CN110433861B - Preparation method and application of self-supporting MOF (Metal organic framework) nano-array composite catalyst - Google Patents
Preparation method and application of self-supporting MOF (Metal organic framework) nano-array composite catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 19
- 238000004070 electrodeposition Methods 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000002086 nanomaterial Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 12
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000002114 nanocomposite Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 6
- 235000008001 rakum palm Nutrition 0.000 claims description 6
- 229940075397 calomel Drugs 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 5
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000000415 inactivating effect Effects 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 58
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 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
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- 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 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 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
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- -1 sodium nitroferricyanide Chemical compound 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- B01J31/22—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
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/33—
-
- B01J35/61—
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
Abstract
The invention discloses a preparation method of a self-supporting MOF (metal organic framework) nano-array composite catalyst and application of the catalyst in electrocatalysis of room-temperature nitrogen reduction, belonging to the technical fields of catalysis and nano-composite materials. Mixing a copper perchlorate solution and a ligand solution to prepare a precursor solution of electrodeposited Cu (II) -sala; in a three-electrode system, a constant potential electrodeposition process is adopted to prepare a copper mesh loaded Cu (II) -sala nano material; mixing and soaking a Cu (II) -sala nano material and a clarified cobalt nitrate solution, washing with water, and then putting into a 250W microwave oven for activation to obtain a self-supporting MOF nano array composite catalyst; the catalyst is applied to electrocatalysis room-temperature nitrogen reduction, and has the advantages of simple preparation process, low energy consumption, low pollution and good industrial prospect.
Description
Technical Field
The invention discloses a preparation method of a self-supporting MOF (metal organic framework) nano-array composite catalyst and application of the catalyst in electrocatalysis of room-temperature nitrogen reduction, belonging to the fields of catalysis technology, nano-composite material technology and the like.
Background
In addition to its use as an anhydrous solution or as a nitrogenous fertilizer in salt form, ammonia has received much attention as a potential energy storage medium and as an alternative fuel for vehicles. In 2015, ammonia production consumed 2% of the energy consumed globally. Recent studies have shown that by electrochemical methods, N2And H2O can produce ammonia with zero CO compared to the Haber-Bosch process2Emission and energy saving. However, since the theoretical potentials of the hydrogen conversion reaction (HER) and the Nitrogen Reduction Reaction (NRR) are very close, H is2Is the main product because the reaction kinetics of the former are very fast. The theoretical calculation result shows that the NRR period is largeMost catalyst surfaces are detrimental to both reactant adsorption and proton/electron transfer. In addition to low faradaic efficiency, slow ammonia production is another big problem. The highest reaction rate of the electrochemical synthesis of ammonia is 1 x 10-8 mol NH3 s-2 cm-2Much lower than the normal ammonia production rate of commercial systems. Therefore, the synthesis of catalysts with high catalytic efficiency and high selectivity is urgent.
The MOFs are materials which are widely concerned in recent years, and the MOFs have huge adsorption capacity and loading capacity due to the overlarge specific surface area and porosity, the special pore channel structure and the open metal sites; meanwhile, the MOFs material structure can be designed, regulated and controlled, and is flexible in change and the like. However, the catalytic activity and water stability of MOFs still remain to be improved.
Disclosure of Invention
One of the technical tasks of the invention is to make up the defects of the prior art and provide a preparation method of the self-supporting MOF nano-array composite catalyst, and the preparation method has the advantages of simple process, low energy consumption and good industrial prospect.
