CN104624218A - Preparation method of transition metal oxide reduction reaction catalyst - Google Patents

Preparation method of transition metal oxide reduction reaction catalyst Download PDF

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CN104624218A
CN104624218A CN201510048281.2A CN201510048281A CN104624218A CN 104624218 A CN104624218 A CN 104624218A CN 201510048281 A CN201510048281 A CN 201510048281A CN 104624218 A CN104624218 A CN 104624218A
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transition metal
catalyst
preparation
riboflavin
solution
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CN104624218B (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

A kind of preparation method of oxo transition metal reduction catalyst
Technical field
The present invention relates to a kind of preparation method of non noble metal oxygen reduction catalysts, be specifically related to simple, the nontoxic high activity of a kind of low cost, technological process and go out the preparation method of oxo transition metal reduction catalyst of color stability.
Background technology
Fuel cell is a kind of energy conversion device.It is isothermally converted into electric energy the chemical energy be stored in fuel and oxidant by electrochemical principle.Today that global air pollution is day by day serious, fuel cell is paid close attention to widely because the advantages such as its low stain, high-energy-density, low-running-temperature and peace and quiet receive.Wherein, the new-energy automobile driven by Proton Exchange Membrane Fuel Cells is in the successful operation of worldwide energy, and the popularization of fuel cell car and development have for the pressure alleviating environmental pollution and act on significantly.
But the high cost of fuel cell is hinder its business-like barrier always.The platinum based catalyst that fuel cell uses is the one of the main reasons causing its high cost, especially for the cathod catalyst of hydrogen reduction, because oxygen reduction reaction dynamic process opposite anode hydroxide process is more slow and complicated, therefore the carrying capacity of required platinum is larger.For this reason, the research and development substituting the non noble metal oxygen reduction catalyst of noble metal become the study hotspot of current Proton Exchange Membrane Fuel Cells.
At present, the base metal cathod catalyst comprising M-N-C type nitrating C catalyst, transition metal macrocyclic compound, transition metal oxide and transition metal nitride receives to be paid close attention to widely and furthers investigate.But wherein, transition metal macrocyclic compound has higher initial catalytic activity, in acid condition poor stability, and there is the shortcomings such as expensive raw material price.Transition metal oxide and transition metal nitride two class catalyst activity on the low side.M-N-C type nitrating C catalyst receives deep research because of higher activity and outstanding stability under its cheap cost, sour environment; But, although the current cost control about M-N-C type catalyst and preparation method have had develop significantly, the current preparation method general test period is long, energy consumption is large, poisonous and harmful, is unfavorable for large-scale production.
Document (R.Jasinski.Nature, 1964,201,1212 ~ 1213) describes the method being prepared non noble metal oxygen reduction catalysts by heat treatment containing the mode of transition metal macrocyclic compound at first.Author has prepared the base metal cathod catalyst with good catalytic activity by the method for heat treatment Cobalt Phthalocyanine.But its stability in sour environment is very poor, and, decline to a great extent although Cobalt Phthalocyanine has had relative to noble metal on cost, but, still higher as the Cobalt Phthalocyanine cost of transition metal macrocyclic compound, be 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. Fe-N-C catalyst is obtained by secondary heat treatment carbon carrier, phenanthroline and frerrous chloride mixture, the active site density of this catalyst is high, and the cathode-current density of its best performance catalyst can be 0.4mg/cm with loading 2pt/C catalyst compare favourably.They think, the active sites of this Fe-N-C catalyst is that on iron ion and the graphite flake of pyridine type nitrogen in micropore, coordination is formed.
