CN105375042A - Biomass carbon catalyst and preparation method and application thereof - Google Patents
Biomass carbon catalyst and preparation method and application thereof Download PDFInfo
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a biomass carbon catalyst and a preparation method and application thereof. The precursor of the catalyst comprises biomass and metal salts, wherein the biomass includes one or more of maize straw, corncob, rice straw, cotton straw, peanut straw, peanut shell, wheat hull, rice hull, wood, sawdust, bamboo wood and weed. Through controlling addition of metal salts in different amounts, adjusting impregnation concentration of the precursor and reaction ambient and carbonization and nitriding treatment temperatures, the biomass carbon catalyst with controllable and adjustable pore structure and specific surface area can be prepared. When used as a fuel battery cathode catalyst, the biomass carbon catalyst shows excellent oxygen reduction reaction activity and stability. The preparation process is simple in flow, short in period and free of environment, provides a novel high-value-added resource recycling way for waste biomass and has dual effects of biomass disposal and energy and power generation.
Description
Technical field
The present invention relates to fuel-cell catalyst, specifically a kind of high-activity biological matter carbon-supported catalysts and preparation method and the application in fuel battery negative pole.
Background technology
Fuel cell is a kind of is directly the energy conversion device of electric energy by the chemical energy being stored in fuel.Fuel cell is without heat engine process, and power generation process does not limit by Carnot cycle, and the chemical energy of most of fuel wherein directly can be converted to electric energy, and energy conversion efficiency can reach 40 ~ 60%.Meanwhile, fuel cell reaction product is the innocuous substances such as water, produces the pollutants such as sulfur dioxide, nitrogen oxide and suspended matter hardly, does not also release GHG carbon dioxide, meet society environmental protection concept.Needed for fuel cell, auxiliary equipment is few, and convenient and reliable operation, flexibility are large.These advantages make fuel cell be acknowledged as clean, the efficient generation technology of 21 century first-selection, are subject to the great attention of national governments and research institution in recent years.
Current eelctro-catalyst is as fuel cell critical material, and its material and preparation cost, electrochemical reaction stability that is active and long-time running realize the maximum obstacle of commercializing fuel cells.For common Pt catalyst, Pt is the catalyst material be most widely used in a fuel cell, and the preparation technology of its limited resource, expensive price and complexity causes holding at high price of fuel cell, becomes the bottleneck of commercializing fuel cells.In recent years, no-Pt catalyst was once becoming emphasis and the focus of various countries fuel cell studies personnel research and development, and non-Pt oxygen reduction cathode catalyst mainly comprises transition metal cluster compound, transition metal macrocyclic compound, transition metal oxide and transition metal carboritride etc.The good catalyst activity of no-Pt catalyst and cheap price become and replace Pt the strongest catalyst based being selected.But because non-Pt material is under the high potential condition of operation of fuel cells, very easily there is the loss that side reaction causes catalyst, thus also there is very large gap in the practical application of stability aspect distance.Therefore, for realizing the Commercialization application of fuel cell, developing a kind of high activity, high stability, cheap non-noble metal fuel cell cathod catalyst are extremely urgent.
Biological qualitative diversity determines that its constituent is also varied.Main component has cellulose, hemicellulose, lignin, starch, protein, hydro carbons (comprise and cover class) etc., wherein cellulose, hemicellulose, lignin are almost the constituents of all biomass, but in different cultivars biomass, the content of these three kinds compositions is also different, and its thermal decomposition product is also variant.Charcoal is the solid residue that a kind of carbon containing of obtaining after pyrolysis biomass is high, is an international study hotspot at present.Charcoal pore structure is flourishing, environmental stability is high, conductivity is good, material with carbon element itself does not have activity to oxygen reduction reaction, but by methods such as doping and modifications, improve material with carbon element structure, composition and surface functional group, material with carbon element itself can be made to produce catalytic activity to oxygen reduction reaction, by biomass precursor power carbon-supported catalysts, there is certain feasibility, but the research of this respect also belongs to blank.Thus, develop a kind of biomass carbon sill with oxygen reduction activity and antioxidant anticorrosive performance and be used as fuel-cell catalyst, effectively will reduce material cost, and improve battery operated stability, significant to the business application of fuel cell.
