain institute
State elctro-catalyst, wherein the metal nanoparticle layer with a thickness of 100nm~500nm.
In above-mentioned technical proposal, by the setting of metal nanoparticle layer, the boundary between MOFs and conductive substrates is reduced
Surface resistance directly improves its electric conductivity, and material of the invention is used directly as cathode electrode.
Preferred technical solution, the metal nanoparticle layer are made of copper nano particles, and the partial size of copper nano particles is
100nm~500nm.
In above-mentioned technical proposal, the preparation method of metal nanoparticle layer is to carry out copper nanometer using three-electrode system
The deposition of grain, using Ag/AgCl as reference electrode, Pt piece is to electrode, and working electrode is conductive substrates, and electrolyte solution is
CuCl2With the mixed aqueous solution of KCl.
In above-mentioned technical proposal, the s of 300 s~800 is deposited under the voltage of -0.2 V of V~-0.5.Preferably, -0.4
500 s are deposited under the voltage of V.
In above-mentioned technical proposal, the method for growth metal-organic framework material layer is, using Ag/AgCl as reference electricity
Pole, Pt piece are to electrode, and working electrode is conductive substrates, and electrolyte solution is 20~40 mM trimesic acids, 20~40 mM
Tetrabutylammonium perchlorate, the volume ratio of second alcohol and water is 3:1 in solution；The s of 100 s~300 is deposited under the voltage of the V of 0V~1,
Obtain HKUST-1, as metal-organic framework material layer；It is subsequently placed into 6 h~12 in 60 DEG C~120 DEG C of vacuum drying oven
h。
Preferred technical solution, electrolyte solution are 25 mM trimesic acids, 25 mM tetrabutylammonium perchlorates, solution
The volume ratio of middle second alcohol and water is 3:1；100 s are deposited under the voltage of 1 V, obtain HKUST-1, as metal organic frame knot
Structure material layer；It is subsequently placed into 12 h in 120 DEG C of vacuum drying oven.
In above-mentioned technical proposal, metal-organic framework material layer with a thickness of 500nm~800nm.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1, the present invention allows MOFs material to be grown directly upon any conductive substrates by using two-step electrochemical sedimentation
On, as elctro-catalyst, the use of binder and conductive agent is avoided, its catalytic performance can be improved to a certain extent.
2, product of the invention can also be effectively prevented active material under conditions of current density is big, gas evolution is violent
Removing provides a kind of easy-to-use method to prepare efficient, low cost MOFs base electrocatalyst materials.
3, the electrocatalyst materials that the present invention obtains can be directly as cathode electrode for evolving hydrogen reaction.
4, the thickness of metal nanoparticle only has several hundred nanometers in the present invention, is covered on carbon paper surface than relatively thin one layer,
So that metallic is converted directly into MOF material in subsequent, it is grown directly upon on carbon paper, carbon paper directly plays electric action；
Compared with the scheme that metallic substrates are directly converted into MOF material in the prior art, substrate can be any kind in the present invention
The collectors such as conductive material, such as carbon paper, nickel screen, and the MOF material being synthesized is Nano grade, is more advantageous to electricity
Catalysis reaction.