The second technical task of the invention is to provide the application of the catalyst, namely the application of the catalyst in electrocatalysis of nitrogen reduction at room temperature. Has high catalytic efficiency and selectivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. preparation method of self-supporting MOF (Metal organic framework) nano-array composite catalyst
(1) Preparation of an electrodeposition precursor solution
Adding 0.8-1.0 mmol of Cu (ClO)4)2·6H2Dissolving O and 1.6-2.0 mmol of benzene in 15-20 mL of methanol MeOH solution, and performing ultrasonic treatment at 180W until the solution is clear to obtain a clear copper perchlorate solution;
0.8-1.0 mmol of ligand H2sala and 0.8-1.0 mmol LiOH were added to 8-10 mL H2Stirring for 25-30 min in O to obtain a clear ligand solution;
mixing the copper perchlorate solution and the ligand solution to obtain a precursor solution of the electrodeposited Cu (II) -sala;
adding 0.8-1.0 mmol of Co (NO)3)2·6H2O dissolved in 8-10 mL of H2In O, carrying out ultrasonic treatment at 180W until the mixture is clarified to obtain a clarified cobalt nitrate solution;
(2) electrodeposition preparation of self-supporting MOF (metal organic framework) nano-array composite catalyst
Adopting an electrochemical workstation three-electrode system, taking a 1.0 cm multiplied by 1.0 cm activated copper net as a working electrode, a platinum sheet as an auxiliary electrode and a calomel electrode as a reference electrode, adopting a constant potential electrodeposition process, and depositing for 8-12 min under a deposition voltage of-1.0 to-1.5V to prepare the copper net loaded Cu (II) -sala nano material;
mixing and soaking a Cu (II) -sala nano material and a clear cobalt nitrate solution for 2-3 h, washing with water, and then putting in a 250W microwave oven for activation for 3 min to obtain the copper mesh loaded Co2+A Cu (II) -sala doped nano composite material, namely a self-supporting MOF nano array composite catalyst.
The activated copper mesh is prepared by removing surface impurities from a 1.0 cm x 1.0 cm copper mesh by ultrasonic treatment for 2-4 min at 180W in 1.5% dilute hydrochloric acid, and then cleaning with distilled water and ethanol respectively.
The basic structural unit of the Cu (II) -sala is [ Cu ]2(sala)(phen)3](ClO4)2·2.5H2O is 2 Cu2+1 ligand sala2-3 Phen molecules, 2 ClO4 -Ions and 2.5 water molecules; the sala has the following structural formula:
2. the application of the self-supporting MOF nano-array composite catalyst prepared by the preparation method in electrocatalysis of room-temperature nitrogen reduction comprises the following steps:
(1) drawing a standard curve
Preparing series NH by adopting ammonium chloride and KOH solution with the concentration of 0.1M4 +A standard solution of (4);
taking 2 mL of standard solution, sequentially adding 2 mL of NaOH solution with the concentration of 1.0M, 1 mL of NaClO solution with the concentration of 0.05M and 0.2 mL of sodium nitroferricyanide solution with the mass fraction of 1%, quickly shaking for several times, standing for 2 h at 25 ℃, detecting the absorbance peak value of the solution at the 653 nm wavelength by using a UV-vis spectrophotometer, and drawing an absorbance-concentration (A-c) standard curve;
the 1.0M NaOH solution contains 5 mass percent of salicylic acid and sodium citrate;
(2) electrocatalytic room temperature nitrogen fixation
Connecting an H-shaped two-chamber electrochemical cell on an electrochemical workstation, wherein the two chambers are separated by a Nafion 115 proton exchange membrane, and 30 mL of KOH solution with the concentration of 0.1M is added into each chamber; a three-electrode system is adopted, a cathode chamber is arranged in a self-supporting MOF nano array composite catalyst to serve as a working electrode, and Ag/AgCl serves as a reference electrode; the anode chamber is arranged on a platinum sheet as an auxiliary electrode; introducing N into the cathode chamber2After 30 min, N is reduced by using-0.8 to-1.2V2Fixing nitrogen, taking reaction liquid obtained after 2 hours of catalytic reaction, and analyzing the concentration of ammonia to test the room-temperature nitrogen fixation performance of electrocatalysis;
the method uses the step (1) and only uses 2 mL of reaction liquid for catalyzing reaction for 2 h to replace 2 mL of standard solution in the step (1), and the yield of ammonia is calculated according to a standard curve;
the 1.0M NaOH solution contains 5% by weight of salicylic acid and sodium citrate.
When the applied voltage is-0.1V vs RHE, the catalyst is reduced into NH by nitrogen at room temperature3At a rate of 25.3-31.9. mu.gNH3 h−1 cm-2The Faraday efficiency is 12.3-14.6%.
