CN103418417A - Nonmetal oxygen reduction catalyst and preparation method thereof - Google Patents
Nonmetal oxygen reduction catalyst and preparation method thereof Download PDFInfo
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- CN103418417A CN103418417A CN2013104036900A CN201310403690A CN103418417A CN 103418417 A CN103418417 A CN 103418417A CN 2013104036900 A CN2013104036900 A CN 2013104036900A CN 201310403690 A CN201310403690 A CN 201310403690A CN 103418417 A CN103418417 A CN 103418417A
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- 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 discloses a nonmetal oxygen reduction catalyst and a preparation method thereof. The nonmetal oxygen reduction catalyst is of a three-dimensional grading porous structure. Main components of the nonmetal oxygen reduction catalyst are carbon, nitrogen and phosphorus. Nitrogen and phosphorus are dopped in carbon. The comparison content of nitrogen and phosphorus is 0-10 at%. The comparison content of phosphorus and carbon is 0-8 at%. The content of nitrogen and the content of phosphorus can not be zero at the same time. Solution of polystyrene microspheres and polyvinyl alcohol is frozen in low temperature, and then is unfrozen at room temperature, so that composite hydrogel of polyvinyl alcohol and polystyrene is prepared. The composite hydrogel is used as a template. Front drive body solution with mixed elements is filled into clearance of the hydrogel, and three-dimensional grading porous element-dopped carbon materials are manufactured through high-temperature calcining. According to the preparation method, raw materials are common and can be obtained easily, cost is low, and the preparation process is simple and safe. Obtained materials have good oxygen reduction catalytic activity in acid, neutralized and alkaline electrolyte and is approximate to the reaction process of four electrons.
Description
Technical field
What the present invention relates to is a kind of fuel cell technology field, particularly oxygen reduction catalyst of a kind of element of the not containing metal for fuel cell and preparation method thereof.
Background technology
Fuel cell is a kind of energy conversion device, can convert chemical energy to electric energy by the redox reaction that occurs in anode and negative electrode, have that operating temperature is low, energy efficiency is high, without characteristics such as electrolyte corrosion, be a study hotspot in electrochemistry and energy science field.Yet up to the present, fuel cell does not obtain commodity production widely, one of them important restriction factor is exactly the problem of its cathod catalyst.The noble metal of current main employing platinum base is as this type of catalyst, but the cost of this class catalyst is too high, originates limited, and shortcoming (Nature2001,414,345 such as not anti-carbon monoxide, methanol poisoning are arranged; Science2007,315,493; J.Am.Chem.Soc.2009,131,15330.).Therefore, finding more preferably cathod catalyst is that fuel cell obtains widespread commercial and needs one of important problem of solution badly.
The material with carbon element of element doping, due to its lower cost, the advantage such as catalytic stability and good anti-carbon monoxide, methanol poisoning preferably, becomes the good oxygen reduction catalyst that substitutes platinum.As Graphene or the CNT of element doping has higher catalytic activity (Angew.Chem.Int.Ed.2012,51,4209; Angew.Chem.Int.Ed.2011,50,11756.), but this class catalyst is in order to obtain the effect of adulterating preferably, and process conditions are loaded down with trivial details, and cost is higher.In addition, suitable carbon source, nitrogenous source and the transition metal (Co, Fe) by pyrolysis, also can obtain high performance oxygen reduction catalyst (Adv.Funct.Mater.2012,22,3500.), yet due to the existence of transition metal, easily cause the problems such as catalyst oxidation and anthracemia.Research simultaneously shows, the porous of the carbon-supported catalysts of element doping also has active influence to catalytic performance, abundant loose structure will provide more reactivity site, and be conducive to the transmission of reactant and product, so control the porous of catalyst and the study hotspot (Adv.Funct.Mater.2012 that pore structure is also non-metal oxygen reducing catalyst, 22,3634).
Summary of the invention
The objective of the invention is to overcome the shortcoming that prior art exists, a kind of effective oxygen reduction catalyst and preparation method thereof is provided, it is as the anti-methanol oxidation of oxygen reduction catalyst, and has the catalytic activity suitable with platinum and the higher catalytic stability than platinum.Concrete technical scheme is as follows:
A kind of nonmetal oxygen reduction catalyst, described catalyst has three-dimensional graded porous structure, main component is carbon and is entrained in nitrogen element and P elements wherein, the content that wherein the nitrogen element is compared with carbon is 0～10at%, the content that P elements is compared with carbon is 0～8at%, and nitrogen, phosphorus element content can not be 0 simultaneously.
