CN104624218B - Preparation method of iron and/or cobalt and/or nickel metal oxide reduction reaction catalyst - Google Patents

Preparation method of iron and/or cobalt and/or nickel metal oxide reduction reaction catalyst Download PDF

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CN104624218B
CN104624218B CN201510048281.2A CN201510048281A CN104624218B CN 104624218 B CN104624218 B CN 104624218B CN 201510048281 A CN201510048281 A CN 201510048281A CN 104624218 B CN104624218 B CN 104624218B
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cobalt
catalyst
ferrum
nickel metal
preparation
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CN104624218A (en
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唐水花
皇甫海新
眭乐萍
戴振
朱振涛
陈永东
黄韵
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Southwest Petroleum University
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    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
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Abstract

The invention relates to a preparation method of a transition metal oxide reduction reaction catalyst. The preparation method comprises the following steps: dissolving riboflavin, feeding a transition metal precursor into the solution, uniformly stirring the solution, wherein the mass ratio of the transition metal to the riboflavin is (1-10): (99-90); heating the solution and drying the solvent while stirring, and grinding the solvent to obtain yellow powder; placing the yellow powder into a tubular furnace, heating the yellow powder in an inert gas atmosphere at a heating rate of 5 to 10 DEG C per minute to 700 to 950 DEG C, and carrying out the carbonization at a constant temperature; grinding a carbonized product into powder, carrying out immersion cleaning on the powder in a HCI solution, carrying out suction filtration on the mixed solution, washing and carrying out vacuum drying on a suction filtration product to obtain the transition metal oxygen reduction reaction catalyst. The riboflavin is used as a nitrogen source and a carbon source, the transition metal precursor is used as a catalyst, and the transition metal oxygen reduction reaction catalyst with relatively high activity and stability is prepared by a heat treatment method. The method is simple in process flow, low in cost, environmentally friendly and easy in mass production.

Description

Ferrum and/or the preparation method of cobalt and/or nickel metal oxygen reduction catalyst
Technical field
The present invention relates to a kind of preparation method of non noble metal oxygen reduction catalysts and in particular to a kind of low cost, Simple, the nontoxic high activity of technological process and the ferrum and/or cobalt and/or the catalysis of nickel metal oxygen reduction reaction that go out color stability The preparation method of agent.
Background technology
Fuel cell is a kind of energy conversion device.It is by electrochemical principle isothermally being stored in fuel and oxidant Chemical energy be converted into electric energy.Global air pollution increasingly serious today, fuel cell is close because of its low stain, high-energy The advantages of degree, low-running-temperature and peace and quiet, is of great interest.Wherein, the new energy being driven by Proton Exchange Membrane Fuel Cells , in worldwide energy successful operation, the popularization of fuel cell car and development are for the pressure alleviating environmental pollution for source automobile Power has and significantly acts on.
However, the high cost of fuel cell always hinders its business-like barrier.The platino that fuel cell is used Catalyst is the one of the main reasons causing its high cost, in particular for the cathod catalyst of hydrogen reduction, because hydrogen reduction is anti- Answer that dynamic process opposite anode hydroxide process is more slow and complicated, the carrying capacity of therefore required platinum is bigger.For this reason, substituting expensive The research and development of the non noble metal oxygen reduction catalyst of metal become the study hotspot of current Proton Exchange Membrane Fuel Cells.
At present, including m-n-c type nitrating C catalyst, transition metal macrocyclic compound, transition metal oxide and transition Metal nitride is interior base metal cathod catalyst is of great interest and further investigation.But wherein, transition metal Macrocyclic compound has higher initial catalytic activity, and stability is poor in acid condition, and it is scarce to there is expensive raw material price etc. Point.Transition metal oxide and transition metal nitride two class catalyst activity are low.M-n-c type nitrating C catalyst because Under its cheap cost, sour environment, higher activity and outstanding stability receive in-depth study；Although however, at present Cost control with regard to m-n-c type catalyst and preparation method have had and have significantly developed, but, current preparation method is general All over test period length, energy consumption be big, poisonous and harmful, it is unfavorable for large-scale production.
Document (r.jasinski.nature, 1964,201,1212～1213) describes at first and contains transition by heat treatment The method that the mode of transition metal macrocycle prepares non noble metal oxygen reduction catalysts.Author passes through heat treatment Cobalt Phthalocyanine Method is prepared for the base metal cathod catalyst with good catalytic activity.However, its stability in sour environment is very poor, Although and, Cobalt Phthalocyanine has with respect to noble metal on cost and declines to a great extent, as transition metal macrocyclic compound Cobalt Phthalocyanine cost is still higher, is unfavorable for commercially producing of base metal cathod catalyst.
