CN110479277A - A method of promoting the catalysis fixed nitrogen reaction of nano-hydroxy cobalt oxide - Google Patents
A method of promoting the catalysis fixed nitrogen reaction of nano-hydroxy cobalt oxide Download PDFInfo
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- CN110479277A CN110479277A CN201910813204.XA CN201910813204A CN110479277A CN 110479277 A CN110479277 A CN 110479277A CN 201910813204 A CN201910813204 A CN 201910813204A CN 110479277 A CN110479277 A CN 110479277A
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- cobalt oxide
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- hydroxy cobalt
- fixed nitrogen
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 31
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 20
- 230000001737 promoting effect Effects 0.000 title claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- DLHSXQSAISCVNN-UHFFFAOYSA-M hydroxy(oxo)cobalt Chemical compound O[Co]=O DLHSXQSAISCVNN-UHFFFAOYSA-M 0.000 claims abstract description 19
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910018916 CoOOH Inorganic materials 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 229920000557 Nafion® Polymers 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000001548 drop coating Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000001788 irregular Effects 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 2
- 244000208235 Borassus flabellifer Species 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000001588 bifunctional effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000004202 carbamide Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 23
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004176 ammonification Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 241001086902 Normanbya normanbyi Species 0.000 description 1
- ITFCTBFBEKRKDC-UHFFFAOYSA-N [O].OC Chemical compound [O].OC ITFCTBFBEKRKDC-UHFFFAOYSA-N 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses the preparation of hydroxy cobalt oxide bifunctional catalyst and the applications of simultaneous oxidation urea and fixed nitrogen, belong to nano material, electrochemical catalysis technical field.It is that raw material is first prepared into cobalt hydroxide that it, which has main steps that using cobalt chloride, and cobalt hydroxide is oxidized to hydroxy cobalt oxide with liquor natrii hypochloritis, obtains dark brown hydroxy cobalt oxide powder after centrifuge washing is dry；The bifunctional catalyst of methanol oxidation and fixed nitrogen is carried out simultaneously.The catalysis material prepares raw materials used at low cost, and preparation process is simple, and energy consumption of reaction is low, has prospects for commercial application.The hydroxy cobalt oxide material has extremely excellent electrochemical catalysis performance and stability for efficiently methanol oxidation simultaneously and fixed nitrogen reaction.
Description
Technical field
The present invention relates to the applications that a kind of nano-hydroxy cobalt oxide catalyst promotes fixed nitrogen to react using methanol oxidation, belong to
Nano material, electrochemical catalysis technical field.
Background technique
Currently, most of bifunctional electrocatalysts concentrate on while (OER) and oxygen reduction reaction (ORR) are reacted in oxygen release
Or evolving hydrogen reaction (HER) and OER, the i.e. application of complete solution water simultaneously.However, another important reaction fixed nitrogen as reduction reaction
Catalysis reaction, i.e. N2Electrochemical reduction ammonification (N2 + 6H+ + 6e-→2NH3) reaction have not been reported.Ammonia (NH3) it is one
The required chemicals of kind annual high yield, especially fertilizer, medicament, dyestuff, explosive and tree essential in many application fields
Rouge prepares industry.In the past decade, ammonia is mainly produced by Haber-Bosch technique.However, due to its stringent reaction item
Part (300-400 DEG C of reaction temperature and 150-250 atm pressure), leads to its high energy demand and excess CO2Discharge.With N2And H2O
For raw material, electro-catalysis synthesizes the advantage that ammonia technology has clean manufacturing and conveniently regulating and controlling external voltage adjustment reaction rate；With
Haber-Bosch technique is compared, and cost substantially reduces.However, electrochemistry fixed nitrogen process needs high overpotential to destroy N ≡ N
The high bond energy of (941kJ moL-1), and the serious obstruction by cathode hydrogen evolution competitive reaction (HER) cause its faraday to be imitated
Rate (FE) is less than 10% or even less than 1%, and NH3Yield is relatively low.
As essential reaction medium, selection has limited proton translocation rate and increases N2The suitable electrolysis of solubility
Matter (proton exchange electrolyte, anion exchange electrolyte etc.) is to evade liberation of hydrogen side reaction and improve selective common method.
However, limitation electron transfer rate using reduce evolving hydrogen reaction be to reduce reaction efficiency and use high cost electrolyte as cost,
This becomes the obstacle of industrial scale applications.Therefore, exploitation is for obtaining high NH3The model electrochemical of yield and optimum performance
Fixed nitrogen strategy is of great significance.
