CN108199052A - Fe-N-C composite materials based on metal organogel and preparation method thereof - Google Patents

Fe-N-C composite materials based on metal organogel and preparation method thereof Download PDF

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CN108199052A
CN108199052A CN201711466959.4A CN201711466959A CN108199052A CN 108199052 A CN108199052 A CN 108199052A CN 201711466959 A CN201711466959 A CN 201711466959A CN 108199052 A CN108199052 A CN 108199052A
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composite materials
preparation
materials based
metal organogel
tpa
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CN201711466959.4A
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CN108199052B (en
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张超
李倩倩
刘天西
郭和乐
封其春
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Donghua University
National Dong Hwa University
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Donghua University
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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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0065—Preparation of gels containing an organic phase
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0069—Post treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Electrochemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a kind of Fe N C composites based on metal organogel and preparation method thereof.The raw material of the Fe N C composites includes terephthalic acid (TPA), o-phenylenediamine and ferric nitrate.Preparation method is：After terephthalic acid (TPA) is mixed with o-phenylenediamine, it is dissolved in N, in 2 methylformamide of N；Ferric nitrate is dissolved in ethyl alcohol；Ultrasound, obtains gel after two kinds of solution are mixed；Gel prepares Fe N C composites through high temperature cabonization.The present invention prepares gel, then the carbon material for the transition metal N doping for obtaining having high catalytic activity by high temperature cabonization technology using metal organic coordination.Prepared Fe N C composites have higher electro catalytic activity and electrochemical stability, are ideal oxygen reduction catalysts.

