CN107346825A - Carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of a kind of nitrogen, phosphor codoping and preparation method thereof - Google Patents

Carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of a kind of nitrogen, phosphor codoping and preparation method thereof Download PDF

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CN107346825A
CN107346825A CN201710521211.3A CN201710521211A CN107346825A CN 107346825 A CN107346825 A CN 107346825A CN 201710521211 A CN201710521211 A CN 201710521211A CN 107346825 A CN107346825 A CN 107346825A
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carbon
nitrogen
hydrogen reduction
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CN107346825B (en
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程元徽
向中华
李东明
郭佳宁
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Beijing University of Chemical Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

Carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of a kind of nitrogen, phosphor codoping and preparation method thereof, belongs to catalyst technical field.A kind of covalent organic polymer rich in nitrogen, phosphorus has been synthesized by simple method on the carbon carrier, make nitrogen source and phosphorus source uniformly, be regularly distributed on carbon source surface, and pass through a step high-temperature calcination carbonisation, prepare nitrogen, phosphor codoping type porous carbon materials.The cost of material is low, easily prepared for this, not only with efficient hydrogen reduction and oxygen evolution reaction catalysis activity, while has preferable stability.There is wide application prospect in fields such as rechargeable metal, regeneratable fuel cells.

Description

The carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of a kind of nitrogen, phosphor codoping and its system Preparation Method
Technical field
The present invention relates to the preparation method of the porous carbon-based nonmetallic hydrogen reduction/precipitation economic benefits and social benefits catalysis material of doping type, specifically It is related to one kind by the use of carbon containing, nitrogen, phosphorus porous material as precursor reagent, the method being then pyrolyzed through a step high-temperature calcination obtains Have the difunctional carbon-based electrocatalysis material that hydrogen reduction and oxygen separate out catalytic performance simultaneously, secondary metals air cell, can The fields such as regenerative fuel cell, zinc air redox flow battery have broad application prospects, and belong to catalyst technical field.
Background technology
Chargeable metal-air battery is that oxygen is as positive active material using in air for one kind, and active metal is as negative A kind of electrochmical power source of pole active material, neutral salt solution or alkaline solution as electrolyte.During electric discharge, the metal on negative pole Lose electronics and be oxidized to corresponding metal ion, the oxygen on positive pole is reduced (is reduced into OH in the basic conditions-), fill Reversible reaction then occurs when electric.Metal-air battery has that energy density is high, power density is big, environment-friendly, and reliability is high The advantages that, critical role will be occupied in future world energy general layout.
At present metal-air battery positive pole oxygen electrode catalyst using the noble metals such as Pt, Ru, Pd, Au, Ag and its alloy as It is main.Existing commercial noble metal catalyst has Pt/C, IrO2/ C etc..But noble metal catalyst price is universal costly, and Precious Metals Resources are rare limited, and these deficiencies limit the development and application of noble metal catalyst.After research shows functionalization Carbon material can be with the progress of catalytic oxidation-reduction or oxygen evolution reaction, the carbon-based non-gold prepared by adulterating nitrogen phosphate and sulfur hetero atom Metal catalyst even can reach good economic benefits and social benefits catalytic effect, while prepare catalyst with nonmetallic raw material, reduce cost, Stability is improved, carbon-based hetero atom codope catalyst has become the important research direction of dual purpose catalyst, however, doping Source mixes inequality with carbon source, adulterates site and negligible amounts, constrains the further lifting of carbon-supported catalysts performance.
The content of the invention