Research shows, the material with carbon element after nitrogen treatment has higher oxygen reduction activity in oxygen reduction reaction; Meanwhile, metal-doped material can obtain higher degree of graphitization in identical heat treatment process, indirectly reduces the preparation cost of graphitized carbon material, improves the antioxidant anticorrosive performance of material with carbon element.Thus, metal-doped nitrogenize biomass carbon sill has good oxygen reduction activity and electrochemical stability, and it can stable existence under the condition of microbiological fuel cell operation.Metal-doped nitrogenize biomass carbon sill has larger specific area and can be the electrochemical site that reaction provides mass efficient; Simultaneously suitable pore structure becomes the passage that reactant and product transmit smoothly; In addition, one of good electrical and thermal conductivity performance application material becoming fuel cell system middle ideal.While being added on of slaine reduces biomass carbon sill graphitization temperature, improve the electrochemical reaction active sites quantity of its formation in nitriding atmosphere.Show certain oxygen reduction activity and stability in a fuel cell through the biomass carbon of metal-doped nitrogen treatment is catalyst based.Therefore, adopt this nonmetallic materials of nitrogenize biomass carbon back as fuel cell electro-catalyst, not only can greatly reduce catalyst material cost, promote the commercial applications of fuel cell, simultaneously also for abandoned biomass provides the disposal of resources approach of a novel high added value, have and dispose biomass and production capacity and to generate electricity double effects.
Summary of the invention
The object of the present invention is to provide the catalyst based and application in a fuel cell of a kind of biomass carbon; The central hole structure that biomass carbon sill has larger specific area, appropriate substances transmits and good electrical and thermal conductivity performance, as fuel battery cathod catalyst, show good corrosion resistance stability and oxygen reduction reaction activity.
Another object of the present invention is the preparation method providing the catalyst based M-B-N of a kind of biomass carbon (M=Fe, Co, Ni, Cu, Zn, Zr, W, Ir, V, Cr, Mn etc.);
For achieving the above object, the technical solution used in the present invention is:
A kind of biomass carbon is catalyst based, and its biomass carbon back is for raw material with biomass and slaine.
Described slaine is the soluble-salt of one or more metallic elements in IVB, VB, VIB, VIIB, VIII, IB and IIB race.
Described soluble-salt is that one or more in the nitrate of metal, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or large ring complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and polymer thereof can cosolvency salt.
Described metallic element is Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W.
Described biomass are one or more in maize straw, corncob, rice straw, cotton stalk, straw, peanut straw, peanut shell, wheat shell, coconut husk, husk, rice husk, walnut shell, hazelnut shell, bagasse, timber, wood chip, bamboo wood, weeds.
The preparation method that biomass carbon is catalyst based, adopts following process to prepare:
(1) biomass pulverized and sieved, obtain powdered biomass after cleaning-drying process, described cleaning solution is the acid solution of 0.5 ~ 5M, eccysis impurity, improves biomass purity;
(2) by process after biomass and solvent in the ratio of 0.1 ~ 10ml solvent/1g biomass, be uniformly mixed and be uniformly dissolved, be uniformly mixed liquid A;
(3) soluble metallic salt is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B;
(4) mixed slurry B Keep agitation 5 ~ 36 hours in 10 ~ 100 DEG C of environment, then puts into vacuum drying chamber drying, takes out and pulverizes grinding, obtain pressed powder C;
(5) by pressed powder C carbonization nitrogen treatment 1 ~ 10 hour in 500 ~ 1200 DEG C of nitriding atmospheres, inert blowing gas is swept to room temperature; Adopt the unreacted slaine of 0.5 ~ 5M acid solution eccysis, namely obtain biomass carbon after drying catalyst based.
Described slaine molal quantity and biomass mass ratio are 0.001 ~ 1:20.
Described acid is nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid; Nitriding atmosphere is NH
3/ N
2, NH
3, CH
3cN or HCN atmosphere.
