CN105435843B - A kind of biporphin method that assembling prepares novel non-noble metal elctro-catalyst altogether - Google Patents

A kind of biporphin method that assembling prepares novel non-noble metal elctro-catalyst altogether Download PDF

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CN105435843B
CN105435843B CN201510767727.7A CN201510767727A CN105435843B CN 105435843 B CN105435843 B CN 105435843B CN 201510767727 A CN201510767727 A CN 201510767727A CN 105435843 B CN105435843 B CN 105435843B
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porphyrin
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CN105435843A (en
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宋玉江
谢妍
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Dalian University of Technology
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • B82—NANOTECHNOLOGY
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Abstract

The invention belongs to field of nano material preparation, provide a kind of biporphin method that assembling prepares novel non-noble metal elctro-catalyst altogether.This method is used for the pattern of controllable preparation base metal elctro-catalyst, and then its electro-chemical activity of modulation and stability.The porphyrin solution dissolved with cation is directly carried out isoconcentration with the porphyrin solution dissolved with anion to mix in equal volume, or will first be mixed dissolved with a kind of porphyrin solution of charge and the surfactant solution with like charges, then the porphyrin solution dissolved with opposite charges is added in equal charges.Obtain the material with certain pattern.Again through high temperature thermal bake-out, after pickling, the pattern of material is kept substantially.Synthetic method of the present invention has universality, simple, quickly and can be with the pattern of Effective Regulation base metal elctro-catalyst, and then the electro-chemical activity and stability of modulation base metal elctro-catalyst can be applied in fuel cell.

Description

A kind of biporphin method that assembling prepares novel non-noble metal elctro-catalyst altogether
Technical field
The invention belongs to field of nano material preparation, and the present invention relates to a kind of biporphin, assembling prepares novel non-noble metal altogether The method of elctro-catalyst.
Background technology
Porphyrin and metalloporphyrin class macrocyclic compound can pass through hydrogen bond, Van der Waals force, electrostatic attraction, coordinate bond or Π-Π The weak interaction self assembly such as sedimentation obtains the different ordered nano-structure of various patterns, these porphyrin nano structures tool There is excellent photoelectric property, has in manual simulation's photosynthesis, dye-sensitized solar cells, catalyst, sensor etc. There is great application potential.However the structure that the self assembly between single Porphyrin Molecule obtains is more single, is showed Performance tends not to be entirely satisfactory, for this purpose, research emphasis is transferred to more porphyrins assembling aspect altogether by people, by double porphins The preferentially combination of quinoline molecule, learns from other's strong points to offset one's weaknesses, and obtained various nanostructures have excellent performance.The team of Shelnutt professors It is assembled altogether using the electrostatic interaction between zwitterion and is prepared for serial nano structure, such as：Nanotube, micro-nano and bunge bedstraw herb Shape structure etc..2004, they were assembled using nonmetallic porphyrin and tin porphyrin and obtain nano tubular structure altogether (J.Am.Chem.Soc.2004,126,15954-15955), in this method metal-free porphyrin protonation need in acid solution Middle progress, and tin porphyrin has photocatalysis, needs avoid light place in experimentation.2010, professor Shelnutt etc. ground Study carefully personnel's research and prepares the nanostructure (J.Am.Chem.Soc.2010,132,8194-8201) with bunge bedstraw herb pattern, it should Methanol and chloroformic solution is utilized during synthesizing anion zinc porphyrin in method, reaction dissolvent is unfriendly to environment.2012 Year, this group of researcher is further mixed with out the piece of micro/nano level using the tin porphyrin of the zinc protoporphyrin of anion and cation Shape structure (Nanoscale, 2012,4,1695-1700), the laminated structure size obtained in this report is larger, and application range has Certain limitation.
