CN109647464A - A kind of electrocatalysis material converting nitrogen to ammonia - Google Patents
A kind of electrocatalysis material converting nitrogen to ammonia Download PDFInfo
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- CN109647464A CN109647464A CN201910017700.4A CN201910017700A CN109647464A CN 109647464 A CN109647464 A CN 109647464A CN 201910017700 A CN201910017700 A CN 201910017700A CN 109647464 A CN109647464 A CN 109647464A
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- mxene
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 65
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 23
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 45
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 230000001603 reducing effect Effects 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 238000005119 centrifugation Methods 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 239000013256 coordination polymer Substances 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000001548 drop coating Methods 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000011946 reduction process Methods 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 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 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 229940083618 sodium nitroprusside Drugs 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910009818 Ti3AlC2 Inorganic materials 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 38
- 235000019441 ethanol Nutrition 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- 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
- C25B11/091—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the fields that the preparation of nano material and nitrogen restore, and are related to a kind of electrocatalysis material for converting nitrogen to ammonia, first use Ti3AlC2Precursor prepares pure Ti3C2TxMXene, then to pure Ti3C2TxMXene is improved by way of solvent heat, finally verifies its application method and catalytic effect, finds Ti3C2Tx/TiO2Its amonia yield of nano-complex can reach 32.17 μ g h in -0.55V‑1mg–1 cat.Its faradic efficiency can reach 16.07% in -0.45V, and pure Ti3C2TxIts amonia yield of MXene -0.55V only reaches 22.19 μ g h‑1mg–1 cat., faradic efficiency reaches 7.09% in -0.45V, and Ti3C2Tx/TiO2The amonia yield and faradic efficiency of nano-complex are TiO respectively211 times of nano particle and 69 times, and Ti3C2Tx/TiO2The catalytic efficiency of nano-complex is higher than current most of elctro-catalysts, shows Ti3C2Tx/TiO2Nano-complex is extraordinary nitrogen reducing material, can be applied to nitrogen reduction field, simple convenient for operation, raw material is easy to get, and preparation cost is low；Preparation efficiency is high, and good product quality obtained, stability is strong, and application environment is good, wide market.
Description
Technical field:
The invention belongs to the fields that the preparation of nano material and nitrogen restore, and are related to a kind of electricity for converting nitrogen to ammonia
Catalysis material, with ethyl alcohol and Ti3AlC2MAX is raw material, synthesizes Ti using HF etching and ethanol-thermal method3C2TxMXene nanometer sheet with
Ti02The compound of nano particle, and any substrate and titanium source need not be added.
Background technique:
Ammonia is a kind of indispensable industrial chemical, in plastics, textile industry, the fields such as agricultural and food production hair
Wave important function.It is considered as can promote the renewable energy intensity fuel of global low-carbon or carbon-free process.Therefore, to ammonia
The great demand of gas promotes exploration of the people in terms of nitrogen fixation.Nitrogen is fixed to convert nitrogen a large amount of in atmosphere to
Ammonia, but since the bond energy of N ≡ N key is very big, nitrogen fixed network is limited by very large.So far, industrial
On prepare ammonia using traditional Haber-Bosch method always.However, the method needs extreme reaction condition (400-500
DEG C, 200-250bar), it consumes a large amount of natural gases and gives off a large amount of carbon dioxide, will cause serious environmental problem.It is based on
The above reason, electro-catalysis nitrogen reduction generate ammonia due to its be just able to achieve at ambient conditions manual nitrogen fix and by pole
Big concern.However, most nitrogen reduction its catalytic efficiency of elctro-catalyst is extremely low, it is therefore desirable to efficient elctro-catalyst with
Reduce the activation energy of nitrogen.So far, noble metal-based catalysts show excellent electro catalytic activity in nitrogen reduction, but
It is since high cost and low abundance limit its extensive use.Therefore, attention is concentrated mainly on transiting metal oxidation by everybody
On object.Wherein titanium dioxide is paid special attention to due to its low cost, environment friendly and excellent chemical stability, still
Due to its low electric conductivity, the problems such as preparation process is complicated and self aggregation, the electrocatalysis characteristic of pure titinium dioxide is nevertheless suffered from
Limitation.Therefore, prepare in a simple manner with high electronic conductivity and excellent catalytic capability based on TiO2The nitrogen of material
Reducing catalyst still has huge meaning.
