CN110433861A - A kind of preparation method and application of self-supporting MOF nano-array composite catalyst - Google Patents
A kind of preparation method and application of self-supporting MOF nano-array composite catalyst Download PDFInfo
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- CN110433861A CN110433861A CN201910813245.9A CN201910813245A CN110433861A CN 110433861 A CN110433861 A CN 110433861A CN 201910813245 A CN201910813245 A CN 201910813245A CN 110433861 A CN110433861 A CN 110433861A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 238000004070 electrodeposition Methods 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000002086 nanomaterial Substances 0.000 claims abstract description 14
- 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 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 11
- 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
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 239000002114 nanocomposite Substances 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 11
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 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
- 238000003491 array Methods 0.000 claims description 6
- 235000008001 rakum palm Nutrition 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 229940075397 calomel Drugs 0.000 claims description 5
- 238000000151 deposition Methods 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
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 57
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 28
- 102100033069 Histone acetyltransferase KAT8 Human genes 0.000 description 25
- 101000944170 Homo sapiens Histone acetyltransferase KAT8 Proteins 0.000 description 25
- 239000012621 metal-organic framework Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 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
- 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
- 238000004458 analytical method Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 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
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000008569 process Effects 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
- 229940083618 sodium nitroprusside Drugs 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 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
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
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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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
It is used for the application of electro-catalysis room temperature under nitrogen reduction the invention discloses a kind of preparation method of self-supporting MOF nano-array composite catalyst and based on the catalyst, belongs to catalysis technique, nanocomposite technical field.It, which has main steps that, mixes cupric perchlorate solution and ligand solution, and the precursor solution of electro-deposition Cu (II)-sala is made;In three-electrode system, using constant potential electrodeposition technology, the nano material of copper mesh loaded Cu (II)-sala is made;Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping, after washing, is placed in 250 W micro-wave ovens and activates, obtain self-supporting MOF nano-array composite catalyst;The catalyst is used for the application of electro-catalysis room temperature under nitrogen reduction, the catalyst preparation process to be simple, and energy consumption is small, and pollution is small, there is good industrial prospect.
Description
Technical field
The invention discloses a kind of preparation method of self-supporting MOF nano-array composite catalyst and it is based on the catalyst
For the application of electro-catalysis room temperature under nitrogen reduction, belong to the fields such as catalysis technique, nanocomposite technology.
Background technique
Other than being used as the nitrogenous fertilizer of anhydrous solution or salt form, ammonia is as a kind of potential energy-accumulating medium and automobile-used substitution
Fuel is receive a lot of attention.2015, ammonia preparation consumption energy accounted for the 2% of global energy.It has recently been demonstrated that logical
Cross electrochemical method, N2And H2O can produce ammonia, compared with Haber-Bosch process, have zero CO2It discharges and energy-efficient excellent
Gesture.However, since the theoretical inspiration of hydrogen conversion reaction (HER) and nitrogen reduction reaction (NRR) is very close, H2It is primary product,
Because the former kinetics is very fast.The calculated results during showing NRR most of catalyst surfaces to reactant
Absorption and proton/electronics transfer are all unfavorable.Other than low faradic efficiency, the formation speed of ammonia is another big problem slowly.Ammonia
The highest response rate of electrochemistry formated is 1 × 10-8 mol NH3 s-2 cm-2, generated far below the common ammonia of commercial system fast
Rate.So it is extremely urgent to synthesize high catalytic efficiency, highly selective catalyst.
MOFs is the material of extensive concern in recent years, because the specific surface area of MOFs material super large and porosity, special
Cellular structure, opening metallic site, so that it is possessed huge adsorption capacity and delivered payload capability;Meanwhile MOFs material structure can
It designs, is controllable, changing the advantages that very flexible.However the catalytic activity of MOFs and water stability are still up for improving.
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 MOF nanometers of battle arrays
The preparation method of column composite catalyst, the preparation method simple process, energy consumption is small, there is good industrial prospect.
The two of technical assignment of the invention are to provide the purposes of the catalyst, i.e., the catalyst are used for electro-catalysis room temperature
The application of nitrogen reduction.With very high catalytic efficiency and selectivity.