Described three-dimensional graded porous structure refers to have the macropore be interconnected, and the aperture of described macropore is 40～4000nm, and the nano-pore of pore diameter range at 3～40nm arranged on the hole wall of described macropore.
The preparation method of described nonmetal oxygen reduction catalyst comprises following steps:
1) aqueous solution of the polystyrene microsphere of 1～10wt% be take to volume ratio with the dimethyl sulphoxide solution of 6～10wt% polyvinyl alcohol evenly mix (preferably mixing temperature be 70 ℃) under 50～90 ℃ as 1:1～2, obtains precursor solution; By described precursor solution under-20～0 ℃ freezing 2～24 hours, then thaw under 20～25 ℃ 0.5～1 hour, obtain the composite aquogel of polyvinyl alcohol and polystyrene; The glutaraldehyde water solution that is 0.15～1.5% with the 50mL mass fraction and the chemical crosslinking of described 0～20g composite aquogel 3～12 hours, obtain crosslinked composite aquogel;
2) described crosslinked composite aquogel is infiltrated in the aqueous solution of cyanamide and phosphoric acid to 10～24 hours, reach the absorption swelling equilibrium; Then under 60～80 ℃ dry 12～24 hours;
3) by step 2) in dried solid carry out high temperature pyrolysis under 600～1000 ℃ in argon gas atmosphere, and be incubated 2～5 hours; Then naturally cool to room temperature, obtain described nonmetal oxygen reduction catalyst.
The particle diameter of described polystyrene microsphere is that 50～5000nm(is preferably 100～500nm).
The mass ratio of the crosslinked composite aquogel step 2) and infiltrate is 0～10:1; The mass ratio of phosphoric acid described in infiltrate and cyanamide is 0.0～0.5:1, and wherein the mass concentration of the aqueous solution of cyanamide is 50%.
The invention has the advantages that raw material is common is easy to get, and with low cost, preparation process is simple and safe.The synergy of nitrogen and phosphorus has changed the electron distributions of carbon, has changed the one-tenth key mode of carbon atom, has improved the catalytic activity of hydrogen reduction; Moreover prepared material has classifying porous structure, micropore wherein and meso-hole structure increase the electrochemistry specific area, and macroporous structure is easy to the transmission of reactant and product.The material of gained all has good hydrogen reduction catalytic activity in acidity, neutrality and alkaline electrolyte, close to the course of reaction of the quadrielectron.
The accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of the graded porous carbon of nitrogen-phosphor codoping;
Fig. 2 is the attached curve map of nitrogen adsorption-desorption of the graded porous carbon of nitrogen-phosphor codoping;
Fig. 3 is the cyclic voltammogram (CV) of graded porous carbon in acid (a), neutral (b) and alkalescence (c) electrolyte of nitrogen-phosphor codoping;
Fig. 4 is the linear sweep voltammetry figure (LSV) of graded porous carbon in acid (a), neutral (b) and alkalescence (c) electrolyte of nitrogen-phosphor codoping, and illustration is the electron transfer number figure under certain potentials;
Fig. 5 is 20% the linear sweep voltammetry figure (LSV) of Pt/C in alkaline electrolyte;
Fig. 6 is the porous carbon materials of nitrogen-phosphor codoping and the time current figure of 20% Pt/C.
The specific embodiment
The specific embodiment
Be below embodiments of the invention, provided detailed embodiment and concrete operating process, its purpose is only being understood content of the present invention better.Therefore protection scope of the present invention is not subject to the restriction of illustrated embodiment.
The method of testing of the catalyst performance that the present invention uses is as follows:
By 2mg, the porous carbon materials of prepared nitrogen-phosphor codoping mixes ultrasonic 30 minutes with 5wt%Nafion emulsion and the ethanol (volume ratio is 1:9) of 1mL, obtains dispersion liquid; Get the described dispersion liquid of 10 μ L and be applied on rotating disk electrode (r.d.e), after room temperature is dried, obtain membrane electrode.Utilizing the Ag/AgCl electrode is the three-electrode system to electrode for reference electrode, Pt silk, at saturated 0.1mol/L KOH, 0.1mol/L PBS, the 0.5mol/L H of process oxygen
2SO
4Carry out cyclic voltammetry and linear sweep voltammetry test in solution.