In view of the above-mentioned problems, this patent provides a kind of biporphin, assembling prepares the nanostructure of different-shape altogether, by ion Self-assembling technique is combined with traditional heat treatment method, prepares the novel non-noble metal elctro-catalyst with certain structure, should Method is module units using the metalloporphyrin of opposite charges, and the structure of different-shape is prepared using ion self-assembling technique, then Through traditional heat treatment method, the novel non-noble metal elctro-catalyst with specific morphology is obtained.This method operating process is simple, The solvent used in building-up process is environmentally friendly, and the nanostructure assembled is novel, and structurally ordered, size uniformity, warp After high-temperature roasting, the pattern of catalyst obtains basic holding.This novel base metal elctro-catalyst in alkaline solution and Preferable oxygen reduction activity and preferable stability are shown in acid solution, it can be by application fuel cell.
Invention content
The purpose of the present invention is to provide a kind of biporphin method that assembling prepares novel non-noble metal elctro-catalyst altogether, institutes Certain oxygen reduction activity and preferable stability are shown under the base metal elctro-catalyst acidity and alkaline condition that obtain, it can quilt It is applied in fuel cell.
A kind of biporphin method that assembling prepares novel non-noble metal elctro-catalyst altogether of the present invention, will contain negative ions Biporphin solution mixed, or pass through be added surfactant, obtain good dispersion, the nanostructure of size uniformity.Through Roasting, pickling obtain novel non-noble metal elctro-catalyst.
A kind of biporphin method that assembling prepares novel non-noble metal elctro-catalyst altogether, steps are as follows：At 0~80 DEG C, Porphyrin solution dissolved with cation is carried out isoconcentration with the porphyrin solution dissolved with anion to mix in equal volume, or will be dissolved with one kind The porphyrin solution of charge and the surfactant solution with like charges are mixed, then equal charges are added dissolved with opposite charges Porphyrin solution, keep electroneutral, after stirring 5min~for 24 hours, stand 1-30 days, filter, drying, obtain product through 600-1000 DEG C heat treatment 30min~6h is carried out under different atmosphere, at 50-80 DEG C, carry out pickling, washing, dry to get novel non-expensive Metal elctro-catalyst.
The porphyrin with anion is meso- tetra- (4- sulfonic groups) Cobalt Porphyrin, (the 4- sulfonic acid of meso- tetra- in the biporphin Base) PORPHYRIN IRON, meso- tetra- (4- sulfonic groups) Manganese Porphyrin, meso- tetra- (4- sulfonic groups) Porphyrin Nickel, meso- tetra- (4- sulfonic groups) porphin Quinoline copper, meso- tetra- (4- carboxyls) Cobalt Porphyrin, meso- tetra- (4- carboxyls) PORPHYRIN IRON, meso- tetra- (4- carboxyls) Manganese Porphyrin, meso- Four (4- carboxyls) Porphyrin Nickels, meso- tetra- (4- carboxyls) porphyrin copper, meso- tetra- (4- carboxyls) Cobalt Porphyrin, meso- tetra- (4- carboxyls) In PORPHYRIN IRON, meso- tetra- (4- carboxyls) Manganese Porphyrin, meso- tetra- (4- carboxyls) Porphyrin Nickel, meso- tetra- (4- carboxyls) porphyrin copper One or more kinds of mixtures, a concentration of 0.1mmoL/L~5moL/L.
