CN104174439A - Preparation and application of electrocatalyst based on transition metal macrocyclic compound - Google Patents
Preparation and application of electrocatalyst based on transition metal macrocyclic compound Download PDFInfo
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- CN104174439A CN104174439A CN201310204504.0A CN201310204504A CN104174439A CN 104174439 A CN104174439 A CN 104174439A CN 201310204504 A CN201310204504 A CN 201310204504A CN 104174439 A CN104174439 A CN 104174439A
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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
The invention relates to preparation and application of an electrocatalyst based on a transition metal macrocyclic compound. The specific steps include: mixing an acidic aqueous solution with an alkaline aqueous solution of the transition metal macrocyclic compound to make the transition metal macrocyclic compound form a nanostructured material by self-assembly, and carrying out washing, drying, heat treatment, pickling and other steps to obtain the non-noble metal electrocatalyst. The prepared non-noble metal electrocatalyst has a nano-structure with different shapes and uniform size distribution. The non-noble metal electrocatalyst prepared by the invention has oxygen reduction activity, and can be applied in proton exchange membrane fuel cells and metal air cells.
Description
Technical field
The invention belongs to fuel cell electro-catalyst field, be specifically related to a kind of preparation and application of the eelctro-catalyst based on transition metal macrocyclic compound.
Background technology
Fuel cell is the continuous generating device that chemical energy is converted into electric energy, have start fast, efficient, pollute the advantages such as little, be described as the most promising High Efficiency Low Pollution Power Generation Technology of 21 century.Eelctro-catalyst based on noble metal (as Pt) is one of core material of fuel cell, but, its expensive, resource-constrained, easily the problem such as poisoning has seriously hindered the commercialization process of fuel cell.A possible solution is the base metal eelctro-catalyst of the alternative platinum of research and development, promotes the development of fuel cell technology.In base metal eelctro-catalyst field, fruitful work (Energy Environ.Sci.2012,5,6081 are carried out both at home and abroad; Science2009,323,760; J.Am.Chem.Soc.2013,135,1386; Science2009,324,71).Base metal eelctro-catalyst can be divided into following several large class: (1) transition metal macrocycle and derivative thereof; (2) transition metal oxide (perovskite, spinelle etc.); (3) Metal-N-C type base metal eelctro-catalyst; (4) doping type base metal eelctro-catalyst.Particularly transition metal macrocycle and derivative thereof have higher activity (J.Phys.Chem.C2011,115,2604 to hydrogen reduction; J.Phys.Chem.C2009,113,20689), be expected to substitute platinum based noble metal eelctro-catalyst, promote the commercialization process of fuel cell.1964, Jasinski found to contain N
4the base metal chelate of-structure can electroreduction oxygen (Nature, 1964,201,1212), has opened base metal eelctro-catalyst new era in oxygen reduction reaction.Since then, transition metal macrocycle and derivative thereof become the study hotspot of base metal eelctro-catalyst gradually.Traditional preparation method is by N
4-transition metal macrocycle is adsorbed on carbon carrier, heat-treats, and then improve hydrogen reduction activity and stability under the protection of inert gas.But the hydrogen reduction activity of the prepared base metal eelctro-catalyst of conventional method also has a certain distance compared with the hydrogen reduction activity of business Pt/C, therefore, the hydrogen reduction activity that how further to improve base metal eelctro-catalyst is a focus of studying at present.For this problem, the present invention is incorporated into molecular self-assembling method in synthesizing of transition metal macrocycle class base metal eelctro-catalyst.