MXenes is a kind of emerging two-dimensional material, is made of transition metal nitride or carbide or carbonitride,
General formula is Mn+1XnTx, wherein " M " represents transition metal element, " X " represents carbon or nitrogen or carbon nitrogen, and TxRepresentative-OH's or-F etc.
End group, n are 1,2 or 3.MXenes has been widely used in biology due to its high electric conductivity, water-wetted surface and flexibility
Sensor, electro-magnetic wave absorption, supercapacitor, lithium ion battery, electronic equipment, the fields such as gas sensor.Simultaneously as
Ti3C2TxTitanium atom on MXenes marginal surface is that thermodynamics is metastable, therefore can be used as nucleation site, to generate phase
To stable titanium dioxide.2D Ti is distributed in so as to be formed3C2TxTiO in nanometer sheet2The heterogeneous junction of nano particle
Structure.And the composite material formed can be TiO2Nano particle provides the support platform of high conductivity, and prevents TiO2Self aggregation
Problem.Therefore, design prepares a kind of electrocatalysis material for converting nitrogen to ammonia, its catalytic performance of the electrocatalysis material is more than
Catalyst known to major part.
Summary of the invention:
It is an object of the invention to overcome disadvantage present on the prior art, a kind of electricity for converting nitrogen to ammonia is designed
Catalysis material, the material are a kind of green, succinct, effective novel nitrogen reduction electrocatalysis materials, and high catalytic efficiency is obtained
Good product quality.
To achieve the goals above, the novel nitrogen of one kind of the present invention restores electrocatalysis material, passes through following skill
Art scheme is realized, Ti is first prepared3C2TxMXene nanometer sheet simultaneously further changes its nitrogen reducing property by hydro-thermal method
Into specific process step is carried out as follows:
S1, Ti is used3AlC2Precursor prepares pure Ti3C2TxMXene；
(1), 4g Ti is weighed3AlC2Powder is put into 250mL polypropylene vial, and is put on magnetic stirring apparatus, and revolving speed is greater than
200 revs/min；
(2), 1g Ti is pressed in the polypropylene vial in step (1)3The ratio of AlC:10mL hydrofluoric acid solution is slowly added dropwise
The hydrofluoric acid solution that 40mL mass fraction is 49% reacts for 24 hours at room temperature under the stirring greater than 200 rpms；
(3), it is put into centrifuge tube after after reaction taking out the suspension in polypropylene vial, centrifuge tube is symmetrically placed
In in centrifuge, with revolving speed centrifugation 10 minutes or more greater than 7000 revs/min, solution after centrifugation is made, is excessive hydrogen fluorine
Acid, impurity containing aluminium and Ti3C2TxMXene, its lower sediment is pure Ti after centrifugation3C2TxMXene；
(4), by pure Ti3C2TxMXene washs centrifugation with deionized water repeatedly, until its for neutrality, it is extra to remove
Fluorine ion and hydrogen ion；
(5), by pure Ti obtained in step (4)3C2TxMXene solid is dried in vacuo 8 hours or more in the case where being greater than 50 DEG C
It is spare；
S2, to the pure Ti prepared in step S13C2TxMXene is improved by way of solvent heat:
(1), the pure Ti of 0.15g is weighed respectively in clean beaker3C2TxMXene powder is added 15mL dehydrated alcohol, stirs
It is spare that black suspension is obtained after mixing；
(2), black suspension prepared by step (1) is transferred in closed PTFE vessel and is put into hydrothermal reaction kettle