Document (michel lefevre, eric proietti, fr é d é ric jaouen, jean-pol Dodelet.science, 2009,324,71～74) etc. by secondary heat treatment carbon carrier, phenanthroline and ferrous chloride mixing Thing is obtained fe-n-c catalyst, and the active site density of this catalyst is high, and the cathode-current density of its best performance catalyst can be with Loading is 0.4mg/cm2Pt/c catalyst compare favourably.They think, the active sites of this fe-n-c catalyst be iron ion with Pyridine type nitrogen is coordinated formation on the graphite flake in micropore.
Document (e.proietti, f.jaouen, m.lefevre.nature commun, 2011,1～9) is boiled by introducing Stone-imidazate frame structure material, the catalyst heating preparation together with iron acetate/phenanthroline can effectively improve catalyst Volume activity and improve its mass-transfer performance, this is because the frame structure of zeolite-imidazate can be phenanthroline and acetic acid is sub- Ferrum forms catalyst precursor and provides place.Using the catalyst of this best performance as cathod catalyst, in hydrogen-oxygen fuel cell In system, during 0.6v, power density is up to 0.75w/cm2The catalyst of the method preparation has higher energy density degree.Concrete mistake Journey is as follows: zeolite imidazole ester frame structure material, phenanthroline, FePC is added to the mixing of dehydrated alcohol and deionized water In solution.The powder ball milling that dry suspension is obtained, during ball milling, the ratio of adjustment ball and powder turns lower ball milling three for 20:1400 Hour.Finally by powder tube furnace, under argon and ammonia atmosphere, heat treatment is twice.Although the catalyst of this method preparation has relatively High energy density, but its preparation cost is higher, technological process is complicated.
Document (g.wu, k l.more, p.zelenay.science, 2011,332,443-447) describes in carbon carrier Upper in-situ polymerization aniline, heat treatment polyaniline, the carbon carrier and transition metal precursor mixture method to prepare catalyst.Tool Body process is as follows: the carbon carrier of aniline and pretreatment is distributed in 0.5m hcl solution, is added thereto to oxidant persulfuric acid Ammonium and transition metal precursor, maintain the temperature at less than 10 DEG C and stir 24 hours so that aniline is fully polymerized and uniform fold in On carbon carrier.The suspension obtaining is vacuum dried under rotary evaporator, subsequently the powder obtaining is placed in nitrogen in tube furnace Heat treatment 1 hour under gas.It is placed in 0.5m h2so4Heat treatment 3 hours again after pickling in solution.Catalyst tool using the method There are higher catalysis activity and outstanding stability, however, technological process is complicated, and aniline has certain poison as nitrogen source Property, it is unfavorable for large-scale commercial production.
Therefore, need that a kind of technological process of exploitation is simple at present badly, low cost, environmental protection and there is high activity and go out color stability Oxo transition metal reduction catalyst preparation method.
Content of the invention
The problem existing for the preparation method of existing non noble metal oxygen reduction catalysts, the invention provides a kind of Simple, the nontoxic ferrum of high activity and stability of low cost, technological process and/or cobalt and/or nickel metal oxygen reduction reaction The preparation method of catalyst, comprises the following steps:
A () riboflavin is dissolved in solvent, then ferrum and/or cobalt and/or nickel metal precursor are added in above-mentioned solution, Stir, wherein, the ferrum containing in ferrum and/or cobalt and/or nickel metal precursor and/or cobalt and/or nickel metal and riboflavin Mass ratio be 1～10:99～90；
B solvent is evaporated by the lower heating of () stirring, obtain yellow powder after grinding；
C () above-mentioned powder is placed in tube furnace, heated with the heating rate of 5～10 DEG C/min in atmosphere of inert gases To 700～950 DEG C, constant temperature carries out carbonization；
D (), by the product grind into powder after carbonization, is placed in hcl solution and embathes, sucking filtration, washing, after vacuum drying i.e. Obtain ferrum and/or cobalt and/or nickel metal oxygen reduction catalyst.
Solvent in above-mentioned steps (a) can be strong base solution, dehydrated alcohol or water, preferably dehydrated alcohol.
Ferrum in above-mentioned steps (a) and/or cobalt and/or nickel metal precursor include one or more of ferrum, cobalt, nickel Presoma, can be anhydrous ferric chloride, Iron trichloride hexahydrate, Ferrox., ferrous sulfate heptahydrate etc., preferably Iron trichloride hexahydrate.
Preferably 800 DEG C of carburizing temperature in above-mentioned steps (c).
