CN103801342B - Animal bone is utilized to prepare the method for porous material and the application as electrode catalyst of fuel cell - Google Patents

Animal bone is utilized to prepare the method for porous material and the application as electrode catalyst of fuel cell Download PDF

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Publication number
CN103801342B
CN103801342B CN201410080389.5A CN201410080389A CN103801342B CN 103801342 B CN103801342 B CN 103801342B CN 201410080389 A CN201410080389 A CN 201410080389A CN 103801342 B CN103801342 B CN 103801342B
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China
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porous material
fuel cell
animal bone
bone
prepare
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CN103801342A (en
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王荣方
宋慧
杨慧娟
王辉
季山
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CHONGQING YUXIANG NEW ENERGY BATTERY CO., LTD.
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Northwest Normal 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
    • 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

Abstract

Does is the invention provides a kind of method utilizing animal bone to prepare porous material, smash to pieces after the miscellaneous material on animal kindred removing top layer, under nitrogen protection, in 500 ~ 1000? 1 ~ 3 is processed at DEG C? h, then in ball mill ball milling 6 ~ 10? h; Then acid treatment 12 ~ 72? h; Wash into neutrality with distillation, dry and get final product.Measuring, better hydrogen reduction performance is shown than traditional commerce XC-72 carbon dust electrode using porous material of the present invention as the electrode of fuel cell, oxygen reduction catalytic activity significantly improves, therefore, as the electrode catalyst of fuel cell, there is cost low, performance high, contribute to applying of fuel cell.In addition, porous material of the present invention for raw material, not only reduces porous material production cost with discarded animal bone, solves treatment of wastes produced problem in actual life simultaneously, decreases the pollution of environment, really achieve the recycling theory turned waste into wealth.