Utilize numerator self-assembly technique (as surfactant auxiliary law and reprecipitation method etc.) to obtain micro Nano material (Chem.Commun., 2011,47,6069 of the transition metal macrocycle of various structures novelty; Adv.Mater.2008,20,3543; Chem.Commun., 2008,3372; Chinese patent CN102898430A; US Patent No. 8,324,342B1).P.L.Chen and M.H.Liu etc. utilize surfactant assisted self assembling method by zinc5,10,15,20-tetra (4-pyridyl)-21H, 23H-porphine(ZnTPyP) chloroformic solution drop to contain cetyltrimethylammonium bromide(CTAB) the aqueous solution in, obtained the nanostructured of different-shape, as nanotube, nanometer rods, nanofiber (J.Am.Chem.Soc., 2010,132,9644).L.J.Wan etc. drop to the dimethyl formamide solution of ZnTPyP in the aqueous solution that contains CTAB, have obtained hollow tubular nanostructured (J.Am.Chem.Soc., 2005,127,17090).John A.Shelnutt etc. are by a kind of tin porphyrin Sn(IV) 5-(4-pyridyl)-10,15,20-triphenyl-porphyrin dichloride(SnPyTriPP) ethanolic solution drop in the aqueous solution, self assembly obtains the micro-nano hollow cubic body structure (J.Am.Chem.Soc. of novel structure, 2007,129,2440).But the transition metal macrocycle obtaining by molecular self-assembling is not also applied to base metal eelctro-catalyst.
The invention provides a kind of preparation method of the eelctro-catalyst based on transition metal macrocyclic compound, first transition metal macrocycle self assembly is obtained to the nanostructured with specific morphology, then prepare active sites through steps such as Overheating Treatment and arrange orderly base metal eelctro-catalyst.This method is taking transition metal macrocycle as construction unit, obtain nano level ordered structure by intermolecular weak interaction assembling, realized the ordered arrangement to active sites, synergy that can enhanced activity interdigit, contributes to improve the hydrogen reduction activity of eelctro-catalyst.The present invention is simple to operate, environmentally friendly, and the base metal eelctro-catalyst obtaining can be used for Proton Exchange Membrane Fuel Cells and metal-air battery.
Summary of the invention
The object of this invention is to provide a kind of preparation and application of the eelctro-catalyst based on transition metal macrocyclic compound; The present invention is by the conciliation to pH value of reaction system, and self assembly obtains the nanostructured of different-shape, through filtering and washing, dry, and roasting, the processing procedure that pickling is dried again, finally obtains the different base metal eelctro-catalyst of pattern.The method is simple to operate, be easy to control, environmentally friendly, and resulting structures nano-scale distributes high compared with homogeneous, good dispersion, hydrogen reduction activity.
The invention provides a kind of preparation method of the eelctro-catalyst based on transition metal macrocyclic compound, the concrete steps of the method are: under 0～100 ° of C, acidic aqueous solution is mixed with the alkaline aqueous solution of transition metal macrocyclic compound, stir 5min～5h, filtering and washing post-drying; Roasting 0.5～5h in carrier gas under 400～1200 ° of C, is cooled to room temperature; Add acidic aqueous solution, return stirring 0.5～24h under 0～100 ° of C, suction filtration, is washed to neutrality, dries.
The preparation method of the eelctro-catalyst based on transition metal macrocyclic compound provided by the invention, described acidic aqueous solution is one or more mixed solutions in boric acid, sulfuric acid, benzene sulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, wolframic acid, phosphotungstic acid, nitric acid, perchloric acid; The concentration of described acidic aqueous solution is 0.1～10moL/L.