Specifically, the present invention is with riboflavin as nitrogen source with carbon source, with ferrum and/or cobalt and/or nickel metal precursor for urging Agent, prepares the ferrum with greater activity and stability and/or cobalt by heat-treating methods and/or nickel metal hydrogen reduction is anti- Answer catalyst.The present invention provide method technological process is simple, with low cost, environmental friendliness, be easy to batch and become to produce.
Brief description
The fe-n-c of Fig. 1 iron chloride, Nickel dichloride., cobaltous chloride respectively ferrum and/or cobalt and/or the preparation of nickel metal precursor, The linear sweep voltammetry curve of ni-n-c and co-n-c catalyst.
Fig. 2 for the present invention prepare with riboflavin as nitrogen source, iron content as 7wt%, heat treatment temperature be 800 DEG C of catalysis The scanning electron microscope image of agent (catalyst in embodiment 1).
Fig. 3 for the present invention prepare with riboflavin as nitrogen source, iron content as 7wt%, heat treatment temperature be 800 DEG C of catalysis The x- ray energy dispersive figure of agent (catalyst in embodiment 1).
Fig. 4 for the present invention prepare with riboflavin as nitrogen source, iron content as 7wt%, the catalyst of different heat treatment temperature Linear sweep voltammetry curve.
Fig. 5 for the present invention prepare with riboflavin as nitrogen source, heat treatment temperature be 800 DEG C, the catalyst of different iron content Linear sweep voltammetry figure.
Fig. 6 is 1000 linear sweep voltammetry curves in front and back of cycles samples in embodiment 1.
Specific embodiment
Below in conjunction with the accompanying drawings embodiments of the invention are described in detail.
Embodiment 1
The preparation process of sample 1 is as follows: under magnetic stirring 1g riboflavin (vb2) is dissolved in 50ml dehydrated alcohol, By 168.8mg fecl3·6h2O is added in above-mentioned solution, stirs, and wherein, fe is 7:93 with the mass ratio of riboflavin； Under magnetic agitation, evaporating ethanol in 80 DEG C of oil bath pans, product is levigate with mortar, is placed in ceramic boat and puts into tube furnace Middle heat treatment, under argon atmosphere, is warming up to 800 DEG C of carbonization 120min with the heating rate of 10 DEG C/min.The product obtaining is ground Clay into power, be placed in 0.5m hcl solution, flow back 4 hours at 80 DEG C, be placed in 70 DEG C of vacuum drying ovens dry after sucking filtration, washing Dry, grind and obtain fe-n-c catalyst 200mg.
Knowable to Fig. 1 linear scanning curve volt-ampere curve, in 0.5v, the electric current density of this fe-n-c catalyst is 3.5ma/cm2, its scanning electron microscope (SEM) photograph is as shown in Fig. 2 x- ray energy dispersive figure is as shown in Figure 3.Documents (xiao et Al, carbon, 2013,57,443-451) the fe-n-c catalyst the prepared electric current density in 0.5v is 3.1ma/cm2, this The catalyst of bright method preparation has more excellent oxygen reduction catalytic activity, and the electric current before and after 1000 circulations of this sample simultaneously is close Degree (Fig. 6) decay is only 0.2ma/cm2@0.5v, illustrates that the catalyst stability of present invention preparation is good.
Embodiment 2
Ni-n-c catalyst preparation process is as follows: under magnetic stirring 1g vb2 is dissolved in 50ml dehydrated alcohol, will 279mg nicl2·6h2O is added in above-mentioned solution, stirs, and wherein, ni is 7:93 with the mass ratio of riboflavin；Magnetic force Under stirring, evaporating ethanol in 80 DEG C of oil bath pans, product is levigate with mortar, it is placed in ceramic boat and put in tube furnace Heat treatment: under argon atmosphere, 800 DEG C of carbonization 120min are warming up to the heating rate of 10 DEG C/min.The product obtaining is ground Become powder, flow back at being placed in 80 DEG C in 0.5m hcl solution 4 hours, be placed in 70 DEG C of vacuum drying ovens after sucking filtration, washing and be dried, Ni-n-c catalyst 200mg is obtained after grinding.
Knowable to the linear sweep voltammetry of Fig. 1 is tested, this ni-n-c catalyst activity is 1.27ma/cm2@0.5v.
