CN104998673A - Nitrogen and sulfur co-doped carbon-loaded non-noble metal type oxygen reduction catalyst and preparation method thereof - Google Patents
Nitrogen and sulfur co-doped carbon-loaded non-noble metal type oxygen reduction catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen and sulfur co-doped carbon-loaded non-noble metal type oxygen reduction catalyst and a preparation method thereof and discloses a M-N-S-C oxygen reduction catalyst and a preparation method thereof. The raw materials of the catalyst comprise copolymer P (TPT+Tp) of tripyrrole-[1,3,5]-triazine (TPT) and thiophene (Tp) and non-noble metal salt. The preparation method of the catalyst includes the following steps that firstly, a Friedel-Crafts reaction is adopted for synthesizing the copolymer P (TPT+Tp) of the tripyrrole-[1,3,5]-triazine (TPT) and the thiophene (Tp); secondly, the P (TPT+Tp) and the non-noble metal salt are added into ethanol, mixtures are placed in an ultrasonic dispersing instrument, a whole system is evenly dispersed due to ultrasound, and then the ethanol is dried by distillation and placed in a vacuum drying box to be dried for 4 h at the temperature of 80 DEG C; thirdly, thermal treatment is performed for the first time and nitrogen doped materials are obtained; fourthly, the nitrogen doped materials are completely washed through dilute acid; fifthly, thermal treatment is performed for the second time, and then the M-N-C oxygen reduction catalyst can be obtained.
Description
Technical field
The present invention relates to a kind of oxygen reduction catalyst and preparation method thereof, specifically, be a kind of M-N-S-C oxygen reduction catalyst and preparation method thereof, belong to fuel cell science and technology field.
Background technology
Oxygen reduction reaction (oxygen reduction reaction, ORR) is one of most important electrocatalytic reaction, is process very crucial in the device such as fuel cell and metal-air battery.Platinum and platinum based catalyst are the high and the most the most frequently used ORR catalyst of current catalytic activity, but its expensive, resource-constrained, and long-play stability is not good enough, seriously hinders the development of the association areas such as fuel cell.Therefore, the non-precious metal catalyst of research and development high activity and high stability, to reduction fuel cell cost, to accelerate its commercialization process significant.
The employing earth preserves abundant cheap metal element substitution platinum and as ORR catalyst, there is considerable prospect undoubtedly.Therefore, to the research of base metal ORR catalysis material be also the focus of current fuel cell field research.Nitrogen-doped carbon-supported base metal (hereinafter referred to as M-N-C) catalyst is generally obtained by the various transition metal of heat treatment, nitrogenous source and carbon source presoma.Nitrogen content in M-N-C catalyst and valence state structure have important impact to catalyst ORR activity and stability.Common nitrogenous source persursor material has nitrogenous organic molecule (as ethylenediamine, ammonia, acetonitrile etc.), nitrogen-containing heterocycle compound (as Phen, phthalocyanine, porphyrin etc.), nitrogenous organic polymer (as polyaniline, polypyrrole etc.).Carbon source presoma cuts much ice to raising M-N-C catalyst activity and stability aspect, and has different impacts to the content of nitrogen in catalyst and valence state structure.
Cote etc., under 1000 DEG C of conditions, adopt different nitrogenous precursor as polyacrylonitrile, phthalocyanine, 7,7,8,8-four cyano 1,4-benzoquinone bismethanes, CH
3cN, NH
3, prepare Fe (OH)
2-N-C catalyst, result of study shows, is that the ORR activity of the catalyst of nitrogenous source presoma is best (Journal of Catalysis, 2006,239:83-86) with phthalocyanine.Enrburger etc. study discovery, for same metal salt and nitrogenous source presoma, the ORR activity higher (Journal of Colloid andInterface Science, 1983,91:151-159) of the M-N-C catalyst using high-specific surface area carbon carrier to prepare.Chinese patent CN101859906A discloses a kind of by cobalt chloride, nitrogenous source (melamine or hexamethylenetetramine), carbon black (acetylene black or Vulcan XC-72R) mechanical lapping mixing, and high-temperature heat treatment obtains M-N-C catalyst under nitrogen protection.Chinese patent CN103170334A discloses a kind of carbon and carries cobalt oxide catalyst and Synthesis and applications thereof, is modified carbon support by solvent thermal reaction, and carbon-carried transition metal oxide under room temperature, the catalyst ORR activity obtained is high, and cost is low.
Above-mentioned method for preparing catalyst is mostly comparatively complicated, and preparation process process conditions are wayward, are unfavorable for catalyst industrialization.Therefore, develop cheap, preparation technology simple and there is the N doping ORR eelctro-catalyst system of high activity and stability, the development and industrialization process promoting fuel cell is significant.