The preparation method of the eelctro-catalyst based on transition metal macrocyclic compound provided by the invention, stating transition metal macrocycle is hemin (Hemin), heme (Heme B, Heme C), meso-tetra-(4-methoxyphenyl) porphyrin copper, meso-tetra-(4-methoxyphenyl) PORPHYRIN IRON, meso-tetra-(4-methoxyphenyl) Cobalt Porphyrin, meso-tetra-(4-methoxyphenyl) zinc porphyrin, meso-tetra-(4-methoxyphenyl) Manganese Porphyrin, meso-tetra-(4-methoxyphenyl) Porphyrin Nickel, protoporphyrin iron chloride, protoporphyrin cobalt chloride, protoporphyrin manganese chloride, protoporphyrin zinc chloride, protoporphyrin copper chloride, protoporphyrin nickel chloride, meso-tetra-(4-carboxyl phenyl) porphines iron chloride, meso-tetra-(4-carboxyl phenyl) porphines copper chloride, meso-tetra-(4-carboxyl phenyl) porphines cobalt chloride, meso-tetra-(4-carboxyl phenyl) porphines zinc chloride, meso-tetra-(4-carboxyl phenyl) porphines manganese chloride, meso-tetra-(4-carboxyl phenyl) porphines nickel chloride, α-tetrahydroxy ZnPc, α-tetrahydroxy cobalt phthalocyanine, α-tetrahydroxy iron-phthalocyanine, α-tetrahydroxy manganese phthalocyanine, α-tetracarbonyl nickle phthalocyanine, α-tetrahydroxy copper phthalocyanine, β-tetrahydroxy ZnPc, β-tetrahydroxy cobalt phthalocyanine, β-tetrahydroxy iron-phthalocyanine, β-tetrahydroxy manganese phthalocyanine, β-tetracarbonyl nickle phthalocyanine, β-tetrahydroxy copper phthalocyanine, 2,3,9,10,16,17,23,24-, eight hydroxyls replace ZnPc, 2,3,9,10,16,17,23,24-, eight hydroxyls replace cobalt phthalocyanine, 2,3,9,10,16,17,23,24-, eight hydroxyls replace iron-phthalocyanine, 2,3,9,10,16,17,23,24-, eight hydroxyls replace manganese phthalocyanine, 2,3,9,10,16,17,23,24-, eight hydroxyls replace nickel phthalocyanine, tetracarboxylic replaces ZnPc, tetracarboxylic replaces copper phthalocyanine, tetracarboxylic replaces cobalt phthalocyanine, tetracarboxylic replaces nickel phthalocyanine, tetracarboxylic replaces iron-phthalocyanine, the mixture of one or more in tetracarboxylic replacement manganese phthalocyanine and its analog and derivative, its concentration in alkaline aqueous solution is 0.1～5000mmoL/L.
The preparation method of the eelctro-catalyst based on transition metal macrocyclic compound provided by the invention, described alkaline aqueous solution is LiOH, NaOH, KOH, LiHCO
3, NaHCO
3, KHCO
3, Li
2cO
3, Na
2cO
3or K
2cO
3in one or more mixed solution; Its concentration is 0.1～4.5moL/L.
The preparation method of the eelctro-catalyst based on transition metal macrocyclic compound provided by the invention, the volume ratio of the alkaline aqueous solution of described acidic aqueous solution and transition metal macrocyclic compound is 1:20 to 10:1.
The preparation method of the eelctro-catalyst based on transition metal macrocyclic compound provided by the invention, described carrier gas is one or two or more kinds the mist in helium, neon, argon gas, nitrogen, ammonia.
Eelctro-catalyst prepared by the inventive method is the nanostructured of different-shape.
Eelctro-catalyst prepared by the inventive method has hydrogen reduction activity, can be applied to Proton Exchange Membrane Fuel Cells and metal-air battery.
Compared with the eelctro-catalyst of existing report, the present invention has the following advantages:
A) the present invention combines the molecular self-assembling method of transition metal macrocycle with traditional heat treatment method, prepares novel base metal eelctro-catalyst.
B) self-assembling method of the present invention is by the regulation and control to pH value in reaction system, the nanostructured of acquisition different-shape, and distribution of sizes is compared with homogeneous, and specific area is larger.
C) preparation method of the present invention is simple to operate, environmentally friendly, is easy to extensive synthetic.
D) the present invention, by the optimization to reaction condition, realizes the regulation and control to material pattern, and successfully active sites has been carried out to orderly arrangement, and after high-temperature process, the hydrogen reduction activity of this catalyst has had significant raising.
E) the novel non-noble metal eelctro-catalyst that the present invention obtains can be used for Proton Exchange Membrane Fuel Cells and metal-air battery.