To achieve the above object, The technical solution adopted by the invention is as follows:
1. a kind of preparation method of self-supporting MOF nano-array composite catalyst
(1) electro-deposition precursor solution is prepared
By 0.8-1.0 mmol Cu (ClO4)2·6H2O and 1.6-2.0 mmol benzene is dissolved in 15-20 mL methanol MeOH solution,
180 W ultrasounds obtain clear cupric perchlorate solution to clarifying;
By 0.8-1.0 mmol ligand H2Sala and 0.8-1.0 mmol LiOH is added to 8-10 mL H2In O, 25-30 is stirred
Min obtains clear ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 0.8-1.0 mmol Co (NO3)2·6H2O is dissolved in 8-10 mL H2In O, 180 W ultrasounds obtain clear to clarifying
Cobalt nitrate solution;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum
Helping electrode, calomel electrode is that reference electrode is deposited under the deposition voltage of -1.0 ~ -1.5 V using constant potential electrodeposition technology
The nano material of copper mesh loaded Cu (II)-sala is made in 8-12 min;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 2-3 h, after washing, are placed in 250 W microwaves
3 min are activated in furnace, and copper mesh load C o is made2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nanometers of battle arrays
Column composite catalyst.
The activation copper mesh, be by the copper mesh of the cm of 1.0 cm × 1.0 mass fraction be 1.5% dilute hydrochloric acid in 180
W ultrasound 2-4 min removes surface irregularities, is made after then being cleaned respectively with distilled water, ethyl alcohol.
Cu (the II)-sala, basic structural unit are [Cu2(sala)(phen)3](ClO4)2·2.5H2O is by 2
A Cu2+, 1 ligand sala2-, 3 benzene phen molecules, 2 ClO4 -Ion and 2.5 hydrones are constituted;The sala, structure
It is as follows to make formula:
。
2. a kind of self-supporting MOF nano-array composite catalyst of preparation method preparation as described above is used for electro-catalysis
The application of room temperature under nitrogen reduction, steps are as follows:
(1) standard curve is drawn
Ammonium chloride and concentration is used to prepare series NH for the KOH solution of 0.1 M4 +Standard solution;
2 mL standard solution are taken, the NaClO that 2 mL concentration are the NaOH solution of 1.0 M, 1 mL concentration is 0.05 M is sequentially added
Solution, the sodium nitroprusside solution that 0.2 mL mass fraction is 1% quickly shake for several times, 25 DEG C of 2 h of placement, with UV-
Vis spectrophotometer detects the absorbance peak at the 653 nm wavelength of solution, draws absorbance-concentration, that is, A-c standard curve;
The NaOH solution of 1.0 M is 5% salicylic acid and sodium citrate containing mass fraction;
(2) electro-catalysis room temperature fixed nitrogen
Two Room electrochemical cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion,
The KOH solution that 30 mL are added in two Room, concentration is 0.1 M;Using three-electrode system, cathode chamber is placed in MOF nanometers of battle arrays of self-supporting
Column composite catalyst is as working electrode, and Ag/AgCl is as reference electrode;Anode chamber is placed in platinized platinum as auxiliary electrode;Cathode
Room is passed through N2After 30 min, N is restored using -0.8 ~ -1.2 V2Fixed nitrogen takes the reaction solution of 2 h of catalysis reaction, analyzes the dense of ammonia
Degree, to test electro-catalysis room temperature fixed nitrogen performance;
The concentration of the analysis ammonia, method only react the reaction solution of 2 h, alternative steps with step (1) with 2 mL catalysis
(1) 2 mL standard solution in calculate the yield of ammonia according to standard curve;
The NaOH solution of 1.0 M is 5% salicylic acid and sodium citrate containing mass fraction.
When applied voltage is -0.1 V vs RHE, NH is reduced into for the catalyst room temperature under nitrogen3Rate be 25.3-
31.9 μg NH3 h−1 cm-2, faradic efficiency 12.3-14.6%.
The beneficial technical effect of the present invention is as follows:
(1) preparation of self-supporting MOF nano-array composite catalyst of the present invention is to use that easy-operating two-step method is facilitated to prepare,
First is that the nano material of copper mesh loaded Cu (II)-sala is made in constant potential electrodeposition technology;Second is that by-sala nanometers of materials of Cu (II)
Material is mixed with dipping with clear cobalt nitrate solution, and copper mesh load C o is made2+The nanocomposite of Cu (II)-sala is adulterated, it should
Preparation method simple process, energy consumption is small, there is good industrial prospect.
(2) it is activated in 250 W micro-wave ovens of the invention, activation efficiency is high, self-supporting MOF nano-array composite catalyzing obtained
Agent is stablized, and after being recycled 10 times, the change of catalytic activity and faradic efficiency can be ignored;The catalyst is used for electricity
It is catalyzed the application of room temperature under nitrogen reduction, microwave activation exposes more active sites, greatly improves the specific surface of catalyst
Product, Co obtained2+The nano material synergistic effect for adulterating Cu (II)-sala is significant, and catalysis fixed nitrogen ammonification activity increases, selectivity
Also more preferable.