Summary of the invention
For above problem, the invention provides the simple and M-N-S-C oxygen reduction electro-catalyst with high activity and stability and preparation method thereof of a kind of cheap, preparation technology, the present invention P (TPT+Tp) used, simultaneously as nitrogenous source, sulphur source and carbon source presoma, prepares the more excellent ORR eelctro-catalyst of performance by simple thermal treatment.
According to the first embodiment of the present invention, a kind of nitrogen is provided, sulphur codope carbon carries base metal type (M-N-S-C) oxygen reduction catalyst (being called for short M-N-S-C oxygen reduction catalyst), it is by comprising (i) tripyrrole-[1, 3, a kind of primary mix of the copolymer of 5]-triazine (TPT) and thiophene (Tp) and P (TPT+Tp) and (ii) base metal salt two kinds of components is in an inert atmosphere at 700-1000 DEG C, preferred 750-950 DEG C, more preferably carry out first time heat treatment at the temperature of 800-900 DEG C and obtain nitrogen-doped carbon material, then the rare inorganic acid of nitrogen-doped carbon material is carried out pickling processes, finally by the material of pickling in an inert atmosphere at 700-1000 DEG C, preferred 750-950 DEG C, more preferably carry out second time heat treatment at the temperature of 800-900 DEG C and finally obtain.
Preferably, as the base metal salt of component (ii) be the salt of transition metal.Be more preferably the nitrate of transition metal, acetate, sulfate or chloride.Be more preferably be selected from Mn, Fe, Co, Ni, Cu one or both or more plant the salt of metal.Preferably be selected from further in Mn, Fe, Co, Ni, Cu one or both or more plant the nitrate of metal, acetate, sulfate or chloride.
Preferably, P (TPT+Tp) as component (i) is 1:0.06-1 with the mass ratio as the base metal salt of component (ii), preferred 1:0.08-0.9, be more preferably 1:0.12-0.8, more preferably 1:0.15-0.7, more preferably 1:0.18-0.6, more preferably 1:0.2-0.5.
Preferably; as component (i); tripyrrole-[1; 3; the copolymer of 5]-triazine (TPT) and thiophene (Tp), i.e. P (TPT+Tp) are by tripyrrole-[1; synthesized by 3,5]-triazine (TPT) and thiophene (Tp) two kinds of monomers are reacted by Friedel-Crafts under dual functional alkylating reagent or acylting agent and the existence of Friedel-Crafts catalysts.
Preferably; component (i); tripyrrole-[1; 3; the copolymer of 5]-triazine (TPT) and thiophene (Tp); i.e. P (TPT+Tp); by the tripyrrole-[1 of 1:0.2-10, the preferably weight ratio of 1:0.4-8, more preferably 1:0.6-6, more preferably 1:0.7-5; synthesized by 3,5]-triazine (TPT) and thiophene (Tp) two kinds of monomers are reacted by Friedel-Crafts under dual functional alkylating reagent or acylting agent and the existence of Friedel-Crafts catalysts.
According to the second embodiment of the present invention, also provide a kind of preparation method of M-N-S-C oxygen reduction catalyst or prepare the method for above-mentioned catalyst, the method comprises the following steps:
(1) preparation of copolymer p (TPT+Tp): by the tripyrrole-[1 of 1:0.2-10, the preferably weight ratio of 1:0.4-8, more preferably 1:0.6-6, more preferably 1:0.7-5; 3; 5]-triazine (TPT) and thiophene (Tp) two kinds of monomers prepare tripyrrole-[1 by Friedel-Crafts reaction in a solvent under dual functional alkylating reagent or acylting agent and the existence of Friedel-Crafts catalysts; 3; the copolymer p (TPT+Tp) of 5]-triazine (TPT) and thiophene (Tp); i.e. component (i)
(2) formation of primary mix: using the P as component (i) (TPT+Tp) of 1 weight portion and 0.06-1 weight portion (preferred 0.08-0.9, more preferably 0.12-0.8, more preferably 0.15-0.7, more preferably 0.18-0.6, more preferably 0.2-0.5 weight portion) the base metal salt as component (ii) dispersed in solvent (as ethanol), dry, acquisition comprises a kind of primary mix of component (i) and component (ii)
(3) first time heat treatment: the primary mix obtained in step (2) is carried out a heat treatment in an inert atmosphere at the temperature of 700-1000 DEG C, preferably 750-950 DEG C, more preferably 800-900 DEG C, obtains nitrogen-doped carbon material.
(4) acid pickling step: pickling is carried out to nitrogen-doped carbon material with rare inorganic acid.
(5) second time heat treatment: the material after overpickling is carried out secondary heat treatment again in an inert atmosphere at the temperature of 700-1000 DEG C, preferably 750-950 DEG C, more preferably 800-900 DEG C, obtains final products M-N-S-C oxygen reduction catalyst.