Technical problem solved by the invention is：Overcome problem of the prior art as mixed between doped source and carbon source in improved Uniformity is closed, a kind of covalent organic polymer rich in nitrogen, phosphorus is synthesized by simple method on the carbon carrier, nitrogen, phosphorus are at this It is evenly distributed and is combined closely on the carbon carrier in polymer, efficient hydrogen reduction/oxygen is not only possessed through high temperature cabonization Evolution reaction catalytic performance, while there is the carbon-based catalysis material of the nitrogen of good stability, phosphor codoping.The material preparation process Simply, easy to operate, cost is cheap, solves that secondary metals air cell catalyst catalytic performance is not high, and stability is poor, and cost is high The problem of being difficult to large-scale promotion.
The present invention is achieved in the following ways, and the carbon-based nonmetallic hydrogen reduction/precipitation economic benefits and social benefits of a kind of nitrogen, phosphor codoping are urged The preparation method of agent, it is characterised in that comprise the following steps：
Step 1) directly synthesizes the covalent organic polymer material containing nitrogen, phosphorus using phosphorus source, nitrogen source in carbon material surface Material, weighs a certain amount of nitrogen source, phosphorus source, carbon material, mixes and be dissolved in organic solvent, is then transferred into reactor heating and keeps For a period of time, generate product with cleaning solution washing and filtering for several times, dry and obtain nitrogenous, phosphorus carbon-based material.
Nitrogenous, phosphorus the carbon-based material of synthesis is transferred in porcelain boat by step 2), and is put into high temperature process furnances high temperature and is forged Solution certain time is heated, it is carbonized in protective gas, natural cooling obtains nitrogen, the carbon-based nonmetallic oxygen of phosphor codoping also Original/precipitation dual purpose catalyst.
Further preferably：
The quality of step 1) phosphorus source and nitrogen source and carbon source ratio scope is (1-2.6):1:(1-1.6), preferably (1-1.8):1: (1-1.3), more preferably (1-1.6):1:(1-1.3).
The reaction of step 1) reactor heats to 100-200 DEG C, preferably 100-130 DEG C, more preferably 110-120 DEG C.Instead It it is 7-30 hours, preferably 18-24 hours, more preferably 20-24 hours between seasonable.
Step 1) organic solvent can be more than one or both of tetrahydrofuran, dimethylformamide, ethanol.
In step 1) washing, filtering and drying step, using vacuum filtration, cleaning solution is deionized water, ethanol, methanol solution Middle one or two.Vacuum drying temperature is 65-150 DEG C, preferably 60-100 DEG C, more preferably 60-80 DEG C.
The protective gas used during the step 2) fumed pyrogenic is high pure nitrogen or argon gas, purity >=99.99%. The inert gas flow that calcination process described in step 2) uses is 100-200mL min-1。
Step 2) the pyrolytic process：300-430 DEG C is warming up to 5-10 DEG C/min speed, is incubated 0.5-5.0 hours, 700-1100 DEG C is warming up to 5-10 DEG C/min speed again, is incubated 0.5-5.0 hours.
Further preferred pyrolytic process：300-380 DEG C is warming up to 5-8 DEG C/min speed, is incubated 0.5-3.0 hours, 800-1000 DEG C is warming up to 5-8 DEG C/min speed again, is incubated 0.5-3.0 hours.
Further, preferably phosphorus-containing compound is more than one or both of triphenylphosphine, phytic acid, chlordene tripolyphosphazene.
Further, preferably nitrogen-containing compound is more than one or both of melamine, urea, cyanamide, thiocarbamide.
Further, preferably carbon material is more than one or both of graphite, CNT, graphene, graphene oxide.
Advantages of the present invention：
The present invention has synthesized carbon-based nonmetallic hydrogen reduction/precipitation economic benefits and social benefits catalysis of nitrogen, phosphor codoping using easy method Material, synthesis condition is gentle, and experimental implementation is simple, and the carbon-based elctro-catalyst of preparation not only possesses efficient hydrogen reduction and oxygen separates out Reacting catalytic performance, meanwhile, there is good stability.To prepare the efficiently difunctional electrocatalysis material of secondary metals air cell Design provide new thinking.Compared with the prior art, the present invention has advantage.
1) present invention prepares the carbon-based elctro-catalyst of nitrogen, phosphor codoping by single sintering reaction and a pyrolytic reaction, Cheap and easy to get using raw material, reaction condition is gentle, easy to operate, and during non-pollution discharge, it is environmentally friendly, be easy to amplify Production.