Brief description of the drawings
Fig. 1 is the structural formula of hemin used (Hemin) in the embodiment of the present invention 1;
Fig. 2 is transmission electron microscope (TEM) figure that the embodiment of the present invention 1 is prepared product;
Fig. 3 is hydrogen reduction (ORR) the polarization curve comparison diagram that the embodiment of the present invention 1 is prepared product and unassembled carbonization hemin;
Fig. 4 is transmission electron microscope (TEM) figure that the embodiment of the present invention 2 is prepared product;
Fig. 5 is transmission electron microscope (TEM) figure that the embodiment of the present invention 3 is prepared product;
Fig. 6 is the structural formula of heme used in the embodiment of the present invention 4 (Heme B);
Fig. 7 is transmission electron microscope (TEM) figure that the embodiment of the present invention 5 is prepared product.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1:
Under 25 ° of C, hemin (Hemin) alkaline aqueous solution (0.6M NaOH) that the aqueous hydrochloric acid solution that is 6M by 3mL concentration is 15mM with 20mL concentration mixes, and stirs 10min, filtering and washing post-drying.Temperature programming to 900 ° C, under argon gas atmosphere, heat treatment 1h, is cooled to room temperature.Again through 0.5M aqueous sulfuric acid return stirring 30min under 25 ° of C conditions, suction filtration, be washed to neutrality, dry and obtain Powdered base metal eelctro-catalyst.
As Fig. 1, the structural formula of hemin (Hemin).
As Fig. 2, TEM transmission electron microscope shows that the product of embodiment 1 gained is the cube structure of distribution of sizes at 30～450nm.
As Fig. 3, the product that ORR polarization curve shows embodiment 1 gained is compared with unassembled carbonization hemin, and hydrogen reduction activity has had significant raising.
Embodiment 2:
Under 80 ° of C, hemin (Hemin) alkaline aqueous solution (0.6M NaOH) that the aqueous hydrochloric acid solution that is 6M by 2mL concentration is 1mM with 0.5mL concentration mixes, and stirs 10min, filtering and washing post-drying.Temperature programming to 900 ° C, under argon gas atmosphere, heat treatment 1h, is cooled to room temperature.Again through 0.5M aqueous sulfuric acid return stirring 30min under 25 ° of C conditions, suction filtration, be washed to neutrality, dry and obtain Powdered base metal eelctro-catalyst.
As Fig. 4, TEM transmission electron microscope shows that the product of embodiment 2 gained is the hemispherical structure of distribution of sizes at 50～450nm.
Embodiment 3:
Under 70 ° of C, hemin (Hemin) alkaline aqueous solution (0.6M NaOH) that the aqueous hydrochloric acid solution that is 0.6M by 2mL concentration is 0.25mM with 3mL concentration mixes, and stirs 10min, filtering and washing post-drying.Temperature programming to 900 ° C, under argon gas atmosphere, heat treatment 1h, is cooled to room temperature.Again through 0.5M aqueous sulfuric acid return stirring 30min under 70 ° of C conditions, suction filtration, be washed to neutrality, dry and obtain Powdered base metal eelctro-catalyst.
As Fig. 5, TEM transmission electron microscope shows that the product of embodiment 3 gained is the chondritic of distribution of sizes at 200～800nm.
Embodiment 4:
Under 25 ° of C, heme (Heme B) alkaline aqueous solution (0.6M NaOH) that the aqueous hydrochloric acid solution that is 6M by 3mL concentration is 15mM with 20mL concentration mixes, and stirs 10min, filtering and washing post-drying.Temperature programming to 900 ° C, under argon gas atmosphere, heat treatment 1h, is cooled to room temperature.Again through 0.5M aqueous sulfuric acid return stirring 30min under 25 ° of C conditions, suction filtration, be washed to neutrality, dry and obtain Powdered base metal eelctro-catalyst.
As Fig. 6, the structural formula of heme (Heme B).
Embodiment 4 gained sample topographies are similar to the product of embodiment 1 gained with size, and distribution of sizes is at the cube structure of 30～450nm.