In, 120 DEG C at a temperature of hydro-thermal 16 hours, be made hydro-thermal after suspension；
(3), after the suspension natural conditions after hydro-thermal drop to room temperature, the polytetrafluoroethylene (PTFE) in hydrothermal reaction kettle is taken out
Tank, and will liquid in polytetrafluoroethyltank tank take out after be put into centrifuge tube, centrifuge tube is symmetrically placed in centrifuge, with big
Be centrifuged 10 minutes in 10000 revs/min of revolving speeds or more, upper layer is colorless and transparent solvent, lower layer Ti after centrifugation3C2Tx/
TiO2Nano-complex；
(4), it takes lower sediment in step (3) to wash centrifugation 2-3 times repeatedly, and is dried in vacuo 8 hours in the case where being greater than 50 DEG C
Ti is obtained above3C2Tx/TiO2Nano-complex；
S3、Ti3C2Tx/TiO2The application method and catalytic effect of nano-complex
(1), 5mg Ti is weighed3C2Tx/TiO2Nano-complex is put into 2mL centrifuge tube, then 490 μ are added into centrifuge tube
The Nafion solution that L distilled water, 490 μ L dehydrated alcohols and 20 μ L mass fractions are 5%, ultrasound 30 minutes in ultrasonic disintegrator
Obtain homogeneous solution；
(2), carbon paper is cleaned by alcohol with spare；
(3), the Ti in step (1) is taken3C2Tx/TiO2The 20 uniform drop coating of μ L of mixed solution of nano-complex is after the cleaning
Carbon paper on, then by Ti in drop coating3C2Tx/TiO2The carbon paper of nano-complex be placed on it is to be dried at room temperature after continue to use；
(4), nitrogen reduction is carried out using electrochemical workstation three-electrode system in nitrogen reduction process, it may be assumed that step (3)
In Ti3C2Tx/TiO2- CP is used as working electrode, and Ag/AgCl electrode is used as reference electrode, platinum plate electrode to electrode；
(5), entire nitrogen reduction process in the H-type electrolytic cell that centre is separated by Nafion membrane (perfluorinated sulfonic acid diaphragm) into
Row, before carrying out nitrogen reduction, high pure nitrogen is continual to be passed into cathode electrolytic cell at least 30 minutes, makes catholyte
Electrolyte in slot is full of nitrogen；
(6), by the Ti in step (3)3C2Tx/TiO2- CP working electrode and Ag/AgCl electrode are inserted respectively into step (5)
In cathode electrolytic cell in, platinum plate electrode is inserted into anode electrolytic tank, and high pure nitrogen is continual during reaction is passed through
Into cathode electrolytic cell；
(7), electrolyte after reaction, is taken out from the cathode electrolytic cell of electrolytic cell and carries out chromogenic reaction, is produced with testing
The content of ammonifying gas.
Pure Ti of the present invention to preparation3C2TxMXene and stratiform Ti3C2Tx/TiO2The nitrogen reducing property of nano-complex
It is tested, finds Ti3C2Tx/TiO2Its amonia yield of nano-complex can reach 32.17 μ g h in -0.55V-1mg–1 catIts
Faradic efficiency can reach 16.07% in -0.45V, and pure Ti3C2TxIts amonia yield of MXene -0.55V only reaches 22.19 μ g
h-1mg–1 cat, faradic efficiency only reaches 7.09% in -0.45V, and Ti3C2Tx/TiO2The amonia yield of nano-complex and
Faradic efficiency is TiO respectively211 times of nano particle and 69 times, and Ti3C2Tx/TiO2The catalytic efficiency of nano-complex is higher than
Current most of elctro-catalysts, show Ti3C2Tx/TiO2Nano-complex is extraordinary nitrogen reducing material, be can be applied to
Nitrogen restores field.