Detailed description of the invention
Fig. 1 is the SEM image of copper nano-particle and HKUST-1 particle deposition on carbon paper in embodiment one；Wherein, (a-
C) copper nano-particle is electroplated；(d) electro-deposition HKUST-1；(e-f) 1 particle of HKUST- individually amplified；
Fig. 2 is the SEM image of comparative example one；(a) HKUST-1 of hydro-thermal method preparation；(b) the HKUST-1 particle individually amplified；
The SEM image of Fig. 3 copper nano-particle and HKUST-1 particle deposition on nickel screen；Wherein, (a-c) electro-coppering nanoparticle
Son；(d-e) electro-deposition HKUST-1；(f) 1 particle of HKUST- individually amplified；
The SEM image of Fig. 4 copper nano-particle and HKUST-1 particle deposition on stainless (steel) wire；Wherein, (a-c) electro-coppering nanometer
Particle；(d-e) electro-deposition HKUST-1；(f) 1 particle of HKUST- individually amplified；
Fig. 5 is HER polarization curve；
Fig. 6 is corresponding Tafel figure；
Fig. 7 and Fig. 8 be current potential be 0.425V~0.625V when, hydro-thermal HKUST-1 and electro-deposition HKUST-1 are in different scanning rates
Under cyclic voltammogram；
Fig. 9 is the electric double layer capacitance of hydro-thermal HKUST-1 and electro-deposition HKUST-1；
Figure 10 is electro-deposition HKUST-1 and hydro-thermal HKUST-1 in 0.5M H2SO4In durability measurement；
Figure 11 is the electrochemical impedance spectroscopy of electro-deposition HKUST-1 and hydro-thermal HKUST-1 in embodiment one；
Figure 12 is the corresponding equivalent circuit of electro-deposition.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and embodiments:
Embodiment one: HKUST-1 metal-organic framework elctro-catalyst is prepared on carbon paper.
(1) copper nano particles are deposited with Autolab electrochemical workstation:
Using three-electrode system, using Ag/AgCl as reference electrode, Pt piece is to electrode, and working electrode is 1 × 2 cm2Carbon paper.
Electrolyte solution is 5 mM CuCl2, the deionized water of 0.1 M KCl and 100 mL deposits 500 under the voltage of -0.4 V
s。
Referring to attached drawing 1, (a, b, c) is it can be seen that copper nano-particle is equably plated on carbon paper from Fig. 1.
(2) under same electrode, electrolyte solution is changed to 25 mM H3BTC(trimesic acid), 25 mM
BTAP(tetrabutylammonium perchlorate), the volume ratio of second alcohol and water is 3:1 in solution.100 s are deposited under the voltage of 1 V, are obtained
HKUST-1。
It is subsequently placed into 12 h in 120 DEG C of vacuum drying oven.
Referring to attached drawing 1, from Fig. 1 d) it can be seen that HKUST-1 is deposited on carbon paper, e, f) be single HKUST-1
Grain, it can be seen that size only has 500 nm or so.
Comparative example one: HKUST-1 is prepared using traditional hydro-thermal method, detailed process is as follows:
By 5 mM CuCl2With 25 mM H3BTC is dissolved in second alcohol and water (ratio 3:1), then 180 DEG C of 24 h of hydro-thermal are set
In 120 DEG C of 12 h of vacuum drying oven.
A) and b) be the HKUST-1 and single HKUST-1 particle enlarged drawing of hydro-thermal in Fig. 2, in comparison diagram 1 e) and
F), it can be found that the size for the HKUST-1 that hydrothermal synthesis goes out is micron-sized, and the HKUST-1 size that electro-deposition is synthesized
Only several hundred nanometers.
The SEM image of Fig. 3 copper nano-particle and HKUST-1 particle deposition on nickel screen
(a-c) copper nano-particle is electroplated；(d-e) electro-deposition HKUST-1;(f) 1 particle of HKUST- individually amplified.
The SEM image of Fig. 4 copper nano-particle and HKUST-1 particle deposition on stainless (steel) wire
(a-c) copper nano-particle is electroplated；(d-e) electro-deposition HKUST-1;(f) 1 particle of HKUST- individually amplified.
As can be seen that substrate is changed to nickel screen and stainless (steel) wire from Fig. 3 and Fig. 4, HKUST-1 still can be synthesized, and
Individual particle is having a size of Nano grade.