Document (E.Proietti, F.Jaouen, M.Lefevre.Nature commun, 2011,1 ~ 9) by introducing zeolite-imidazate frame structure material, the catalyst adding hot preparation together with ferric acetate/phenanthroline effectively can improve the volume activity of catalyst and improve its mass-transfer performance, this is because the frame structure of zeolite-imidazate can provide place for phenanthroline and ferrous acetate form catalyst precursor.Using the catalyst of this best performance as cathod catalyst, in hydrogen-oxygen fuel cell system, during 0.6V, power density can reach 0.75W/cm 2catalyst prepared by the method has higher energy density degree.Detailed process is as follows: zeolite imidazole ester frame structure material, phenanthroline, FePC are joined in the mixed solution of absolute ethyl alcohol and deionized water.Powder ball milling dry suspension obtained, the ratio adjusting ball and powder during ball milling is that 20:1400 turns lower ball milling three hours.Finally by powder tube furnace, heat treatment twice under argon gas and ammonia atmosphere.Although the standby catalyst of this legal system has higher 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-situ polymerization aniline on the carbon carrier, and heat treatment polyaniline, carbon carrier and transition metal precursor mixture carry out the method for Kaolinite Preparation of Catalyst.Detailed process is as follows: aniline and pretreated carbon carrier are distributed in 0.5M HCl solution, add oxidant ammonium persulfate and transition metal precursor wherein, maintain the temperature at less than 10 DEG C and stir within 24 hours, make aniline fully be polymerized and uniform fold on carbon carrier.By the suspension vacuum drying under rotary evaporator obtained, subsequently the powder obtained to be placed under tube furnace nitrogen heat treatment 1 hour.Be placed in 0.5M H 2sO 4heat treatment 3 hours again after pickling in solution.Adopt the catalyst of the method to have higher catalytic activity and outstanding stability, but technological process is complicated, and aniline has certain toxicity as nitrogenous source, is unfavorable for that large-scale commercial is produced.
Therefore, need that a kind of technological process of exploitation is simple, cost is low at present badly, environmental protection and there is high activity and go out the preparation method of oxo transition metal reduction catalyst of color stability.
Summary of the invention
For preparation method's Problems existing of existing non noble metal oxygen reduction catalysts, the invention provides the preparation method of the oxo transition metal reduction catalyst of simple, the nontoxic high activity and stability of a kind of low cost, technological process, comprise the following steps:
A riboflavin is dissolved in solvent by (), then added in above-mentioned solution by transition metal precursor, stirs, and wherein, the transition metal contained in transition metal precursor and the mass ratio of riboflavin are 1 ~ 10:99 ~ 90;
B () stirs lower heating by solvent evaporate to dryness, obtain yellow powder after grinding;
C above-mentioned powder is placed in tube furnace by (), in atmosphere of inert gases, be heated to 700 ~ 950 DEG C with the heating rate of 5 ~ 10 DEG C/min, and constant temperature carries out carbonization;
D (), by the product grind into powder after carbonization, is placed in HCl solution and embathes, suction filtration, washing, namely obtains oxo transition metal reduction catalyst after vacuum drying.
Solvent in above-mentioned steps (a) can be strong base solution, absolute ethyl alcohol or water, preferred absolute ethyl alcohol.
Transition metal precursor in above-mentioned steps (a) comprises one or more the presoma in the transition metal such as iron, cobalt, nickel, can be anhydrous ferric chloride, Iron trichloride hexahydrate, ferrous oxalate, ferrous sulfate heptahydrate etc., preferred Iron trichloride hexahydrate.
Carburizing temperature in above-mentioned steps (c) preferably 800 DEG C.
Specifically, the present invention is nitrogenous source and carbon source with riboflavin, take transition metal precursor as catalyst, is prepared the oxo transition metal reduction catalyst with greater activity and stability by heat-treating methods.Method technological process provided by the invention is simple, with low cost, environmental friendliness, be easy to batch become produce.
Accompanying drawing explanation
Fig. 1 iron chloride, nickel chloride, cobalt chloride are respectively the linear sweep voltammetry curve of Fe-N-C, Ni-N-C and Co-N-C catalyst prepared by transition metal precursor.
The scanning electron microscope image that what Fig. 2 was prepared by the present invention take riboflavin as nitrogenous source, iron content is 7wt%, heat treatment temperature is the catalyst (catalyst in embodiment 1) of 800 DEG C.
The X-ray energy dispersive figure that what Fig. 3 was prepared by the present invention take riboflavin as nitrogenous source, iron content is 7wt%, heat treatment temperature is the catalyst (catalyst in embodiment 1) of 800 DEG C.
