CN111744554A - Preparation method and application of palladium-doped organic metal framework catalytic material - Google Patents
Preparation method and application of palladium-doped organic metal framework catalytic material Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract 2
- 229920006395 saturated elastomer Polymers 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 45
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000013110 organic ligand Substances 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- 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 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052763 palladium Inorganic materials 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- 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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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a preparation method and application of a palladium-doped organic metal framework catalytic material, belonging to the field of electrochemistry, wherein the preparation method of the catalytic material comprises the following steps: synthesizing a nickel-organic metal framework by a hydrothermal method, and doping palladium into the nickel-organic metal framework by an in-situ reduction method to obtain the palladium-doped organic metal framework catalytic material, wherein the catalyst prepared by the method has the advantages of high charge transfer efficiency and excellent alkaline hydrogen evolution performance: in N2The initial potential of the catalytic material (i.e., the current density of-1 mA cm) in a saturated 1M KOH solution‑2Potential at) is shifted up to 660 mV relative to the Ni-MOF frame and the current density is-10 mA cm‑2When it is precipitatedThe hydrogen overpotential is 50 mV, which is 633 mV lower than the nickel-metal organic framework (683 mV).
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a preparation method and application of a palladium-doped organic metal framework catalytic material.
Background
With the increasing world energy consumption and environmental pollution, the development of new sustainable clean energy is urgently needed. Hydrogen energy is considered an ideal energy carrier to replace traditional fossil energy sources due to its high energy density and non-polluting nature. It is well known that hydrogen can be produced by various methods, such as electrolysis of water, chemical methods, and biological processes. Among them, the hydrogen production by water electrolysis is considered to be one of the cleanest methods and has a wide application prospect. Currently, noble metal materials, such as platinum or platinum-based materials, have proven to be the best electrocatalysts for the electrolysis of water to produce hydrogen. However, its high price and scarcity limit its practical applications. Therefore, the search for stable, cheap and efficient electrocatalysts is one of the major and difficult points of current research.
Recently developed organometallic frameworks (MOFs) have proven to be a new ideal precursor for the simple synthesis of a variety of porous carbon-based nanomaterials, with uniform and customizable porosity, high specific surface area, etc. Some MOFs-derived porous carbon-based materials have been demonstrated in many areas to be active electrocatalysts. But its poor conductivity has less application in the field of electrocatalysis. In view of the above problems, the invention of doping guest metals in MOFs to enhance the conductivity thereof and for electrocatalytic hydrogen evolution is one of the best solutions to solve the above problems.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a preparation method and application of a palladium-doped organic metal framework catalytic material; the second purpose is to provide a palladium-doped organic metal framework catalytic material; the third purpose is to provide the application of the catalytic material in electrocatalytic hydrogen evolution reaction in alkaline solution.
In order to achieve the above object, the present invention provides the following technical solutions:
1. dissolving a metal nickel source in deionized water to form a solution A, dispersing an organic ligand and a surfactant in a mixed solvent of N, N-dimethylformamide and absolute ethyl alcohol to form a solution B, uniformly mixing the solution A and the solution B, transferring the mixed solution A and the solution B to a stainless steel reaction kettle, reacting at the temperature of 180 ℃ and 220 ℃ for 8-16h, centrifuging to obtain a precipitate, washing the precipitate, and drying in vacuum to obtain a nickel-metal organic frame; the mass ratio of the metal nickel source, the organic ligand and the surfactant is 1-10:1-5: 1-5.
Taking a certain amount of nickel-organic metal framework, surfaceActive agent, palladium chloride (PdCl)2) And sodium Borohydride (BH)4Na) is sequentially added into a mixed solvent of deionized water and absolute ethyl alcohol to be uniformly dispersed under the stirring of a magnetic stirrer, then the mixture is transferred into a stainless steel reaction kettle to react for 8 to 16 hours at the temperature of 180-220 ℃, then the precipitate is centrifugally taken out, and the precipitate is washed and then dried in vacuum to obtain the palladium-doped organic metal framework catalytic material; the nickel-organometallic framework, a surfactant, palladium chloride (PdCl)2) And sodium Borohydride (BH)4Na) in a mass ratio of 200-500:1-10:0.1-1: 1-10.
Preferably, the solution A and the solution B are uniformly mixed, specifically, the solution A and the solution B are subjected to ultrasonic treatment for 10 to 60 minutes under the conditions that the ultrasonic power is 60 to 100W and the ultrasonic frequency is 20 to 40Hz, then the solution B is stirred for 10 to 20 minutes by magnetic force, finally the solution B is dripped into the solution A, and the stirring is continued for 20 to 60 minutes.