The beneficial technical effects of the invention are as follows:
(1) the preparation of the self-supporting MOF nano-array composite catalyst is a two-step method which is convenient and easy to operate, and firstly, a copper mesh loaded Cu (II) -sala nano-material is prepared by a constant potential electrodeposition process; secondly, mixing and impregnating the Cu (II) -sala nano material with a clear cobalt nitrate solution to prepare the copper mesh loaded with Co2+The preparation method of the Cu (II) -sala doped nano composite material has simple process and energy consumptionSmall size and good industrial prospect.
(2) The self-supporting MOF nano-array composite catalyst prepared by the method is good in stability, and the change of catalytic activity and Faraday efficiency can be ignored after the catalyst is recycled for 10 times; the catalyst is applied to electrocatalysis room-temperature nitrogen reduction, more active sites are exposed by microwave activation, the specific surface area of the catalyst is greatly improved, and the prepared Co2+The Cu (II) -sala doped nano material has obvious synergistic effect, increases the activity of catalyzing nitrogen fixation to form ammonia and has better selectivity.
Detailed Description
The present invention is further described with reference to the following examples, but the scope of the present invention is not limited to the examples, and modifications made by those skilled in the art to the technical solutions of the present invention should fall within the scope of the present invention.
Example 1 preparation method of self-supporting MOF nano-array composite catalyst
(1) Preparation of an electrodeposition precursor solution
0.8 mmol of Cu (ClO)4)2·6H2Dissolving O and 1.6 mmol of benzene in 15 mL of methanol MeOH solution, and carrying out ultrasonic treatment at 180W until the solution is clear to obtain a clear copper perchlorate solution;
0.8 mmol of ligand H2sala and 0.8 mmol LiOH were added to 8 mL H2Stirring for 25 min in O to obtain a clear ligand solution;
mixing the copper perchlorate solution and the ligand solution to obtain a precursor solution of the electrodeposited Cu (II) -sala;
0.8 mmol of Co (NO)3)2·6H2O dissolved in 8 mL H2In O, carrying out ultrasonic treatment at 180W until the mixture is clarified to obtain a clarified cobalt nitrate solution;
(2) electrodeposition preparation of self-supporting MOF (metal organic framework) nano-array composite catalyst
Adopting an electrochemical workstation three-electrode system, taking a 1.0 cm multiplied by 1.0 cm activated copper mesh as a working electrode, a platinum sheet as an auxiliary electrode and a calomel electrode as a reference electrode, adopting a constant potential electrodeposition process, and depositing for 8 min at a deposition voltage of-1.0V to prepare the copper mesh loaded Cu (II) -sala nano material;
mixing and soaking a Cu (II) -sala nano material and a clear cobalt nitrate solution for 2 h, washing with water, and then putting in a 250W microwave oven for activation for 3 min to obtain the copper mesh loaded with Co2+A Cu (II) -sala doped nanocomposite, namely a self-supporting MOF nanoarray composite catalyst;
the basic structural unit of the Cu (II) -sala is [ Cu ]2(sala)(phen)3](ClO4)2·2.5H2O is 2 Cu2+1 ligand sala2-3 Phen molecules, 2 ClO4 -Ions and 2.5 water molecules; the sala has the following structural formula:
example 2 preparation method of self-supporting MOF nano-array composite catalyst
(1) Preparation of an electrodeposition precursor solution
0.9 mmol of Cu (ClO)4)2·6H2Dissolving O and 1.8 mmol of benzene in 17 mL of methanol MeOH solution, and carrying out ultrasonic treatment at 180W until the solution is clear to obtain a clear copper perchlorate solution;
0.9 mmol of ligand H2sala and 0.9 mmol LiOH were added to 9 mL H2Stirring for 27 min in O to obtain a clear ligand solution;
mixing the copper perchlorate solution and the ligand solution to obtain a precursor solution of the electrodeposited Cu (II) -sala;
0.9 mmol of Co (NO)3)2·6H2O dissolved in 9 mL H2In O, carrying out ultrasonic treatment at 180W until the mixture is clarified to obtain a clarified cobalt nitrate solution;
(2) electrodeposition preparation of self-supporting MOF (metal organic framework) nano-array composite catalyst
Adopting an electrochemical workstation three-electrode system, taking a 1.0 cm multiplied by 1.0 cm activated copper mesh as a working electrode, a platinum sheet as an auxiliary electrode and a calomel electrode as a reference electrode, adopting a constant potential electrodeposition process, and depositing for 10 min at a deposition voltage of-1.2V to prepare the copper mesh loaded Cu (II) -sala nano material;
mixing and soaking a Cu (II) -sala nano material and a clear cobalt nitrate solution for 2.5 h, washing with water, and then putting in a 250W microwave oven for activation for 3 min to obtain the copper mesh loaded with Co2+A Cu (II) -sala doped nanocomposite, namely a self-supporting MOF nanoarray composite catalyst;
the structure of the Cu (II) -sala is the same as that of example 1.