The porphyrin with cation is meso- tetra- (4- ethyl -4- pyridyl groups) PORPHYRIN IRON, meso- tetra- in the biporphin (4- ethyl -4- pyridyl groups) Cobalt Porphyrin, meso- tetra- (4- ethyl -4- pyridyl groups) Manganese Porphyrin, (4- ethyl -4- pyridines of meso- tetra- Base) porphyrin copper, meso- tetra- (4- ethyl -4- pyridyl groups) zinc porphyrin, meso- tetra- (4- ethyl alcohol base -4- pyridyl groups) porphyrin, meso- Four (4- methyl -4- pyridyl groups) PORPHYRIN IRONs, meso- tetra- (4- methyl -4- pyridyl groups) Cobalt Porphyrin, (4- methyl -4- pyrroles of meso- tetra- Piperidinyl) Manganese Porphyrin, meso- tetra- (4- methyl -4- pyridyl groups) porphyrin copper, meso- tetra- (4- methyl -4- pyridyl groups) zinc porphyrin, The mixture of one or more of meso- tetra- (4- methyl -4- pyridyl groups) porphyrin, a concentration of 0.1mmoL/L~ 5moL/L。
The surfactant is cetyl trimethylammonium bromide (hexadecyltrimethyl ammonium Bromide, cetyltrimethylammonium bromide, CTAB), lauryl sodium sulfate (sodium dodecyl Sulfate, SDS), Brij-35 (Brij 35), hexadecyltrimethylammonium chloride (N- Hexadecyltrimethylammonium Chloride, CTAC), one kind or two in oleyl amine (Octadecenylamine) Kind or more hybrid solid, a concentration of 0.1~20mmoL/L.
The different atmosphere is one or two or more kinds of mixed gas in helium, neon, argon gas, nitrogen, ammonia.
The acid of the pickling is boric acid, sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, wolframic acid, phosphotungstic acid, nitric acid, height The mixed solution of one or more of chloric acid, a concentration of 0.1~10moL/L.
Compared with other self-assembly preparation method thereofs reported, advantages of the present invention is as follows：
1) for preparation method of the invention using the biporphin with positive and negative charge as structural unit, prepared structure is new Grain husk, the performance shown are various；
2) preparation method of the invention is easy to operate, easily controllable, reaction solution is environmentally friendly；
3) ion self-assembling technique is combined by preparation method of the invention with traditional method of roasting, is prepared novel non-expensive Metal elctro-catalyst, synthetic method are novel；
4) structure novel that the made Preparation Method of the present invention obtains, stable structure, orderly, size uniformity；
5) pattern that ion assembles altogether can be regulated and controled by the addition of surfactant, pattern obtains substantially after heat treatment It keeps；
6) pattern by adjusting base metal elctro-catalyst is realized to control the activity and stability of its electrochemistry.
Description of the drawings
Fig. 1 (a) is a kind of structural formula of tetra- (4- sulfonic groups) PORPHYRIN IRONs of MESO- used in the embodiment of the present invention 1.
Fig. 1 (b) is a kind of structure of tetra- (4- methyl -4- pyridyl groups) PORPHYRIN IRONs of MESO- used in the embodiment of the present invention 1 Formula.
Fig. 2 is transmission electron microscope (TEM) figure that the embodiment of the present invention 1 prepares products therefrom.
Fig. 3 is that the embodiment of the present invention 1 prepares living with hydrogen reduction of the business Pt/C in 0.1M KOH solutions for products therefrom Property comparison diagram.
Fig. 4 is the stability pair with business Pt/C in 0.1M KOH solutions that the embodiment of the present invention 1 prepares products therefrom Than figure.
Fig. 5 be the embodiment of the present invention 1 prepare products therefrom with business Pt/C in 0.1M HClO4Stability in solution Comparison diagram.
Fig. 6 be the embodiment of the present invention 1 prepare products therefrom with business Pt/C in 0.1M HClO4Stability in solution Comparison diagram.
Fig. 7 is the TEM figures that the embodiment of the present invention 2 prepares products therefrom.
Fig. 8 is that the embodiment of the present invention 2 prepares living with hydrogen reduction of the business Pt/C in 0.1M KOH solutions for products therefrom Property comparison diagram.
Fig. 9 is the stability pair with business Pt/C in 0.1M KOH solutions that the embodiment of the present invention 2 prepares products therefrom Than figure.
Figure 10 be the embodiment of the present invention 2 prepare products therefrom with business Pt/C in 0.1M HClO4Stability in solution Comparison diagram.
Figure 11 be the embodiment of the present invention 2 prepare products therefrom with business Pt/C in 0.1M HClO4Stability in solution Comparison diagram.