Embodiment 5:
Under 25 ° of C, hemin (Hemin) alkaline aqueous solution (0.6M NaOH) that the aqueous hydrochloric acid solution that is 0.6M by 2mL concentration is 1mM with 3mL concentration mixes, and stirs 20min, filtering and washing post-drying.Temperature programming to 900 ° C, under argon gas atmosphere, heat treatment 1h, is cooled to room temperature.Again through 0.5M aqueous sulfuric acid return stirring 30min under 25 ° of C conditions, suction filtration, be washed to neutrality, dry and obtain Powdered base metal eelctro-catalyst.
As Fig. 7, TEM transmission electron microscope shows that the product of embodiment 5 gained is the membrane structure that contains space.Embodiment 6:
Under 25 ° of C, hemin (Hemin) alkaline aqueous solution (0.6M NaOH) that the aqueous hydrochloric acid solution that is 6M by 3mL concentration is 15mM with 20mL concentration mixes, and stirs 10min, filtering and washing post-drying.Temperature programming to 800 ° C, under argon gas atmosphere, heat treatment 2h, is cooled to room temperature.Again through 3M aqueous hydrochloric acid solution return stirring 30min under 25 ° of C conditions, suction filtration, be washed to neutrality, dry and obtain Powdered base metal eelctro-catalyst.
Embodiment 6 gained sample topographies are similar to the product of embodiment 1 gained with size, and distribution of sizes is at the cube structure of 30～450nm.
Embodiment 7:
Under 25 ° of C, hemin (Hemin) alkaline aqueous solution (0.6M KOH) that the aqueous hydrochloric acid solution that is 6M by 3mL concentration is 15mM with 20mL concentration mixes, and stirs 10min, filtering and washing post-drying.Temperature programming to 900 ° C, under nitrogen atmosphere, heat treatment 1h, is cooled to room temperature.Again through 3M aqueous hydrochloric acid solution return stirring 30min under 25 ° of C conditions, suction filtration, be washed to neutrality, dry and obtain Powdered base metal eelctro-catalyst.
Embodiment 7 gained sample topographies are similar to the product of embodiment 1 gained with size, and distribution of sizes is at the cube structure of 30～450nm.
Embodiment 8:
Under 25 ° of C, hemin (Hemin) alkaline aqueous solution (0.5M NaOH) that the aqueous sulfuric acid that is 0.5M by 3mL concentration is 15mM with 20mL concentration mixes, and stirs 10min, filtering and washing post-drying.Temperature programming to 800 ° C, under argon gas atmosphere, heat treatment 1h, is cooled to room temperature.Again through 0.5M aqueous sulfuric acid return stirring 30min under 25 ° of C conditions, suction filtration, be washed to neutrality, dry and obtain Powdered base metal eelctro-catalyst.
Embodiment 8 gained sample topographies are similar to the product of embodiment 1 gained with size, and distribution of sizes is at the cube structure of 30～450nm.
Claims (8)
1. a preparation method for the eelctro-catalyst based on transition metal macrocyclic compound, is characterized in that: the concrete steps of the method are:
Under 0～100 ° of C, acidic aqueous solution is mixed with the alkaline aqueous solution of transition metal macrocyclic compound, stir 5min～5h, filtering and washing post-drying; Roasting 0.5～5h in carrier gas under 400～1200 ° of C, is cooled to room temperature; Add acidic aqueous solution, return stirring 0.5～24h under 0～100 ° of C, suction filtration, is washed to neutrality, dries.
2. according to the preparation method of the eelctro-catalyst based on transition metal macrocyclic compound described in claim 1, it is characterized in that: described acidic aqueous solution is one or more mixed solutions in boric acid, sulfuric acid, benzene sulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, wolframic acid, phosphotungstic acid, nitric acid, perchloric acid; The concentration of described acidic aqueous solution is 0.1～10moL/L.