Further, the cleaning mode of carbon paper is as follows in the present invention, and carbon paper is entered in 50mL beaker, is added into beaker
The ethanol solution of 30mL, in ultrasonic disintegrator ultrasound 30 minutes to obtain clean carbon paper.
Further, the optimum size of carbon paper is 1 x 1cm in the present invention2。
Further, chromogenic reaction mode of operation is as follows in the present invention: taking 2mL to be electrolysed from the cathode electrolytic cell of electrolytic cell
The mixed solution of 2mL 1.0M NaOH, 5wt% salicylic acid and 5wt% sodium citrate is added as aobvious in 10mL centrifuge tube in liquid
Toner adds 1mL of 0.05M sodium hypochlorite as oxidant, adds the conduct of 0.2mL sodium nitroprusside solution and urge
Agent carries out chromogenic reaction.
Compared with prior art, the present invention using ethyl alcohol as solvent in preparation process, it is not necessary that any substrate and titanium is added
Source, designs a kind of new nitrogen reduction electrocatalysis material, and technical process is environmentally protective；Simple convenient for operation, raw material is easy to get, and makes
It is standby at low cost；Preparation efficiency is high, and good product quality obtained, stability is strong, can be realized large-scale production manufacture, using ring
Border is good, wide market.
Detailed description of the invention:
Fig. 1 is Ti of the present invention3C2Tx/TiO2Nano-complex nitrogen reduction mechanism schematic diagram.
Fig. 2A and Fig. 2 B is that dehydrated alcohol of the present invention makees the Ti after Solvents Solvent heat3C2Tx MXene、
Ti3C2Tx/TiO2The scanning electron microscopic picture of nano-complex.
Fig. 3 is the Ti after the solvent heat of the present invention with ethanol as solvent3C2Tx/TiO2The nitrogen of nano-complex is also
Former the performance test results figure.
Fig. 4 A-4C is the Ti after the solvent heat of the present invention with ethanol as solvent3C2Tx/TiO2Nano-complex with
Ti3C2Tx MXene、TiO2Performance comparison figure.
Specific embodiment:
Below by example with reference, the present invention is further described.
Embodiment 1:
The one step hydro thermal method that the present embodiment is related to prepares nitrogen reduction elctro-catalyst, the specific process step of this method according to
As under type carries out:
S1, Ti is used3AlC2Precursor prepares pure Ti3C2TxMXene；
(1), 4g Ti is weighed3AlC2Powder is put into 250mL polypropylene vial, and is put on magnetic stirring apparatus, and revolving speed is greater than
200 revs/min；
(2), 1g Ti is pressed in the polypropylene vial in step (1)3The ratio of AlC:10mL hydrofluoric acid solution is slowly added dropwise
The hydrofluoric acid solution that 40mL mass fraction is 49% reacts for 24 hours at room temperature under the stirring greater than 200 rpms；
(3), it is put into centrifuge tube after after reaction taking out the suspension in polypropylene vial, centrifuge tube is symmetrically placed
In in centrifuge, with revolving speed centrifugation 10 minutes or more greater than 7000 revs/min, solution after centrifugation is made, is excessive hydrogen fluorine
Acid, impurity containing aluminium and Ti3C2TxMXene, its lower sediment is pure Ti after centrifugation3C2TxMXene；
(4), by pure Ti3C2TxMXene washs centrifugation with deionized water repeatedly, until its for neutrality, it is extra to remove
Fluorine ion and hydrogen ion；
(5), by pure Ti obtained in step (4)3C2TxMXene solid is dried in vacuo 8 hours or more in the case where being greater than 50 DEG C
It is spare；
S2, to the pure Ti prepared in step S13C2TxMXene is improved by way of hydro-thermal:
(1), the pure Ti of 0.15g is weighed respectively in clean beaker3C2TxMXene powder is added 15mL dehydrated alcohol, stirs
It is spare that black suspension is obtained after mixing；
(2), black suspension prepared by step (1) is transferred in closed PTFE vessel and is put into hydrothermal reaction kettle
In, 120 DEG C at a temperature of hydro-thermal 16 hours, be made hydro-thermal after suspension；
(3), after the suspension natural conditions after hydro-thermal drop to room temperature, the polytetrafluoroethylene (PTFE) in hydrothermal reaction kettle is taken out
Tank, and will liquid in polytetrafluoroethyltank tank take out after be put into centrifuge tube, centrifuge tube is symmetrically placed in centrifuge, with big
Be centrifuged 10 minutes in 10000 revs/min of revolving speeds or more, upper layer is colorless and transparent solvent, lower layer Ti after centrifugation3C2Tx/
TiO2Nano-complex；
(4), it takes lower sediment in step (3) to wash centrifugation 2-3 times repeatedly, and is dried in vacuo 8 hours in the case where being greater than 50 DEG C
Ti is obtained above3C2Tx/TiO2Nano-complex.
