CN110449185A - A kind of preparation method and application of self-supporting bimetallic CoNi-MOF nano-array composite catalyst - Google Patents
A kind of preparation method and application of self-supporting bimetallic CoNi-MOF nano-array composite catalyst Download PDFInfo
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- CN110449185A CN110449185A CN201910813047.2A CN201910813047A CN110449185A CN 110449185 A CN110449185 A CN 110449185A CN 201910813047 A CN201910813047 A CN 201910813047A CN 110449185 A CN110449185 A CN 110449185A
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012621 metal-organic framework Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910001868 water Inorganic materials 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- 238000004176 ammonification Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000006722 reduction reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 108010020943 Nitrogenase Proteins 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 2
- AHBDJJPEQJQYMC-UHFFFAOYSA-N ethanol nickel(2+) dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] AHBDJJPEQJQYMC-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- -1 2,6- Pyridinedicarboxylic acid anion Chemical class 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XEYBHCRIKKKOSS-UHFFFAOYSA-N disodium;azanylidyneoxidanium;iron(2+);pentacyanide Chemical compound [Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N XEYBHCRIKKKOSS-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 229940083618 sodium nitroprusside Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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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
- B01J31/22—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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
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Abstract
The invention discloses a kind of preparation method of self-supporting bimetallic CoNi-MOF nano-array composite catalyst and the applications restored based on the catalyst in electrochemistry nitrogen, belong to nanocomposite, electrochemical catalysis technical field.It has main steps that dipicolimic acid 2, nickel nitrate, lithium hydroxide, ammonium persulfate are raw material with 2, and the nano-array composite material of cobalt piece load C o-MOF is made；The nano-array composite material is impregnated into nickel nitrate-ethanol solution, self-supporting bimetallic CoNi-MOF nano-array composite catalyst is made.The catalyst preparation low cost of raw materials, preparation process is simple, and energy consumption of reaction is low, has wide prospects for commercial application.The catalyst is used for efficient electro-catalysis nitrogen reduction reaction, has good electrochemistry nitrogenase activity.
Description
Technical field
The present invention relates to the preparation methods and base of a kind of self-supporting bimetallic CoNi-MOF nano-array composite catalyst
In the application of the catalyst electro-catalysis nitrogen reduction reaction, belong to nanocomposite, electrochemical catalysis technical field.
Background technique
NH3It is presently most important one of chemicals, annual output occupy various chemicals first place, and China is to close
At NH3Industrial power synthesizes NH as high energy consumption industry3The energy of industrial consumption accounts for the 1-2% of global total amount, NH3Downstream
Product is mainly chemical fertilizer, other such as synthetic fibers, explosive, industrial fuels are also its important chemical products.Pass through every year
Haber-Bosch technique produces the NH more than 1.4 hundred million tons3, and demand is also increasing.Since it is not as must in fertilizer production
The precursor that can lack, ammonia play an important role in terms of supporting population in the world.However, the process required on energy it is very high and
It is associated with poor efficiency.Typical reaction needs about 500 DEG C and > 200atm of temperature and pressure and uses Fe/Ru catalyst.
Therefore, the world energy sources budget of whole world estimation about 2% is used for NH3Production.In view of the limited and global gas of current fossil fuel
The challenge of variation is waited, exploration synthesizes NH in a mild condition3Catalysis reaction be particularly important.
Electrochemical reduction N2Room temperature synthesizes NH3Reaction, using natural water as hydrogen source, reaction condition is mild and can pass through voltage tune
Control, thus attract wide attention.The core that the synthesis is realized is the catalyst of efficient stable, for this purpose, research and development synthesis technology letter
Single economy, catalytic performance efficient stable catalyst be the having very much prospect and challenge of the task.
Summary of the invention
Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, providing a kind of self-supporting bimetallic
CoNi- MOF nano-array composite catalyst, i.e. cobalt piece load Ni2+The Co-MOF nano-array composite catalyst of doping
Preparation method, the composite material preparation process is simple, and cost of material is low, and energy consumption of reaction is low, has prospects for commercial application.
The two of technical assignment of the invention are to provide the purposes of the composite material, i.e., by self-supporting bimetallic CoNi-MOF
Nano-array composite catalyst is used for efficient electro-catalysis nitrogen reduction reaction, which has good electro-catalysis nitrogenase activity
With electrochemical stability.
