CN110512224A - A kind of method that electrochemistry oxygen metaplasia nitrogen simultaneously restores fixed nitrogen ammonification simultaneously - Google Patents
A kind of method that electrochemistry oxygen metaplasia nitrogen simultaneously restores fixed nitrogen ammonification simultaneously Download PDFInfo
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- CN110512224A CN110512224A CN201910812985.0A CN201910812985A CN110512224A CN 110512224 A CN110512224 A CN 110512224A CN 201910812985 A CN201910812985 A CN 201910812985A CN 110512224 A CN110512224 A CN 110512224A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004176 ammonification Methods 0.000 title claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000001301 oxygen Substances 0.000 title claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 21
- 206010054949 Metaplasia Diseases 0.000 title claims abstract description 20
- 230000015689 metaplastic ossification Effects 0.000 title claims abstract description 20
- 230000005518 electrochemistry Effects 0.000 title claims description 22
- 239000013084 copper-based metal-organic framework Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000004744 fabric Substances 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000002604 ultrasonography Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229940075397 calomel Drugs 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000006056 electrooxidation reaction Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 34
- 229910021529 ammonia Inorganic materials 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 8
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 230000010354 integration Effects 0.000 description 3
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LDOMKUVUXZRECL-UHFFFAOYSA-N 2-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=C(C(O)=O)C=CC=C1C(O)=O LDOMKUVUXZRECL-UHFFFAOYSA-N 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 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
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000013110 organic ligand 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
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a kind of methods that chemical oxygen metaplasia nitrogen simultaneously restores fixed nitrogen ammonification simultaneously, belong to electrochemical catalysis technical field.It has main steps that using potentiostatic electrodeposition technology, and the Cu-MOF composite catalyst being supported on carbon cloth is made；It is electrolyte by urea-containing KOH solution, is passed through without nitrogen, under permanent oxidizing potential, catalyzing urea is oxidized to nitrogen and restores fixed nitrogen ammonification simultaneously, and this method is convenient and simple for operation, and catalyst has good electro catalytic activity and electrochemical stability.This method can not only solve in environment urea pollution problem green is clean again to be prepared for ammonia, energy consumption of reaction is low, with prospects for commercial application using being electrolyte containing urea wastewater.
Description
Technical field
The present invention relates to a kind of methods that electrochemistry oxygen metaplasia nitrogen simultaneously restores fixed nitrogen ammonification simultaneously, belong to nano material, electricity
Chemical catalysis technical field.
Background technique
From start for the first time twenty years ago electrochemistry nitrogen reduction (NRR) prepare ammonia since, ever-increasing ecological requirements and it
Mild reaction conditions make it more more attractive than traditional Haber-Bosch method.NRR is to utilize nitrogen and H2O conduct
Nitrogen and hydrogen source control voltage by electro-catalysis under the conditions of environment reaction and complete the reaction that nitrogen is restored to ammonia.Although NRR is grasped
Make convenient and abundant raw material, but since tri- key of N ≡ N strong between nitrogen-atoms, kinetics and its reaction efficiency are up for improving.
In recent years, researcher develops many approach for improving NRR, such as by ionic liquid as electrolyte progress NRR and benefit
With the catalyst with high catalytic efficiency such as Ru, Au and high Lacking oxygen material etc..These methods exist catalyst it is at high cost and
Inefficient bottleneck problem, therefore, seeking can be improved nitrogen-fixing efficiency and low-cost method is of great significance.
To reduce cost, exploitation non-precious metal catalyst be numerous researchers frequently with approach.Using oxidizable
Waste water solution does electrolyte solution, it generates the nitrogen source that nitrogen is reacted as NRR to electrochemical oxidation, and reduce simultaneously electrolyte at
Up to the present this strategy has no research achievement as far as we know.Therefore we have developed a kind of electrochemistry fixed nitrogen newly to think
Road makes its selfdecomposition generate nitrogen, not only can achieve the purpose of processing sewage, but also can be with fixed nitrogen, In using certain predetermined substance
Solve the reduction that nitrogen is completed while nitrogen pollution problem in environment.In the same electrolytic cell, it is anti-that fixed nitrogen belongs to reduction
It answers, belongs to competitive relation with evolving hydrogen reaction, however the two complements each other again, we aoxidize the electron-transport efficiency at end by improving
The efficiency of reduction reaction entirety is improved, NRR and HER can be correspondingly improved.In numerous catalyst, have for metal-
The research of machine framework material (Metal-OrganicFrameworks, MOFs) is more and more extensive and gos deep into.MOFs refers to transition gold
Belong to ion and organic ligand passes through the crystalline porous material with periodic network structure being self-assembly of.It has high hole
Rate, low-density, bigger serface, duct rule, aperture is adjustable and topological structure diversity and the advantages that Scalability, so that
MOFs has been widely used in fields such as gas storage, separation, catalysis, identification and drug deliveries.