What Fig. 4 was prepared by the present invention take riboflavin as nitrogenous source, iron content is 7wt%, the linear sweep voltammetry curve of the catalyst of different heat treatment temperature.
What Fig. 5 was prepared by the present invention take riboflavin as nitrogenous source, heat treatment temperature is 800 DEG C, the linear sweep voltammetry figure of the catalyst of different iron content.
Fig. 6 is the linear sweep voltammetry curve of cycles samples 1000 front and back in embodiment 1.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail.
Embodiment 1
The preparation process of sample 1 is as follows: be dissolved in 50mL absolute ethyl alcohol, by 168.8mg FeCl by 1g riboflavin (VB2) under magnetic stirring 36H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Fe and riboflavin is 7:93; Under magnetic agitation, evaporating ethanol in 80 DEG C of oil bath pans, product mortar is levigate, is placed in ceramic boat and puts into tube furnace heat treatment, under argon atmosphere, is warming up to 800 DEG C of carbonization 120min with the heating rate of 10 DEG C/min.By the product grind into powder obtained, be placed in 0.5M HCl solution, reflux 4 hours at 80 DEG C, suction filtration, washing are placed in 70 DEG C of vacuum drying ovens dry, and grinding obtains Fe-N-C catalyst 200mg.
From Fig. 1 linear scan curve volt-ampere curve, when 0.5V, the current density of this Fe-N-C catalyst is 3.5mA/cm 2, as shown in Figure 2, X-ray energy dispersive figure as shown in Figure 3 for its scanning electron microscope (SEM) photograph.Fe-N-C catalyst current density when 0.5V prepared by documents (Xiao et al, Carbon, 2013,57,443-451) is 3.1mA/cm 2, catalyst prepared by method of the present invention has more excellent oxygen reduction catalytic activity, and current density (Fig. 6) decay before and after this sample 1000 circulations is simultaneously only 0.2mA/cm 2@0.5V, illustrates that catalyst stability prepared by the present invention is good.
Embodiment 2
Ni-N-C catalyst preparation process is as follows: be dissolved in 50mL absolute ethyl alcohol by 1g VB2 under magnetic stirring, by 279mg NiCl 26H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Ni and riboflavin is 7:93; Under magnetic agitation, evaporating ethanol in 80 DEG C of oil bath pans, by levigate for product mortar, be placed in ceramic boat and put into tube furnace heat treatment: under argon atmosphere, being warming up to 800 DEG C of carbonization 120min with the heating rate of 10 DEG C/min.By the product grind into powder obtained, reflux 4 hours at being placed in 0.5M HCl solution 80 DEG C, suction filtration, washing are placed in 70 DEG C of vacuum drying ovens dry, obtain Ni-N-C catalyst 200mg after grinding.
Test from the linear sweep voltammetry of Fig. 1, this Ni-N-C catalyst activity is 1.27mA/cm 2@0.5V.
Embodiment 3
The preparation process of Co-N-C catalyst is as follows: be dissolved in 50mL absolute ethyl alcohol by 1g VB2 under magnetic stirring, by 303mg CoCl 26H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Co and riboflavin is 7:93; Under magnetic agitation, evaporating ethanol in 80 DEG C of oil bath pans, by levigate for product mortar, be placed in ceramic boat and put into tube furnace heat treatment: under argon atmosphere, being warming up to 800 DEG C of carbonization 120min with the heating rate of 10 DEG C/min.By the product grind into powder obtained, reflux 4 hours at being placed in 0.5M HCl solution 80 DEG C, suction filtration, washing are placed in 70 DEG C of vacuum drying ovens dry, obtain Co-N-C catalyst 200mg after grinding.
From the linear sweep voltammetry curve of Fig. 1, this Co-N-C catalyst activity is 1.88mA/cm 2@0.5V.Known by comparing the current density of catalyst when 0.5V in figure, be that catalyst prepared by transition metal precursor has higher catalytic activity with iron chloride.The following examples will mainly be demonstrated with iron transition metal precursor.