To achieve the above object, The technical solution adopted by the invention is as follows:
1. a kind of preparation method of self-supporting bimetallic CoNi-MOF nano-array composite catalyst
(1) Co-MOF/Co nano-array composite material is prepared by the 2 of 1.5-2.0mmol, dipicolimic acid 2 and 2.0-
After 4.5mmol lithium hydroxide is codissolved in 5-8mL water, 1.2- 3.0mmol ammonium persulfate is added, obtains clear ammonium persulfate -2,
Dipicolimic acid 2 aqueous slkali；
1cm × 1cm cobalt piece of activation is immersed in ammonium persulfate -2, in dipicolimic acid 2 aqueous slkali, after reacting at room temperature 2-3h,
It is washed with water 3 times, it is cobalt piece load C o-MOF nano-array composite material that product, which is made, i.e. Co-MOF/Co nano-array is compound
Material；
(2) self-supporting bimetallic CoNi-MOF nano-array composite catalyst is prepared by Co-MOF/Co nano-array composite material
It is impregnated into the 10mL ethanol solution of the nickel nitrate containing 1.5-4.0g, reacts at room temperature 1.5-2h；Successively rushed with deionized water and ethyl alcohol
It washes 3 times, 85 DEG C of dryings to constant weight, cobalt piece is made and loads Ni2+The Co- MOF nano-array composite material of doping, i.e. self-supporting are double
Metal CoNi-MOF nano-array composite catalyst.
1cm × 1cm cobalt piece of the activation is that 180W ultrasound 2-4min is gone in the dilute hydrochloric acid that mass fraction is 1.5%
Except surface irregularities, it is made after then being cleaned respectively with distilled water, ethyl alcohol.
The Co-MOF, belongs to Metal-organic frame, and chemical formula is [Co2(PDCA)2(H2O)5] n, PDCA 2,6-
Pyridinedicarboxylic acid anion；One structural unit of Co-MOF nanometer sheet, by two Co (II) ions, two PDCA anions and
Five H2O molecule is constituted；The PDCA, structural formula are as follows:
2. the self-supporting bimetallic CoNi-MOF nano-array composite catalyst of preparation method preparation described in is urged for electricity
Change the application of nitrogen reduction ammonification
(1) two Room electrolytic cell of H-type is connected on electrochemical workstation by electro-catalysis nitrogen reduction, and 115 proton of Nafion is used between two Room
Exchange membrane separates, the PBS buffer solution that 30mL is added in two Room, concentration is 0.1M；By CoNi-MOF nanometers of self-supporting bimetallic
Array composite catalyst is placed in the electrolyte of cathode chamber as working electrode, Ag/AgCl reference electrode；Platinized platinum auxiliary electrode is set
In the electrolyte of anode chamber；N is passed through into cathode chamber electrolyte2After 10min, the external voltage of -0.6~-1.8V of setting is carried out
The reduction of electro-catalysis nitrogen takes the reaction solution of catalysis reaction 2h, measures NH in reaction solution4 +Concentration, with test be based on bimetallic CoNi-
MOF nanometer sheet catalyst nitrogen reducing property；
(2) the 0.1MPBS buffer solution of drafting standard curve ammonium chloride and pH=7, compound concentration 0.01mM, 0.02mM,
The serial NH of 0.03mM, 0.05mM, 0.1mM4 +Standard solution；
2mL series standard solution is pipetted, sequentially adds the NaOH solution that 2mL concentration is 1.0M, 1mL concentration is 0.05M's
NaClO solution, the sodium nitroprusside solution that 0.2mL mass fraction is 1%, quickly shake up, 25 DEG C of placement 2h, with UV-vis
Spectrophotometer detects the absorbance peak at solution 653nm wavelength, draws absorbance-concentration, that is, A-c standard curve, obtains
To calibration curve equation；
The NaOH solution of the 1.0M is 5% salicylic acid and 5% sodium citrate containing mass fraction；
(3) NH in nitrogen reduction ammonification calculation of yield measurement reaction solution4 +Concentration, pipette 2mL catalysis reaction 2h reaction solution, replace
The 2mL standard solution ridden instead of walk in rapid (2), the yield of ammonia is calculated according to calibration curve equation.
3. above-mentioned self-supporting bimetallic CoNi-MOF nano-array composite catalyst restores ammonification for electro-catalysis nitrogen, when outer
When making alive is -1.2V vs Ag/AgCl, ammonia yield is 37.8-43.2 μ gNH3·h-1·mg-1 catalyst, faradic efficiency is
23.8-30.1% illustrates the efficient electro-catalysis nitrogenase activity of the material.