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 MOF nano-array composite catalyst of embodiment 1
(1) electro-deposition precursor solution is prepared
By 0.8 mmol Cu (ClO4)2·6H2O and 1.6 mmol benzene are dissolved in 15 mL methanol MeOH solution, and 180 W ultrasounds are to clear
Clearly, clear cupric perchlorate solution is obtained;
By 0.8 mmol ligand H2Sala and 0.8 mmol LiOH are added to 8 mL H2In O, 25 min are stirred, are clarified
Ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 0.8 mmol Co (NO3)2·6H2O is dissolved in 8 mL H2In O, it is molten to obtain clear cobalt nitrate to clarifying for 180 W ultrasounds
Liquid;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum
Electrode, calomel electrode is helped to deposit 8 min under the deposition voltage of -1.0 V using constant potential electrodeposition technology for reference electrode,
The nano material of copper mesh loaded Cu (II)-sala is made;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 2 h, after washing, are placed in 250 W micro-wave ovens
Copper mesh load C o is made in 3 min of middle activation2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nano-array
Composite catalyst;
Cu (the II)-sala, basic structural unit are [Cu2(sala)(phen)3](ClO4)2·2.5H2O is by 2
Cu2+, 1 ligand sala2-, 3 benzene phen molecules, 2 ClO4 -Ion and 2.5 hydrones are constituted;The sala, construction
Formula is as follows:
。
A kind of preparation method of the self-supporting MOF nano-array composite catalyst of embodiment 2
(1) electro-deposition precursor solution is prepared
By 0.9 mmol Cu (ClO4)2·6H2O and 1.8 mmol benzene are dissolved in 17 mL methanol MeOH solution, and 180 W ultrasounds are to clear
Clearly, clear cupric perchlorate solution is obtained;
By 0.9 mmol ligand H2Sala and 0.9 mmol LiOH are added to 9 mL H2In O, 27 min are stirred, are clarified
Ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 0.9 mmol Co (NO3)2·6H2O is dissolved in 9 mL H2In O, it is molten to obtain clear cobalt nitrate to clarifying for 180 W ultrasounds
Liquid;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum
Electrode, calomel electrode is helped to deposit 10 under the deposition voltage of -1.2 V using constant potential electrodeposition technology for reference electrode
The nano material of copper mesh loaded Cu (II)-sala is made in min;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 2.5 h, after washing, are placed in 250 W microwaves
3 min are activated in furnace, and copper mesh load C o is made2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nanometers of battle arrays
Column composite catalyst;
The structure of Cu (the II)-sala is the same as embodiment 1.
A kind of preparation method of the self-supporting MOF nano-array composite catalyst of embodiment 3
(1) electro-deposition precursor solution is prepared
By 1.0 mmol Cu (ClO4)2·6H2O and 2.0 mmol benzene are dissolved in 20 mL methanol MeOH solution, and 180 W ultrasounds are to clear
Clearly, clear cupric perchlorate solution is obtained;
By 1.0 mmol ligand H2Sala and 1.0 mmol LiOH are added to 10 mL H2In O, 30 min are stirred, are clarified
Ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 1.0 mmol Co (NO3)2·6H2O is dissolved in 10 mL H2In O, 180 W ultrasounds obtain clear cobalt nitrate to clarifying
Solution;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum
Electrode, calomel electrode is helped to deposit 12 under the deposition voltage of -1.5 V using constant potential electrodeposition technology for reference electrode
The nano material of copper mesh loaded Cu (II)-sala is made in min;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 3 h, after washing, are placed in 250 W micro-wave ovens
Copper mesh load C o is made in 3 min of middle activation2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nano-array
Composite catalyst;
The structure of Cu (the II)-sala is the same as embodiment 1.
Embodiment 4
Copper mesh is activated described in embodiment 1-3, is the dilute hydrochloric acid for being 1.5% in mass fraction by the copper mesh of the cm of 1.0 cm × 1.0
In 180 W ultrasound 2-4 min remove surface irregularities, it is obtained after then being cleaned respectively with distilled water, ethyl alcohol.