Embodiment 1
By mass fraction is 10%, particle diameter is 160nm the polystyrene microsphere aqueous solution with evenly mix under 70 ℃ of conditions with volume ratio 1:1 with the dimethyl sulphoxide solution of 10% polyvinyl alcohol, then resulting precursor solution is freezing 4 hours at-20 ℃, 25 ℃ thaw 1 hour, obtain the composite aquogel of polyvinyl alcohol and polystyrene.The glutaraldehyde water solution chemical crosslinking 10g composite aquogel that is 0.75% with the 50mL mass fraction 6 hours.Composite aquogel after chemical crosslinking is infiltrated in the aqueous solution of the cyanamide of 10mL and phosphoric acid (mass ratio of phosphoric acid and cyanamide is 0.2:1) to 12 hours, reach the absorption swelling equilibrium.Then under 80 ℃ of conditions dry 24 hours.Carry out high temperature pyrolysis through infiltrating dried solid in inert atmosphere under 900 ℃, and be incubated 3 hours.Then naturally cool to room temperature, obtain the material with carbon element of classifying porous nitrogen-phosphor codoping, as shown in Figure 1, the attached curve map of nitrogen adsorption-desorption is as shown in Fig. 2 (comprising graph of pore diameter distribution) for its SEM photo.
As can be seen from Figure 1, material has three-dimensional macroporous structure, and macropore diameter is in the 100nm left and right, and macropore is interconnected.As can be seen from Figure 2, the specific area of prepared material is 755.7m
2g
-1, pore volume is 1.39cm
3g
-1.Known in conjunction with Fig. 1 and Fig. 2, products therefrom has three-dimensional classifying porous structure.
By mass fraction, be 10%, the polystyrene microsphere aqueous solution that particle diameter is 160nm and evenly mixing under 70 ℃ of conditions with volume ratio 1:1 with the dimethyl sulphoxide solution of 10% polyvinyl alcohol, then resulting precursor solution is freezing 4 hours at-20 ℃, 25 ℃ thaw 1 hour, obtain the composite aquogel of polyvinyl alcohol and polystyrene.The glutaraldehyde water solution chemical crosslinking 10g composite aquogel that is 0.75% with the 50mL mass fraction 6 hours.Composite aquogel after chemical crosslinking is infiltrated in the aqueous solution of 50% cyanamide of 10mL to 12 hours, reach the absorption swelling equilibrium.Then under 80 ℃ of conditions dry 24 hours.Carry out high temperature pyrolysis through infiltrating dried solid in inert atmosphere under 900 ℃, and be incubated 3 hours.Then naturally cool to room temperature, obtain the material with carbon element of classifying porous nitrogen doping.
Embodiment 3
By mass fraction, be 10%, the polystyrene microsphere aqueous solution that particle diameter is 160nm and evenly mixing under 70 ℃ of conditions with volume ratio 1:1 with the dimethyl sulphoxide solution of 10% polyvinyl alcohol, then resulting precursor solution is freezing 4 hours at-20 ℃, 25 ℃ thaw 1 hour, obtain the composite aquogel of polyvinyl alcohol and polystyrene.The glutaraldehyde water solution chemical crosslinking 10g composite aquogel that is 0.75% with the 50mL mass fraction 6 hours.Composite aquogel after chemical crosslinking is infiltrated in the aqueous solution of the phosphoric acid that the mass fraction of 10mL is 30% to 12 hours, reach the absorption swelling equilibrium.Then under 80 ℃ of conditions dry 24 hours.Carry out high temperature pyrolysis through infiltrating dried solid in inert atmosphere under 900 ℃, and be incubated 3 hours.Then naturally cool to room temperature, obtain the material with carbon element of classifying porous phosphorus doping.
Embodiment 4
The material with carbon element of the 2mg nitrogen-phosphor codoping of embodiment 1 gained is mixed ultrasonic 30 minutes with 5wt%Nafion emulsion and the ethanol (volume ratio is 1:9) of 1mL, obtain dispersion liquid; Get the described dispersion liquid of 10 μ L and be applied on rotating disk electrode (r.d.e), after room temperature is dried, obtain membrane electrode.Utilizing the Ag/AgCl electrode is the three-electrode system to electrode for reference electrode, Pt silk, at saturated 0.1mol/L KOH, 0.1mol/L PBS, the 0.5mol/L H of process oxygen
2SO
4Carry out cyclic voltammetry in solution, sweep speed is 50mV/s, and sweep limits is-1.0V～0.2V; The linear sweep voltammetry test: sweep speed is 10mV/s, and sweep limits is-1.0V～0.2V; The time current curve: time 60h, voltage-0.3V, electrolyte is 0.1mol/L KOH.
