CN106311224A - Preparation method of charcoal-based oxygen reduction catalyst - Google Patents
Preparation method of charcoal-based oxygen reduction catalyst Download PDFInfo
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- CN106311224A CN106311224A CN201610814133.1A CN201610814133A CN106311224A CN 106311224 A CN106311224 A CN 106311224A CN 201610814133 A CN201610814133 A CN 201610814133A CN 106311224 A CN106311224 A CN 106311224A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract
The invention discloses a preparation method of a charcoal-based oxygen reduction catalyst. The preparation method includes the steps of (1), cleaning cornstalks with deionized water, drying the cleaned cornstalks for 24-72 hours, pulverizing the dried cornstalks in a pulverizer and screening so as to obtain biomass powder; (2), evenly mixing the biomass powder with a pore former KOH in a mass ratio of 1 to 1, subjecting a mixture to pyrolysis in the presence of nitrogen and cooling to reach the room temperature so as to obtain pyrolyzed biomass charcoal; (3), soaking the pyrolyzed biomass charcoal in a HCl solution prior to cleaning, subjecting the cleaned biomass charcoal to suction filtration and washing with deionized water until a pH value reaches 7, and drying for 6-8 hours at 80-100 DEG C; (4), soaking the cleaned pyrolyzed biomass charcoal in a 0.05-0.1 M NaOH solution prior to cleaning for 0.5-2 hours, subjecting the cleaned biomass charcoal to suction filtration and washing with deionized water until a pH value reaches 7, and drying for 6-8 hours at 80-100 DEG C so as to obtain the charcoal-based oxygen reduction catalyst. The preparation method has the advantages of simplicity in operation, short preparation time and low preparation cost, and the oxygen reduction catalysis performance of the charcoal-based oxygen reduction catalyst is equivalent to that of a Pt/C catalyst.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method thereof, concretely relate to a kind of charcoal base hydrogen reduction catalysis
The preparation method of agent.
Background technology
Fuel battery negative pole oxygen reduction reaction reversibility is the lowest, and exchange current density is less by (10-9～10-10 A/cm2), often
It is attended by the highest overpotential；Utilize Cathodic oxygen reduction catalyst degradation cathode overpotential, improve battery operated performance without
The commercialized development of fuel cell is still all extremely important by opinion in basic research field.At present, that commonly uses urges
Agent is Pt/C catalyst, but, this catalyst uses Pt, owing to Pt is rare and expensive, it is impossible to realize extensive raw
Producing, therefore, development low price, efficient non noble metal oxygen reduction catalyst have become the task of top priority for fuel cell.
At present, the Land use systems of agricultural crop straw is direct burning, direct returning to farmland or decomposition into field.Directly burn, not only
Waste resource, and pollute the environment, a large amount of C0 produced in combustion process2Greenhouse effect can be caused with black carbon aerosol.
There is document to report in recent years, obtained by biomass such as pyrolysis Os Sus domestica, Flammulina velutiper (Fr.) Sing, Semen sojae atricolor, Herba Typhae and Mel
Charcoal is used for oxygen reduction catalyst, but, the cost of material of above-mentioned biomass is high, is difficult to obtain, complicated process of preparation, operation
Loaded down with trivial details, therefore we to develop a kind of raw material extensive, preparation method simply and comprehensively utilizes solution environmental problem and really realizes becoming
Waste be changed into values is particularly important.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of charcoal base oxygen reduction catalyst
Preparation method, the method is simple to operate, preparation time is short, and the catalyst oxygen reduction catalytic performance that it is prepared is good, its catalytic
Can be suitable with the catalytic performance of existing Pt/C catalyst.