Summary of the invention
Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, a kind of nano-hydroxy cobalt oxide is provided and is urged
The preparation method of agent, this method is raw materials used at low cost, and preparation process is simple, and energy consumption of reaction is low, has prospects for commercial application.
The two of technical assignment of the invention are to provide a kind of purposes of hydroxy cobalt oxide bifunctional catalyst, i.e., should
Hydroxy cobalt oxide nanometer sheet is for simultaneous oxidation methanol and efficiently promotes fixed nitrogen reaction, and this method is easy to operate, and catalytic performance is excellent
It is different and have good stability.
To achieve the above object, The technical solution adopted by the invention is as follows:
(1) nano Co OOH catalyst is prepared
1.56-1.60 g cobalt chloride is blended with the mixed solution that 4-6 mL ethylene glycol and 1.5-1.9 mL water form, 180 W
After ultrasonic dissolution, with ammonium hydroxide tune pH=9, moves into reaction kettle and be heated to 110 DEG C of 12 h of heat preservation;It is washed with water, is centrifugated three
After secondary, obtained solid is dispersed in 5 mL water, 5 mL are added dropwise, black palm fibre occurs in the liquor natrii hypochloritis that mass fraction is 10%
Color precipitating；It washed, be centrifugated twice respectively with water and methanol, drying to constant weight by 85 DEG C obtained of dark brown precipitating, obtains
Nano-hydroxy cobalt oxide catalyst, i.e. nano Co OOH catalyst；
(2) CoOOH/GCE electrode is prepared
10 mg nano-hydroxy cobalt oxide catalysts are blended with 720 μ L water, 250 μ L methanol and 30 μ L Nafion, 180 W
Hydroxy cobalt oxide suspension is made after 30 min of ultrasound, takes 10 μ L solution drop coatings on the glass-carbon electrode that diameter is 4 mm, room temperature
It is dried overnight, the glass-carbon electrode of load nano-hydroxy cobalt oxide catalyst, i.e. CoOOH/GCE electrode has been made；
(3) nano-hydroxy cobalt oxide is promoted to be catalyzed fixed nitrogen
Two Room electrolytic cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion, a Room
It is electrolyte that the 0.5 M KOH solution containing 1.0 M methanol, which is added, and the working electrode of electrochemical workstation is connected to a CoOOH/
On GCE electrode；Another room uses 0.5 M KOH solution for electrolyte, and the reference electrode of electrochemical workstation is connected with to electrode
On another CoOOH/GCE electrode；After being continually fed into 10 min of nitrogen to the Room containing 0.5 M KOH electrolyte, use
The voltage of 0.3-0.5 V carries out methanol and promotes the catalysis fixed nitrogen reaction of nano-hydroxy cobalt oxide, i.e. promotion nano-hydroxy cobalt oxide is urged
Change fixed nitrogen reaction.
The nano-hydroxy cobalt oxide catalyst, pattern are flaky nanometer structure, are in irregular nanoporous shape, piece between piece
With a thickness of 50-60 nm.
When applied voltage is 0.3 V, it is 75-79 μ g h that ammonia, which generates rate,-1 mgcat -1, faradic efficiency 10-
13 %, and nitrogen-fixing efficiency is only 42-44 μ g h in the promotion of no methanol oxidation-1 mgcat -1, illustrate that this method is efficient
Enhance nitrogen fixing capacity；And after recycling 10 times in the environment for having methanol, ammonia generates rate and faradic efficiency is not found
Apparent variation, shows that hydroxy cobalt oxide nanometer sheet catalyst is also with good stability.
Beneficial technical effect of the invention:
1. the preparation method of hydroxy cobalt oxide bifunctional catalyst of the present invention, raw materials used at low cost, preparation process is simple, instead
It answers that low energy consumption, there is prospects for commercial application.
2. the method that the present invention promotes nano-hydroxy cobalt oxide catalysis fixed nitrogen is used for using hydroxy cobalt oxide catalyst
The catalysis oxidation of methanol is simultaneously reacted for being catalyzed high-efficiency nitrogen-fixing ammonification simultaneously.Since the oxidation of methanol is prior to existing for no methanol
Oxygen evolution reaction, and the Strong oxdiative ability of hydroxy cobalt oxide catalyst increases methanol oxidative activity, thus causes to cathode
Electron-transport efficiency improves, so that reduction reaction electron transfer rate is also increase accordingly in entire cell system, promotes
The efficiency of fixed nitrogen ammonification reduction reaction；In addition, the substitution of the waste liquid containing methanol, therefore, the party can be used in methanol used in the reaction
Method is a kind of new way for promoting fixed nitrogen ammonification catalytic activity, and the operation is easy, and industrial prospect is wide.