More specifically, also provide a kind of preparation method of M-N-S-C oxygen reduction catalyst, the method comprises the following steps:
(1) preparation of copolymer p (TPT+Tp): according to 1:0.2-10, preferred 1:0.4-8, more preferably 1:0.6-6, more preferably the weight ratio of 1:0.7-5, by the tripyrrole of 1 weight portion-[1, 3, 5]-triazine (TPT) and 0.2-10 weight portion (preferred 0.4-8, more preferably 0.6-6, more preferably 0.7-5) thiophene (Tp) be dissolved in solvent (such as 15-50 weight portion, as 20-40 weight portion) in, add dual functional alkylating reagent or the acylting agent of 0.5-10 weight portion (preferred 1-4 weight portion) again, add the Friedel-Crafts catalysts that weight portion is 0.5-12 weight portion (preferred 1.2-6 weight portion), under agitation reaction (such as, in 25-50 DEG C of stirring reaction 2-10 hour (preferred 3-6 hour), rise to 60-100 DEG C of stirring reaction 15-25 hour again), react complete, pour separation in methyl alcohol or ethanol (such as 60-400 weight portion), filtration, washing, drying into, obtain (P (TPT+Tp)),
(2) formation of primary mix: using the P as component (i) (TPT+Tp) of 1 weight portion and 0.06-1 weight portion (preferred 0.08-0.9, more preferably 0.12-0.8, more preferably 0.15-0.7, more preferably 0.18-0.6, more preferably 0.2-0.5 weight portion) the base metal salt as component (ii) join in ethanol or methyl alcohol (such as 50 ~ 200 parts), ultrasonic wave process (such as 120 ~ 300min) makes whole system be uniformly dispersed; Evaporate to dryness ethanol or methyl alcohol, dry (being such as placed in vacuum drying chamber in 60-100 DEG C of dry 2-10h), obtains the primary mix comprising copolymer and base metal salt;
(3) first time heat treatment: step (2) gained mixture is carried out first time heat treatment in inert gas at the temperature of 700-1000 DEG C, preferably 750-950 DEG C, more preferably 800-900 DEG C, obtains nitrogen-doped carbon material;
(4) pickling: the rare inorganic acid (such as washing 5 ~ 10h with rare inorganic acid in 50 ~ 80 DEG C) of gained nitrogen-doped carbon material, filter, be washed to neutral rear dry (being such as placed in vacuum drying chamber in 60-100 DEG C of dry 2-10h);
(5) second time heat treatment: nitrogen-doped carbon material step (4) obtained carries out second time heat treatment again in inert gas at the temperature of 700-1000 DEG C, preferably 750-950 DEG C, more preferably 800-900 DEG C, obtains M-N-S-C oxygen reduction catalyst.
Preferably, dual functional alkylating reagent described in step (1) is that two halo C2-C6 alkane, straight or branched C2-C12 olefine, straight or branched C3-C10 dihydroxylic alcohols or the bis ether with 3-18 carbon atom are altogether (as dimethoxymethane CH
3oCH
2oCH
3) in one or more; And/or
Dual functional acylting agent be altogether have 3-12 C carbon atom the two carboxylic acid halides of straight or branched, altogether have 4-8 C carbon atom straight or branched bisgallic acid acid anhydride or altogether have in the straight or branched pair carboxylic acid of 4-10 C carbon atom one or more.
Preferably, solvent described in step (1) is one or more in nitrobenzene, nitromethane, tetrachloroethanes, dichloroethanes, carbon tetrachloride, carbon disulfide.
Preferably, described in step (1), Friedel-Crafts catalysts is AlCl
3, FeCl
3, SnCl
4, ZnCl
2, H
2sO
4, H
3pO
4, BF
3, one or more in HF etc.
Preferably, the base metal salt as component (ii) described in step (2) is the salt of transition metal.Be more preferably the nitrate of transition metal, acetate, sulfate or chloride.Be more preferably be selected from Mn, Fe, Co, Ni, Cu one or both or more plant the salt of metal.Be more preferably be selected from Mn, Fe, Co, Ni, Cu one or both or more plant the nitrate of metal, acetate, sulfate or chloride.
Preferably, step (3) and the inert gas described in (5) are: Ar, He, N
2in one or more.
Preferably, the rare inorganic acid described in step (4) is the one in the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrofluoric acid.Generally, the concentration of rare inorganic acid is 0.05 ~ 5mol/L, is preferably 0.1 ~ 3mol/L, is more preferably 0.2 ~ 1mol/L.
Preferably, the halogen atom in above-mentioned pair of halogenated paraffin is one or more in fluorine, chlorine, bromine, iodine.
Preferably, heat treatment time described in step (3) and (5) is 30 ~ 120min.
The structural formula of tripyrrole in the present invention-[1,3,5]-triazine (TPT) is:
The copolymer obtained due to the application has cross-linked structure, therefore, is difficult to represent its structure with structural formula accurately.