Summary of the invention
Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, provide a kind of electrochemistry oxygen metaplasia nitrogen simultaneously
The method for restoring fixed nitrogen ammonification simultaneously, this method is raw materials used at low cost, and preparation process is simple, and energy consumption of reaction is low, the catalyst
With good electro catalytic activity and electrochemical stability, there is prospects for commercial application.
To achieve the above object, electrochemistry oxygen metaplasia nitrogen of the present invention simultaneously restores the technical solution of fixed nitrogen ammonification use such as simultaneously
Under:
(1) Cu-MOF/CC composite catalyst is prepared
By 0.30-0.50 g H4L powder and 0.10-0.30 g copper nitrate are dissolved in 4-6 mL n,N-Dimethylformamide, are dripped
After adding 60-100 μ L water, 180 W ultrasounds 1-3 minutes obtain green clear solution, and the nitre that 90-110 μ L mass fraction is 68% is added dropwise
Acid is stirred until homogeneous, and obtains copper ion and H4The mixed solution of L；
Using this mixed solution as electrolyte, using three-electrode electro Chemical work station, by the activated cm carbon cloth of 0.5 cm × 2 CC
As working electrode, platinized platinum is to electrode, and calomel electrode is reference electrode, is supported on using the synthesis of constant potential electrochemical deposition method
Cu-MOF composite material on carbon cloth CC；Obtained composite material is activated to constant weight in 85 DEG C, it is compound that Cu-MOF/CC is made
Catalyst；
The H4L, structural formula are as follows:
。
The activation carbon cloth is successively to remove carbon cloth in acetone, dehydrated alcohol and distillation underwater ultrasound 2-4min, washing
Surface irregularities, then carbon cloth is immersed in the nitric acid ultrasound 1-3min that mass fraction is 40 %, it is washed with water to wash and is made three times.
The Cu-MOF, basic structural unit are [Cu24L12(H2O)12]·30DMF·14H2O, DMF N, N- diformazan
Base formamide；A structural unit of Cu-MOF is by 24 Cu2+, 12 L4-, 12 main body hydrones, 30 object DMF molecules
It is formed with 14 object hydrones；The L4-, structural formula is as follows:
。
The H4L is the ligand of Cu-MOF preparation, and preparation step is as follows:
By 0.02 mol amino isophthalic acid, 0.03 mol NaOH and 5 mol NaHCO3It is added in 60 ml distilled water,
30 min are stirred after mixing at room temperature；The 1,4- dioxane solution of cyanuric trichloride is added dropwise dropwise simultaneously；The mixed liquor is at 110 DEG C
12 h of lower heating adjust the pH=2 of mixture solution with HCl, and filtering is washed with distilled water several times, obtain after drying at room temperature
H4L ligand, yield are 81.3 %.
Isosorbide-5-Nitrae-dioxane solution of the cyanuric trichloride is the Isosorbide-5-Nitrae-that the cyanuric trichloride of 0.01 mol is dissolved in 10 mL
Six alkane of dioxy is made.
The Cu-MOF/CC composite catalyst is the composite material that nanometer stick array is supported on activation carbon cloth, nanometer rods
Shape crystal is formed along the longitudinal arrangement, and nano-micrometre is porous high-visible between crystal, and it is compound to belong to self-supporting integration nanometer three-dimensional
Material.
The constant potential electrochemical deposition method, current potential are -1.6~-2.0V, and sedimentation time is 5-15 min.
(2) electrochemistry oxygen metaplasia nitrogen simultaneously restores fixed nitrogen ammonification simultaneously
By 80 mL, 0.50 molL containing urea-10.5 molL-1KOH solution as electrolyte, electrochemical workstation
Working electrode connects a Cu-MOF/CC composite catalyst, and being connected to electrode and reference electrode for electrochemical workstation is another
A Cu-MOF/CC composite catalyst, two composite catalysts are immersed in same electrolyte, are passed through without nitrogen, utilize perseverance
0.5 V method of current potential, the raw nitrogen of electrochemical oxidation urea simultaneously restore fixed nitrogen ammonification simultaneously.