Figure 12 is the TEM figures that the embodiment of the present invention 3 prepares products therefrom.
Figure 13 is that the embodiment of the present invention 3 prepares living with hydrogen reduction of the business Pt/C in 0.1M KOH solutions for products therefrom Property comparison diagram.
Figure 14 is the stability pair with business Pt/C in 0.1M KOH solutions that the embodiment of the present invention 3 prepares products therefrom Than figure.
Figure 15 be the embodiment of the present invention 3 prepare products therefrom with business Pt/C in 0.1M HClO4Stability in solution Comparison diagram.
Figure 16 be the embodiment of the present invention 3 prepare products therefrom with business Pt/C in 0.1M HClO4Stability in solution Comparison diagram.
Specific implementation mode
Specific implementation mode is further illustrated the present invention below in conjunction with technical solution and attached drawing.
Embodiment 1：The preparation of nano flower
At 25 DEG C, by the MESO- tetra- of the solution and 10mL 5mM of MESO- tetra- (4- sulfonic groups) PORPHYRIN IRON of 10mL 5mM The solution of (4- methyl -4- pyridyl groups) PORPHYRIN IRON mixes, and after stirring 20min, stands 2 days, filters, is dry, obtaining product through 775 After DEG C being heat-treated under argon gas, at 80 DEG C, with 0.5M H2SO4It is washed to neutrality after solution washing 30min, it is non-ly dry Noble metal electrocatalyst.
Such as Fig. 1 (a), (b), a kind of tetra- (4- sulfonic groups) PORPHYRIN IRONs of MESO- used in embodiment 1 and tetra- (4- of MESO- Methyl -4- pyridyl groups) PORPHYRIN IRON structural formula.
Such as Fig. 2, TEM transmission electron microscopes are shown as nanometer flower structure, and the average-size of the outer diameter of nano flower is distributed in 300- 400nm。
Such as Fig. 3, prepared base metal elctro-catalyst and oxygen of the business Pt/C in 0.1M KOH solutions in embodiment 1 Reduction activation comparison diagram.The oxygen reduction activity that prepared base metal elctro-catalyst shows and 20wt% business Pt/C institutes Show oxygen reduction activity is almost the same.
Such as Fig. 4, prepared base metal elctro-catalyst and business Pt/C are steady in 0.1M KOH solutions in embodiment 1 Qualitative figure.After the cyclic voltammetry scan of 2500 circles, prepared base metal elctro-catalyst does not have any decaying, and 20wt% Business Pt/C has then decayed about 60%.
Such as Fig. 5, in embodiment 1 prepared base metal elctro-catalyst with business Pt/C in 0.1M HClO4In solution Oxygen reduction activity comparison diagram.The oxygen reduction activity that prepared base metal elctro-catalyst shows and 20wt% business Pt/C Show oxygen reduction activity is closer to.
Such as Fig. 6, in embodiment 1 prepared base metal elctro-catalyst with business Pt/C in 0.1M HClO4In solution Stability contrast figure.After the cyclic voltammetry scan of 2500 circles, prepared base metal elctro-catalyst decays to 78%, and 20wt% business Pt/C then decays to 56%.
Embodiment 2：Reaction temperature is different：The preparation of nano flower
At 0 DEG C, by the MESO- tetra- of the solution and 10mL 5mM of MESO- tetra- (4- sulfonic groups) PORPHYRIN IRON of 10mL 5mM The solution of (4- methyl -4- pyridyl groups) PORPHYRIN IRON mixes, and after stirring 20min, stands 2 days, filters, is dry, obtaining product through 775 After DEG C being heat-treated under argon gas, at 80 DEG C, with 0.5M H2SO4It is washed to neutrality after solution washing 30min, it is non-ly dry Noble metal electrocatalyst.