Such as, when use bis ether is (as dimethoxymethane CH
3oCH
2oCH
3) maybe when using two halo C2-C6 alkane (i.e. X-(CH2) n-X, wherein n is 2-6) as alkylating agent, in the present invention, the part-structure of polymer P (TPT+Tp) is:
Wherein alkylidene-(CH2) n-is the methylene (n=1) derived from dimethoxymethane, or derive from two halo C2-C6 alkane, such as 1,2-dichloroethanes (n=2), 1,3-dibromopropane (n=3).
Oxygen reduction catalyst provided by the invention has the following advantages:
The present invention adopts the polymer of Friedel-Crafts Reactive Synthesis (P (TPT+Tp)) to be cross-linked structure, the M-N-S-C oxygen reduction catalyst obtained through successively twice heat treatment is loose structure, have larger specific area, degree of graphitization is higher.Loose structure defines more catalytic active center, and be also beneficial to reactant and electrolytical diffusion transmission, therefore gained catalyst not only has good ORR catalytic activity, also has excellent stability and methanol tolerance performance.
Rotating disk electrode (r.d.e) and linear voltammetric scan method, electrochemical AC impedance method, chronoamperometry is adopted to investigate this catalyst oxygen reduction catalytic activity in the basic conditions.Result shows, this catalyst has stability and the methanol tolerance performance of higher ORR catalytic activity and excellence: take Ag/AgCl as reference electrode, Pt silk is to electrode, is coated with glass-carbon electrode that the diameter of catalyst is 3mm for working electrode and forms three electrode test systems, with O
2saturated 0.1mol/L KOH solution is that electrolyte carries out a series of electro-chemical test, and result shows, oxygen reduction catalyst of the present invention has good take-off potential (0.042V), is better than the take-off potential (0V) of business Pt/C; Meanwhile, this catalyst has excellent stability, and through the test of 10000s, current density loss late is 10%, and the current density loss late of business Pt/C is 30%.This catalyst has excellent methanol tolerance performance, and after 145s adds methyl alcohol, current density there is no and significantly decay occurs, and the current density of business Pt/C decays to rapidly 71% of initial value.
Accompanying drawing explanation
Fig. 1, infrared spectrogram by the polymer prepared by embodiment 1.
Fig. 2, nitrogen adsorption desorption isotherm figure by the catalyst prepared by embodiment 1.
Fig. 3, pore size distribution figure by the catalyst prepared by embodiment 1.
Fig. 4, cyclic voltammetry curve (test condition: O by the catalyst prepared by embodiment 1 and business Pt/C catalyst (Johnson Matthey)
2saturated 0.1M KOH solution, sweeps speed for 50mV/s)
Fig. 5, by the catalyst prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4 and business Pt/C catalyst (Johnson Matthey) rotating disk electrode (r.d.e) polarization curve (test condition: rotating disk electrode (r.d.e), O under rotating speed 1600rpm
2saturated 0.1M KOH solution, sweeps speed for 10mV/s).
Fig. 6, timing ampere curve by the electric current ~ time of the catalyst prepared by embodiment 1 and business Pt/C catalyst (Johnson Matthey).(test condition: rotating disk electrode (r.d.e), O
2saturated 0.1MKOH solution, sweeps speed for 10mV/s, operating voltage-0.25V, rotating speed 1600rpm)
Fig. 7, timing ampere curve by the electric current ~ time of the catalyst prepared by embodiment 1 and business Pt/C catalyst (Johnson Matthey).(test condition: rotating disk electrode (r.d.e), O
2saturated 0.1MKOH solution, sweep speed for 10mV/s, operating voltage-0.25V, the time that rotating speed 1600rpm, 10wt% methyl alcohol adds is about 145s).
Detailed description of the invention
The raw material used in an embodiment
Thiophene: Aladdin chemical reagents corporation, AR.
Nitrobenzene: Tianjin Fu Yu Fine Chemical Co., Ltd, AR.。
Anaesthetie Ether: Aladdin chemical reagents corporation, AR.
Alchlor: Sa En chemical technology Co., Ltd, AR.
Methyl alcohol: Tianjin Kermel Chemical Reagent Co., Ltd., AR.
Ferric trichloride: Aladdin chemical reagents corporation, AR.
Ethanol: Tianjin Fu Yu Fine Chemical Co., Ltd, AR.
Sulfuric acid: Tianjin great Mao chemical reagent factory, AR.
Nafion solution: U.S. DuPont, 5%.
Nickel acetate: Aladdin chemical reagents corporation, AR.
Copper sulphate: Aladdin chemical reagents corporation, AR.
Tripyrrole-[1,3,5]-triazine: reference literature Electrochim.Acta 38 (1993) 2481 – 2484. synthesizes.
The equipment used in an embodiment: rotating disk electrode (r.d.e): ATA-1B, river, Jiangsu is divided.Fourier transform infrared spectroscopy (FTIR): Thermo Nieolet 6700, Thermo Fischer Scient Inc..Transmission electron microscope TEM:JEOL-2010, Japan.Specific area and Porosimetry: Tristar II 3020, Micromeritics company of the U.S..