Preferably, the centrifugation is specifically performed at a speed of 8000-12000r/min for 3-5 min.
Preferably, the vacuum drying is specifically drying for 12-48h at 50-80 ℃ under 0.08-0.10 MPa.
Preferably, the metal nickel source is one of nickel chloride, nickel sulfate, nickel nitrate or nickel acetate; the organic ligand is one of trimesic acid or terephthalic acid; the surfactant is one or more of citric acid, trisodium citrate, CTAB or PVP.
2. A palladium doped organometallic framework catalytic material prepared by the method.
3. An electrochemical hydrogen evolution system comprises an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrolyte, and is characterized in that the surface of the working electrode is coated with the palladium-doped organic metal framework catalytic material.
Preferably, the working electrode is prepared as follows:
dispersing the palladium-doped organic metal framework catalytic material into water according to the proportion concentration of 5 mg/mL to obtain an electrode modification solution, coating the electrode modification solution on a working electrode, drying, coating an electrode protection solution, and drying again.
Preferably, the amount of the catalytic material loaded with the working electrode is 0.20-0.25 mg-cm-2.
Preferably, the electrode protection solution is a Nafion solution, and the mass fraction of Nafion in the Nafion solution is 0.05%.
4. The electrochemical hydrogen evolution system is applied to electrocatalytic hydrogen evolution under the condition of alkaline solution.
The invention has the beneficial effects that: the invention provides a preparation method and application of a palladium-doped organic metal framework catalytic material, belonging to the field of electrochemistry2) And sodium Borohydride (BH)4Na) and reasonably selecting the types of a metal source, an organic ligand and a surfactant, so that the finally prepared palladium-doped organic metal framework catalytic material has excellent catalytic activity close to commercial platinum carbon and long-term catalytic stability in the electrocatalytic hydrogen evolution reaction. The organic metal framework is used as a precursor, uniform and customizable porosity, high specific surface area and stable three-dimensional framework are provided, the catalytic stability of the catalyst is improved, and a method of palladium doping and in-situ reduction is selected, so that the electrical conductivity of the organic metal framework is enhanced, more active sites are exposed, and the catalytic activity of the organic metal framework is enhanced. Initial potential of the Palladium-doped organometallic framework under alkaline solution conditions (i.e., Current Density of-1 mA cm)-2Potential of time) is shifted up to 660 mV compared with the simple substance nickel, and the current density is-10 mA cm-2When the catalyst is used, the hydrogen evolution overpotential is 50 mV, which is reduced by 633 mV compared with a nickel-organic metal framework (683 mV), the hydrogen evolution performance is improved by 12 times, and the catalytic performance is not changed greatly after an Accelerated Durability Test (ADT) is carried out. Compared with the traditional hydrogen evolution system, the hydrogen evolution system prepared by the catalytic material has higher hydrogen evolution performance and stability, and has important prospect in the aspect of electrocatalytic hydrogen evolution. The material has simple and convenient preparation process and excellent performance, and can replace commercial platinum-carbon catalysts to a certain extent.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings, in which:
FIG. 1 is an X-ray powder diffraction pattern (XRD) of example 1 (Ni-MOF), example 2 (Pd/Ni-MOF);
FIG. 2 is a Scanning Electron Microscope (SEM) image of example 1, example 2; (wherein a in FIG. 2 is an SEM picture of Ni-MOF, and b in FIG. 2 is an SEM picture of Pd/Ni-MOF)
FIG. 3 is an X-ray spectral analysis (EDS) of example 2;
FIG. 4 is a hydrogen evolution linear scan plot (LSV) of example 1, example 2 and commercial 50% Pt/C;
FIG. 5 is a graph of Electrochemical Impedance Spectroscopy (EIS) versus charge transfer resistance for example 1, example 2; (wherein a in FIG. 5 is an EIS diagram and an equivalent circuit diagram, and b in FIG. 5 is a comparison diagram of charge transfer resistance)
Fig. 6 is an acceleration durability test chart (ADT) of example 2.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparing nickel-metal organic frame catalytic material and working electrode coated with the same, and constructing electrochemical hydrogen evolution system
1) Nickel chloride hexahydrate (NiCl)2·6H2O) dissolved in deionized water as solution A, trimesic acid and citric acid (C)6H8O7) Dispersing the mixture into a mixed solvent of N, N-dimethylformamide and absolute ethyl alcohol to form a solution B; respectively carrying out ultrasonic treatment on the A and B for 30min under the conditions that the ultrasonic power is 80W and the ultrasonic frequency is 40Hz, then carrying out magnetic stirring for 20min, finally dropwise adding the B solution into the A solution, and continuing stirring for 30 min; uniformly mixing the solution A and the solution B, transferring the solution A and the solution B into a stainless steel reaction kettle, reacting at 180 ℃ for 12 hours, centrifuging at 12000r/min for 3 minutes, taking a precipitate, washing the precipitate, and drying in vacuum at 0.085MPa and 60 ℃ for 12 hours to obtain a nickel-metal organic framework (Ni-MOF); wherein the mass ratio of the metal nickel source, the organic ligand and the surfactant is 5.6:1.2: 1-2.