Such as Fig. 7, TEM transmission electron microscopes are shown as nanometer flower structure, and the average-size of the outer diameter of nano flower is distributed in 300- 400nm。
Such as Fig. 8, in embodiment 2 prepared base metal elctro-catalyst with business Pt/C in 0.1M KOH solutions Oxygen reduction activity comparison diagram.The oxygen reduction activity that prepared base metal elctro-catalyst shows and 20wt% business Pt/C Show oxygen reduction activity is almost the same.
Such as Fig. 9, prepared base metal elctro-catalyst and business Pt/C are steady in 0.1M KOH solutions in embodiment 2 Qualitative comparison diagram.After the cyclic voltammetry scan of 2500 circles, prepared base metal elctro-catalyst has only decayed about 10%, and 20wt% business Pt/C has then decayed 60%.
Such as Figure 10, in embodiment 2 prepared base metal elctro-catalyst with business Pt/C in 0.1M HClO4In solution Oxygen reduction activity comparison diagram.The oxygen reduction activity that prepared base metal elctro-catalyst shows and 20wt% business Pt/C show oxygen reduction activity is closer to.
Such as Figure 11, in embodiment 2 prepared base metal elctro-catalyst with business Pt/C in 0.1M HClO4In solution Stability contrast figure.After the cyclic voltammetry scan of 2500 circles, prepared base metal elctro-catalyst decays to 59%, and 20wt% business Pt/C then decays to 56%.
Embodiment 3：Surfactant is added：Half bowl-shape preparation of nanometer
At 25 DEG C, by the solution of MESO- tetra- (4- methyl -4- pyridyl groups) PORPHYRIN IRON of 10mL 5mM and it is mixed with 2mM The solution of MESO- tetra- (4- sulfonic groups) PORPHYRIN IRON of the 10mL 5mM of 5mL sodium dodecyl sulfate solutions with mix, stir After 20min, 2 days are stood, filters, is dry, obtaining product after 775 DEG C are heat-treated under argon gas, at 80 DEG C, use 0.5M H2SO4It is washed to neutrality after solution washing 30min, dry base metal elctro-catalyst.
Such as Figure 12, TEM transmission electron microscopes are shown as nanometer flower structure, the average-size distribution of the outer diameter of half bowl structure of nanometer In 300-400nm.
Such as Figure 13, in embodiment 3 prepared base metal elctro-catalyst with business Pt/C in 0.1M KOH solutions Oxygen reduction activity comparison diagram.The oxygen reduction activity that prepared base metal elctro-catalyst shows and 20wt% business Pt/C Show oxygen reduction activity is almost the same.
Such as Figure 14, in embodiment 3 prepared base metal elctro-catalyst with business Pt/C in 0.1M KOH solution Stability contrast figure.After the cyclic voltammetry scan of 2500 circles, prepared base metal elctro-catalyst has only decayed about 20%, And 20wt% business Pt/C has then decayed 60%.
Such as Figure 15, in embodiment 3 prepared base metal elctro-catalyst with business Pt/C in 0.1M HClO4In solution Oxygen reduction activity comparison diagram.The oxygen reduction activity that prepared base metal elctro-catalyst shows and 20wt% business Pt/C show oxygen reduction activity is closer to.
Such as Figure 16, in embodiment 3 prepared base metal elctro-catalyst with business Pt/C in 0.1M HClO4In solution Stability contrast figure.After the cyclic voltammetry scan of 2500 circles, prepared base metal elctro-catalyst decays to 73%, and 20wt% business Pt/C then decays to 56%.
Embodiment 4：The type and concentration of porphyrin are different：
At 25 DEG C, by the MESO- tetra- of the solution and 10mL 5mM of MESO- tetra- (4- sulfonic groups) Cobalt Porphyrin of 10mL 5mM The solution of (4- ethyl -4- pyridyl groups) Cobalt Porphyrin mixes, and after stirring 20min, stands 2 days, filters, is dry, obtaining product through 775 After DEG C being heat-treated under argon gas, at 80 DEG C, with 0.5M H2SO4It is washed to neutrality after solution washing 30min, it is non-ly dry Noble metal electrocatalyst.