Comparative Examples 1
The Pt/C of the 20wt% of 2mg is mixed ultrasonic 30 minutes with 5wt%Nafion emulsion and the ethanol (volume ratio is 1:9) of 1mL, obtain dispersion liquid; Get the described dispersion liquid of 10 μ L and be applied on rotating disk electrode (r.d.e), after room temperature is dried, obtain membrane electrode.Utilizing the Ag/AgCl electrode is the three-electrode system to electrode for reference electrode, Pt silk, and carry out the linear sweep voltammetry test in the 0.1mol/L KOH solution saturated through oxygen: sweep speed is 10mV/s, and sweep limits is-1.0V～0.2V; The time current curve: time 60h, voltage-0.3V, electrolyte is 0.1mol/L KOH.
The cyclic voltammogram (CV) of the porous carbon materials that Fig. 3 is the nitrogen-phosphor codoping that records in embodiment 4 in acid (a), neutral (b) and alkaline (c) electrolyte.As can be seen from Figure 3, obvious hydrogen reduction peak has all appearred in three kinds of electrolyte.The linear sweep voltammetry figure (LSV) of the porous carbon materials that Fig. 4 is the nitrogen-phosphor codoping that records in embodiment 4 in acid (a), neutral (b) and alkaline (c) electrolyte.Fig. 5 is the linear sweep voltammetry figure (LSV) of Pt/C material in alkaline electrolyte recorded in Comparative Examples 1.From the linear sweep voltammetry figure of Fig. 4, can find out, the porous carbon materials of the nitrogen-phosphor codoping of gained all has good hydrogen reduction catalytic activity in acidity, neutrality and alkaline electrolyte, and electron transfer number figure shows it is the course of reaction close to the quadrielectron.Contrast its hydrogen reduction catalytic activity of Pt/C material in alkaline electrolyte that hydrogen reduction catalytic activity and Fig. 5 show in alkaline electrolyte, there is no significant difference.The time current figure of the porous carbon materials that Fig. 6 is the nitrogen-phosphor codoping that records of embodiment 4 and the time current figure of the Pt/C material that Comparative Examples 1 records, the porous carbon materials of nitrogen-phosphor codoping has better catalytic stability with respect to the Pt/C material as can be seen from Figure 6.
Claims (5)
1. a nonmetal oxygen reduction catalyst, it is characterized in that, described catalyst has three-dimensional graded porous structure, main component is carbon and is entrained in nitrogen element and P elements wherein, the content that wherein the nitrogen element is compared with carbon is 0～10at%, the content that P elements is compared with carbon is 0～8at%, and nitrogen, phosphorus element content are 0 when different.
2. nonmetal oxygen reduction catalyst according to claim 1, it is characterized in that, described three-dimensional graded porous structure refers to have the macropore be interconnected, and the aperture of described macropore is 40～4000nm, and the nano-pore of pore diameter range at 3～40nm arranged on the hole wall of described macropore.
3. the preparation method of claim 1 or 2 described nonmetal oxygen reduction catalyst, is characterized in that, comprises following steps:
1) aqueous solution of the polystyrene microsphere of 1～10wt% be take to volume ratio with the dimethyl sulphoxide solution of 6～10wt% polyvinyl alcohol and evenly mix under 50～90 ℃ as 1:1～2, obtain precursor solution; By described precursor solution under-20～0 ℃ freezing 2～24 hours, then thaw under 20～25 ℃ 0.5～1 hour, obtain the composite aquogel of polyvinyl alcohol and polystyrene; The glutaraldehyde water solution that is 0.15～1.5% with the 50mL mass fraction and the chemical crosslinking of described 0～20g composite aquogel 3～12 hours, obtain crosslinked composite aquogel;
2) described crosslinked composite aquogel is infiltrated in the aqueous solution of cyanamide and phosphoric acid to 10～24 hours, reach the absorption swelling equilibrium; Then under 60～80 ℃ dry 12～24 hours;
3) by step 2) in dried solid carry out high temperature pyrolysis under 600～1000 ℃ in argon gas atmosphere, and be incubated 2～5 hours; Then naturally cool to room temperature, obtain described nonmetal oxygen reduction catalyst.