During described preparation mixed liquor A, described solvent is the stirring ambient temperature of water is 20 ~ 80 DEG C, solvent is the stirring ambient temperature of ethanol is 20 ~ 78 DEG C, and solvent is the stirring ambient temperature of isopropyl alcohol is 20 ~ 82 DEG C, and solvent is the stirring ambient temperature of ethylene glycol is 60 ~ 100 DEG C.
The application of catalyst of the present invention is the application in microbiological fuel cell, Proton Exchange Membrane Fuel Cells or alkaline membrane fuel cell.
Advantage of the present invention is:
1. effect is good.Biomass carbon is catalyst based as a kind of non-metal kind eelctro-catalyst, when fuel battery negative pole is applied, shows higher oxygen reduction reaction activity and stability.
2. present invention process flow process is simple, the cycle is short, and by the once nitrogenize of carbonization simultaneously of precursor component, can prepare high-specific surface area, the biomass carbon of high stability is catalyst based; The solvent safety used in biomass carbon sill preparation process, nontoxic, environmentally safe.In addition, at same treatment temperature, adding of metallics not only introduces active sites, and improves the catalyst based degree of graphitization of biomass carbon, ensure that activity and the stability of biomass carbon sill.
3. biomass of the present invention are in metal-modified process, by controlling the adding of different amount slaine, regulating precursor mixed liquor composition and reaction environment temperature, and carbonization nitrogen treatment temperature, ascending order programming rate controls, and can prepare pore structure and the controllable biomass carbon sill of specific area.
4. catalyst of the present invention with low cost, have wide range of applications.The nonmetal electrocatalysis material of carbon back of biomass carbon is catalyst based to be a kind of with abandoned biomass be raw material, compare with noble metals such as Pt in the past, material cost reduces greatly; In addition, this catalyst material not only can apply neutral microbiological fuel cell, acidic proton exchange membrane fuel cell, and the catalytic activity in alkaline environment is higher, and the catalytic activity with noble metals such as Pt is suitable.
Embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
10g corn straw smashing is sieved, with the H of 0.5M
2sO
4powdered biomass is obtained after solution cleaning, dry process, added in 10ml deionized water by this powder, be uniformly mixed 4 hours, be uniformly mixed liquid A, 0.33M cobalt chloride is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 4 hours in 20 DEG C of environment, then the dry 2d of vacuum drying chamber is put into, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
3in 800 DEG C of carbonization nitrogen treatment 3h, N
2air-blowing is swept to room temperature, 0.5MH
2sO
4solution eccysis slaine, obtains the catalyst based Co-B-30 of biomass carbon of cobalt chloride mole and biomass mass ratio 1:30 after drying.
Comparative example
10g corn straw smashing is sieved, with 0.5MH
2sO
4powdered biomass is obtained after solution cleaning, dry process, this powder is added in 10ml deionized water, be uniformly mixed 4 hours, be uniformly mixed liquid A, mixed slurry A Keep agitation 4 hours in 20 DEG C of environment, then puts into the dry 2d of vacuum drying chamber, pulverizes grinding after taking-up, obtain pressed powder B, by pressed powder B in NH
3in 800 DEG C of carbonization nitrogen treatment 3h, N
2air-blowing is swept to room temperature, 0.5MH
2sO
4solution eccysis slaine, obtains the catalyst based B-0 of blank's biomass carbon after drying.
Embodiment 2
10g peanut straw is pulverized and sieved, with the H of 0.5M
2sO
4obtain powdered biomass after solution cleaning, dry process, this powder is added in 8ml deionized water, is uniformly mixed 4 hours, be uniformly mixed liquid A, 0.5M ferric nitrate is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 4 hours in 25 DEG C of environment, then put into the dry 2d of vacuum drying chamber, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C 700 DEG C of carbonization nitrogen treatment 3h, N in acetonitrile atmosphere
2air-blowing is swept to room temperature, 0.5MH
2sO
4solution eccysis slaine, obtains the catalyst based Fe-B-20 of biomass carbon of ferric nitrate mole and biomass mass ratio 1:20 after drying.