(3) electrochemistry oxygen metaplasia nitrogen simultaneously restores fixed nitrogen ammonification performance simultaneously
Above-mentioned electrochemistry oxygen metaplasia nitrogen and the method for restoring fixed nitrogen ammonification simultaneously, ammonia yield are 63-77 μ g h-1 mgcat -1,
Faradic efficiency is 12-14%, and after the stability test for having carried out 12 h, ammonia yield is still able to maintain the water being basically unchanged
It is flat, illustrate that this method can be realized without the efficient generation nitrogen fixed nitrogen certainly under additional condition of nitrogen gas, and have good stability.
The fixed nitrogen ammonification, yield test method are as follows:
1) standard curve is drawn
With 0.1 M PBS buffer solution of ammonium chloride and pH=7, the NH of series of concentrations is prepared4 +Standard solution；
2mL series standard solution is pipetted, sequentially adds that 2 mL concentration are the NaOH solution of 1.0 M, 1 mL concentration is 0.05 M
NaClO solution, the sodium nitroprusside solution that 0.2 mL mass fraction is 1%, quickly shake up, 25 DEG C of 2 h of placement, with UV-
Vis spectrophotometer detects the absorbance peak at the 655 nm wavelength of solution, and it is bent to draw absorbance-concentration, that is, A-c standard
Line obtains calibration curve equation；
The NaOH solution of 1.0 M is 5% salicylic acid and 5% sodium citrate containing mass fraction；
2) fixed nitrogen ammonification calculation of yield
Measure NH in reaction solution4 +Concentration, pipette the reaction solution of 2 h of 2mL catalysis reaction, the 2mL standard in alternative steps (2)
Solution calculates the yield of ammonia according to calibration curve equation.
Beneficial technical effect of the invention:
1. a kind of electrochemistry oxygen metaplasia nitrogen produced by the present invention and the method for restoring fixed nitrogen ammonification simultaneously, this method, which can be used, to be contained
Urea industry waste liquid aoxidizes under constant potential as electrolyte, because of the nitrogen that urea oxidation generates, is urging with the water in electrolyte
It is synchronized under the conditions of change and is reduced to ammonia, the method had not only handled urea pollution problem in environment but also had been the clean production ammonia of green
Provide new direction.
2. the present invention is method, raw materials used at low cost, preparation process is simple, and energy consumption of reaction is low, before having industrial application
Scape.
3. Cu-MOF/CC composite catalyst produced by the present invention, Cu-MOF therein refer to transition metal Cu2+With it is organic
Ligand H4L passes through the crystalline porous material with periodic network structure that is self-assembly of, it is with high porosity, low close
Degree, bigger serface, duct rule, aperture is adjustable and topological structure diversity and the advantages that Scalability.Cu-MOF/CC is multiple
Closing catalyst is the composite material that nanometer stick array is supported on activation carbon cloth, and nanoclub-like crystal is formed along the longitudinal arrangement, brilliant
Nano-micrometre is porous high-visible between body, belongs to self-supporting integration nanometer three-dimensional composite material.The structure exposes more
Active site, collaboration enhance conductive and catalytic performance, high catalytic efficiency.Because of the weak acid (- OH) and weak base (pyrrole contained in ligand
Pyridine N, imido grpup N) special soda acid buffering to structure, enables fixed nitrogen process high stability to carry out.
4. two reactions of catalysis fixed nitrogen and oxidation occurred present invention uses an electrolytic cell, it is anti-that fixed nitrogen belongs to reduction
It answers, complements each other with urea oxidation reaction, the electron-transport efficiency for improving oxidation end, Lai Tigao fixed nitrogen are aoxidized by catalyzing urea
The efficiency of reduction reaction entirety has prior meaning.
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.
1 H of embodiment4The preparation method of L ligand
By 0.02 mol amino isophthalic acid, 0.03 mol NaOH and 5 mol NaHCO3It is added in 60 ml distilled water,
30 min are stirred after mixing at room temperature；The 1,4- dioxane solution of cyanuric trichloride is added dropwise dropwise simultaneously；The mixed liquor is at 110 DEG C
12 h of lower heating adjust the pH=2 of mixture solution with HCl, and filtering is washed with distilled water several times, obtain after drying at room temperature
H4L ligand, yield are 81.3 %.