Beneficial technical effect of the invention is as follows:
(1) the self-supporting bimetallic CoNi-MOF nano-array composite catalyst that the present invention obtains, preparation process simple process, letter
Single easily-controllable, product preparation efficiency is high, is easy to industrialize.
(2) self-supporting bimetallic CoNi-MOF nano-array composite catalyst obtained is not necessarily to pyrolysis-oxidation by the present invention,
Porous CoNi-MOF is completely remained, large specific surface area exposes more active sites；In addition, the material is cobalt piece
Load Ni2+The Co-MOF nano-array composite material of doping, Ni in composite material2+、Co2+Synergistic effect, so that the composite material
It is catalyzed fixed nitrogen ammonification activity to increase, the yield that room temperature electro-catalysis NRR produces ammonia is higher.
Specific embodiment
The present invention will be further described below with reference to examples, but protection scope of the present invention is not only limited to implement
Example, professionals in the field change to made by technical solution of the present invention, are within the scope of protection of the invention interior.
A kind of preparation method of the self-supporting bimetallic CoNi-MOF nano-array composite catalyst of embodiment 1
(1) Co-MOF/Co nano-array composite material is prepared by the 2 of 1.5mmol, dipicolimic acid 2 and 2.0mmol hydroxide
After lithium is codissolved in 5mL water, 1.2mmol ammonium persulfate is added, obtains clear ammonium persulfate -2, dipicolimic acid 2 aqueous slkali；
1cm × 1cm cobalt piece of activation is immersed in ammonium persulfate -2, in dipicolimic acid 2 aqueous slkali, after reacting at room temperature 2h, is used
Water washing 3 times, it is cobalt piece load C o-MOF nano-array composite material, i.e. Co-MOF/Co nano-array composite wood that product, which is made,
Material；
(2) self-supporting bimetallic CoNi-MOF nano-array composite catalyst is prepared by Co-MOF/Co nano-array composite material
It is impregnated into the 10mL ethanol solution of the nickel nitrate containing 1.5g, reacts at room temperature 1.5 h；Successively rinsed 3 times with deionized water and ethyl alcohol,
85 DEG C of dryings are made cobalt piece and load Ni to constant weight2+The Co-MOF nano-array composite material of doping, i.e. self-supporting bimetallic
CoNi-MOF nano-array composite catalyst.
1cm × 1cm cobalt piece of the activation is the 180W ultrasound 2min removal in the dilute hydrochloric acid that mass fraction is 1.5%
Surface irregularities are made after then being cleaned respectively with distilled water, ethyl alcohol.
The Co-MOF, belongs to Metal-organic frame, and chemical formula is [Co2(PDCA)2(H2O)5] n, PDCA 2,6-
Pyridinedicarboxylic acid anion；One structural unit of Co-MOF nanometer sheet, by two Co (II) ions, two PDCA anions and
Five H2O molecule is constituted；The PDCA, structural formula are as follows:
A kind of preparation method of the self-supporting bimetallic CoNi-MOF nano-array composite catalyst of embodiment 2
(1) Co-MOF/Co nano-array composite material is prepared by the 2 of 1.7mmol, dipicolimic acid 2 and 3.2mmol hydroxide
After lithium is codissolved in 6.5mL water, 2.1mmol ammonium persulfate is added, obtains clear ammonium persulfate -2, dipicolimic acid 2 alkali soluble
Liquid；
1cm × 1cm cobalt piece of activation is immersed in ammonium persulfate -2, in dipicolimic acid 2 aqueous slkali, after reacting at room temperature 2.5h,
It is washed with water 3 times, it is cobalt piece load C o-MOF nano-array composite material that product, which is made, i.e. Co-MOF/Co nano-array is compound
Material；
(2) self-supporting bimetallic CoNi-MOF nano-array composite catalyst is prepared by Co-MOF/Co nano-array composite material
It is impregnated into the 10mL ethanol solution of the nickel nitrate containing 2.7g, reacts at room temperature 1.2 h；Successively rinsed 3 times with deionized water and ethyl alcohol,
85 DEG C of dryings are made cobalt piece and load Ni to constant weight2+The Co-MOF nano-array composite material of doping, i.e. self-supporting bimetallic
CoNi-MOF nano-array composite catalyst.