Preparation example
The synthesis of tripyrrole-[1,3,5]-triazine (TPT):
By 6.78g (0.10mol) pyrroles, 80mL anhydrous tetrahydro furan is added in the single necked round bottom flask of 250mL, under ice bath, by KOH (8.86g, 0.15mol) add in above-mentioned system, rise to room temperature reaction 3h, then add 5.59g (0.03mol) cyanuric trichloride in batches, at room temperature continue to stir 18h.React complete, reaction system is poured into sedimentation in 250mL ice-water bath, filtration, then spend deionized water three times (200mL × 3), be then placed in the dry 24h of 80 DEG C of vacuum drying chambers.Gained crude product 15mL acetone and alcohol mixed solvent (acetone: ethanol is 4:1) recrystallization, filtration, ethanol washing, be dried to constant weight, 4.64g by gained pale solid room temperature in vacuo, productive rate 56%, fusing point: 210 DEG C.
Embodiment 1
(1) (P (TPT+Tp)) is synthesized: by 55g (0.2mol) tripyrrole-[1,3,5]-triazine (TPT), 50.5g (0.6mol) thiophene (Tp) are dissolved in 2000mL nitrobenzene, add 18.26g (0.24mol) dimethoxymethane and 32.28g (0.24mol) aluminum trichloride (anhydrous) again, stir 5h in 45 DEG C, then rise to 80 DEG C of stirring 19h; React complete, pour sedimentation in 10L methyl alcohol, filtration, washing (1000mL × 2) into, drying for standby; The infrared spectrum of polymer P (TPT+Tp) as shown in Figure 1.
The part-structure (i.e. repetitive) of polymer is as follows:
n=1 in formula;
(2) join in 300mL ethanol by 2.5g (P (TPT+Tp)), 0.7g ferric trichloride, ultrasonic 180min makes whole system be uniformly dispersed, then evaporate to dryness ethanol, is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(3) gained 3.2g pulverulent solids is at N
2in 900 DEG C of heat treatment 1h in atmosphere, obtain 0.9g nitrogen-doped carbon material;
(4) gained nitrogen-doped carbon material is with 2000mL0.5M dilute sulfuric acid in 80 DEG C of washing 8h, filters, is washed to neutrality and is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(5) pickling dried nitrogen-doped carbon material 0.5g is again at N
2in 900 DEG C of heat treatment 1h in atmosphere, obtain 0.4gM-N-S-C oxygen reduction catalyst, be designated as Fe-N-S-C-900.
Catalyst performance method of testing (following embodiment obtains catalyst and the business Pt/C (Johnson Matthey) for contrasting all tests by the method)
(1) catalyst 2mg is taken, join in 1mL Nafion-ethanol (1.5/98.5vol/vol) solution, ultrasonic disperse 30min, pipette above-mentioned catalyst suspension 20 μ L, gradation is added drop-wise on the rotating circular disk glass-carbon electrode that diameter is 3mm, natural drying.
(2) electro-chemical test instrument is CHI760D electrochemical workstation (Shanghai occasion China).Above-mentioned electrode is placed in O as working electrode
2in saturated 0.1M KOH solution, with Ag/AgCl be reference electrode, Pt silk for electrode, with the speed of sweeping of 10mV/s, the polarization curve of test rotating disk electrode (r.d.e) under 1600rpm rotating speed, investigates the kinetics of this catalyst oxygen reduction process.
(3) in above-mentioned system, under voltage-0.25V, the timing ampere curve of the catalyst prepared by testing with rotating speed 1600rpm and the electric current ~ time of business Pt/C catalyst (Johnson Matthey).
(4) in above-mentioned system, under voltage-0.25V, the timing ampere curve (time that 10wt% methyl alcohol adds is about 145s) of the catalyst prepared by testing with rotating speed 1600rpm and the electric current ~ time of business Pt/C catalyst (Johnson Matthey).
The properties of the product of the present embodiment is listed in accompanying drawing 1-6.
Embodiment 2
(1) (P (TPT+Tp)) is synthesized: by 55g (0.2mol) tripyrrole-[1,3,5]-triazine (TPT), 50.5g (0.6mol) thiophene (Tp) are dissolved in 2000mL nitrobenzene, add 24g (0.24mol) dichloroethanes and 32.28g (0.24mol) aluminum trichloride (anhydrous) again, stir 5h in 45 DEG C, then rise to 80 DEG C of stirring 19h; React complete, pour sedimentation in 10L methyl alcohol, filtration, washing (1000mL × 2) into, drying for standby; The infrared spectrogram of polymer P (TPT+Tp) as shown in Figure 1;
(2) 2.5g (P (TPT+Tp)), 0.7g ferric trichloride are joined in 300mL ethanol, ultrasonic 180min makes whole system be uniformly dispersed, evaporate to dryness ethanol again, is placed in vacuum drying chamber in 80 DEG C of dry 4h, obtains primary mix;
(3) gained 3.2g pulverulent solids is at N
2in 800 DEG C of heat treatment 1h in atmosphere, obtain 0.95g nitrogen-doped carbon material;
(4) gained nitrogen-doped carbon material is with 2000mL 0.5M dilute sulfuric acid in 80 DEG C of washing 8h, filters, is washed to neutrality and is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(5) pickling dried nitrogen-doped carbon material 0.5g is again at N
2in 800 DEG C of heat treatment 1h in atmosphere, obtain 0.41g M-N-S-C oxygen reduction catalyst, be designated as Fe-N-S-C-900.