Description

Animal bone is utilized to prepare the method for porous material and the application as electrode catalyst of fuel cell
Technical field
The invention belongs to new material technology field, relate to a kind of method utilizing animal bone to prepare porous material; The invention still further relates to the application of this porous material as electrode catalyst of fuel cell.
Background technology
Fuel cell is that a kind of operating efficiency is high, environmentally friendly, the novel power generation device that answer speed is fast, and chemical energy can be directly electric energy by it, therefore becomes the main energy sources of 21st century.In addition, fuel cell also has original advantage: normal temperature uses, fuel carries supply convenience, volume and weight specific energy density is high, infrared signal is weak, especially be suitable as small movable and compact power, have splendid potential application foreground in fields such as national defence, the energy, environmental protection, communications.
Electrode catalyst is the important part of fuel cell, directly affects the performance of fuel cell, efficiency, stability and service life.Pt catalyst is the commercial catalysts of comparative maturity, has a lot of application at fuel cell catalyst, especially has higher activity to methanol catalytic oxidation, and in the middle of sour environment, have preferably stability.But Pt is expensive rare precious metals, the cost of catalyst accounts for 30% ~ 45% of low-temperature fuel cell cost.Therefore, the fuel-cell catalyst developing low-cost and high-performance becomes the focus of research fuel cell.
Porous material, be a kind ofly form the material of network structure by through or blind bore hole mutually, the border of hole or surface are made up of pillar or flat board.It is assemble by a large amount of polygonal hole the two-dimensional structure formed in the plane that typical pore structure has a kind of, is called as " honeycomb " material because its shape is similar to the hexagonal structure of honeycomb.More generally the three-dimensional structure formed at space clustering by hole polyhedron-shaped in a large number, is referred to as " foam " material usually.Porous material has unique optical property, therefore in the porous electrode making fuel cell, has good application prospect.
China is carnivorous first big country of the world, and the annual animal bone produced just has more than 1,500 ten thousand tons.At present for the process of these animal bones, mainly abandon as refuse, not only pollute to dynamic tier, and cause the waste of origin.Therefore, the recycling tool for these animal bones is of great significance.Animal bone (i.e. bone tissue) is made up of living cells and mineral matter (mainly calcium and squama) mixing, mainly calcium hydroxy phosphate (Ca 10(PO 4) 6(OH) 2), these mineral matters make bone have solid physical property just, calcium hydroxy phosphate is made to be not easy to decompose in the process of calcining, the gas infiltration produced in calcination process wherein makes it occur cavernous structure, therefore, utilize animal bone to prepare porous material, not only can reduce the cost of porous material, but also the recycling of animal bone can be realized.
Summary of the invention
The first object of the present invention is to provide a kind of method utilizing animal bone to prepare porous material;
Another object of the present invention is to provide the application of this porous material as electrode catalyst of fuel cell.
The preparation method of porous material of the present invention, be by animal kindred removing top layer miscellaneous material after smash to pieces, be placed in tube furnace, under nitrogen protection, high-temperature process 1 ~ 3h at 500 ~ 1000 DEG C, then in ball mill ball milling 6 ~ 10h; Then acid treatment 12 ~ 72h; Wash into neutrality with distillation, dry and get final product.
Described animal bone is pig bone, Os Bovis seu Bubali, Fishbone, sheep bone.
Described acid treatment is the HNO first using 1 ~ 5mol/L 3process 12 ~ 72h, then with the HCl process 12 ~ 72h of 1 ~ 5mol/L;
Described oven dry is in convection oven, carries out at 50 ~ 70 DEG C.
Physical characterization and performance test are carried out to porous material prepared by the present invention below.
1, X-ray diffraction
Fig. 1 is the x-ray diffraction pattern of porous material prepared by the present invention.As can be seen from Figure 1, occurred many peaks after direct carbonization, the peak wherein corresponding to " ◆ " is the peak of calcium hydroxy phosphate.
2, ESEM (SEM) figure
Fig. 2 is ESEM (SEM) figure of porous material prepared by the present invention.As can be seen from Figure 2, the material that prepared by the present invention is pore structure.
3, nitrogen adsorption desorption curve and graph of pore diameter distribution
Fig. 3 is that the nitrogen of porous material prepared by the present invention washes desorption curve and graph of pore diameter distribution (BET) figure, and can find out that the aperture of this material is about 3.18nm from figure, this material is mesoporous material as seen, and in addition, its specific area is 294.074m 2g -1.
4, ORR test
Fig. 3 is the ORR test of porous material in the KOH solution of 0.1mol/L prepared by the present invention.As can be seen from Figure 3, porous material prepared by the present invention is compared with traditional XC-72, and have good ORR performance, its take-off potential is advanced by 111.7mV.
In sum, porous material prepared by the present invention has obvious pore structure, contributes to the increase of specific area; Through HNO 3process makes oxygen-containing functional group wherein increase, and the existence of P element also serves certain facilitation to its ORR performance.Measuring, using porous material of the present invention as the electrode material of fuel cell, better hydrogen reduction performance is shown than traditional commerce XC-72 carbon dust electrode, oxygen reduction catalytic activity significantly improves, therefore, as the electrode catalyst of fuel cell, there is cost low, performance high, contributes to applying of fuel cell.In addition, porous material of the present invention for raw material, not only reduces porous material production cost with discarded animal bone, solves treatment of wastes produced problem in actual life simultaneously, decreases the pollution of environment, really achieve the recycling theory turned waste into wealth.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of porous material prepared by the present invention.
Fig. 2 is ESEM (SEM) figure of porous material prepared by the present invention.
Fig. 3 is nitrogen adsorption desorption curve and graph of pore diameter distribution (BET) figure of porous material prepared by the present invention
Fig. 4 be the porous material prepared of the present invention in the KOH solution of 0.1mol/L with the ORR test and comparison figure of traditional X-ray C-72.
Detailed description of the invention
Below for pig bone, by specific embodiment, porous material preparation method of the present invention is described further.
embodiment 1
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 800 DEG C, then ball milling 6 ~ 10h in ball mill; The HNO of gained sample 3mol/L 3process 24h, washes into neutrality with distillation afterwards, puts into convection oven in 60 DEG C of oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 35mV, and this may be because the calcium phosphate inside bone is completely caused by dissolving.
embodiment 2
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 800 DEG C, then ball milling 6 ~ 10h in ball mill; The HNO of 3mol/L first used by gained sample 3process 24h, then with the HCl process 72h of 2mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 111.7mV.This is mainly because first use HNO 3process makes its oxygen-containing functional group increase, and then with HCl process, calcium phosphate is dissolved completely, forms larger pore structure, thus increase its specific area, finally make ORR performance improve further.
embodiment 3
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 800 DEG C, then ball milling 6 ~ 10h in ball mill; By the HCl process 72h of gained sample 2mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 68.4mV, this is mainly because make calcium phosphate dissolve completely with HCl process, form pore structure, thus increase its specific area, finally make performance increase to some extent, but after not having first nitric acid treatment, again HCl treatment, the sample performance of gained is good.
embodiment 4
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 700 DEG C, then ball milling 6h in ball mill; Gained sample is first used the HNO of 3mol/L 3process 24h, then with the HCl process 72h of 3mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 98.4mV.
embodiment 5
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 900 DEG C, then ball milling 6h in ball mill; Gained sample is first used the HNO of 3mol/L 3process 24h, then with the HCl process 72h of 3mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 100.1mV.
embodiment 6
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 1h at 800 DEG C, then ball milling 6h in ball mill; Gained sample is first used the HNO of 3mol/L 3process 24h, then with the HCl process 48h of 3mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 65.6mV.
embodiment 7
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 3h at 800 DEG C, then ball milling 6h in ball mill; Gained sample is first used the HNO of 3mol/L 3process 24h, then with the HCl process 48h of 3mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 93.1mV.
embodiment 8
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 800 DEG C, then ball milling 6h in ball mill; Gained sample is first used the HNO of 1mol/L 3process 24h, then with the HCl process 72h of 3mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 76.6mV.
embodiment 9
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 800 DEG C, then ball milling 6h in ball mill; Gained sample is first used the HNO of 5mol/L 3process 24h, then with the HCl process 72h of 3mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 110.3mV.
embodiment 10
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 800 DEG C, then ball milling 6h in ball mill; Gained sample is first used the HNO of 3mol/L 3process 24h, then with the HCl process 48h of 3mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 74.5mV.
embodiment 11
Smash to pieces after the miscellaneous material on the pig bone of collection removing top layer, be placed in tube furnace, under nitrogen protection, high-temperature process 2h at 800 DEG C, then ball milling 6h in ball mill; Gained sample is first used the HNO of 3mol/L 3process 24h, then with the HCl process 96h of 3mol/L, wash into neutrality with distillation afterwards, put into convection oven 60 DEG C oven dry.
In the KOH solution of 0.1mol/L, test ORR find, compared with XC-72, its take-off potential is advanced by 83.6mV.
A large amount of experiments shows, take Os Bovis seu Bubali as raw material, the ORR performance of the porous material adopting said method to prepare and pig bone basic simlarity.