1cm × 1cm cobalt piece of the activation is the 180W ultrasound 3min removal in the dilute hydrochloric acid that mass fraction is 1.5%
Surface irregularities are made after then being cleaned respectively with distilled water, ethyl alcohol.
The structure of the Co-MOF is the same as embodiment 1.
A kind of preparation method of the self-supporting bimetallic CoNi-MOF nano-array composite catalyst of embodiment 3
(1) Co-MOF/Co nano-array composite material is prepared by the 2 of 2.0mmol, dipicolimic acid 2 and 4.5mmol hydroxide
After lithium is codissolved in 8mL water, 3.0mmol ammonium persulfate is added, obtains clear ammonium persulfate -2, dipicolimic acid 2 aqueous slkali；
1cm × 1cm cobalt piece of activation is immersed in ammonium persulfate -2, in dipicolimic acid 2 aqueous slkali, after reacting at room temperature 3h, is used
Water washing 3 times, it is cobalt piece load C o-MOF nano-array composite material, i.e. Co-MOF/Co nano-array composite wood that product, which is made,
Material；
(2) self-supporting bimetallic CoNi-MOF nano-array composite catalyst is prepared
Co-MOF/Co nano-array composite material is impregnated into the 10mL ethanol solution of the nickel nitrate containing 4.0g, room temperature reaction 2
h；It is successively rinsed 3 times with deionized water and ethyl alcohol, 85 DEG C of dryings to constant weight, cobalt piece is made and loads Ni2+The Co-MOF nanometer of doping
Array composite material, i.e. self-supporting bimetallic CoNi-MOF nano-array composite catalyst.
1cm × 1cm cobalt piece of the activation is the 180W ultrasound 4min removal in the dilute hydrochloric acid that mass fraction is 1.5%
Surface irregularities are made after then being cleaned respectively with distilled water, ethyl alcohol.
The structure of the Co-MOF is the same as embodiment 1.
4 self-supporting bimetallic CoNi-MOF nano-array composite catalyst of embodiment is answered for electro-catalysis nitrogen reduction ammonification
With
(1) electro-catalysis nitrogen restores
Two Room electrolytic cell of H-type is connected on electrochemical workstation, is separated between two Room with Nafion115 proton exchange membrane, two Room
30mL is added, the pH=7PBS buffer solution that concentration is 0.1M；The load self-supporting bimetallic that will be prepared in embodiment 1
CoNi-MOF nano-array composite catalyst is working electrode, Ag/AgCl reference electrode is placed in the electrolyte of cathode chamber；Platinized platinum
Auxiliary electrode is placed in the electrolyte of anode chamber；N is passed through into cathode chamber electrolyte2After 10min, the external voltage of setting -1.2V
The reduction of electro-catalysis nitrogen is carried out, the reaction solution of catalysis reaction 2h is taken, measures NH in reaction solution4 +Concentration, with test be based on bimetallic
CoNi-MOF nanometer sheet catalyst nitrogen reducing property；
(2) standard curve is drawn
With the 0.1MPBS buffer solution of ammonium chloride and pH=7, compound concentration 0.01mM, 0.02mM, 0.03mM, 0.05mM,
The serial NH of 0.1mM4 +Standard solution；
2mL series standard solution is pipetted, sequentially adds the NaOH solution that 2mL concentration is 1.0M, 1mL concentration is 0.05M's
NaClO solution, the sodium nitroprusside solution that 0.2mL mass fraction is 1%, quickly shake up, 25 DEG C of placement 2h, with UV-vis
Spectrophotometer detects the absorbance peak at solution 653nm wavelength, draws absorbance-concentration, that is, A-c standard curve, obtains
To calibration curve equation；
The NaOH solution of the 1.0M is 5% salicylic acid and 5% sodium citrate containing mass fraction；
(3) NH in nitrogen reduction ammonification calculation of yield measurement reaction solution4 +Concentration, pipette 2mL catalysis reaction 2h reaction solution, replace
The 2mL standard solution ridden instead of walk in rapid (2), the yield of ammonia is calculated according to calibration curve equation.
Above-mentioned self-supporting bimetallic CoNi-MOF nano-array composite catalyst restores ammonification for electro-catalysis nitrogen, when additional
When voltage is -1.2V vs Ag/AgCl, ammonia yield is 37.8 μ gNH3·h-1·mg-1 catalyst, faradic efficiency 23.8%,
Illustrate the efficient electro-catalysis nitrogenase activity of the material.