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 method for promoting nano-hydroxy cobalt oxide catalysis fixed nitrogen of embodiment 1
(1) nano Co OOH catalyst is prepared
1.56 g cobalt chlorides are blended with the mixed solution that 4 mL ethylene glycol and 1.5 mL water form, after 180 W ultrasonic dissolutions,
With ammonium hydroxide tune pH=9, moves into reaction kettle and be heated to 110 DEG C of 12 h of heat preservation;After being washed with water, being centrifugated three times, it will obtain
Solid be dispersed in 5 mL water, 5 mL are added dropwise, dark brown precipitating occurs in the liquor natrii hypochloritis that mass fraction is 10%；Use water
It washs, be centrifugated twice respectively with methanol, drying to constant weight by 85 DEG C obtained of dark brown precipitating, obtains nano-hydroxy oxygen
Change Co catalysts, i.e. nano Co OOH catalyst；
(2) CoOOH/GCE electrode is prepared
10 mg nano-hydroxy cobalt oxide catalysts are blended with 720 μ L water, 250 μ L methanol and 30 μ L Nafion, 180 W
Hydroxy cobalt oxide suspension is made after 30 min of ultrasound, takes 10 μ L solution drop coatings on the glass-carbon electrode that diameter is 4 mm, room temperature
It is dried overnight, the glass-carbon electrode of load nano-hydroxy cobalt oxide catalyst, i.e. CoOOH/GCE electrode has been made；
(3) nano-hydroxy cobalt oxide is promoted to be catalyzed fixed nitrogen
Two Room electrolytic cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion, a Room
It is electrolyte that the 0.5 M KOH solution containing 1.0 M methanol, which is added, and the working electrode of electrochemical workstation is connected to a CoOOH/
On GCE electrode；Another room uses 0.5 M KOH solution for electrolyte, and the reference electrode of electrochemical workstation is connected with to electrode
On another CoOOH/GCE electrode；After being continually fed into 10 min of nitrogen to the Room containing 0.5 M KOH electrolyte, 0.3 is used
The voltage of V carries out methanol and promotes the catalysis fixed nitrogen reaction of nano-hydroxy cobalt oxide, i.e. promotion nano-hydroxy cobalt oxide catalysis fixed nitrogen is anti-
It answers.
The nano-hydroxy cobalt oxide catalyst, pattern are flaky nanometer structure, are in irregular nanoporous shape, piece between piece
With a thickness of 50-60 nm.
When applied voltage is 0.3 V, it is 75 μ g h that ammonia, which generates rate,-1 mgcat -1, faradic efficiency 10.6
%, and nitrogen-fixing efficiency is only 42 μ g h in the promotion of no methanol oxidation-1 mgcat -1, illustrating this method efficiently enhances admittedly
Nitrogen ability；And after recycling 10 times in the environment for having methanol, ammonia generates rate and faradic efficiency is not found significantly
Variation, shows that hydroxy cobalt oxide nanometer sheet catalyst is also with good stability.
A kind of method for promoting nano-hydroxy cobalt oxide catalysis fixed nitrogen of embodiment 2
(1) nano Co OOH catalyst is prepared
1.58 g cobalt chlorides are blended with the mixed solution that 5 mL ethylene glycol and 1.7 mL water form, after 180 W ultrasonic dissolutions,
With ammonium hydroxide tune pH=9, moves into reaction kettle and be heated to 110 DEG C of 12 h of heat preservation;After being washed with water, being centrifugated three times, it will obtain
Solid be dispersed in 5 mL water, 5 mL are added dropwise, dark brown precipitating occurs in the liquor natrii hypochloritis that mass fraction is 10%；Use water
It washs, be centrifugated twice respectively with methanol, drying to constant weight by 85 DEG C obtained of dark brown precipitating, obtains nano-hydroxy oxygen
Change Co catalysts, i.e. nano Co OOH catalyst；
(2) CoOOH/GCE electrode is prepared
10 mg nano-hydroxy cobalt oxide catalysts are blended with 720 μ L water, 250 μ L methanol and 30 μ L Nafion, 180 W
Hydroxy cobalt oxide suspension is made after 30 min of ultrasound, takes 10 μ L solution drop coatings on the glass-carbon electrode that diameter is 4 mm, room temperature
It is dried overnight, the glass-carbon electrode of load nano-hydroxy cobalt oxide catalyst, i.e. CoOOH/GCE electrode has been made；
(3) nano-hydroxy cobalt oxide is promoted to be catalyzed fixed nitrogen
Two Room electrolytic cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion, a Room
It is electrolyte that the 0.5 M KOH solution containing 1.0 M methanol, which is added, and the working electrode of electrochemical workstation is connected to a CoOOH/
On GCE electrode；Another room uses 0.5 M KOH solution for electrolyte, and the reference electrode of electrochemical workstation is connected with to electrode
On another CoOOH/GCE electrode；After being continually fed into 10 min of nitrogen to the Room containing 0.5 M KOH electrolyte, 0.3 is used
The voltage of V carries out methanol and promotes the catalysis fixed nitrogen reaction of nano-hydroxy cobalt oxide, i.e. promotion nano-hydroxy cobalt oxide catalysis fixed nitrogen is anti-
It answers.