Example 3 preparation method of self-supporting MOF nano-array composite catalyst
(1) Preparation of an electrodeposition precursor solution
1.0 mmol of Cu (ClO)4)2·6H2Dissolving O and 2.0 mmol of benzene in 20 mL of methanol MeOH solution, and carrying out ultrasonic treatment at 180W until the solution is clear to obtain a clear copper perchlorate solution;
1.0 mmol of ligand H2sala and 1.0 mmol LiOH were added to 10 mL H2Stirring for 30 min in O to obtain a clear ligand solution;
mixing the copper perchlorate solution and the ligand solution to obtain a precursor solution of the electrodeposited Cu (II) -sala;
1.0 mmol of Co (NO)3)2·6H2O dissolved in 10 mL H2In O, carrying out ultrasonic treatment at 180W until the mixture is clarified to obtain a clarified cobalt nitrate solution;
(2) electrodeposition preparation of self-supporting MOF (metal organic framework) nano-array composite catalyst
Adopting an electrochemical workstation three-electrode system, taking a 1.0 cm multiplied by 1.0 cm activated copper mesh as a working electrode, a platinum sheet as an auxiliary electrode and a calomel electrode as a reference electrode, adopting a constant potential electrodeposition process, and depositing for 12 min at a deposition voltage of-1.5V to prepare the copper mesh loaded Cu (II) -sala nano material;
mixing and soaking a Cu (II) -sala nano material and a clear cobalt nitrate solution for 3 h, washing with water, and then putting in a 250W microwave oven for activation for 3 min to obtain a copper mesh loaded with Co2+A Cu (II) -sala doped nanocomposite, namely a self-supporting MOF nanoarray composite catalyst;
the structure of the Cu (II) -sala is the same as that of example 1.
Example 4
The activated copper mesh described in examples 1 to 3 was prepared by removing surface impurities from a 1.0 cm x 1.0 cm copper mesh by ultrasonic treatment at 180W in 1.5% by mass of dilute hydrochloric acid for 2 to 4 min, and then washing the mesh with distilled water and ethanol, respectively.
Example 5
Use of the self-supporting MOF nanoarray composite catalyst described in example 1 or example 2 or example 3 for electrocatalytic room temperature nitrogen reduction
(1) Drawing a standard curve
Preparing series NH by adopting ammonium chloride and KOH solution with the concentration of 0.1M4 +A standard solution of (4);
taking 2 mL of standard solution, sequentially adding 2 mL of NaOH solution with the concentration of 1.0M, 1 mL of NaClO with the concentration of 0.05M and 0.2 mL of sodium nitroferricyanide solution with the mass fraction of 1%, quickly shaking for several times, standing for 2 h at 25 ℃, detecting the absorbance peak value of the solution at the 653 nm wavelength by using a UV-vis spectrophotometer, and drawing an absorbance-concentration (A-c) standard curve;
the 1.0M NaOH solution contains 5 mass percent of salicylic acid and sodium citrate;
(2) electrocatalytic room temperature nitrogen fixation
Connecting an H-shaped two-chamber electrochemical cell on an electrochemical workstation, separating the two chambers by using a Nafion 115 proton exchange membrane, adding 30 mL of KOH solution with the concentration of 0.1M into the two chambers, adopting a three-electrode system, placing a cathode chamber in a self-supporting MOF nano array composite catalyst to serve as a working electrode, and taking Ag/AgCl as a reference electrode; the anode chamber is arranged on a platinum sheet as an auxiliary electrode; introducing N into the cathode chamber2After 30 min, N is reduced by using-0.8 to-1.2V2Fixing nitrogen, taking reaction liquid obtained after 2 hours of catalytic reaction, and analyzing the concentration of ammonia to test the room-temperature nitrogen fixation performance of electrocatalysis;
the method uses the step (1) and only uses 2 mL of reaction liquid for catalyzing reaction for 2 h to replace 2 mL of standard solution in the step (1), and the yield of ammonia is calculated according to a standard curve;
the 1.0M NaOH solution contains 5% by weight of salicylic acid and sodium citrate.