Embodiment 3
10g peanut straw is pulverized and sieved, with the H of 1M
2sO
4powdered biomass is obtained after solution cleaning, dry process, added in 15ml deionized water by this powder, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.2M cobalt nitrate is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 4 hours in 20 DEG C of environment, then the dry 1d of vacuum drying chamber is put into, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
31000 DEG C of carbonization nitrogen treatment 3h, N in atmosphere
2air-blowing is swept to room temperature, 1MH
2sO
4solution eccysis slaine, obtains the catalyst based Co-B-50 of biomass carbon of cobalt nitrate mole and biomass mass ratio 1:50 after drying.
Embodiment 4
10g rice straw pulverized and sieved, cleans with the HCl solution of 1M, obtain powdered biomass after dry process, added in 12ml deionized water by this powder, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.125M cobalt acetate is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 4 hours in 50 DEG C of environment, then the dry 2d of vacuum drying chamber is put into, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
3600 DEG C of carbonization nitrogen treatment 5h, N in atmosphere
2air-blowing is swept to room temperature, 1MHCl solution eccysis slaine, obtains the catalyst based Co-B-80 of biomass carbon of cobalt acetate mole and biomass mass ratio 1:80 after drying.
Embodiment 5
10g fruit tree branch pulverized and sieved, cleans with the HCl solution of 3M, obtain powdered biomass after dry process, added in 15ml deionized water by this powder, be uniformly mixed 3 hours, be uniformly mixed liquid A, 0.1M ferric acetate is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 4 hours in 50 DEG C of environment, then the dry 2d of vacuum drying chamber is put into, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
31200 DEG C of carbonization nitrogen treatment 1h, N in atmosphere
2air-blowing is swept to room temperature, 3MHCl solution eccysis slaine, obtains the catalyst based Co-B-100 of biomass carbon of ferric acetate mole and biomass mass ratio 1:80 after drying.
Embodiment 6
10g peanut shell pulverized and sieved, cleans with the phosphoric acid solution of 1M, obtain powdered biomass after dry process, this powder is added in 12ml deionized water, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.05M cobalt acetate is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 4 hours in 50 DEG C of environment, then put into the dry 1d of vacuum drying chamber, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C 1000 DEG C of carbonization nitrogen treatment 2.5h, N in acetonitrile atmosphere
2air-blowing is swept to room temperature, 1M phosphoric acid solution eccysis slaine, obtains the catalyst based Co-B-200 of biomass carbon of cobalt acetate mole and biomass mass ratio 1:200 after drying.
Embodiment 7
10g rice straw pulverized and sieved, cleans with the HCl solution of 1M, obtain powdered biomass after dry process, added in 18ml deionized water by this powder, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.125M Schweinfurt green is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 4 hours in 60 DEG C of environment, then the dry 2d of vacuum drying chamber is put into, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
3600 DEG C of carbonization nitrogen treatment 5h, N in atmosphere
2air-blowing is swept to room temperature, 1MHCl solution eccysis slaine, obtains the catalyst based Co-B-80 of biomass carbon of Schweinfurt green mole and biomass mass ratio 1:80 after drying.
Embodiment 8
10g cotton stalk is pulverized and sieves, with the HNO of 1M
3powdered biomass is obtained after solution cleaning, dry process, this powder is added in 20ml deionized water, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.033M zinc nitrate is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 6 hours in 40 DEG C of environment, then puts into CO
2supercritical drying 2d, pulverizes grinding after taking-up, obtains pressed powder C, by pressed powder C 800 DEG C of carbonization nitrogen treatment 3h, N in acetonitrile atmosphere
2air-blowing is swept to room temperature, 1MHNO
3solution eccysis slaine, obtains the catalyst based Zn-B-300 of biomass carbon of zinc nitrate mole and biomass mass ratio 1:300 after drying.