Catalyst performance method of testing (following embodiment obtains catalyst and the business Pt/C (Johnson Matthey) for contrasting all tests by the method)
(1) catalyst 2mg is taken, join in 1mL Nafion-ethanol (1.5/98.5vol/vol) solution, ultrasonic disperse 30min, pipette above-mentioned catalyst suspension 20 μ L, gradation is added drop-wise on the rotating circular disk glass-carbon electrode that diameter is 3mm, natural drying.
(2) electro-chemical test instrument is CHI760D electrochemical workstation (Shanghai occasion China).Above-mentioned electrode is placed in O as working electrode
2in saturated 0.1M KOH solution, with Ag/AgCl be reference electrode, Pt silk for electrode, with the speed of sweeping of 10mV/s, the polarization curve of test rotating disk electrode (r.d.e) under 1600rpm rotating speed, investigates the kinetics of this catalyst oxygen reduction process.
(3) in above-mentioned system, under voltage-0.25V, the timing ampere curve of the catalyst prepared by testing with rotating speed 1600rpm and the electric current ~ time of business Pt/C catalyst (Johnson Matthey).
(4) in above-mentioned system, under voltage-0.25V, the timing ampere curve (time that 10wt% methyl alcohol adds is about 145s) of the catalyst prepared by testing with rotating speed 1600rpm and the electric current ~ time of business Pt/C catalyst (Johnson Matthey).
Embodiment 3
(1) (P (TPT+Tp)) is synthesized: by 55g (0.2mol) tripyrrole-[1,3,5]-triazine (TPT), 50.5g (0.6mol) thiophene (Tp) are dissolved in 2000mL nitrobenzene, add 24g (0.24mol) dichloroethanes and 32.28g (0.24mol) aluminum trichloride (anhydrous) again, stir 5h in 45 DEG C, then rise to 80 DEG C of stirring 19h; React complete, pour sedimentation in 10L methyl alcohol, filtration, washing (1000mL × 2) into, drying for standby;
(2) join in 300mL ethanol by 2.5g (P (TPT+Tp)), 0.7g nickel acetate, ultrasonic 180min makes whole system be uniformly dispersed, then evaporate to dryness ethanol, is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(3) gained 3.2g pulverulent solids is at N
2in 900 DEG C of heat treatment 1h in atmosphere, obtain 1.0g nitrogen-doped carbon material;
(4) gained nitrogen-doped carbon material is with 2000mL0.5M dilute sulfuric acid in 80 DEG C of washing 8h, filters, is washed to neutrality and is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(5) pickling dried nitrogen-doped carbon material 0.6g is again at N
2in 900 DEG C of heat treatment 1h in atmosphere, obtain 0.5gM-N-S-C oxygen reduction catalyst, be designated as Ni-N-S-C-900.
Embodiment 4
(1) (P (TPT+Tp)) is synthesized: by 55g (0.2mol) tripyrrole-[1,3,5]-triazine (TPT), 50.5g (0.6mol) thiophene (Tp) are dissolved in 2000mL nitrobenzene, add 24g (0.24mol) dichloroethanes and 32.28g (0.24mol) aluminum trichloride (anhydrous) again, stir 5h in 45 DEG C, then rise to 80 DEG C of stirring 19h; React complete, pour sedimentation in 10L methyl alcohol, filtration, washing (1000mL × 2) into, drying for standby;
(2) join in 300mL ethanol by 2.5g (P (TPT+Tp)), 0.7g copper sulphate, ultrasonic 180min makes whole system be uniformly dispersed, then evaporate to dryness ethanol, is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(3) gained 3.2g pulverulent solids is at N
2in 900 DEG C of heat treatment 1h in atmosphere, obtain 1.0g nitrogen-doped carbon material;
(4) gained nitrogen-doped carbon material is with 2000mL0.5M dilute sulfuric acid in 80 DEG C of washing 8h, filters, is washed to neutrality and is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(5) pickling dried nitrogen-doped carbon material 0.7g is again at N
2in 900 DEG C of heat treatment 1h in atmosphere, obtain 0.5gM-N-S-C oxygen reduction catalyst, be designated as Cu-N-S-C-900.