Embodiment 5：Reaction temperature, mixing time and time of repose are different：
At 80 DEG C, by the MESO- tetra- of the solution and 10mL 5mM of MESO- tetra- (4- sulfonic groups) PORPHYRIN IRON of 10mL 5mM The solution of (4- methyl -4- pyridyl groups) PORPHYRIN IRON mixes, and after stirring for 24 hours, stands 30 days, filters, is dry, obtaining product through 775 After DEG C being heat-treated under argon gas, at 80 DEG C, with 0.5M H2SO4It is washed to neutrality after solution washing 30min, it is non-ly dry Noble metal electrocatalyst.
Embodiment 6：Calcination temperature and atmosphere difference：
At 25 DEG C, by the MESO- tetra- of the solution and 10mL 5mM of MESO- tetra- (4- sulfonic groups) PORPHYRIN IRON of 10mL 5mM The solution of (4- methyl -4- pyridyl groups) PORPHYRIN IRON mixes, and after stirring 20min, stands 2 days, filters, is dry, obtaining product through 800 After DEG C being heat-treated under a nitrogen, at 80 DEG C, with 0.5M H2SO4It is washed to neutrality after solution washing 30min, it is non-ly dry Noble metal electrocatalyst.
Embodiment 7：Acid reaction variables are different：
At 25 DEG C, by the MESO- tetra- of the solution and 10mL 5mM of MESO- tetra- (4- sulfonic groups) PORPHYRIN IRON of 10mL 5mM The solution of (4- methyl -4- pyridyl groups) PORPHYRIN IRON mixes, and after stirring 20min, stands 2 days, filters, is dry, obtaining product through 800 After DEG C being heat-treated under a nitrogen, at 50 DEG C, neutrality is washed to after washing 30min with 0.5M hydrochloric acid solutions, it is non-ly dry Noble metal electrocatalyst.
Embodiment 8：The surfactant of addition is different
At 25 DEG C, by the solution of MESO- tetra- (4- methyl -4- pyridyl groups) PORPHYRIN IRON of 10mL 5mM and it is mixed with 2mM The solution of MESO- tetra- (4- sulfonic groups) PORPHYRIN IRON of the 10mL 5mM of 5mL cetyl trimethylammonium bromides with mix, stir After 20min, 2 days are stood, filters, is dry, obtaining product after 775 DEG C are heat-treated under argon gas, at 80 DEG C, use 0.5M H2SO4It is washed to neutrality after solution washing 30min, dry base metal elctro-catalyst.

Claims (2)

1. a kind of biporphin method that assembling prepares base metal elctro-catalyst altogether, which is characterized in that steps are as follows：At 0 DEG C or At 25 DEG C, by (the 4-N- first of MESO- tetra- of the solution and 10mL5mM of MESO- tetra- (4- sulfonic groups phenyl) PORPHYRIN IRON of 10mL 5mM Yl pyridines base) PORPHYRIN IRON solution mixing, after stirring 20min, stand 2 days, filter, is dry, obtaining product through 775 DEG C in argon gas Under be heat-treated after, at 80 DEG C, with 0.5M H2SO4It is washed to neutrality after solution washing 30min, dry nanometer flower structure Base metal elctro-catalyst.
2. a kind of biporphin method that assembling prepares base metal elctro-catalyst altogether, which is characterized in that steps are as follows：At 25 DEG C Under, by the solution of MESO- tetra- (4-N- picolyls) PORPHYRIN IRON of 10mL 5mM and it is mixed with 2mM 5mL lauryl sodium sulfate The solution of MESO- tetra- (4- sulfonic groups phenyl) PORPHYRIN IRON of the 10mL 5mM of solution mixes, and after stirring 20min, stands 2 days, takes out Filter, drying, obtain product after 775 DEG C are heat-treated under argon gas, at 80 DEG C, with 0.5M H2SO4Solution washs 30min After be washed to neutrality, the base metal elctro-catalyst of dry half bowl structure of nanometer.
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