Embodiment 3
The preparation process of co-n-c catalyst is as follows: under magnetic stirring 1g vb2 is dissolved in 50ml dehydrated alcohol, By 303mg cocl2·6h2O is added in above-mentioned solution, stirs, and wherein, co is 7:93 with the mass ratio of riboflavin；Magnetic Under power stirring, evaporating ethanol in 80 DEG C of oil bath pans, product is levigate with mortar, it is placed in ceramic boat and put into tube furnace Middle heat treatment: under argon atmosphere, 800 DEG C of carbonization 120min are warming up to the heating rate of 10 DEG C/min.The product obtaining is ground Clay into power, flow back at being placed in 80 DEG C in 0.5m hcl solution 4 hours, be placed in 70 DEG C of vacuum drying ovens dry after sucking filtration, washing Dry, obtain co-n-c catalyst 200mg after grinding.
Knowable to the linear sweep voltammetry curve of Fig. 1, this co-n-c catalyst activity is 1.88ma/cm2@0.5v.Pass through In figure compares the electric current density in 0.5v for the catalyst and understands, the catalyst prepared for metal precursor with iron chloride has higher Catalysis activity.The following examples are mainly demonstrated with ferrous metal presoma.
Embodiment 4
The preparation process of fe-n-c catalyst is as follows: under magnetic stirring 1g vb2 is dissolved in 50ml dehydrated alcohol, By 168.8mg fecl3·6h2O is added in above-mentioned solution, stirs, and wherein, fe is 7:93 with the mass ratio of riboflavin； Under magnetic agitation, evaporating ethanol at 80 DEG C of water-bath, product is levigate with mortar, is placed in ceramic boat and puts into tube furnace and enter Row heat treatment: in argon atmosphere, 700 DEG C of carbonization 120min are warming up to the heating rate of 5 DEG C/min.The product obtaining is ground Become powder, be placed in 0.5m hcl solution, flow back at 80 DEG C 4 hours, be placed in 70 DEG C of vacuum drying ovens dry after sucking filtration, washing Dry, grind the fe-n-c catalyst obtaining about 250mg.
Knowable to Fig. 4 linear scanning curve volt-ampere curve, the hydrogen reduction electric current density of this catalyst is 0.7ma/cm2@ 0.5v.
Embodiment 5
The preparation process of fe-n-c catalyst is as follows: under magnetic stirring 1g vb2 is dissolved in 50ml naoh solution, By 168.8mg fecl3·6h2O is added in above-mentioned solution, stirs, and wherein, fe is 7:93 with the mass ratio of riboflavin； Under magnetic agitation, evaporation in 80 DEG C of oil bath pans removes water, and product is levigate with mortar, is placed in ceramic boat and puts into tube furnace Middle heat treatment, under argon atmosphere, is warming up to 900 DEG C of carbonization 120min with the heating rate of 5 DEG C/min.The product obtaining is ground Become powder, flow back at being placed in 80 DEG C in 0.5m hcl solution 4 hours, be placed in 70 DEG C of vacuum drying ovens dry after sucking filtration, washing Dry, grind and obtain fe-n-c catalyst 200mg.
Knowable to Fig. 4 linear scanning curve volt-ampere curve, the electric current density of this catalyst is 2.3ma/cm2@0.5v.
Embodiment 6
The preparation process of fe-n-c catalyst is as follows: under magnetic stirring 1g vb2 is dissolved in 50ml dehydrated alcohol, By 24.1mg fecl3·6h2O is added in above-mentioned solution, stirs, and wherein, fe is 1:99 with the mass ratio of riboflavin；Magnetic Under power stirring, evaporating ethanol in 80 DEG C of oil bath pans, product is levigate with mortar, it is placed in ceramic boat and put into tube furnace Middle heat treatment: in nitrogen atmosphere, 800 DEG C of carbonization 120min are warming up to the heating rate of 5 DEG C/min.The product obtaining is ground into Powder, flow back at being placed in 80 DEG C in 0.5m hcl solution 4 hours, is placed in 70 DEG C of vacuum drying ovens and is dried, grind after sucking filtration, washing Grind to obtain fe-n-c catalyst 220mg.
Knowable to Fig. 5 linear scanning curve volt-ampere curve, the electric current density of this catalyst is 1.5ma/cm2@0.5v.
Embodiment 7
The preparation process of fe-n-c catalyst is as follows: under magnetic stirring 1g vb2 is dissolved in 50ml koh solution, By 72.3mg fecl3·6h2O is added in above-mentioned solution, stirs, and wherein, fe is 3:97 with the mass ratio of riboflavin；Magnetic Under power stirring, evaporation in 80 DEG C of oil bath pans removes water, and product is levigate with mortar, is placed in ceramic boat and puts in tube furnace Heat treatment: under argon atmosphere, 800 DEG C of carbonization 120min are warming up to the heating rate of 5 DEG C/min.The product obtaining is ground to form Powder, is placed in 4 hours of 80 DEG C of backflows in 0.5m hcl solution, is placed in 70 DEG C of vacuum drying ovens and is dried, grind after sucking filtration, washing Obtain fe-n-c catalyst 200mg.