Embodiment 5
Embodiment 1 or embodiment 2 or self-supporting MOF nano-array composite catalyst described in embodiment 3 are used for electro-catalysis room temperature
The application of nitrogen reduction
(1) standard curve is drawn
Ammonium chloride and concentration is used to prepare series NH for the KOH solution of 0.1 M4 +Standard solution;
Take 2 mL standard solution, sequentially add 2 mL concentration are the NaOH solution of 1.0 M, 1 mL concentration is 0.05 M NaClO,
The sodium nitroprusside solution that 0.2 mL mass fraction is 1% quickly shakes for several times, and 25 DEG C of 2 h of placement are divided with UV-vis
Photometer detects the absorbance peak at the 653 nm wavelength of solution, draws absorbance-concentration, that is, A-c standard curve;
The NaOH solution of 1.0 M is 5% salicylic acid and sodium citrate containing mass fraction;
(2) electro-catalysis room temperature fixed nitrogen
Two Room electrochemical cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion,
The KOH solution that 30 mL are added in two Room, concentration is 0.1 M, using three-electrode system, cathode chamber is placed in MOF nanometers of battle arrays of self-supporting
Column composite catalyst is as working electrode, and Ag/AgCl is as reference electrode;Anode chamber is placed in platinized platinum as auxiliary electrode;Cathode
Room is passed through N2After 30 min, N is restored using -0.8 ~ -1.2 V2Fixed nitrogen takes the reaction solution of 2 h of catalysis reaction, analyzes the dense of ammonia
Degree, to test electro-catalysis room temperature fixed nitrogen performance;
The concentration of the analysis ammonia, method only react the reaction solution of 2 h, alternative steps with step (1) with 2 mL catalysis
(1) 2 mL standard solution in calculate the yield of ammonia according to standard curve;
The NaOH solution of 1.0 M is 5% salicylic acid and sodium citrate containing mass fraction.
(4) when applied voltage is -0.1 V vs RHE, catalyst room temperature under nitrogen prepared by embodiment 1 is reduced into NH3
Rate be 25.3 μ gNH3 h−1 cm-2, faradic efficiency 12.3%;Catalyst room temperature under nitrogen prepared by embodiment 2 is reduced into
NH3Rate be 31.9 μ gNH3 h−1 cm-2, faradic efficiency 14.6%;Catalyst prepared by embodiment 3, room temperature under nitrogen is also
Original is at NH3Rate be 27 μ gNH3 h−1 cm-2, faradic efficiency 13%.
Claims (4)
1. a kind of preparation method of self-supporting MOF nano-array composite catalyst, which is characterized in that steps are as follows:
(1) electro-deposition precursor solution is prepared
By 0.8-1.0 mmol Cu (ClO4)2·6H2O and 1.6-2.0 mmol benzene is dissolved in 15-20 mL methanol MeOH solution, 180
W ultrasound obtains clear cupric perchlorate solution to clarifying;
By 0.8-1.0 mmol ligand H2Sala and 0.8-1.0 mmol LiOH is added to 8-10 mL H2In O, 25-30 is stirred
Min obtains clear ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 0.8-1.0 mmol Co (NO3)2·6H2O is dissolved in 8-10 mL H2In O, 180 W ultrasounds obtain clear nitre to clarifying
Acidic cobalt solution;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum
Helping electrode, calomel electrode is that reference electrode is deposited under the deposition voltage of -1.0 ~ -1.5 V using constant potential electrodeposition technology
The nano material of copper mesh loaded Cu (II)-sala is made in 8-12 min;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 2-3 h, after washing, are placed in 250 W microwaves
3 min are activated in furnace, and copper mesh load C o is made2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nanometers of battle arrays
Column composite catalyst.
2. a kind of preparation method of self-supporting MOF nano-array composite catalyst according to claim 1, feature exist
In the activation copper mesh is that 180 W are ultrasonic in the dilute hydrochloric acid that mass fraction is 1.5% by the copper mesh of the cm of 1.0 cm × 1.0
2-4 min removes surface irregularities, is made after then being cleaned respectively with distilled water, ethyl alcohol.
3. a kind of preparation method of self-supporting MOF nano-array composite catalyst according to claim 1, feature exist
In Cu (the II)-sala, basic structural unit is [Cu2(sala)(phen)3](ClO4)2·2.5H2O is by 2 Cu2 +, 1 ligand sala2-, 3 benzene phen molecules, 2 ClO4 -Ion and 2.5 hydrones are constituted;The sala, structural formula is such as
Under:
。
4. a kind of self-supporting MOF nano-array composite catalyst of preparation method preparation according to claim 1 is for electricity
It is catalyzed the application of room temperature under nitrogen reduction.
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