In order to achieve the above object, the present invention takes techniques below scheme:
1. the preparation method of a kind of charcoal base oxygen reduction catalyst of the present invention, it is characterised in that have following process engineering and
Step:
(1). corn stalk is cleaned with deionized water and removes surface impurity, and at 105 DEG C, dry 24-72 h, then will dry
After corn stalk be placed in pulverizer pulverizing, and cross the sieve of 100 mesh, obtain powdered biomass；
(2). the powdered biomass that above-mentioned steps (1) prepares is mixed according to the ratio uniform of mass ratio 1:1 with pore creating material KOH,
Be placed in quartz boat, 850 DEG C, be pyrolyzed 30 min under nitrogen atmosphere, be cooled to room temperature and take out, obtain being pyrolyzed biomass carbon；
(3). pyrolysis biomass carbon above-mentioned steps (2) obtained is placed in the solution of the HCl that concentration is 0.1～0.05 M mol/L
In carry out soaking and washing, clean 0.5～2 hour, be then 7 by deionized water filtering and washing to pH value, at 80～100 DEG C
At a temperature of dry 6～8 hours, the pyrolysis biomass carbon after the cleaning obtained；
(4). the pyrolysis biomass carbon after the cleaning obtain above-mentioned steps (3) puts into the NaOH that concentration is 0.1～0.05 M
Solution carries out soaking and washing, cleans 0.5～2 hour, and be 7 by deionized water filtering and washing to pH value, 80～100 DEG C of temperature
Degree is lower dries 6～8 hours, obtains charcoal base oxygen reduction catalyst.
This have the advantage that:
Charcoal base oxygen reduction catalyst method prepared by the present invention compared to prepare other catalyst method simple to operate, preparation
Time is short, does not use rare Pt metal, reduces the manufacturing cost of oxygen reduction catalyst, and its hydrogen reduction catalytic performance is with existing
The hydrogen reduction catalytic performance of Pt/C catalyst suitable.
Accompanying drawing explanation
Fig. 1 is charcoal base oxygen reduction catalyst (BC-K) the SEM collection of illustrative plates that embodiment 1 prepares.
Fig. 2 is the XRD collection of illustrative plates of the charcoal base oxygen reduction catalyst BC-K that embodiment 1 prepares, and in Fig. 2, transverse axis represents
The angle of diffraction, the longitudinal axis represents diffracted intensity, in figure, two peaks (it is 43.8 ° with the angle of diffraction that the angle of diffraction is 23.6 °) that curve occurs
It is 002 and 100 crystal faces of disordered carbon, shows that charcoal prepared by the present invention has graphite-like structure.
Fig. 3 is charcoal base oxygen reduction catalyst (BC) the SEM collection of illustrative plates that embodiment 2 prepares.
Fig. 4 is that the charcoal base oxygen reduction catalyst for preparing of the present invention and existing Pt/C catalyst are in 0.1 M KOH
Polarization curve comparison diagram, in Fig. 4, transverse axis represents that current potential, the longitudinal axis represent that electric current density, the curve at little triangle place represent Pt/C
Catalyst, the curve at roundlet place represents the charcoal BC of directly pyrolysis, and the curve at little square frame place represents the biology that KOH activates
Charcoal BC-K.By in Fig. 4 it can be seen that the take-off potential of different materials and electric current density are different, Pt/C catalyst, KOH activate
Charcoal BC-K and the take-off potential of charcoal BC of directly pyrolysis and electric current density be respectively-0.07 V and-2.61mA
cm-2,-0.16 V and-3.42mA cm-2,-0.37 V and-1.09mA cm-2.Test result indicate that, without the material of activation processing
No matter material is the most bad in take-off potential (more negative) or electric current density (relatively low), and the hydrogen reduction prepared by KOH activation is urged
Agent take-off potential is the most negative relative to Pt/C catalyst current potential, but electric current density is relatively big, thus activation processing prepared by the present invention
After charcoal base performance of oxygen-reducing catalyst on can compare favourably with Pt/C catalyst.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
This example is the preparation of charcoal base oxygen reduction catalyst
(1). corn stalk is cleaned with deionized water and removes surface impurity, and at 105 DEG C, dry 24 h, after then drying
Corn stalk be placed in pulverizer pulverizing, and cross the sieve of 100 mesh, obtain powdered biomass；
(2). the powdered biomass that above-mentioned steps (1) prepares is mixed according to the ratio uniform of mass ratio 1:1 with pore creating material KOH,
Be placed in quartz boat, 850 DEG C, be pyrolyzed 30 min under nitrogen atmosphere, be cooled to room temperature and take out, obtain being pyrolyzed biomass carbon；
(3). pyrolysis biomass carbon above-mentioned steps (2) obtained is placed in the solution of the HCl that concentration is 0.05 M mol/L
Row soaking and washing, cleans 2 hours, is then 7 by deionized water filtering and washing to pH value, dries 6 little at a temperature of 80～100 DEG C
Time, the pyrolysis biomass carbon after the cleaning obtained；
(4). it is in 0.05 M NaOH solution that the pyrolysis biomass carbon after the cleaning obtain above-mentioned steps (3) puts into concentration
Carry out soaking and washing, clean 2 hours, and be 7 by deionized water filtering and washing to pH, then dry 6 hours at 80～100 DEG C
Obtain charcoal base oxygen reduction catalyst, as shown in Figure 1 and Figure 2.