Embodiment 4
The preparation process of Fe-N-C catalyst is as follows: be dissolved in 50mL absolute ethyl alcohol by 1g VB2 under magnetic stirring, by 168.8mg FeCl 36H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Fe and riboflavin is 7:93; Under magnetic agitation, evaporating ethanol at water-bath 80 DEG C, product mortar is levigate, is placed in ceramic boat and puts into tube furnace to heat-treat: argon atmosphere, is warming up to 700 DEG C of carbonization 120min with the heating rate of 5 DEG C/min.By the product grind into powder obtained, be placed in 0.5M HCl solution, reflux 4 hours at 80 DEG C, suction filtration, washing are placed in 70 DEG C of vacuum drying ovens dry, and grinding obtains the Fe-N-C catalyst of about 250mg.
From Fig. 4 linear scan curve volt-ampere curve, the hydrogen reduction current density of this catalyst is 0.7mA/cm 2@0.5V.
Embodiment 5
The preparation process of Fe-N-C catalyst is as follows: be dissolved in 50mL NaOH solution by 1g VB2 under magnetic stirring, by 168.8mg FeCl 36H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Fe and riboflavin is 7:93; Under magnetic agitation, evaporating in 80 DEG C of oil bath pans except anhydrating, by levigate for product mortar, be placed in ceramic boat and put into tube furnace heat treatment, under argon atmosphere, be warming up to 900 DEG C of carbonization 120min with the heating rate of 5 DEG C/min.By the product grind into powder obtained, reflux 4 hours at being placed in 0.5M HCl solution 80 DEG C, be placed in 70 DEG C of vacuum drying ovens dry through suction filtration, washing, grinding obtains Fe-N-C catalyst 200mg.
From Fig. 4 linear scan curve volt-ampere curve, the current density of this catalyst is 2.3mA/cm 2@0.5V.
Embodiment 6
The preparation process of Fe-N-C catalyst is as follows: be dissolved in 50mL absolute ethyl alcohol by 1g VB2 under magnetic stirring, by 24.1mg FeCl 36H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Fe and riboflavin is 1:99; Under magnetic agitation, evaporating ethanol in 80 DEG C of oil bath pans, by levigate for product mortar, be placed in ceramic boat and put into tube furnace heat treatment: nitrogen atmosphere, being warming up to 800 DEG C of carbonization 120min with the heating rate of 5 DEG C/min.By the product pulverize obtained, reflux 4 hours at being placed in 0.5M HCl solution 80 DEG C, suction filtration, washing are placed in 70 DEG C of vacuum drying ovens dry, grind to obtain Fe-N-C catalyst 220mg.
From Fig. 5 linear scan curve volt-ampere curve, the current density of this catalyst is 1.5mA/cm 2@0.5V.
Embodiment 7
The preparation process of Fe-N-C catalyst is as follows: be dissolved in 50mL KOH solution by 1g VB2 under magnetic stirring, by 72.3mg FeCl 36H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Fe and riboflavin is 3:97; Under magnetic agitation, evaporating in 80 DEG C of oil bath pans except anhydrating, by levigate for product mortar, be placed in ceramic boat and put into tube furnace heat treatment: under argon atmosphere, being warming up to 800 DEG C of carbonization 120min with the heating rate of 5 DEG C/min.By the product grind into powder obtained, be placed in 0.5M HCl solution 80 DEG C backflow 4 hours, suction filtration, washing are placed in 70 DEG C of vacuum drying ovens dry, and grinding obtains Fe-N-C catalyst 200mg.
From Fig. 5 linear scan curve volt-ampere curve, the current density of this catalyst is 2.0mA/cm 2@0.5V.
Embodiment 8
The preparation process of Fe-N-C catalyst is as follows: be dissolved in 50mL water by 1g VB2 under magnetic stirring, by 120.5mg FeCl 36H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Fe and riboflavin is 5:95; Under magnetic agitation, evaporating in 80 DEG C of oil bath pans except anhydrating, by levigate for product mortar, be placed in ceramic boat and put into tube furnace and heat-treating: argon atmosphere, being warming up to 800 DEG C of carbonization 120min with the heating rate of 5 DEG C/min.By the product grind into powder obtained, be placed in 0.5M HCl solution 80 DEG C backflow 4 hours, suction filtration, washing are placed in 70 DEG C of vacuum drying ovens dry, and grinding obtains Fe-N-C catalyst 200mg.