Embodiment 5
(1) (P (TPT+Tp)) is synthesized: by 55g (0.2mol) tripyrrole-[1,3,5]-triazine (TPT), 50.5g (0.6mol) thiophene (Tp) are dissolved in 2000mL nitrobenzene, add 24g (0.24mol) dichloroethanes and 32.28g (0.24mol) aluminum trichloride (anhydrous) again, stir 5h in 45 DEG C, then rise to 80 DEG C of stirring 19h; React complete, pour sedimentation in 10L methyl alcohol, filtration, washing (1000mL × 2) into, drying for standby;
(2) join in 300mL ethanol by 2.5g (P (TPT+Tp)), 0.7g ferric trichloride, ultrasonic 180min makes whole system be uniformly dispersed, then evaporate to dryness ethanol, is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(3) gained 3.2g pulverulent solids is at N
2in 1000 DEG C of heat treatment 1h in atmosphere, obtain 0.7g nitrogen-doped carbon material;
(4) gained nitrogen-doped carbon material is with 2000mL0.5M dilute sulfuric acid in 80 DEG C of washing 8h, filters, is washed to neutrality and is placed in vacuum drying chamber in 80 DEG C of dry 4h;
(5) pickling dried nitrogen-doped carbon material 0.5g is again at N
2in 1000 DEG C of heat treatment 1h in atmosphere, obtain 0.3gM-N-S-C oxygen reduction catalyst, be designated as Fe-N-S-C-1000.
Claims (10)
1. a M-N-S-C oxygen reduction catalyst, it is by comprising (i) tripyrrole-[1, 3, a kind of primary mix of the copolymer of 5]-triazine (TPT) and thiophene (Tp) and P (TPT+Tp) and (ii) base metal salt two kinds of components is in an inert atmosphere at 700-1000 DEG C, preferred 750-950 DEG C, more preferably carry out first time heat treatment at the temperature of 800-900 DEG C and obtain nitrogen-doped carbon material, then the rare inorganic acid of nitrogen-doped carbon material is carried out pickling processes, finally by the material of pickling in an inert atmosphere at 700-1000 DEG C, preferred 750-950 DEG C, more preferably carry out second time heat treatment at the temperature of 800-900 DEG C and finally obtain.
2. catalyst according to claim 1 is wherein the salt of transition metal as the base metal salt of component (ii); Be preferably the nitrate of transition metal, acetate, sulfate or chloride; Be more preferably be selected from Mn, Fe, Co, Ni, Cu one or both or more plant the salt of metal, be more preferably be selected from Mn, Fe, Co, Ni, Cu one or both or more plant the nitrate of metal, acetate, sulfate or chloride.
3. catalyst according to claim 1 and 2, wherein as component (i) P (TPT+Tp) be 1:0.06-1 as the mass ratio of the base metal salt of component (ii), preferred 1:0.08-0.9, be more preferably 1:0.12-0.8, more preferably 1:0.15-0.7, more preferably 1:0.18-0.6, more preferably 1:0.2-0.5.
4. according to any one catalyst in claim 1-3; wherein component (i); tripyrrole-[1; 3; the copolymer of 5]-triazine (TPT) and thiophene (Tp); i.e. P (TPT+Tp); by tripyrrole-[1; synthesized by 3,5]-triazine (TPT) and thiophene (Tp) two kinds of monomers are reacted by Friedel-Crafts under dual functional alkylating reagent or acylting agent and the existence of Friedel-Crafts catalysts.
5. according to the catalyst in claim 1-4 described in any one; wherein component (i); tripyrrole-[1; 3; the copolymer of 5]-triazine (TPT) and thiophene (Tp); i.e. P (TPT+Tp); by the tripyrrole-[1 of 1:0.2-10, the preferably weight ratio of 1:0.4-8, more preferably 1:0.6-6, more preferably 1:0.7-5; synthesized by 3,5]-triazine (TPT) and thiophene (Tp) two kinds of monomers are reacted by Friedel-Crafts under dual functional alkylating reagent or acylting agent and the existence of Friedel-Crafts catalysts.
6. any one the method for catalyst in the preparation method of M-N-S-C oxygen reduction catalyst or preparation claim 1-5, the method comprises the following steps:
(1) preparation of copolymer p (TPT+Tp): by the tripyrrole-[1 of 1:0.2-10, the preferably weight ratio of 1:0.4-8, more preferably 1:0.6-6, more preferably 1:0.7-5; 3; 5]-triazine (TPT) and thiophene (Tp) two kinds of monomers prepare tripyrrole-[1 by Friedel-Crafts reaction in a solvent under dual functional alkylating reagent or acylting agent and the existence of Friedel-Crafts catalysts; 3; the copolymer p (TPT+Tp) of 5]-triazine (TPT) and thiophene (Tp); i.e. component (i)
(2) formation of primary mix: using the P as component (i) (TPT+Tp) of 1 weight portion and 0.06-1 weight portion (preferred 0.08-0.9, more preferably 0.12-0.8, more preferably 0.15-0.7, more preferably 0.18-0.6, more preferably 0.2-0.5 weight portion) the base metal salt as component (ii) dispersed in solvent (as ethanol), dry, acquisition comprises a kind of primary mix of component (i) and component (ii)
(3) first time heat treatment: the primary mix obtained in step (2) is carried out a heat treatment in an inert atmosphere at the temperature of 700-1000 DEG C, preferably 750-950 DEG C, more preferably 800-900 DEG C, obtains nitrogen-doped carbon material.