Embodiment 2
This example is the preparation of charcoal base oxygen reduction catalyst:
The present embodiment 2 is substantially the same manner as Example 1, is in place of its difference: " inciting somebody to action described in step (2) in the present embodiment 2
The corn stalk powder prepared " instead of in embodiment 1 described in step (2) " by prepared corn stalk powder and pore creating material
KOH uniformly mix according to mass ratio 1:1 be placed in quartz boat ", prepare charcoal base oxygen reduction catalyst, as shown in Figure 3.
The catalytic performance of charcoal base oxygen reduction catalyst is measured:
In three-electrode system (Hg/HgO is that reference electrode, Pt sheet are for being working electrode to electrode, glass-carbon electrode), electrolyte is
In the case of 0.1 M KOH, it is each that above-described embodiment 1 and embodiment 2 are prepared by employing CHI660A Electrochemical Comprehensive Tester
The catalytic performance planting charcoal base oxygen reduction catalyst is tested, and its test result shows, the oxygen reduction catalyst of the present invention
Catalytic performance higher than other the catalytic performance of catalyst, as shown in Figure 4.
Claims (1)
1. the preparation method of a kind of charcoal base oxygen reduction catalyst of the present invention, it is characterised in that the method includes following step
Rapid:
Corn stalk is cleaned with deionized water and removes surface impurity, and at 105 DEG C, dry 24-72 h, after then drying
Corn stalk is placed in pulverizer pulverizing, and the sieve of 100 mesh excessively, obtains powdered biomass；
The powdered biomass that above-mentioned steps (1) prepares is mixed according to the ratio uniform of mass ratio 1:1 with pore creating material KOH, is placed in
In quartz boat, 850 DEG C, be pyrolyzed 30 min under nitrogen atmosphere, be cooled to room temperature and take out, obtain being pyrolyzed biomass carbon；
Pyrolysis biomass carbon above-mentioned steps (2) obtained is placed in the solution of the HCl that concentration is 0.1～0.05 M mol/L
Row soaking and washing, cleans 0.5～2 hour, is then 7 by deionized water filtering and washing to pH value, at a temperature of 80～100 DEG C
Dry 6～8 hours, the pyrolysis biomass carbon after the cleaning obtained；
Pyrolysis biomass carbon after the cleaning obtain above-mentioned steps (3) puts into the NaOH solution that concentration is 0.1～0.05 M
In carry out soaking and washing, clean 0.5～2 hour, and be 7 by deionized water filtering and washing to pH value, 80～100 DEG C of temperature
Lower drying 6～8 hours, obtain charcoal base oxygen reduction catalyst.
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Cited By (4)
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| CN111129523A (en) * | 2019-12-17 | 2020-05-08 | 中国科学院广州能源研究所 | Preparation method of ultrathin flexible carbon nanosheet oxygen reduction catalyst based on anaerobic fermentation biogas residues |
| CN111900415A (en) * | 2020-07-10 | 2020-11-06 | 上海大学 | Method for preparing metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge |
| CN112647091A (en) * | 2020-12-09 | 2021-04-13 | 中国科学院广州能源研究所 | N/P/Ca in-situ doped biochar and application thereof in electrolysis of water for hydrogen evolution |
| CN114538408A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院广州能源研究所 | Method for preparing high electrocatalytic activity biochar through micro-aerobic pyrolysis |
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| CN111900415A (en) * | 2020-07-10 | 2020-11-06 | 上海大学 | Method for preparing metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge |
| CN114538408A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院广州能源研究所 | Method for preparing high electrocatalytic activity biochar through micro-aerobic pyrolysis |
| CN112647091A (en) * | 2020-12-09 | 2021-04-13 | 中国科学院广州能源研究所 | N/P/Ca in-situ doped biochar and application thereof in electrolysis of water for hydrogen evolution |
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