2) present invention using materials such as graphene, CNTs as carbon source, by by nitrogen phosphorus atoms Uniform Doped in carbon material In generate more avtive spots, using carbon material increase electric conductivity, promote electronics and shifted from catalyst to oxygen molecule, added Fast hydrogen reduction and oxygen precipitation process,
3) synergy of the carbon material of the invention that nitrogen, phosphor codoping are formd by pyroreaction, nitrogen and phosphorus promotes Hydrogen reduction and oxygen evolution reaction process, the catalytic performance than single Heteroatom doping structure are good.
4) present invention has good economic benefits and social benefits electro-catalysis as a kind of carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst Performance and superior stability, it is highly suitable for the fields such as secondary metals air cell.
Brief description of the drawings
The carbon-based dual purpose catalyst of Fig. 1 nitrogen-phosphor codopings cyclic voltammetry curve in the case where difference sweeps speed；
Constant current charge-discharge curve of the carbon-based dual purpose catalyst of Fig. 2 nitrogen-phosphor codopings under different current densities.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Weigh 0.238g (0.907mmol) triphenyl phosphorus, 0.180g (1.428mmol) melamine, 0.060g oxidation stones Black alkene is added in 20ml tetrahydrofurans, and ultrasonic mixing is uniform, is then transferred into 50ml reactors, is warming up to 110 DEG C, reaction 24 hours.
Generate product deionized water, ethanol filtering and washing for several times, be put into baking oven and dry, 60 DEG C of dry 12h.Contained The carbon-based material of nitrogen, phosphorus.Nitrogenous, phosphorus the carbon-based material of synthesis is moved into high temperature furnace and calcined, and through-current capacity is 100mL min-1's Argon gas, high temperature furnace are warming up to 350 DEG C with 5-10 DEG C/min speed, are incubated 2 hours, then are warming up to 900 DEG C, after being incubated 2 hours Temperature fall the carbon-based dual purpose catalyst of nitrogen-phosphor codoping.
Embodiment 2
Weigh 0.190g (0.546mmol) chlordene tripolyphosphazene, 0.200g (1.587mmol) melamine, 0.060g carbon Nanotube is added in 20ml tetrahydrofurans, and ultrasonic mixing is uniform, is then transferred into 50ml reactors, is warming up to 120 DEG C, instead Answer 24 hours.
Generate product deionized water, ethanol filtering and washing for several times, be put into baking oven and dry, 70 DEG C of dry 12h.Contained The carbon-based material of nitrogen, phosphorus.Being moved into containing nitrogenous, phosphorus carbon-based material in high temperature furnace for synthesis is calcined, and through-current capacity is 100mL min-1 Argon gas, high temperature furnace is warming up to 350 DEG C with 5-10 DEG C/min speed, is incubated 3 hours, then is warming up to 950 DEG C, is incubated 2 hours Afterwards Temperature fall the carbon-based dual purpose catalyst of nitrogen-phosphor codoping.
Comparative example 1
0.190g (0.546mmol) chlordene tripolyphosphazene is weighed, 0.060g graphene oxides are added to 20ml tetrahydrofurans In, ultrasonic mixing is uniform, is then transferred into 50ml reactors, is warming up to 110 DEG C, reacts 24 hours.
Generate product deionized water, ethanol filtering and washing for several times, be put into baking oven and dry, 60 DEG C of dry 12h.Contained The carbon-based material of phosphorus.The phosphorous carbon-based material of synthesis, which is moved into high temperature furnace, to be calcined, and through-current capacity is 100mL min-1Argon gas, it is high Warm stove is warming up to 350 DEG C with 5-10 DEG C/min speed, is incubated 2 hours, then is warming up to 900 DEG C, Temperature fall after being incubated 2 hours The carbon-based dual purpose catalyst of phosphorus doping.
Comparative example 2
0.200g (1.587mmol) melamine is weighed, 0.060g graphene oxides are added in 20ml tetrahydrofurans, are surpassed Sound is well mixed, and is then transferred into 50ml reactors, is warming up to 110 DEG C, is reacted 24 hours.
Generate product deionized water, ethanol filtering and washing for several times, be put into baking oven and dry, 60 DEG C of dry 12h.Contained The carbon-based material of nitrogen.The nitrogenous carbon-based material of synthesis, which is moved into high temperature furnace, to be calcined, and through-current capacity is 100mL min-1 argon gas, High temperature furnace is warming up to 350 DEG C with 5-10 DEG C/min speed, is incubated 2 hours, then is warming up to 900 DEG C, and insulation is dropped naturally after 2 hours Temperature the carbon-based dual purpose catalyst of N doping.