S2, to the pure Ti prepared in step S13C2TxMXene is improved by way of solvent heat:
(1), the pure Ti of 0.15g is weighed respectively in clean beaker3C2TxMXene powder is added 15mL dehydrated alcohol, stirs
It is spare that black suspension is obtained after mixing；
(2), black suspension prepared by step (1) is transferred in closed PTFE vessel and is put into hydrothermal reaction kettle
In, 120 DEG C at a temperature of hydro-thermal 16 hours, be made hydro-thermal after suspension；
(3), after the suspension natural conditions after hydro-thermal drop to room temperature, the polytetrafluoroethylene (PTFE) in hydrothermal reaction kettle is taken out
Tank, and will liquid in polytetrafluoroethyltank tank take out after be put into centrifuge tube, centrifuge tube is symmetrically placed in centrifuge, with big
Be centrifuged 10 minutes in 10000 revs/min of revolving speeds or more, upper layer is colorless and transparent solvent, lower layer Ti after centrifugation3C2Tx/
TiO2Nano-complex；
(4), it takes lower sediment in step (3) to wash centrifugation 2-3 times repeatedly, and is dried in vacuo 8 hours in the case where being greater than 50 DEG C
Ti is obtained above3C2Tx/TiO2Nano-complex.
S3、Ti3C2Tx/TiO2The application method and catalytic effect of nano-complex
(1), 5mg Ti is weighed3C2Tx/TiO2Nano-complex is put into 2mL centrifuge tube, then 490 μ are added into centrifuge tube
The Nafion solution that L distilled water, 490 μ L dehydrated alcohols and 20 μ L mass fractions are 5%, ultrasound 30 minutes in ultrasonic disintegrator
Obtain homogeneous solution.
(2), carbon paper is cut into 1 x 1cm2Size is put into 50mL beaker, and the dehydrated alcohol that 30mL is added into beaker is molten
Liquid, in ultrasonic disintegrator ultrasound 30 minutes to obtain clean carbon paper.
(3), the Ti in step (1) is taken3C2Tx/TiO2The 20 uniform drop coating of μ L of mixed solution of nano-complex is in 1 x
1cm2Carbon paper on, then by Ti in drop coating3C2Tx/TiO2The carbon paper of nano-complex be placed on it is to be dried at room temperature after continue to make
With.
(4), nitrogen reduction is carried out using electrochemical workstation three-electrode system in nitrogen reduction process, it may be assumed that step (3)
In Ti3C2Tx/TiO2- CP is used as working electrode, and Ag/AgCl electrode is used as reference electrode, platinum plate electrode to electrode.
(5), entire nitrogen reduction process carries out in the H-type electrolytic cell that centre is separated by Nafion membrane.Carrying out nitrogen
Before reduction experiment, high pure nitrogen is continual to be passed into cathode electrolytic cell 30 minutes, makes the electrolyte in cathode electrolytic cell
Full of nitrogen.