Embodiment 9
10g corn straw smashing sieved, cleans with the HCl solution of 1M, obtain powdered biomass after dry process, this powder is added in 20ml deionized water, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.143M tetra-hydrated sulfuric acid vanadyl is joined in above-mentioned mixed liquor A, stirs dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 6 hours in 50 DEG C of environment, then puts into CO
2supercritical drying 2d, pulverizes grinding after taking-up, obtains pressed powder C, by pressed powder C in NH
3600 DEG C of carbonization nitrogen treatment 5h, N in atmosphere
2air-blowing is swept to room temperature, 1MHCl solution eccysis slaine, obtains the catalyst based V-B-70 of biomass carbon of vanadic sulfate mole and biomass mass ratio 1:70 after drying.
Embodiment 10
10g peanut straw pulverized and sieved, cleans with the phosphoric acid solution of 1M, obtain powdered biomass after dry process, added in 18ml deionized water by this powder, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.033M Schweinfurt green is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 4 hours in 60 DEG C of environment, then the dry 2d of vacuum drying chamber is put into, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
31100 DEG C of carbonization nitrogen treatment 2h, N in atmosphere
2air-blowing is swept to room temperature, 1M phosphoric acid solution eccysis slaine, obtains the catalyst based Cu-B-300 of biomass carbon of Schweinfurt green mole and biomass mass ratio 1:300 after drying.
Embodiment 11
10g rice straw pulverized and sieved, cleans with the HCl solution of 1M, obtain powdered biomass after dry process, added in 20ml deionized water by this powder, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.125M manganese nitrate is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 6 hours in 30 DEG C of environment, then CO2 supercritical drying 2d is put into, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
3800 DEG C of carbonization nitrogen treatment 5h, N in atmosphere
2air-blowing is swept to room temperature, 1MHCl solution eccysis slaine, obtains the catalyst based Mn-B-80 of biomass carbon of manganese nitrate mole and biomass mass ratio 1:80 after drying.
Embodiment 12
10g corn straw smashing sieved, cleans with the HCl solution of 1M, obtain powdered biomass after dry process, added in 20ml deionized water by this powder, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.067M ammonium molybdate is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 6 hours in 50 DEG C of environment, then CO2 supercritical drying 2d is put into, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
3900 DEG C of carbonization nitrogen treatment 5h, N in atmosphere
2air-blowing is swept to room temperature, 1MHCl solution eccysis slaine, obtains the catalyst based Mo-B-150 of biomass carbon of ammonium molybdate mole and biomass mass ratio 1:150 after drying.
Embodiment 13
10g walnut shell pulverized and sieved, cleans with the HCl solution of 1M, obtain powdered biomass after dry process, this powder is added in 20ml deionized water, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.033M cabaltous nitrate hexahydrate and 0.033M Fe(NO3)39H2O are joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 5 hours in 60 DEG C of environment, then freeze drying 2d, pulverize grinding after taking-up, obtain pressed powder C, by pressed powder C in NH
31000 DEG C of carbonization nitrogen treatment 5h, N in atmosphere
2air-blowing is swept to room temperature, 1MHCl solution eccysis slaine, obtains the catalyst based CoFe-B-300 of biomass carbon of cobalt nitrate, ferric nitrate mole and biomass mass ratio 1:1:300 after drying.
Embodiment 14
10g peanut shell is pulverized and sieved, with 2MHNO
3powdered biomass is obtained after solution cleaning, dry process, this powder is added in 15ml deionized water, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.01M Gerhardite and 0.015M tetra-hydration cobalt acetate are joined in above-mentioned mixed liquor A, stirs dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 5 hours in 60 DEG C of environment, then CO
2supercritical drying 5d, pulverizes grinding after taking-up, obtains pressed powder C, by pressed powder C in NH
31000 DEG C of carbonization nitrogen treatment 5h, N in atmosphere
2air-blowing is swept to room temperature, 2MHNO
3solution eccysis slaine, obtains the catalyst based Cu of biomass carbon of copper nitrate, cobalt acetate mole and biomass quality 2:3:400 after drying
2co
3-B-400.