2) Dispersing the catalytic material prepared in the step 1) in water according to the proportioning concentration of 5mg to obtain an electrode modification solution, coating the electrode modification solution on a working electrode, wherein the loading capacity is 0.21 mg-cm-2And coating the electrode protection solution after drying, and drying again.
3) And (3) assembling the working electrode coated with the nickel-metal organic framework catalytic material on the surface, which is prepared in the step 2), with an electrochemical workstation, a counter electrode (carbon rod), a reference electrode (Ag/AgCl electrode), an electrolytic cell and electrolyte (1M KOH) together to form an electrochemical hydrogen evolution system under the condition of alkaline solution.
The XRD pattern of the nickel-organometallic framework is shown as 1 in fig. 1.
In fig. 2, a is an SEM image of the nickel-organometallic framework material prepared in example 1, and as can be seen from fig. 1 a, the framework has a three-dimensional spherical structure, providing a large specific surface area.
Example 2
1) Taking the nickel-organic metal framework of the step 1) of the example 1, a surfactant and palladium chloride (PdCl)2) And sodium Borohydride (BH)4Na) is added into the mixed solvent of the deionized water and the absolute ethyl alcohol in turn under the stirring of a magnetic stirrer to be evenly dispersed, and thenTransferring the mixture into a stainless steel reaction kettle, reacting at 180 ℃ for 12h, centrifuging at 12000r/min for 3min, taking a precipitate, washing the precipitate, and drying in vacuum at 60 ℃ for 12h under 0.085MPa to obtain a palladium-doped organic metal framework catalytic material (Pd/Ni-MOF); the nickel-organometallic framework, a surfactant, palladium chloride (PdCl)2) And sodium Borohydride (BH)4Na) in a mass ratio of 400:5:0.3: 5.
2) Dispersing the catalytic material prepared in the step 1) in water according to the proportioning concentration of 5mg to obtain an electrode modification solution, coating the electrode modification solution on a working electrode, wherein the loading capacity is 0.21 mg-cm-2And coating the electrode protection solution after drying, and drying again.
3) And (3) assembling the working electrode coated with the palladium-doped organic metal framework catalytic material on the surface, which is prepared in the step 2), with an electrochemical workstation, a counter electrode (carbon rod), a reference electrode (Ag/AgCl electrode), an electrolytic cell and electrolyte (1M KOH) together to form an electrochemical hydrogen evolution system under the condition of alkaline solution.
Fig. 1, 2, is an XRD spectrum of the palladium-doped organic metal framework catalytic material, and it can be known from two curves in fig. 1 that the crystal structure and size of the precursor Ni-MOF are changed after palladium doping.
Fig. 2 b is an SEM image of the palladium-doped organic metal framework catalytic material prepared in example 2, and fig. 1 a shows that the structure of the organic metal framework is adjusted after doping Pd metal, so that a nano-scale particle structure is formed, a large number of active sites are exposed, and the catalytic activity of the material is improved.
FIG. 3 is the EDS chart corresponding to example 2, which shows that the elements in the sample include Ni, C, O and Pd, which are respectively from the Ni-metal organic framework and palladium chloride, and the atomic ratio of the elements is: c, Ni, O, Pd =44.6, 21.8, 12.5.
Example 3
The hydrogen evolution systems constructed in examples 1 and 2 were tested at a sweep rate of 0-1V and 5mV/s by linear sweep voltammetry to obtain hydrogen evolution reaction curves of the catalytic material shown in FIG. 4, and the initial potential of Pd/Ni-MOF (i.e., the current density was-1 mA cm) can be determined from FIG. 4-2Potential at) is shifted by 660 mV more positively than Ni-MOF, and current is passedThe density is-10 mA cm-2When the catalyst is used, the hydrogen evolution overpotential is 50 mV, which is 633 mV lower than that of Ni-MOF (683 mV), and the hydrogen evolution performance is close to the commercial 50% Pt/C.