(6), by the Ti in step (3)3C2Tx/TiO2- CP working electrode and Ag/AgCl electrode are inserted into step (5)
In cathode electrolytic cell, platinum plate electrode is inserted into anode electrolytic tank, and high pure nitrogen is continual during the experiment is passed into yin
In the electrolytic cell of pole.
(7), it after testing, from 2mL electrolyte is taken out in the cathode electrolytic cell of electrolytic cell in 10mL centrifuge tube, is added
The mixed solution of 2mL 1.0M NaOH, 5wt% salicylic acid and 5wt% sodium citrate adds 1mL of as color developing agent
0.05M sodium hypochlorite as oxidant, add 0.2mL sodium nitroprusside solution as catalyst carry out chromogenic reaction with
Test generates the content of ammonia.
Embodiment 2:
Pure Ti of the present invention to preparation3C2TxMXene and stratiform Ti3C2Tx/TiO2The nitrogen reducing property of nano-complex
It is tested, finds Ti3C2Tx/TiO2Its amonia yield of nano-complex can reach 32.17 μ g h in -0.55V-1mg–1 catIts
Faradic efficiency can reach 16.07% in -0.45V, be higher than pure Ti3C2TxMXene and TiO2The amonia yield of nano particle and
Faraday, and Ti3C2Tx/TiO2The catalytic efficiency of nano-complex is higher than current most of elctro-catalysts.Show Ti3C2Tx/TiO2
Nano-complex is extraordinary nitrogen reducing material, can be applied to nitrogen reduction field；Show the layer prepared in embodiment 1
Shape Ti3C2TxMXene nanometer sheet is extraordinary electrocatalysis material, can be applied to nitrogen reduction field.
Claims (5)
1. a kind of novel nitrogen restores electrocatalysis material, it is characterised in that be achieved through the following technical solutions, first prepare
Ti3C2TxMXene nanometer sheet is simultaneously further improved its nitrogen reducing property by hydro-thermal method, specific process step according to
As under type carries out:
S1, Ti is used3AlC2Precursor prepares pure Ti3C2TxMXene；
(1), 4g Ti is weighed3AlC2Powder is put into 250mL polypropylene vial, and is put on magnetic stirring apparatus, and revolving speed is greater than 200
Rev/min；
(2), 1g Ti is pressed in the polypropylene vial in step (1)340mL matter is slowly added dropwise in the ratio of AlC:10mL hydrofluoric acid solution
The hydrofluoric acid solution that score is 49% is measured, is reacted at room temperature for 24 hours under the stirring greater than 200 rpms；
(3), after reaction will suspension in polypropylene vial take out after be put into centrifuge tube, by centrifuge tube it is symmetrically placed in from
In scheming, be centrifuged 10 minutes with the revolving speed greater than 7000 revs/min or more, solution after centrifugation is made, for excessive hydrofluoric acid, contains
Aluminium impurity and Ti3C2TxMXene, its lower sediment is pure Ti after centrifugation3C2TxMXene；
(4), by pure Ti3C2TxMXene washs centrifugation with deionized water repeatedly, until its for neutrality, with remove extra fluorine from
Son and hydrogen ion；
(5), by pure Ti obtained in step (4)3C2TxMXene solid be greater than 50 DEG C at be dried in vacuo 8 hours or more it is spare；
S2, to the pure Ti prepared in step S13C2TxMXene is improved by way of solvent heat:
(1), the pure Ti of 0.15g is weighed respectively in clean beaker3C2Tx15mL dehydrated alcohol is added, after stirring in MXene powder
It is spare to obtain black suspension；
(2), black suspension prepared by step (1) is transferred in closed PTFE vessel and is put into hydrothermal reaction kettle,
120 DEG C at a temperature of hydro-thermal 16 hours, be made hydro-thermal after suspension；
(3), after the suspension natural conditions after hydro-thermal drop to room temperature, the polytetrafluoroethyltank tank in hydrothermal reaction kettle is taken out,