The nano-hydroxy cobalt oxide catalyst, pattern are flaky nanometer structure, are in irregular nanoporous shape, piece between piece
With a thickness of 50-60 nm.
When applied voltage is 0.3 V, it is 79 μ g h that ammonia, which generates rate,-1 mgcat -1, faradic efficiency is 13 %,
And nitrogen-fixing efficiency is only 44 μ g h in the promotion of no methanol oxidation-1 mgcat -1, illustrate that this method efficiently enhances fixed nitrogen
Ability；And after recycling 10 times in the environment for having methanol, ammonia generates rate and faradic efficiency does not find significantly to become
Change, shows that hydroxy cobalt oxide nanometer sheet catalyst is also with good stability.
A kind of method for promoting nano-hydroxy cobalt oxide catalysis fixed nitrogen of embodiment 3
(1) nano Co OOH catalyst is prepared
1.60 g cobalt chlorides are blended with the mixed solution that 6 mL ethylene glycol and 1.9 mL water form, after 180 W ultrasonic dissolutions,
With ammonium hydroxide tune pH=9, moves into reaction kettle and be heated to 110 DEG C of 12 h of heat preservation;After being washed with water, being centrifugated three times, it will obtain
Solid be dispersed in 5 mL water, 5 mL are added dropwise, dark brown precipitating occurs in the liquor natrii hypochloritis that mass fraction is 10%；Use water
It washs, be centrifugated twice respectively with methanol, drying to constant weight by 85 DEG C obtained of dark brown precipitating, obtains nano-hydroxy oxygen
Change Co catalysts, i.e. nano Co OOH catalyst；
(2) CoOOH/GCE electrode is prepared
10 mg nano-hydroxy cobalt oxide catalysts are blended with 720 μ L water, 250 μ L methanol and 30 μ L Nafion, 180 W
Hydroxy cobalt oxide suspension is made after 30 min of ultrasound, takes 10 μ L solution drop coatings on the glass-carbon electrode that diameter is 4 mm, room temperature
It is dried overnight, the glass-carbon electrode of load nano-hydroxy cobalt oxide catalyst, i.e. CoOOH/GCE electrode has been made；
(3) nano-hydroxy cobalt oxide is promoted to be catalyzed fixed nitrogen
Two Room electrolytic cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion, a Room
It is electrolyte that the 0.5 M KOH solution containing 1.0 M methanol, which is added, and the working electrode of electrochemical workstation is connected to a CoOOH/
On GCE electrode；Another room uses 0.5 M KOH solution for electrolyte, and the reference electrode of electrochemical workstation is connected with to electrode
On another CoOOH/GCE electrode；After being continually fed into 10 min of nitrogen to the Room containing 0.5 M KOH electrolyte, 0.3 is used
Voltage, carry out methanol promote nano-hydroxy cobalt oxide catalysis fixed nitrogen reaction, i.e., promotion nano-hydroxy cobalt oxide catalysis fixed nitrogen it is anti-
It answers.
The nano-hydroxy cobalt oxide catalyst, pattern are flaky nanometer structure, are in irregular nanoporous shape, piece between piece
With a thickness of 50-60 nm.
When applied voltage is 0.3 V, it is 77 μ g h that ammonia, which generates rate,-1 mgcat -1, faradic efficiency 12.8
%, and nitrogen-fixing efficiency is only 43.5 μ g h in the promotion of no methanol oxidation-1 mgcat -1, illustrate that this method efficiently enhances
Nitrogen fixing capacity；And after recycling 10 times in the environment for having methanol, ammonia generates rate and faradic efficiency is not found obviously
Variation, show that hydroxy cobalt oxide nanometer sheet catalyst is also with good stability.