4. preparation method according to claim 3, is characterized in that, the particle diameter of described polystyrene microsphere is 50～5000nm.
5. preparation method according to claim 3, is characterized in that step 2) described in crosslinked composite aquogel and the mass ratio of infiltrate be 0～10:1; The mass ratio of phosphoric acid described in infiltrate and cyanamide is 0.0～0.5:1, and wherein the mass concentration of the aqueous solution of cyanamide is 50%.
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Cited By (8)
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| CN103972517A (en) * | 2014-05-22 | 2014-08-06 | 胡国良 | Preparation method of fuel cell film electrode |
| CN106040121A (en) * | 2016-05-25 | 2016-10-26 | 中国科学院大学 | Method for synthesizing skeleton microsphere material |
| CN106602090A (en) * | 2016-12-30 | 2017-04-26 | 太原理工大学 | Method for preparing nonmetallic catalyst for oxygen reduction reaction by using crab shell |
| CN106784893A (en) * | 2016-12-16 | 2017-05-31 | 中国石油大学(华东) | A kind of high activity for fuel cell anode is without metal N, P codope conjugated backbone material |
| CN109560293A (en) * | 2018-11-01 | 2019-04-02 | 江苏可兰素汽车环保科技有限公司 | Oxygen reduction catalyst and its preparation method and application |
| CN109728246A (en) * | 2018-12-13 | 2019-05-07 | 太原理工大学 | A kind of nitrogen-phosphor codoping ordered mesoporous carbon material and its preparation method and application |
| CN109786764A (en) * | 2018-01-29 | 2019-05-21 | 北京化工大学 | One kind having grading-hole, the nonmetallic carbon-based oxygen reduction catalyst of nitrogen sulphur codope and preparation |
| CN112820886A (en) * | 2020-12-29 | 2021-05-18 | 北京化工大学 | Three-dimensional grading porous nonmetal carbon-based material and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103972517A (en) * | 2014-05-22 | 2014-08-06 | 胡国良 | Preparation method of fuel cell film electrode |
| CN106040121A (en) * | 2016-05-25 | 2016-10-26 | 中国科学院大学 | Method for synthesizing skeleton microsphere material |
| CN106784893A (en) * | 2016-12-16 | 2017-05-31 | 中国石油大学(华东) | A kind of high activity for fuel cell anode is without metal N, P codope conjugated backbone material |
| CN106602090A (en) * | 2016-12-30 | 2017-04-26 | 太原理工大学 | Method for preparing nonmetallic catalyst for oxygen reduction reaction by using crab shell |
| CN109786764A (en) * | 2018-01-29 | 2019-05-21 | 北京化工大学 | One kind having grading-hole, the nonmetallic carbon-based oxygen reduction catalyst of nitrogen sulphur codope and preparation |
| CN109786764B (en) * | 2018-01-29 | 2021-11-26 | 北京化工大学 | Nitrogen-sulfur double-doped non-metallic carbon-based oxygen reduction catalyst with graded holes and preparation method thereof |
| CN109560293A (en) * | 2018-11-01 | 2019-04-02 | 江苏可兰素汽车环保科技有限公司 | Oxygen reduction catalyst and its preparation method and application |
| WO2020087990A1 (en) * | 2018-11-01 | 2020-05-07 | 江苏可兰素汽车环保科技有限公司 | Oxygen reduction catalyst and preparation method therefor and use thereof |
| CN109728246A (en) * | 2018-12-13 | 2019-05-07 | 太原理工大学 | A kind of nitrogen-phosphor codoping ordered mesoporous carbon material and its preparation method and application |
| CN109728246B (en) * | 2018-12-13 | 2021-08-06 | 太原理工大学 | Nitrogen-phosphorus co-doped ordered mesoporous carbon material and preparation method and application thereof |
| CN112820886A (en) * | 2020-12-29 | 2021-05-18 | 北京化工大学 | Three-dimensional grading porous nonmetal carbon-based material and preparation method and application thereof |
| CN112820886B (en) * | 2020-12-29 | 2023-05-26 | 北京化工大学 | Three-dimensional hierarchical porous nonmetal carbon-based material, and preparation method and application thereof |
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Application publication date: 20131204 |