Claims (4)

1. utilize animal bone to prepare the method for porous material, be smash to pieces after miscellaneous material animal bone being removed top layer, be placed in tube furnace, under nitrogen protection, at 500 ~ 1000 DEG C, process 1 ~ 3h, then in ball mill ball milling 6 ~ 10h; Then through acid treatment, then wash into neutrality with distillation, dry and get final product; Described acid treatment is the HNO first using 1 ~ 5mol/L 3process 12 ~ 72h, then with the HCl process 12 ~ 72h of 1 ~ 5mol/L.
2. utilize animal bone to prepare the method for porous material as claimed in claim 1, it is characterized in that: described animal bone is pig bone, Os Bovis seu Bubali, Fishbone, sheep bone.
3. utilize animal bone to prepare the method for porous material as claimed in claim 1 or 2, it is characterized in that: described oven dry is in convection oven, carry out at 50 ~ 70 DEG C.
4. as claimed in claim 1 the porous material prepared of method as the application of electrode catalyst of fuel cell.
CN201410080389.5A 2014-03-06 2014-03-06 Animal bone is utilized to prepare the method for porous material and the application as electrode catalyst of fuel cell Expired - Fee Related CN103801342B (en)

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CN101993068A (en) * 2010-10-27 2011-03-30 北京化工大学 Preparation method of porous structured active carbon

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Publication number Priority date Publication date Assignee Title
CN101993068A (en) * 2010-10-27 2011-03-30 北京化工大学 Preparation method of porous structured active carbon

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