Isosorbide-5-Nitrae-dioxane solution of the cyanuric trichloride is the Isosorbide-5-Nitrae-that the cyanuric trichloride of 0.01 mol is dissolved in 10 mL
Six alkane of dioxy is made.
A kind of preparation method of the Cu-MOF/CC composite catalyst of embodiment 2
By 0.30 g H4L powder and 0.10 g copper nitrate are dissolved in 4 mL n,N-Dimethylformamide, after 60 μ L water are added dropwise,
180 W ultrasound obtains green clear solution in 1 minute, and the nitric acid that 90 μ L mass fractions are 68% is added dropwise, is stirred until homogeneous, obtains copper ion
And H4The mixed solution of L；
Using this mixed solution as electrolyte, using three-electrode electro Chemical work station, by the activated cm carbon cloth of 0.5 cm × 2 CC
As working electrode, platinized platinum is to electrode, and calomel electrode is reference electrode, is supported on using the synthesis of constant potential electrochemical deposition method
Cu-MOF composite material on carbon cloth CC；Obtained composite material is activated to constant weight in 85 DEG C, it is compound that Cu-MOF/CC is made
Catalyst；
The H4L, structural formula are as follows:
；
The activation carbon cloth is by carbon cloth successively in acetone, dehydrated alcohol and distillation underwater ultrasound 2min, and it is miscellaneous that washing removes surface
Object, then carbon cloth is immersed in nitric acid 1 min of ultrasound that mass fraction is 40 %, it is washed with water to wash and is made three times；
The Cu-MOF, basic structural unit are [Cu24L12(H2O)12]·30DMF·14H2O, DMF N, N- dimethyl methyl
Amide；A structural unit of Cu-MOF is by 24 Cu2+, 12 L4-, 12 main body hydrones, 30 object DMF molecules and 14
A object hydrone composition；The L4-, structural formula is as follows:
；
The Cu-MOF/CC composite catalyst, is the composite material that nanometer stick array is supported on activation carbon cloth, and nano bar-shape is brilliant
Body is formed along the longitudinal arrangement, and nano-micrometre is porous high-visible between crystal, belongs to self-supporting integration nanometer three-dimensional composite wood
Material；
The constant potential electrochemical deposition method, current potential are -1.6V, and sedimentation time is 15 min.
A kind of preparation method of the Cu-MOF/CC composite catalyst of embodiment 2
By 0.40 g H4L powder and 0.20 g copper nitrate are dissolved in 5 mL n,N-Dimethylformamide, after 80 μ L water are added dropwise,
180 W ultrasound 2 minutes green clear solution, be added dropwise 100 μ L mass fractions be 68% nitric acid, be stirred until homogeneous, obtain copper from
Son and H4The mixed solution of L；
Using this mixed solution as electrolyte, using three-electrode electro Chemical work station, by the activated cm carbon cloth of 0.5 cm × 2 CC
As working electrode, platinized platinum is to electrode, and calomel electrode is reference electrode, is supported on using the synthesis of constant potential electrochemical deposition method
Cu-MOF composite material on carbon cloth CC；Obtained composite material is activated to constant weight in 85 DEG C, it is compound that Cu-MOF/CC is made
Catalyst；
The H4L, structural formula is the same as embodiment 2；
The activation carbon cloth is that carbon cloth is successively removed surface in acetone, dehydrated alcohol and distillation 3 min of underwater ultrasound, washing
Sundries, then carbon cloth is immersed in nitric acid 2 min of ultrasound that mass fraction is 40 %, it is washed with water to wash and is made three times；
The Cu-MOF, basic structural unit and composition are the same as embodiment 2；
The L4-, structural formula is the same as embodiment 2；
The Cu-MOF/CC composite catalyst, structure is the same as embodiment 2；
The constant potential electrochemical deposition method, current potential are -1.8V, and sedimentation time is 10 min.