Claims (10)

  1. A kind of 1. preparation method of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, phosphor codoping, it is characterised in that bag Include following steps：
    Step 1) is directly synthesized the covalent organic polymer material containing nitrogen, phosphorus in carbon material surface, claimed using phosphorus source, nitrogen source A certain amount of nitrogen source, phosphorus source, carbon material are taken, mixes and is dissolved in organic solvent, reactor heating is then transferred into and is kept for one section Time, generation product for several times, are dried with cleaning solution washing and filtering and obtain nitrogenous, phosphorus carbon-based material；
    Nitrogenous, phosphorus the carbon-based material of synthesis is transferred in porcelain boat by step 2), and is put into high temperature process furnances high temperature calcining heat Certain time is solved, it is carbonized in protective gas, natural cooling obtains nitrogen, the carbon-based nonmetallic hydrogen reduction/analysis of phosphor codoping Go out dual purpose catalyst.
  2. 2. according to a kind of preparation of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, the phosphor codoping described in claim 1 Method, it is characterised in that the quality of step 1) phosphorus source and nitrogen source and carbon source ratio scope is (1-2.6):1:(1-1.6), preferably (1- 1.8):1:(1-1.3), more preferably (1-1.6):1:(1-1.3).
  3. 3. according to a kind of preparation of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, the phosphor codoping described in claim 1 Method, it is characterised in that the reaction of step 1) reactor heats to 100-200 DEG C, preferably 100-130 DEG C, more preferably 110- 120℃；Reaction time is 7-30 hours, preferably 18-24 hours, more preferably 20-24 hours.
  4. 4. according to a kind of preparation of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, the phosphor codoping described in claim 1 Method, it is characterised in that step 1) organic solvent is more than one or both of tetrahydrofuran, dimethylformamide, ethanol；
    In washing, filtering and drying step, using vacuum filtration, cleaning solution is one kind or two in deionized water, ethanol, methanol solution Kind；Dry using vacuum drying, temperature is 65-150 DEG C；
    The protective gas used during the step 2) fumed pyrogenic is high pure nitrogen or argon gas, purity >=99.99%.
  5. 5. according to a kind of preparation of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, the phosphor codoping described in claim 1 Method, it is characterised in that the step 2) pyrolytic process：300-430 DEG C is warming up to 5-10 DEG C/min speed, is incubated 0.5- 5.0 hours, then 700-1100 DEG C is warming up to 5-10 DEG C/min speed, it is incubated 0.5-5.0 hours.
  6. 6. according to a kind of preparation of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, the phosphor codoping described in claim 5 Method, it is characterised in that pyrolytic process：300-380 DEG C is warming up to 5-8 DEG C/min speed, is incubated 0.5-3.0 hours, then 800-1000 DEG C is warming up to 5-8 DEG C/min speed, is incubated 0.5-3.0 hours.
  7. 7. according to a kind of preparation of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, the phosphor codoping described in claim 1 Method, it is characterised in that phosphorus-containing compound is more than one or both of triphenylphosphine, phytic acid, chlordene tripolyphosphazene.
  8. 8. according to a kind of preparation of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, the phosphor codoping described in claim 1 Method, it is characterised in that nitrogen-containing compound is more than one or both of melamine, urea, cyanamide, thiocarbamide.
  9. 9. according to a kind of preparation of the carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of nitrogen, the phosphor codoping described in claim 1 Method, it is characterised in that carbon material is more than one or both of graphite, CNT, graphene, graphene oxide.
  10. 10. the carbon-based nonmetallic hydrogen reduction/precipitation of the nitrogen being prepared according to any one of claim 1-9 method, phosphor codoping is double Imitate catalyst.
CN201710521211.3A 2017-06-30 2017-06-30 Nitrogen and phosphorus co-doped carbon-based nonmetal oxygen reduction/precipitation double-effect catalyst and preparation method thereof Active CN107346825B (en)