Description

Fe-N-C composite materials based on metal organogel and preparation method thereof
Technical field
The present invention relates to a kind of Fe-N-C composite materials based on metal organogel and preparation method thereof, belong to a nanometer material Expect technical field.
Background technology
Pt bases catalyst used in low-temperature fuel cell cathode at present, due to it is expensive, reserves are rare, CO poisoning, The features such as anode fuel infiltration is poisoned, dynamics is slow and stability is poor, hinders commercializing fuel cells.Therefore, it is necessary to grind Study carefully develop cheap, high activity, high stability non noble metal oxygen reduction catalysts come replace at present used in Platinum based catalyst.Design prepares high-specific surface area and the advanced carbon nanomaterial of stable structure is urged to non noble metal oxygen reduction reaction Agent can not only shift for electronics and provide maximized electro-catalysis specific surface area, but also the electricity that can improve long-play is urged Change stability.Therefore, nonmetallic heteroatoms doped carbon, transition metal nitrogen-doped carbon and carbon-carried transition metal nano particle is prepared to urge Agent is highly desirable.
Fe-N-C composite materials after metal organic gel carbonization have higher porosity and specific surface area, Yi Jibao More active sites are revealed.
Invention content
Problem to be solved by this invention is：It is low, electrochemical to provide a kind of preparation process simple, cleaning, environmental protection, manufacturing cost Learn a kind of Fe-N-C composite materials based on metal organogel haveing excellent performance and preparation method thereof.
To solve the above-mentioned problems, the present invention provides a kind of Fe-N-C composite materials based on metal organogel, It is characterized in that, raw material includes terephthalic acid (TPA), o-phenylenediamine and ferric nitrate.
Preferably, the weight ratio of the terephthalic acid (TPA) and o-phenylenediamine is 1: 1~2；Terephthalic acid (TPA) and ferric nitrate Weight ratio is 1: 1.
The present invention also provides a kind of preparation methods of the above-mentioned Fe-N-C composite materials based on metal organogel, special Sign is, includes the following steps：
Step 1)：After terephthalic acid (TPA) is mixed with o-phenylenediamine, it is dissolved in N, in N-2 methylformamide；
Step 2)：Ferric nitrate is dissolved in ethyl alcohol；
Step 3)：By step 1), 2) ultrasound after the solution mixing obtained, obtains gel；
Step 4)：Gel prepares Fe-N-C composite materials through high temperature cabonization.
Preferably, it is dried under 60 DEG C, vacuum condition before gel high temperature cabonization in the step 4).
Preferably, the technological parameter of the high temperature cabonization in the step 5) is：Under inert gas atmosphere, carburizing temperature is 800~1000 DEG C, heating rate is 5 DEG C/min, keeps the temperature 2h.
It is highly preferred that the inert gas is argon gas.
Preferably, Fe-N-C composite materials made from the step 4) are successively through pickling, dry post processing.
It is highly preferred that the acid cleaning process is：8h is stirred in the hydrochloric acid of a concentration of 1mol/L.
The present invention prepares gel, then obtain having high catalytic activity by high temperature cabonization technology using metal organic coordination The carbon material of transition metal N doping.Prepared Fe-N-C composite materials are steady with higher electro catalytic activity and electrochemistry It is qualitative, it is ideal oxygen reduction catalyst.
Compared with prior art, the beneficial effects of the present invention are：
(1) preparation process is simple, cleans, is easily operated, is a kind of green chemical synthesis method；
(2) experimental design is ingenious.By high temperature cabonization technology, metal-organic coordination is simply and effectively utilized Gel is prepared, Fe-N-C composite materials are prepared using simple high temperature cabonization.
Description of the drawings
Fig. 1 is the linear volt-ampere curve of Fe-N-C composite materials made from embodiment 1-5；
Fig. 2 is the linear volt-ampere curve under Fe-N-C composite materials different rotating speeds made from embodiment 1.
Specific embodiment
To be clearer and more comprehensible the present invention, hereby with preferred embodiment, and attached drawing is coordinated to be described in detail below.
Embodiment 1
A kind of preparation method of the Fe-N-C composite materials based on metal organogel：
(1) terephthalic acid (TPA) and o-phenylenediamine are mixed, are dissolved in N, in N-2 methylformamide, terephthalic acid (TPA) with it is adjacent The mass ratio of phenylenediamine is：2∶3；
(2) ferric nitrate is dissolved in ethyl alcohol, the mass ratio of terephthalic acid (TPA) and ferric nitrate is：2∶3；
(3) obtained two kinds of solution is mixed, rear ultrasound obtains gel；
(4) gel drying that will be obtained is vacuumized at 60 DEG C；
(5) high temperature cabonization prepares Fe-N-C composite materials, and inert gas is the argon gas of high-purity, and carburizing temperature is 900 DEG C, Heating rate is 5 DEG C/min, after being raised to target temperature, keeps the temperature 2h；
(6) hydrochloric acid dry by the Fe-N-C composite material pickling of preparation, that acid used is a concentration of 1mol/L, stirring 8h carries out pickling.
Embodiment 2
With embodiment 1 the difference lies in the mass ratio of terephthalic acid (TPA) and o-phenylenediamine be 1: 1, finally obtained Composite material is denoted as Fe-N-C-1.
Embodiment 3
With embodiment 1 the difference lies in the mass ratio of terephthalic acid (TPA) and o-phenylenediamine be 1: 2, finally obtained Composite material is denoted as Fe-N-C-2.
Embodiment 4
With embodiment 1 the difference lies in carburizing temperature be 800 DEG C, the composite material finally obtained is denoted as Fe-N- C-3。
Embodiment 5
With embodiment 1 the difference lies in carburizing temperature be 1000 DEG C, the composite material finally obtained is denoted as Fe-N- C-4。
By Fe-N-C composite materials made from embodiment 1-5 through electro-chemical test.The result shows that Fe-N-C composite materials have There is higher electro catalytic activity, under saturation oxygen and in the potassium hydroxide solution of 0.1M, obtained when sweeping speed with 0.05V s-l There is apparent hydrogen reduction peak in cyclic voltammogram, and take-off potential is about 0.94V, as shown in Figure 1.800,1200,1600, 2000th, under the rotating speed of 2400rpm/s, in the linear volt-ampere curve tested, half wave potential reaches 0.78V, as shown in Figure 2.