A kind of preparation method of the Cu-MOF/CC composite catalyst of embodiment 4
By 0.50 g H4L powder and 0.30 g copper nitrate are dissolved in 6 mL n,N-Dimethylformamide, after 100 μ L water are added dropwise,
180 W ultrasound 3 minutes green clear solution, be added dropwise 110 μ L mass fractions be 68% nitric acid, be stirred until homogeneous, obtain copper from
Son and H4The mixed solution of L；
Using this mixed solution as electrolyte, using three-electrode electro Chemical work station, by the activated cm carbon cloth of 0.5 cm × 2 CC
As working electrode, platinized platinum is to electrode, and calomel electrode is reference electrode, is supported on using the synthesis of constant potential electrochemical deposition method
Cu-MOF composite material on carbon cloth CC；Obtained composite material is activated to constant weight in 85 DEG C, it is compound that Cu-MOF/CC is made
Catalyst；
The H4L, structural formula is the same as embodiment 2；
The activation carbon cloth is by carbon cloth successively in acetone, dehydrated alcohol and distillation underwater ultrasound 4min, and it is miscellaneous that washing removes surface
Object, then carbon cloth is immersed in the nitric acid ultrasound 3min that mass fraction is 40 %, it is washed with water to wash and is made three times；
The Cu-MOF, basic structural unit and composition are the same as embodiment 2；
The L4-, structural formula is the same as embodiment 2；
The Cu-MOF/CC composite catalyst, structure is the same as embodiment 2；The constant potential electrochemical deposition method, current potential be-
2.0V, sedimentation time are 5 min.
5 electrochemistry oxygen metaplasia nitrogen of embodiment simultaneously restores fixed nitrogen ammonification simultaneously
By 70 mL 0.42-0.55 containing urea molL-10.5 molL-1KOH solution is as electrolyte, electrochemical operation
The working electrode stood connects a Cu-MOF/CC composite catalyst, and electrochemical workstation is connected to electrode and reference electrode
Another Cu-MOF/CC composite catalyst, two composite catalysts are immersed in same electrolyte, are passed through without nitrogen, benefit
With constant potential 0.4-0.6 V method, the raw nitrogen of electrochemical oxidation urea simultaneously restores fixed nitrogen ammonification simultaneously.
(3) electrochemistry oxygen metaplasia nitrogen simultaneously restores fixed nitrogen ammonification performance simultaneously
Above-mentioned electrochemistry oxygen metaplasia nitrogen and the method for restoring fixed nitrogen ammonification simultaneously, under the oxidation constant potential of 0.4-0.6 V, ammonia
Yield is 63-77 μ g h-1 mgcat -1, faradic efficiency 12-14%, and after the stability test for carrying out 12h, ammonia
Yield is still able to maintain the level being basically unchanged, and illustrates that this method can be realized without solid efficiently from nitrogen is generated under additional condition of nitrogen gas
Nitrogen, and have good stability.
6 electrochemistry oxygen metaplasia nitrogen of embodiment and the method for restoring fixed nitrogen ammonification simultaneously
By 80 mL, 0.50 molL containing urea-10.5 molL-1KOH solution as electrolyte, electrochemical workstation
Working electrode connects a Cu-MOF/CC composite catalyst, and being connected to electrode and reference electrode for electrochemical workstation is another
A Cu-MOF/CC composite catalyst, two composite catalysts are immersed in same electrolyte, are passed through without nitrogen, utilize perseverance
0.5 V method of current potential, the raw nitrogen of electrochemical oxidation urea simultaneously restore fixed nitrogen ammonification simultaneously；
Cu-MOF/CC composite catalyst made from embodiment 1, ammonia yield are 63 μ g h-1 mgcat -1, faradic efficiency is
12%, and after the stability test for carrying out 12h, ammonia yield is still able to maintain the level being basically unchanged, and illustrates that this method can be real
Now without the efficient generation nitrogen fixed nitrogen certainly under additional condition of nitrogen gas, and have good stability；
Cu-MOF/CC composite catalyst made from embodiment 2, ammonia yield are 77 μ g h-1 mgcat -1, faradic efficiency is
17%, and after the stability test for carrying out 12h, ammonia yield is still able to maintain the level being basically unchanged, and illustrates that this method can be real
Now without the efficient generation nitrogen fixed nitrogen certainly under additional condition of nitrogen gas, and have good stability；
Cu-MOF/CC composite catalyst made from embodiment 3, ammonia yield are 70 μ g h-1 mgcat -1, faradic efficiency is
13%, and after the stability test for carrying out 12h, ammonia yield is still able to maintain the level being basically unchanged, and illustrates that this method can be real
Now without the efficient generation nitrogen fixed nitrogen certainly under additional condition of nitrogen gas, and have good stability.