And will liquid in polytetrafluoroethyltank tank take out after be put into centrifuge tube, centrifuge tube is symmetrically placed in centrifuge, to be greater than
Revolving speed centrifugation 10 minutes or more of 10000 revs/min, upper layer is colorless and transparent solvent, lower layer Ti after centrifugation3C2Tx/TiO2
Nano-complex；
(4), it takes lower sediment in step (3) to wash centrifugation 2-3 times repeatedly, and is dried in vacuo 8 hours or more in the case where being greater than 50 DEG C
Obtain Ti3C2Tx/TiO2Nano-complex；
S3、Ti3C2Tx/TiO2The application method and catalytic effect of nano-complex
(1), 5mg Ti is weighed3C2Tx/TiO2Nano-complex is put into 2mL centrifuge tube, then 490 μ L distillation is added into centrifuge tube
The Nafion solution that water, 490 μ L dehydrated alcohols and 20 μ L mass fractions are 5% obtains for ultrasound 30 minutes in ultrasonic disintegrator
Homogeneous solution；
(2), carbon paper is cleaned by alcohol with spare；
(3), the Ti in step (1) is taken3C2Tx/TiO2The carbon paper of the 20 uniform drop coating of μ L of mixed solution of nano-complex after the cleaning
On, then by Ti in drop coating3C2Tx/TiO2The carbon paper of nano-complex be placed on it is to be dried at room temperature after continue to use；
(4), nitrogen reduction is carried out using electrochemical workstation three-electrode system in nitrogen reduction process, it may be assumed that in step (3)
Ti3C2Tx/TiO2- CP is used as working electrode, and Ag/AgCl electrode is used as reference electrode, platinum plate electrode to electrode；
(5), entire nitrogen reduction process carries out in the H-type electrolytic cell that centre is separated by Nafion membrane (perfluorinated sulfonic acid diaphragm),
Before carrying out nitrogen reduction, high pure nitrogen is continual to be passed into cathode electrolytic cell at least 30 minutes, makes cathode electrolytic cell
In electrolyte be full of nitrogen；
(6), by the Ti in step (3)3C2Tx/TiO2- CP working electrode and Ag/AgCl electrode are inserted respectively into step (5)
In cathode electrolytic cell, platinum plate electrode is inserted into anode electrolytic tank, and high pure nitrogen is continual during reaction is passed into yin
In the electrolytic cell of pole；
(7), electrolyte after reaction, is taken out from the cathode electrolytic cell of electrolytic cell and carries out chromogenic reaction, to test generation ammonia
The content of gas.
2. the novel nitrogen of one kind according to claim 1 restores electrocatalysis material, it is characterised in that the present invention is to preparation
Pure Ti3C2TxMXene and stratiform Ti3C2Tx/TiO2The nitrogen reducing property of nano-complex is tested, and finds Ti3C2Tx/
TiO2Its amonia yield of nano-complex can reach 32.17 μ g h in -0.55V-1mg–1 cat.Its faradic efficiency is in -0.45V
It can reach 16.07%, and pure Ti3C2TxIts amonia yield of MXene -0.55V only reaches 22.19 μ g h-1mg–1 cat., faraday's effect
Rate only reaches 7.09% in -0.45V, and Ti3C2Tx/TiO2The amonia yield and faradic efficiency of nano-complex are TiO respectively2
11 times of nano particle and 69 times, show Ti3C2Tx/TiO2Nano-complex is a kind of nitrogen reducing material of high quality, can
Field is restored applied to nitrogen.
3. the novel nitrogen of one kind according to claim 1 restores electrocatalysis material, it is characterised in that carbon paper in the present invention
Cleaning mode it is as follows, carbon paper is entered in 50mL beaker, into beaker be added 30mL ethanol solution, in ultrasonic disintegrator
Middle ultrasonic 30 minutes to obtain clean carbon paper.