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CN108002378A (en) * 2017-11-30 2018-05-08 嘉兴学院 A kind of preparation method of structure-reinforced nitrogen-phosphor codoping carbon tube bundle
CN108232118A (en) * 2017-12-15 2018-06-29 江苏大学 A kind of preparation method of FeP/ nitrogen, phosphor codoping graphene electrochemistry storage sodium combination electrode
CN108231425A (en) * 2017-12-28 2018-06-29 盐城工学院 It is a kind of for nitrogen-phosphor codoping porous carbon of electrode material for super capacitor and preparation method thereof
CN108963275A (en) * 2018-06-01 2018-12-07 北京化工大学 A kind of nonmetallic self-supporting air electrode and preparation method thereof
CN109444250A (en) * 2018-09-30 2019-03-08 中国科学院山西煤炭化学研究所 A kind of preparation of graphene/porous carbon complex and mass spectral analysis application of double heteroatoms doping
CN109455701A (en) * 2018-09-10 2019-03-12 北京理工大学 A kind of preparation method of the highly doped nitrogen phosphorus carbon nanosheet of highly effective hydrogen yield
CN109786764A (en) * 2018-01-29 2019-05-21 北京化工大学 One kind having grading-hole, the nonmetallic carbon-based oxygen reduction catalyst of nitrogen sulphur codope and preparation
CN110112427A (en) * 2019-04-11 2019-08-09 北京化工大学 A kind of preparation method of the nitrogen of electrochemistry auxiliary, the carbon-based air electrode of phosphorus codope
CN110197905A (en) * 2018-02-27 2019-09-03 湖南省银峰新能源有限公司 A kind of modifying carbon material and the electrode of liquid flow cell of class graphene nanometer sheet prepared therefrom modification
CN110194453A (en) * 2018-02-27 2019-09-03 湖南省银峰新能源有限公司 A kind of modifying carbon material and nitrogen-rich liquid stream battery electrode prepared therefrom
CN110255534A (en) * 2019-06-06 2019-09-20 江苏大学 It is a kind of to adulterate three-dimensional porous graphene aerogel and preparation method and application
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CN111841595A (en) * 2019-04-28 2020-10-30 中国科学院福建物质结构研究所 Nitrogen-phosphorus co-doped carbon dioxide reduction electro-catalysis material and preparation method and application thereof
CN114959785A (en) * 2022-05-06 2022-08-30 浙江大学衢州研究院 Phosphorus-nitrogen co-doped carbon gel electrocatalyst and preparation method and application thereof
CN115663152A (en) * 2022-11-11 2023-01-31 哈尔滨工业大学 Hard carbon-nitrogen-phosphorus double-doped nano carbon composite carbon material and preparation method thereof
CN117069094A (en) * 2023-09-26 2023-11-17 河北省科学院能源研究所 Preparation method and application of coralline phosphorus-rich porous carbon electrode material
CN114959785B (en) * 2022-05-06 2024-05-31 浙江大学衢州研究院 Phosphorus-nitrogen co-doped carbon gel electrocatalyst and preparation method and application thereof

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CN109786764B (en) * 2018-01-29 2021-11-26 北京化工大学 Nitrogen-sulfur double-doped non-metallic carbon-based oxygen reduction catalyst with graded holes and preparation method thereof
CN110194453A (en) * 2018-02-27 2019-09-03 湖南省银峰新能源有限公司 A kind of modifying carbon material and nitrogen-rich liquid stream battery electrode prepared therefrom
CN110197905A (en) * 2018-02-27 2019-09-03 湖南省银峰新能源有限公司 A kind of modifying carbon material and the electrode of liquid flow cell of class graphene nanometer sheet prepared therefrom modification
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CN110508308A (en) * 2019-08-13 2019-11-29 三峡大学 A kind of preparation method and application of CoMn-P-NCNT multifunction catalyst
CN110508308B (en) * 2019-08-13 2022-07-15 三峡大学 Preparation method and application of CoMn-P-NCNT multifunctional catalyst
CN114959785A (en) * 2022-05-06 2022-08-30 浙江大学衢州研究院 Phosphorus-nitrogen co-doped carbon gel electrocatalyst and preparation method and application thereof
CN114959785B (en) * 2022-05-06 2024-05-31 浙江大学衢州研究院 Phosphorus-nitrogen co-doped carbon gel electrocatalyst and preparation method and application thereof
CN115663152A (en) * 2022-11-11 2023-01-31 哈尔滨工业大学 Hard carbon-nitrogen-phosphorus double-doped nano carbon composite carbon material and preparation method thereof
CN115663152B (en) * 2022-11-11 2024-03-26 哈尔滨工业大学 Hard carbon-nitrogen-phosphorus double-doped nano carbon composite carbon material and preparation method thereof
CN117069094A (en) * 2023-09-26 2023-11-17 河北省科学院能源研究所 Preparation method and application of coralline phosphorus-rich porous carbon electrode material
CN117069094B (en) * 2023-09-26 2024-05-07 河北省科学院能源研究所 Preparation method and application of coralline phosphorus-rich porous carbon electrode material

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