3. according to the preparation method of the eelctro-catalyst based on transition metal macrocyclic compound described in claim 1, it is characterized in that: described transition metal macrocycle is hemin (Hemin), heme (Heme B, Heme C), meso-tetra-(4-methoxyphenyl) porphyrin copper, meso-tetra-(4-methoxyphenyl) PORPHYRIN IRON, meso-tetra-(4-methoxyphenyl) Cobalt Porphyrin, meso-tetra-(4-methoxyphenyl) zinc porphyrin, meso-tetra-(4-methoxyphenyl) Manganese Porphyrin, meso-tetra-(4-methoxyphenyl) Porphyrin Nickel, protoporphyrin iron chloride, protoporphyrin cobalt chloride, protoporphyrin manganese chloride, protoporphyrin zinc chloride, protoporphyrin copper chloride, protoporphyrin nickel chloride, meso-tetra-(4-carboxyl phenyl) porphines iron chloride, meso-tetra-(4-carboxyl phenyl) porphines copper chloride, meso-tetra-(4-carboxyl phenyl) porphines cobalt chloride, meso-tetra-(4-carboxyl phenyl) porphines zinc chloride, meso-tetra-(4-carboxyl phenyl) porphines manganese chloride, meso-tetra-(4-carboxyl phenyl) porphines nickel chloride, α-tetrahydroxy ZnPc, α-tetrahydroxy cobalt phthalocyanine, α-tetrahydroxy iron-phthalocyanine, α-tetrahydroxy manganese phthalocyanine, α-tetracarbonyl nickle phthalocyanine, α-tetrahydroxy copper phthalocyanine, β-tetrahydroxy ZnPc, β-tetrahydroxy cobalt phthalocyanine, β-tetrahydroxy iron-phthalocyanine, β-tetrahydroxy manganese phthalocyanine, β-tetracarbonyl nickle phthalocyanine, β-tetrahydroxy copper phthalocyanine, 2,3,9,10,16,17,23,24-, eight hydroxyls replace ZnPc, 2,3,9,10,16,17,23,24-, eight hydroxyls replace cobalt phthalocyanine, 2,3,9,10,16,17,23,24-, eight hydroxyls replace iron-phthalocyanine, 2,3,9,10,16,17,23,24-, eight hydroxyls replace manganese phthalocyanine, 2,3,9,10,16,17,23,24-, eight hydroxyls replace nickel phthalocyanine, tetracarboxylic replaces ZnPc, tetracarboxylic replaces copper phthalocyanine, tetracarboxylic replaces cobalt phthalocyanine, tetracarboxylic replaces nickel phthalocyanine, tetracarboxylic replaces iron-phthalocyanine, the mixture of one or more in tetracarboxylic replacement manganese phthalocyanine and its analog and derivative, its concentration in alkaline aqueous solution is 0.1～5000mmoL/L.
4. according to the preparation method of the eelctro-catalyst based on transition metal macrocyclic compound described in claim 1, it is characterized in that: described alkaline aqueous solution is LiOH, NaOH, KOH, LiHCO
3, NaHCO
3, KHCO
3, Li
2cO
3, Na
2cO
3or K
2cO
3in one or more mixed solution; Its concentration is 0.1～4.5moL/L.
5. according to the preparation method of the eelctro-catalyst based on transition metal macrocyclic compound described in claim 1, it is characterized in that: the volume ratio of the alkaline aqueous solution of described acidic aqueous solution and transition metal macrocyclic compound is 1:20 to 10:1.
6. according to the preparation method of the eelctro-catalyst based on transition metal macrocyclic compound described in claim 1, it is characterized in that: described carrier gas is one or two or more kinds the mist in helium, neon, argon gas, nitrogen, ammonia.
7. the eelctro-catalyst that described in claim 1 prepared by method, is characterized in that: the nanostructured that this catalyst is different-shape.
8. the application of the eelctro-catalyst that described in claim 1 prepared by method, is characterized in that: this catalyst has hydrogen reduction activity, is applied to Proton Exchange Membrane Fuel Cells and metal-air battery.
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