Example 4
The hydrogen evolution systems constructed in examples 1 and 2 were tested by electrochemical impedance spectroscopy under the conditions of 275mV, frequency range of 100 kHz to 1Hz, and alternating current amplitude of 5mV, to obtain fig. 5, where a is EIS diagram (the inset is equivalent circuit diagram), b is charge transfer resistance comparison diagram, and it can be known from fig. 5a that the semicircle of Pd/Ni-MOF is far smaller than that of Ni-MOF at high frequency, which indicates that Pd/Ni-MOF has better charge transfer efficiency, and it can be known from fig. 5b that after palladium doping, the conductivity of Ni-MOF is significantly enhanced, the resistance reduction amplitude is as high as 95.6%, and the catalytic performance is greatly improved.
Example 5
The hydrogen evolution systems constructed in examples 1 and 2 were tested by cyclic voltammetry, and subjected to Accelerated Durability Test (ADT) for 5000 cycles, and the results are shown in FIG. 6, in which the initial curve and the subsequent curve of ADT and LSV curves were 20 mA cm-2The overpotential in time is shifted only 8 mV negatively. The Pd/Ni-MOF showed satisfactory stability, which can be attributed to the stable three-dimensional structure of the Ni-MOF.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The invention is not the best known technology.
Claims (6)
1. A preparation method and application of a palladium-doped organic metal framework catalytic material are characterized by comprising the following steps:
1) dissolving a metal nickel source in deionized water to form a solution A, dispersing an organic ligand and a surfactant in a mixed solvent of N, N-dimethylformamide and absolute ethyl alcohol to form a solution B, uniformly mixing the solution A and the solution B, transferring the mixed solution A and the solution B into a stainless steel reaction kettle, reacting at 180-220 ℃ for 8-16h, centrifuging to obtain a precipitate, washing the precipitate, and drying in vacuum to obtain a nickel-metal organic framework; the mass ratio of the metal nickel source, the organic ligand and the surfactant is 1-10:1-5: 1-5.
2.2) taking a certain amount of nickel-organic metal framework, surfactant and palladium chloride (PdCl)2) And sodium Borohydride (BH)4Na) is sequentially added into a mixed solvent of deionized water and absolute ethyl alcohol under magnetic stirring to be uniformly dispersed, then the mixture is transferred into a stainless steel reaction kettle to react at the temperature of 180 ℃ and 220 ℃ for 8 to 16 hours, then the precipitate is centrifugally taken, and the precipitate is washed and then dried in vacuum to obtain the palladium-doped organic metal framework catalytic material; the nickel-organometallic framework, a surfactant, palladium chloride (PdCl)2) And sodium Borohydride (BH)4Na) in a mass ratio of 200-500:1-10:0.1-1: 1-10.
3. The method according to claim 1, wherein in the step 1), the solutions A and B are uniformly mixed, specifically, the solutions A and B are respectively subjected to ultrasonic treatment for 10-60min under the conditions that the ultrasonic power is 60-100W and the ultrasonic frequency is 20-40Hz, then the solution B is stirred for 10-20min by magnetic force, finally the solution B is dropwise added into the solution A, and the stirring is continued for 20-60 min.
4. The method as claimed in claim 1, wherein the centrifugation is specifically at a speed of 8000- > 12000r/min for 3-5 min; and vacuum drying is carried out for 12-48h at 50-80 ℃ under 0.08-0.10 MPa.
5. The method of any one of claims 1-3, wherein the metallic nickel source is one of nickel chloride, nickel sulfate, nickel nitrate, or nickel acetate; the organic ligand is one of trimesic acid or terephthalic acid; the surfactant is one of citric acid, trisodium citrate, CTAB or PVP.
6. An electrochemical hydrogen evolution system comprises an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and electrolyte, and is characterized in that the working electrodeThe polar surface is coated with the nickel-organometallic framework and palladium-doped organometallic framework catalytic material of claim 1 and the application in electrocatalytic hydrogen evolution; and the alkaline hydrogen evolution performance is excellent: in N2The initial potential of the catalytic material (i.e., the current density of-1 mA cm) in a saturated 1M KOH solution-2Potential at) is shifted up to 660 mV relative to the Ni-MOF frame and the current density is-10 mA cm-2When the catalyst is used, the hydrogen evolution overpotential is 50 mV, which is reduced by 633 mV compared with a nickel-metal organic framework (683 mV).
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