Claims (8)

1. a kind of Fe-N-C composite materials based on metal organogel, which is characterized in that raw material includes terephthalic acid (TPA), adjacent benzene Diamines and ferric nitrate.
2. the preparation method of the Fe-N-C composite materials based on metal organogel as described in claim 1, which is characterized in that The weight ratio of the terephthalic acid (TPA) and o-phenylenediamine is 1: 1~2；The weight ratio of terephthalic acid (TPA) and ferric nitrate is 1: 1.
3. a kind of preparation method of the Fe-N-C composite materials based on metal organogel described in claims 1 or 2, feature It is, includes the following steps：
Step 1)：After terephthalic acid (TPA) is mixed with o-phenylenediamine, it is dissolved in N, in N-2 methylformamide；
Step 2)：Ferric nitrate is dissolved in ethyl alcohol；
Step 3)：By step 1), 2) ultrasound after the solution mixing obtained, obtains gel；
Step 4)：Gel prepares Fe-N-C composite materials through high temperature cabonization.
4. the preparation method of the Fe-N-C composite materials based on metal organogel as claimed in claim 3, which is characterized in that It is dried under 60 DEG C, vacuum condition before gel high temperature cabonization in the step 4).
5. the preparation method of the Fe-N-C composite materials based on metal organogel as claimed in claim 3, which is characterized in that The technological parameter of high temperature cabonization in the step 5) is：Under inert gas atmosphere, carburizing temperature is 800~1000 DEG C, heating Rate is 5 DEG C/min, keeps the temperature 2h.
6. the preparation method of the Fe-N-C composite materials based on metal organogel as claimed in claim 5, which is characterized in that The inert gas is argon gas.
7. the preparation method of the Fe-N-C composite materials based on metal organogel as claimed in claim 3, which is characterized in that Fe-N-C composite materials made from the step 4) are successively through pickling, dry post processing.
8. the preparation method of the Fe-N-C composite materials based on metal organogel as claimed in claim 7, which is characterized in that The acid cleaning process is：8h is stirred in the hydrochloric acid of a concentration of 1mol/L.
CN201711466959.4A 2017-12-28 2017-12-28 Fe-N-C composite material based on metal organogel and preparation method thereof Active CN108199052B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111647164A (en) * 2020-06-23 2020-09-11 河南工业大学 Guanosine supramolecular metal organogel/MOF composite material and preparation method and application thereof
CN112582628A (en) * 2020-12-21 2021-03-30 华南理工大学 FeMn bimetallic monatomic oxygen reduction catalyst and preparation method and application thereof
CN113644259A (en) * 2021-06-17 2021-11-12 上海工程技术大学 High-activity metal organogel electrode material, and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101837967A (en) * 2009-03-19 2010-09-22 清华大学 Method for preparing carbon composite material
CN103143378A (en) * 2013-03-04 2013-06-12 太原理工大学 Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell
CN104174424A (en) * 2014-08-19 2014-12-03 中南大学 Preparation method of nitrogen-doped graphene aerogel supported non-precious metal oxygen reduction catalyst
KR20160110649A (en) * 2015-03-10 2016-09-22 한국과학기술원 Nitrogen and Metal doped Porous Carbon Materials and Method of Manufacturing the Same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101837967A (en) * 2009-03-19 2010-09-22 清华大学 Method for preparing carbon composite material
CN103143378A (en) * 2013-03-04 2013-06-12 太原理工大学 Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell
CN104174424A (en) * 2014-08-19 2014-12-03 中南大学 Preparation method of nitrogen-doped graphene aerogel supported non-precious metal oxygen reduction catalyst
KR20160110649A (en) * 2015-03-10 2016-09-22 한국과학기술원 Nitrogen and Metal doped Porous Carbon Materials and Method of Manufacturing the Same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111647164A (en) * 2020-06-23 2020-09-11 河南工业大学 Guanosine supramolecular metal organogel/MOF composite material and preparation method and application thereof
CN112582628A (en) * 2020-12-21 2021-03-30 华南理工大学 FeMn bimetallic monatomic oxygen reduction catalyst and preparation method and application thereof
CN113644259A (en) * 2021-06-17 2021-11-12 上海工程技术大学 High-activity metal organogel electrode material, and preparation method and application thereof

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