Embodiment 5
Method is with embodiment 4, and only self-supporting bimetallic CoNi-MOF nano-array is compound urges for the load made from embodiment 2
Agent replaces the composite catalyst in embodiment 1；When applied voltage is -1.2V vs Ag/AgCl, ammonia yield is 43.2 μ
gNH3·h-1·mg-1 catalyst, faradic efficiency 30.1% illustrates the efficient electro-catalysis nitrogenase activity of the material.
Embodiment 6
Method is with embodiment 4, and only self-supporting bimetallic CoNi-MOF nano-array is compound urges for the load made from embodiment 3
Agent replaces composite catalyst obtained in embodiment 1；When applied voltage is -1.2V vs Ag/AgCl, ammonia yield is 40.5
μgNH3·h-1·mg-1 catalyst, faradic efficiency 26.7% illustrates the efficient electro-catalysis nitrogenase activity of the material.
Claims (4)
1. a kind of preparation method of self-supporting bimetallic CoNi-MOF nano-array composite catalyst, which is characterized in that step is such as
Under:
(1) Co-MOF/Co nano-array composite material is prepared
By the 2 of 1.5-2.0mmol, after dipicolimic acid 2 and 2.0-4.5mmol lithium hydroxide are codissolved in 5-8mL water, it is added
1.2-3.0mmol ammonium persulfate obtains clear ammonium persulfate -2, dipicolimic acid 2 aqueous slkali；
1cm × 1cm cobalt piece of activation is immersed in ammonium persulfate -2, in dipicolimic acid 2 aqueous slkali, after reacting at room temperature 2-3h,
It is washed with water 3 times, it is cobalt piece load C o-MOF nano-array composite material that product, which is made, i.e. Co-MOF/Co nano-array is compound
Material；
(2) self-supporting bimetallic CoNi-MOF nano-array composite catalyst is prepared
Co-MOF/Co nano-array composite material is impregnated into the 10mL ethanol solution of the nickel nitrate containing 1.5-4.0g, room temperature is anti-
Answer 1.5-2h；It is successively rinsed 3 times with deionized water and ethyl alcohol, 85 DEG C of dryings to constant weight, cobalt piece is made and loads Ni2+The Co- of doping
MOF nano-array composite material, i.e. self-supporting bimetallic CoNi-MOF nano-array composite catalyst.
2. a kind of preparation method of self-supporting bimetallic CoNi-MOF nano-array composite catalyst as described in claim 1,
It is characterized in that, 1cm × 1cm cobalt piece of the activation, is the 180W ultrasound 2-4min in the dilute hydrochloric acid that mass fraction is 1.5%
Surface irregularities are removed, are made after then being cleaned respectively with distilled water, ethyl alcohol.
3. a kind of preparation method of self-supporting bimetallic CoNi-MOF nano-array composite catalyst as described in claim 1,
It is characterized in that, the Co-MOF, belongs to Metal-organic frame, chemical formula is [Co2(PDCA)2(H2O)5] n, PDCA 2,
Dipicolimic acid 2 anion；One structural unit of Co-MOF nanometer sheet, by two Co (II) ions, two PDCA anions
With five H2O molecule is constituted；The PDCA, structural formula are as follows:
4. the self-supporting bimetallic CoNi-MOF nano-array composite catalyst of preparation method preparation as described in claim 1 is used
In the application of electro-catalysis nitrogen reduction ammonification.
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| CN111701620A (en) * | 2020-03-30 | 2020-09-25 | 河南师范大学 | Synthetic method of tungsten trioxide/ZIF-8 composite catalyst |
| CN113755874A (en) * | 2021-07-13 | 2021-12-07 | 杭州师范大学 | CoNi/C nano composite material, preparation method thereof and application thereof in synthesizing ammonia by electrocatalysis nitrogen fixation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101912737A (en) * | 2010-08-26 | 2010-12-15 | 南京工业大学 | Method for preparing metal organic frame supported film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912737A (en) * | 2010-08-26 | 2010-12-15 | 南京工业大学 | Method for preparing metal organic frame supported film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111701620A (en) * | 2020-03-30 | 2020-09-25 | 河南师范大学 | Synthetic method of tungsten trioxide/ZIF-8 composite catalyst |
| CN113755874A (en) * | 2021-07-13 | 2021-12-07 | 杭州师范大学 | CoNi/C nano composite material, preparation method thereof and application thereof in synthesizing ammonia by electrocatalysis nitrogen fixation |
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