From Fig. 5 linear scan curve volt-ampere curve, the current density of this catalyst is 2.2mA/cm 2@0.5V.
Embodiment 9
The preparation process of Fe-N-C catalyst is as follows: be dissolved in 50mL absolute ethyl alcohol by 1g VB2 under magnetic stirring, by 241mg FeCl 36H 2o joins in above-mentioned solution, stirs, and wherein, the mass ratio of Fe and riboflavin is 10:90; Under magnetic agitation, evaporating ethanol in 80 DEG C of oil bath pans, by levigate for product mortar, be placed in ceramic boat and put into tube furnace heat treatment, under argon atmosphere, is warming up to 800 DEG C of carbonization 120min with the heating rate of 10 DEG C/min.By the product grind into powder obtained, reflux 4 hours at being placed in 0.5M HCl solution 80 DEG C, suction filtration, washing are placed in 70 DEG C of vacuum drying ovens dry, and grinding obtains Fe-N-C catalyst 200mg.
From Fig. 5 linear scan curve volt-ampere curve, when 0.5V, the current density of this catalyst is 2.7mA/cm 2.
Can reach a conclusion thus: when transition metal and riboflavin ratio are less than 7:93, the oxygen reduction activity of catalyst improves along with the increase of levels of transition metals; But when transition metal and riboflavin ratio are greater than 7:93, the activity of catalyst progressively reduces.So when transition metal and riboflavin ratio are 7:93, now catalyst activity reaches the highest.

Claims (4)

1. a preparation method for oxo transition metal reduction catalyst, comprises the following steps:
A riboflavin is dissolved in solvent by (), then added in above-mentioned solution by transition metal precursor, stirs; Wherein, the mass ratio of transition metal and riboflavin is 1 ~ 10:99 ~ 90;
B () stirs lower heating by dry for solvent evaporation, obtain yellow powder after grinding;
C above-mentioned powder is placed in tube furnace by (), in atmosphere of inert gases, be heated to 700 ~ 950 DEG C with the heating rate of 5 ~ 10 DEG C/min, constant temperature carries out carbonization;
D (), by the product grind into powder after carbonization, is placed in HCl solution and embathes, suction filtration, washing, namely obtains oxo transition metal reduction catalyst after vacuum drying.
2. the preparation method of oxo transition metal reduction catalyst as claimed in claim 1, is characterized in that, the preferred absolute ethyl alcohol of the solvent in described step (a).
3. the preparation method of oxo transition metal reduction catalyst as claimed in claim 1, is characterized in that, the preferred Iron trichloride hexahydrate of the transition metal precursor in described step (a).
4. the preparation method of oxo transition metal reduction catalyst as claimed in claim 1, is characterized in that, the carburizing temperature in described step (c) preferably 800 DEG 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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CN109659567A (en) * 2018-11-30 2019-04-19 天津大学 The sugared cell anode catalyst and preparation method and application of nickel and cobalt containing nitrogen
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CN106784892A (en) * 2016-12-15 2017-05-31 天津工业大学 A kind of preparation method and applications of corrdination type high efficiency composition electrocatalysis material
CN106784892B (en) * 2016-12-15 2019-08-20 天津工业大学 A kind of preparation method and applications of corrdination type high efficiency composition electrocatalysis material
CN107331870A (en) * 2017-06-09 2017-11-07 同济大学 A kind of preparation method of graphene/riboflavin composite
CN108767272A (en) * 2018-04-13 2018-11-06 东华大学 A kind of nitrogen co-doped porous carbon materials of cobalt and its preparation and application
CN109659567A (en) * 2018-11-30 2019-04-19 天津大学 The sugared cell anode catalyst and preparation method and application of nickel and cobalt containing nitrogen
CN114849760A (en) * 2022-06-08 2022-08-05 四川轻化工大学 Catalyst and preparation method and application thereof
CN114849760B (en) * 2022-06-08 2023-10-17 四川轻化工大学 Catalyst and preparation method and application thereof

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