4. the novel nitrogen of one kind according to claim 3 restores electrocatalysis material, it is characterised in that the best ruler of carbon paper
Very little is 1x1cm2。
5. the novel nitrogen of one kind described in any claim restores electrocatalysis material, feature in -4 according to claim 1
It is in the present invention that chromogenic reaction mode of operation is as follows: 2mL electrolyte is taken to be centrifuged from the cathode electrolytic cell of electrolytic cell in 10mL
Guan Zhong is added the mixed solution of 2mL 1.0M NaOH, 5wt% salicylic acid and 5wt% sodium citrate as color developing agent, adds
1mL of 0.05M sodium hypochlorite adds 0.2mL sodium nitroprusside solution and is shown as catalyst as oxidant
Colour response.
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| CN110284144A (en) * | 2019-06-29 | 2019-09-27 | 华南理工大学 | A kind of organic electrolyte and the preparation method and application thereof of electro-catalysis synthesis ammonia |
| CN111058054A (en) * | 2020-01-03 | 2020-04-24 | 大连理工大学 | Device and method for synthesizing ammonia by electrocatalytic nitrogen reduction by using salt bridge to replace Nafion membrane |
| CN111151276A (en) * | 2020-01-19 | 2020-05-15 | 中南大学 | Full-spectrum photocatalytic synthesis of ammonia Ti3C2Tx/TiO2Composite material and preparation method and application thereof |
| CN111282586A (en) * | 2020-03-24 | 2020-06-16 | 福州大学 | Preparation method and application of in-situ alumina coated titanium carbide catalyst |
| CN112553646A (en) * | 2020-12-08 | 2021-03-26 | 湖南省益思迪科技有限公司 | MXene loaded nano alloy catalyst, preparation method and application thereof |
| CN113061913A (en) * | 2021-03-26 | 2021-07-02 | 辽宁大学 | BiOCl @ Ti3C2Electrocatalytic material, preparation method and application thereof |
| CN114481195A (en) * | 2022-01-24 | 2022-05-13 | 辽宁大学 | TiO2-MXene/IL modified electrode and its application in electrocatalysis of N2Conversion to NH3In (1) |
| CN118218008A (en) * | 2024-05-24 | 2024-06-21 | 北京大学 | Application of MAX phase material in ammonia production by thermocatalysis under mild condition |
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| CN111058054A (en) * | 2020-01-03 | 2020-04-24 | 大连理工大学 | Device and method for synthesizing ammonia by electrocatalytic nitrogen reduction by using salt bridge to replace Nafion membrane |
| CN111058054B (en) * | 2020-01-03 | 2022-01-18 | 大连理工大学 | Device and method for synthesizing ammonia by electrocatalytic nitrogen reduction by using salt bridge to replace Nafion membrane |
| CN111151276A (en) * | 2020-01-19 | 2020-05-15 | 中南大学 | Full-spectrum photocatalytic synthesis of ammonia Ti3C2Tx/TiO2Composite material and preparation method and application thereof |
| CN111282586A (en) * | 2020-03-24 | 2020-06-16 | 福州大学 | Preparation method and application of in-situ alumina coated titanium carbide catalyst |
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| CN113061913A (en) * | 2021-03-26 | 2021-07-02 | 辽宁大学 | BiOCl @ Ti3C2Electrocatalytic material, preparation method and application thereof |
| CN114481195A (en) * | 2022-01-24 | 2022-05-13 | 辽宁大学 | TiO2-MXene/IL modified electrode and its application in electrocatalysis of N2Conversion to NH3In (1) |
| CN118218008A (en) * | 2024-05-24 | 2024-06-21 | 北京大学 | Application of MAX phase material in ammonia production by thermocatalysis under mild condition |
| CN118218008B (en) * | 2024-05-24 | 2024-07-16 | 北京大学 | Application of MAX phase material in ammonia production by thermocatalysis under mild condition |
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