(4) acid pickling step: pickling is carried out to nitrogen-doped carbon material with rare inorganic acid.
(5) second time heat treatment: the material after overpickling is carried out secondary heat treatment again in an inert atmosphere at the temperature of 700-1000 DEG C, preferably 750-950 DEG C, more preferably 800-900 DEG C, obtains final products M-N-S-C oxygen reduction catalyst.
7. the preparation method of M-N-S-C oxygen reduction catalyst or a method according to claim 6, the method comprises the following steps:
(1) preparation of copolymer p (TPT+Tp): by the tripyrrole of 1 weight portion-[1, 3, 5]-triazine (TPT) and 0.2-10 weight portion (preferred 0.4-8, more preferably 0.6-6, more preferably 0.7-5) thiophene (Tp) be dissolved in solvent (such as 15-50 weight portion, as 20-40 weight portion) in, add dual functional alkylating reagent or the acylting agent of 0.5-10 weight portion (preferred 1-4 weight portion) again, add the Friedel-Crafts catalysts that weight portion is 0.5-12 weight portion (preferred 1.2-6 weight portion), under agitation reaction (such as, in 25-50 DEG C of stirring reaction 2-10 hour (preferred 3-6 hour), rise to 60-100 DEG C of stirring reaction 15-25 hour again), react complete, pour separation in methyl alcohol or ethanol (such as 60-400 weight portion), filtration, washing, drying into, obtain P (TPT+Tp),
(2) formation of primary mix: using the P as component (i) (TPT+Tp) of 1 weight portion and 0.06-1 weight portion (preferred 0.08-0.9, more preferably 0.12-0.8, more preferably 0.15-0.7, more preferably 0.18-0.6, more preferably 0.2-0.5 weight portion) the base metal salt as component (ii) join in ethanol or methyl alcohol (such as 50 ~ 200 parts), ultrasonic wave process (such as 120 ~ 300min) makes whole system be uniformly dispersed; Evaporate to dryness ethanol or methyl alcohol, dry (being such as placed in vacuum drying chamber in 60-100 DEG C of dry 2-10h), obtains the primary mix comprising copolymer and base metal salt;
(3) first time heat treatment: step (2) gained mixture is carried out first time heat treatment in inert gas at the temperature of 700-1000 DEG C, preferably 750-950 DEG C, more preferably 800-900 DEG C, obtains nitrogen-doped carbon material;
(4) pickling: the rare inorganic acid (such as washing 5 ~ 10h with rare inorganic acid in 50 ~ 80 DEG C) of gained nitrogen-doped carbon material, filter, be washed to neutral rear dry (being such as placed in vacuum drying chamber in 60-100 DEG C of dry 2-10h);
(5) second time heat treatment: nitrogen-doped carbon material step (4) obtained carries out second time heat treatment again in inert gas at the temperature of 700-1000 DEG C, preferably 750-950 DEG C, more preferably 800-900 DEG C, obtains M-N-S-C oxygen reduction catalyst.
8. the method according to claim 6 or 7, wherein, dual functional alkylating reagent described in step (1) is that two halo C2-C6 alkane, straight or branched C2-C12 olefine, straight or branched C3-C10 dihydroxylic alcohols or the bis ether with 3-18 carbon atom are altogether (as dimethoxymethane CH
3oCH
2oCH
3) in one or more; And/or
Dual functional acylting agent be altogether have 3-12 C carbon atom the two carboxylic acid halides of straight or branched, altogether have 4-8 C carbon atom straight or branched bisgallic acid acid anhydride or altogether have in the straight or branched pair carboxylic acid of 4-10 C carbon atom one or more.
9. the method according to claim 6 or 7, wherein solvent described in step (1) is one or more in nitrobenzene, nitromethane, tetrachloroethanes, dichloroethanes, carbon tetrachloride, carbon disulfide, and/or
Described in step (1), Friedel-Crafts catalysts is AlCl
3, FeCl
3, SnCl
4, ZnCl
2, H
2sO
4, H
3pO
4, BF
3, one or more in HF etc.
10. according to the method in claim 6-9 described in any one, it is characterized in that: the base metal salt as component (ii) described in step (2) is the salt of transition metal; Be preferably the nitrate of transition metal, acetate, sulfate or chloride; Be more preferably be selected from Mn, Fe, Co, Ni, Cu one or both or more plant the salt of metal, be more preferably be selected from Mn, Fe, Co, Ni, Cu one or both or more plant the nitrate of metal, acetate, sulfate or chloride.
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