Embodiment 15
10g fruit tree branch is pulverized and sieved, with 2MH
2sO
4powdered biomass is obtained after solution cleaning, dry process, this powder is added in 15ml deionized water, be uniformly mixed 2 hours, be uniformly mixed liquid A, 0.005M bis-nitric hydrate oxygen zirconium and 0.015M Fe(NO3)39H2O are joined in above-mentioned mixed liquor A, stirs dipping evenly, obtain mixed slurry B, mixed slurry B Keep agitation 3 hours in 60 DEG C of environment, then CO
2supercritical drying 2d, pulverizes grinding after taking-up, obtains pressed powder C, by pressed powder C in NH
3800 DEG C of carbonization nitrogen treatment 4h in atmosphere, Ar air-blowing is swept to room temperature, 2MH
2sO
4solution eccysis slaine, obtains the catalyst based Zr of biomass carbon of zirconyl nitrate, ferric nitrate mole and biomass quality 1:3:500 after drying
1fe
3-B-500.
Claims (10)
1. a biomass carbon is catalyst based, it is characterized in that: described biomass carbon back with biomass and slaine for raw material.
2. according to catalyst according to claim 1, it is characterized in that: described slaine is the soluble-salt of one or more metallic elements in IVB, VB, VIB, VIIB, VIII, IB and IIB race.
3. according to catalyst according to claim 2, it is characterized in that: described soluble-salt is that one or more in the nitrate of metal, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or large ring complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and polymer thereof can cosolvency salt.
4. according to catalyst according to claim 2, it is characterized in that: described metallic element is Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W.
5. according to catalyst according to claim 1, it is characterized in that: described biomass are one or more in maize straw, corncob, rice straw, cotton stalk, straw, peanut straw, peanut shell, wheat shell, coconut husk, husk, rice husk, walnut shell, hazelnut shell, bagasse, timber, wood chip, bamboo wood, weeds.
6. the preparation method that biomass carbon is catalyst based as claimed in claim 1, is characterized in that:
Following process is adopted to prepare:
(1) biomass pulverized and sieved, obtain powdered biomass after cleaning-drying process, described cleaning solution is the acid solution of 0.5 ~ 5M, eccysis impurity, improves biomass purity;
(2) by process after biomass and solvent in the ratio of 0.1 ~ 10ml solvent/1g biomass, be uniformly mixed and be uniformly dissolved, be uniformly mixed liquid A;
(3) soluble metallic salt is joined in above-mentioned mixed liquor A, stir dipping evenly, obtain mixed slurry B;
(4) mixed slurry B Keep agitation 5 ~ 36 hours in 10 ~ 100 DEG C of environment, then puts into vacuum drying chamber drying, takes out and pulverizes grinding, obtain pressed powder C;
(5) by pressed powder C carbonization nitrogen treatment 1 ~ 10 hour in 500 ~ 1200 DEG C of nitriding atmospheres, inert blowing gas is swept to room temperature; Adopt the unreacted slaine of 0.5 ~ 5M acid solution eccysis, namely obtain biomass carbon after drying catalyst based.
7. according to the preparation method that biomass carbon according to claim 6 is catalyst based, it is characterized in that: described slaine molal quantity and biomass mass ratio are 0.001 ~ 1:20.
8., according to the preparation method that biomass carbon according to claim 6 is catalyst based, it is characterized in that:, described acid is nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid; Nitriding atmosphere is NH
3/ N
2, NH
3, CH
3cN or HCN atmosphere.
9. according to the preparation method that biomass carbon according to claim 6 is catalyst based, it is characterized in that: during preparation mixed liquor A, described solvent is the stirring ambient temperature of water is 20 ~ 80 DEG C, solvent is the stirring ambient temperature of ethanol is 20 ~ 78 DEG C, solvent is the stirring ambient temperature of isopropyl alcohol is 20 ~ 82 DEG C, and solvent is the stirring ambient temperature of ethylene glycol is 60 ~ 100 DEG C.
10. an application for catalyst as claimed in claim 1, is characterized in that: the application in microbiological fuel cell, Proton Exchange Membrane Fuel Cells or alkaline membrane fuel cell.
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