(4) The catalyst prepared in example 1 was reduced to NH at room temperature with nitrogen at an applied voltage of-0.1V vs RHE3At a rate of 25.3. mu.gNH3 h−1 cm-2Faraday efficiency was 12.3%; catalyst prepared in example 2 reduction of nitrogen to NH at ambient temperature3At a rate of 31.9. mu.gNH3 h−1 cm-2Faraday efficiency was 14.6%; catalyst prepared in example 3, room temperature reduction of Nitrogen to NH3At a rate of 27 μ gNH3 h−1 cm-2The Faraday efficiency was 13%.
Claims (4)
1. A preparation method of a self-supporting MOF nano-array composite catalyst is characterized by comprising the following steps:
(1) preparation of an electrodeposition precursor solution
Adding 0.8-1.0 mmol of Cu (ClO)4)2·6H2Dissolving O and 1.6-2.0 mmol of benzene in 15-20 mL of methanol MeOH solution, and performing ultrasonic treatment at 180W until the solution is clear to obtain a clear copper perchlorate solution;
0.8-1.0 mmol of ligand H2sala and 0.8-1.0 mmol LiOH were added to 8-10 mL H2Stirring for 25-30 min in O to obtain a clear ligand solution;
mixing the copper perchlorate solution and the ligand solution to obtain a precursor solution of the electrodeposited Cu (II) -sala;
adding 0.8-1.0 mmol of Co (NO)3)2·6H2O dissolved in 8-10 mL of H2In O, carrying out ultrasonic treatment at 180W until the mixture is clarified to obtain a clarified cobalt nitrate solution;
(2) electrodeposition preparation of self-supporting MOF (metal organic framework) nano-array composite catalyst
Adopting an electrochemical workstation three-electrode system, taking a 1.0 cm multiplied by 1.0 cm activated copper net as a working electrode, a platinum sheet as an auxiliary electrode and a calomel electrode as a reference electrode, adopting a constant potential electrodeposition process, and depositing for 8-12 min under a deposition voltage of-1.0 to-1.5V to prepare the copper net loaded Cu (II) -sala nano material;
mixing and soaking a Cu (II) -sala nano material and a clear cobalt nitrate solution for 2-3 h, washing with water, and placing inActivating in a 250W microwave oven for 3 min to obtain copper mesh loaded Co2+A Cu (II) -sala doped nanocomposite, namely a self-supporting MOF nanoarray composite catalyst;
the sala has the following structural formula:
2. the preparation method of the self-supporting MOF nano-array composite catalyst according to claim 1, wherein the activated copper mesh is prepared by removing surface impurities from a 1.0 cm x 1.0 cm copper mesh in 1.5% by mass of dilute hydrochloric acid by ultrasonic treatment at 180W for 2-4 min, and then cleaning the surface impurities with distilled water and ethanol respectively.
3. The method for preparing the self-supporting MOF nano-array composite catalyst according to claim 1, wherein the basic structural unit of the Cu (II) -sala is [ Cu [ ] -Sala2(sala)(phen)3](ClO4)2·2.5H2O is 2 Cu2 +1 ligand sala2-3 phen molecules, 2 ClO4 -Ions and 2.5 water molecules.
4. Use of a self-supporting MOF nanoarray composite catalyst prepared according to the preparation method of claim 1 for electrocatalytic room temperature nitrogen reduction.
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