Knowable to Fig. 5 linear scanning curve volt-ampere curve, the electric current density of this catalyst is 2.0ma/cm2@0.5v.
Embodiment 8
The preparation process of fe-n-c catalyst is as follows: under magnetic stirring 1g vb2 is dissolved in 50ml water, will 120.5mg fecl3·6h2O is added in above-mentioned solution, stirs, and wherein, fe is 5:95 with the mass ratio of riboflavin；Magnetic Under power stirring, evaporation in 80 DEG C of oil bath pans removes water, and product is levigate with mortar, is placed in ceramic boat and puts in tube furnace Carry out heat treatment: in argon atmosphere, 800 DEG C of carbonization 120min are warming up to the heating rate of 5 DEG C/min.The product obtaining is ground Clay into power, be placed in 4 hours of 80 DEG C of backflows in 0.5m hcl solution, be placed in 70 DEG C of vacuum drying ovens after sucking filtration, washing and be dried, Grinding obtains fe-n-c catalyst 200mg.
Knowable to Fig. 5 linear scanning curve volt-ampere curve, the electric current density of this catalyst is 2.2ma/cm2@0.5v.
Embodiment 9
The preparation process of fe-n-c catalyst is as follows: under magnetic stirring 1g vb2 is dissolved in 50ml dehydrated alcohol, By 241mg fecl3·6h2O is added in above-mentioned solution, stirs, and wherein, fe is 10:90 with the mass ratio of riboflavin；Magnetic Under power stirring, evaporating ethanol in 80 DEG C of oil bath pans, product is levigate with mortar, it is placed in ceramic boat and put into tube furnace Middle heat treatment, under argon atmosphere, is warming up to 800 DEG C of carbonization 120min with the heating rate of 10 DEG C/min.The product obtaining is ground Clay into power, flow back at being placed in 80 DEG C in 0.5m hcl solution 4 hours, be placed in 70 DEG C of vacuum drying ovens dry after sucking filtration, washing Dry, grind and obtain fe-n-c catalyst 200mg.
Knowable to Fig. 5 linear scanning curve volt-ampere curve, in 0.5v, the electric current density of this catalyst is 2.7ma/cm2.
It can be inferred that: when ferrum and/or cobalt and/or nickel metal and riboflavin ratio are less than 7:93, catalyst Oxygen reduction activity improves with the increase of ferrum and/or cobalt and/or nickel tenor；But when ferrum and/or cobalt and/or nickel metal with When riboflavin ratio is more than 7:93, the activity of catalyst gradually reduces.So, ferrum and/or cobalt and/or nickel metal and riboflavin ratio When example is for 7:93, now catalyst activity reaches highest.

Claims (4)

1. the preparation method of a kind of ferrum and/or cobalt and/or nickel metal oxygen reduction catalyst, comprises the following steps:
A () riboflavin is dissolved in solvent, then ferrum and/or cobalt and/or nickel metal precursor are added in above-mentioned solution, stirring Uniformly；Wherein, ferrum and/or cobalt and/or nickel metal are 1～10:99～90 with the mass ratio of riboflavin；
B the lower heating of () stirring will be dry for solvent evaporation, obtain yellow powder after grinding；
C () above-mentioned powder is placed in tube furnace, in atmosphere of inert gases, be heated to 700 with the heating rate of 5～10 DEG C/min ～950 DEG C, constant temperature carries out carbonization；
D (), by the product grind into powder after carbonization, is placed in hcl solution and embathes, sucking filtration, washing, obtains after vacuum drying Ferrum and/or cobalt and/or nickel metal oxygen reduction catalyst.
2. the preparation method of ferrum as claimed in claim 1 and/or cobalt and/or nickel metal oxygen reduction catalyst, its feature It is, the preferred dehydrated alcohol of the solvent in described step (a).
3. the preparation method of ferrum as claimed in claim 1 and/or cobalt and/or nickel metal oxygen reduction catalyst, its feature It is, the ferrum in described step (a) and/or cobalt and/or the preferred Iron trichloride hexahydrate of nickel metal precursor.
4. the preparation method of ferrum as claimed in claim 1 and/or cobalt and/or nickel metal oxygen reduction catalyst, its feature It is, preferably 800 DEG C of the carburizing temperature in described step (c).
CN201510048281.2A 2015-01-30 2015-01-30 Preparation method of iron and/or cobalt and/or nickel metal oxide reduction reaction catalyst Expired - Fee Related CN104624218B (en)

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