Fig. 5 and Fig. 6 be electro-deposition HKUST-1, the HKUST-1 of hydro-thermal and three kinds of samples of pure carbon paper Hydrogen Evolution Performance curve and
Corresponding Tafel curve, what the HKUST-1 Hydrogen Evolution Performance that as can be seen from the figure electro-deposition is prepared was prepared than hydro-thermal
HKUST-1 performance is good, and Tafel slope is lower, and liberation of hydrogen overpotential probably reduces 100 mV or so.Fig. 7 is hydro-thermal HKUST-1
Electrochemical surface area figure, Fig. 8 are electro-deposition HKUST-1 electrochemical surface area, it can be seen that the electrification of electro-deposition HKUST-1
Learn active area it is bigger than the electrochemical surface area of hydro-thermal HKUST-1, and in Fig. 9 electro-deposition HKUST-1 electric double layer capacitance
It is also bigger than the electric double layer capacitance of hydro-thermal HKUST-1.Figure 10 is stability test, it is found that the stability of electrochemical deposition is obviously excellent
In the material of hydro-thermal.
Figure 11 is the electrochemical impedance spectroscopy of electro-deposition HKUST-1 and hydro-thermal HKUST-1, and Figure 12 is corresponding equivalent circuit.
Resistance value such as the following table 1 of corresponding EIS spectrum fitting each element of equivalent circuit.
| HKUST-1 electro-deposition | HKUST-1 HT hydro-thermal | |
| Rs (Ω) | 1.65 | 1.80 |
| Rf (Ω) | 30.90 | 66.20 |
| Rct (Ω) | 98.35 | 126.30 |
The R of electro-deposition HKUST-1 as can be seen from Table 1f、RctR than hydro-thermal HKUST-1f、RctWant small (RfFor catalysis
Agent resistance, RctFor Charge-transfer resistance).
Claims (8)
1. a kind of preparation method of metal-organic framework elctro-catalyst, it is characterised in that: first on conductive substrates using electricity
Conductive substrates that one layer of metal nanoparticle layer of deposition method obtains that treated, then by Anodic dissolution method in conduction
Metal-organic framework material layer is directly grown in substrate, obtains the elctro-catalyst, wherein the metal nanoparticle layer
With a thickness of 100nm~500nm.
2. the preparation method of metal-organic framework elctro-catalyst according to claim 1, it is characterised in that: the metal
Nanoparticle layers are made of copper nano particles, and the partial size of copper nano particles is the nm of 100 nm~500.
3. the preparation method of metal-organic framework elctro-catalyst according to claim 2, it is characterised in that: metal nano
The preparation method of particle layer is that the deposition of copper nano particles, using Ag/AgCl as reference electrode, Pt are carried out using three-electrode system
Piece is to electrode, and working electrode is conductive substrates, and electrolyte solution is CuCl2With the mixed aqueous solution of KCl.
4. the preparation method of metal-organic framework elctro-catalyst according to claim 3, it is characterised in that: -0.2
The s of 300 s~800 is deposited under the voltage of the V of V~-0.5.
5. the preparation method of metal-organic framework elctro-catalyst according to claim 4, it is characterised in that: -0.4
500 s are deposited under the voltage of V.
6. the preparation method of metal-organic framework elctro-catalyst according to claim 1, it is characterised in that: growth metal
The method of organic framework material layer is, using Ag/AgCl as reference electrode, Pt piece is to electrode, and working electrode is conductive base
Bottom, electrolyte solution are 20~40 mM trimesic acids, 20~40 mM tetrabutylammonium perchlorates, second alcohol and water in solution
Volume ratio is 3:1；The s of 100s~300 is deposited under the voltage of the V of 0 V~1, obtains HKUST-1, as metal organic frame knot
Structure material layer；The dry h of 6 h~12 is subsequently placed into 60 DEG C~120 DEG C of vacuum drying oven.
7. the preparation method of metal-organic framework elctro-catalyst according to claim 6, it is characterised in that: electrolyte is molten
Liquid is 25 mM trimesic acids, and 25 mM tetrabutylammonium perchlorates, the volume ratio of second alcohol and water is 3:1 in solution；In the electricity of 1 V
Pressure 100 s of deposition, obtain HKUST-1, as metal-organic framework material layer；It is subsequently placed into 120 DEG C of vacuum drying oven
In 12 h.
8. the preparation method of metal-organic framework elctro-catalyst according to claim 1, it is characterised in that: metal is organic
Frame structure material layer with a thickness of 500nm~800nm.
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