Fixed nitrogen ammonification described in 7 embodiment 6 of embodiment, yield performance test methods
(1) standard curve is drawn
With 0.1 M PBS buffer solution of ammonium chloride and pH=7, the NH of series of concentrations is prepared4 +Standard solution；
2mL series standard solution is pipetted, sequentially adds that 2 mL concentration are the NaOH solution of 1.0 M, 1 mL concentration is 0.05 M
NaClO solution, the sodium nitroprusside solution that 0.2 mL mass fraction is 1%, quickly shake up, 25 DEG C of 2 h of placement, with UV-
Vis spectrophotometer detects the absorbance peak at the 655 nm wavelength of solution, and it is bent to draw absorbance-concentration, that is, A-c standard
Line obtains calibration curve equation；
The NaOH solution of 1.0 M is 5% salicylic acid and 5% sodium citrate containing mass fraction；
(2) fixed nitrogen ammonification calculation of yield
Measure NH in reaction solution4 +Concentration, pipette the reaction solution of 2 h of 2mL catalysis reaction, the 2mL standard in alternative steps (2)
Solution calculates the yield of ammonia according to calibration curve equation.
Claims (5)
1. a kind of electrochemistry oxygen metaplasia nitrogen and the method for restoring fixed nitrogen ammonification simultaneously, which is characterized in that steps are as follows:
(1) Cu-MOF/CC composite catalyst is prepared
By 0.30-0.50 g H4L powder and 0.10-0.30 g copper nitrate are dissolved in 4-6 mL n,N-Dimethylformamide, are added dropwise
After 60-100 μ L water, 180 W ultrasounds 1-3 minutes obtain green clear solution, and the nitre that 90-110 μ L mass fraction is 68% is added dropwise
Acid is stirred until homogeneous, and obtains copper ion and H4The mixed solution of L；
Using this mixed solution as electrolyte, using three-electrode electro Chemical work station, by the activated cm carbon cloth of 0.5 cm × 2 CC
As working electrode, platinized platinum is to electrode, and calomel electrode is reference electrode, is supported on using the synthesis of constant potential electrochemical deposition method
Cu-MOF composite material on carbon cloth CC；Obtained composite material is activated to constant weight in 85 DEG C, it is compound that Cu-MOF/CC is made
Catalyst；
(2) electrochemistry oxygen metaplasia nitrogen simultaneously restores fixed nitrogen ammonification simultaneously
By 70-90 mL 0.42-0.55 containing urea molL-10.5 molL-1KOH solution is as electrolyte, electrochemistry work
Make the working electrode stood and connect a Cu-MOF/CC composite catalyst, electrochemical workstation connects electrode with reference electrode
In another Cu-MOF/CC composite catalyst, two composite catalysts are immersed in same electrolyte, are passed through without nitrogen,
Using constant potential 0.4-0.6 V method, the raw nitrogen of electrochemical oxidation urea simultaneously restores fixed nitrogen ammonification simultaneously.
2. a kind of electrochemistry oxygen metaplasia nitrogen as described in claim 1 and the method for restoring fixed nitrogen ammonification simultaneously, which is characterized in that
The H4L, structural formula are as follows:
。
3. a kind of electrochemistry oxygen metaplasia nitrogen as described in claim 1 and the method for restoring fixed nitrogen ammonification simultaneously, which is characterized in that
The activation carbon cloth is by carbon cloth successively in acetone, dehydrated alcohol and distillation underwater ultrasound 2-4min, and it is miscellaneous that washing removes surface
Object, then carbon cloth is immersed in the nitric acid ultrasound 1-3min that mass fraction is 40 %, it is washed with water to wash and is made three times.
4. a kind of electrochemistry oxygen metaplasia nitrogen as described in claim 1 and the method for restoring fixed nitrogen ammonification simultaneously, which is characterized in that
The Cu-MOF, basic structural unit are [Cu24L12(H2O)12]·30DMF·14H2O, DMF are n,N-Dimethylformamide；
A structural unit of Cu-MOF is by 24 Cu2+, 12 L4-, 12 main body hydrone, 30 object DMF molecules and 14 visitors
Body hydrone composition；The L4-, structural formula is as follows:
。
5. a kind of electrochemistry oxygen metaplasia nitrogen as described in claim 1 and the method for restoring fixed nitrogen ammonification simultaneously, which is characterized in that
The constant potential electrochemical deposition method, current potential are -1.6~-2.0V, and sedimentation time is 5-15 min.
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