Claims (2)
1. a kind of method for promoting the catalysis fixed nitrogen reaction of nano-hydroxy cobalt oxide, which is characterized in that steps are as follows:
(1) nano Co OOH catalyst is prepared
1.56-1.60 g cobalt chloride is blended with the mixed solution that 4-6 mL ethylene glycol and 1.5-1.9 mL water form, 180 W
After ultrasonic dissolution, with ammonium hydroxide tune pH=9, moves into reaction kettle and be heated to 110 DEG C of 12 h of heat preservation;It is washed with water, is centrifugated three
After secondary, obtained solid is dispersed in 5 mL water, 5 mL are added dropwise, black palm fibre occurs in the liquor natrii hypochloritis that mass fraction is 10%
Color precipitating；It washed, be centrifugated twice respectively with water and methanol, drying to constant weight by 85 DEG C obtained of dark brown precipitating, obtains
Nano-hydroxy cobalt oxide catalyst, i.e. nano Co OOH catalyst；
(2) CoOOH/GCE electrode is prepared
10 mg nano-hydroxy cobalt oxide catalysts are blended with 720 μ L water, 250 μ L methanol and 30 μ L Nafion, 180 W
Hydroxy cobalt oxide suspension is made after 30 min of ultrasound, takes 10 μ L solution drop coatings on the glass-carbon electrode that diameter is 4 mm, room temperature
It is dried overnight, the glass-carbon electrode of load nano-hydroxy cobalt oxide catalyst, i.e. CoOOH/GCE electrode has been made；
(3) nano-hydroxy cobalt oxide is promoted to be catalyzed fixed nitrogen
Two Room electrolytic cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion, a Room
It is electrolyte that the 0.5 M KOH solution containing 1.0 M methanol, which is added, and the working electrode of electrochemical workstation is connected to a CoOOH/
On GCE electrode；Another room uses 0.5 M KOH solution for electrolyte, and the reference electrode of electrochemical workstation is connected with to electrode
On another CoOOH/GCE electrode；After being continually fed into 10 min of nitrogen to the Room containing 0.5 M KOH electrolyte, use
The voltage of 0.3-0.5 V carries out methanol and promotes the catalysis fixed nitrogen reaction of nano-hydroxy cobalt oxide, i.e. promotion nano-hydroxy cobalt oxide is urged
Change fixed nitrogen reaction.
2. promoting the method for nano-hydroxy cobalt oxide catalysis fixed nitrogen reaction as described in claim 1, which is characterized in that described to receive
Rice hydroxy cobalt oxide catalyst, pattern are flaky nanometer structure, are in irregular nanoporous shape between piece, piece is with a thickness of 50-60
nm。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910813204.XA CN110479277B (en) | 2019-08-30 | 2019-08-30 | Method for promoting catalytic nitrogen fixation reaction of nano cobalt oxyhydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910813204.XA CN110479277B (en) | 2019-08-30 | 2019-08-30 | Method for promoting catalytic nitrogen fixation reaction of nano cobalt oxyhydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110479277A true CN110479277A (en) | 2019-11-22 |
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Cited By (3)
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| CN111270254A (en) * | 2020-03-12 | 2020-06-12 | 济南大学 | Method for promoting room-temperature nitrogen reduction by Cu/Ca-MOF nano composite catalyst |
| CN112551594A (en) * | 2020-08-31 | 2021-03-26 | 深圳市深源动力高纯硅技术有限公司 | Lamellar nano cobalt oxyhydroxide and preparation method and application thereof |
| CN113457679A (en) * | 2020-03-31 | 2021-10-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of cobalt oxyhydroxide catalyst |
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| CN110038637A (en) * | 2019-05-05 | 2019-07-23 | 济南大学 | Preparation method and application of ternary nanocomposite |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111270254A (en) * | 2020-03-12 | 2020-06-12 | 济南大学 | Method for promoting room-temperature nitrogen reduction by Cu/Ca-MOF nano composite catalyst |
| CN111270254B (en) * | 2020-03-12 | 2022-03-11 | 济南大学 | Method for promoting room-temperature nitrogen reduction by Cu/Ca-MOF nano composite catalyst |
| CN113457679A (en) * | 2020-03-31 | 2021-10-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of cobalt oxyhydroxide catalyst |
| CN112551594A (en) * | 2020-08-31 | 2021-03-26 | 深圳市深源动力高纯硅技术有限公司 | Lamellar nano cobalt oxyhydroxide and preparation method and application thereof |
| CN112551594B (en) * | 2020-08-31 | 2023-02-28 | 深圳市本征方程石墨烯技术股份有限公司 | Lamellar nano cobalt oxyhydroxide and preparation method and application thereof |
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