CN116093351A - Composite nano catalyst loaded on nitrogen-doped carbon and preparation method and application thereof - Google Patents

Composite nano catalyst loaded on nitrogen-doped carbon and preparation method and application thereof Download PDF

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CN116093351A
CN116093351A CN202211584753.2A CN202211584753A CN116093351A CN 116093351 A CN116093351 A CN 116093351A CN 202211584753 A CN202211584753 A CN 202211584753A CN 116093351 A CN116093351 A CN 116093351A
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stirring
transition metal
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邵志刚
索妮
曹龙生
秦晓平
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses a composite nano catalyst loaded on nitrogen-doped carbon, and a preparation method and application thereof, and belongs to the technical field of synthesis of nano catalysts. The nitrogen doped carbon is used as a carrier, and Pt-M intermetallic compound and PtP are loaded on the carrier 2 Wherein M is a transition metal atom; the Pt-M intermetallic compoundAnd PtP 2 The molar ratio of total platinum atoms to transition metal M atoms in the complex of (a) is 0.3 to 3, and the molar ratio of carbon in the carrier to transition metal M atoms is 1.7 to 37.5. The nitrogen-doped carbon loads Pt-M and PtP 2 The composite nano catalyst is applied to catalysts of oxyhydrogen fuel cells, metal-air cells and electrolytic water cells, has higher catalytic activity and stability, improves the catalytic activity and stability, solves the defect that metal nano particles are easy to agglomerate, and has simple preparation process, convenient operation and low cost.

Description

Composite nano catalyst loaded on nitrogen-doped carbon and preparation method and application thereof
Technical Field
The invention belongs to the technical field of synthesis of nano catalysts, and particularly relates to a composite nano catalyst loaded on nitrogen-doped carbon, and a preparation method and application thereof.
Background
The development of environment-friendly, economical and efficient energy conversion technologies such as fuel cells and water electrolysis cells is important to solve the problems of energy demand increase, rapid consumption of fossil fuels, serious environmental pollution and the like. Currently, platinum (Pt) has a unique electronic structure and irreplaceable combination of properties, and is still the preferred catalyst for key reactions in clean energy technologies such as Oxygen Reduction Reaction (ORR) and hydrogen evolution/oxygen reaction (HER/HOR). Nevertheless, the most active Pt catalysts have some serious drawbacks that prevent their large-scale commercial application. In addition to being low in reserves and expensive, the dissolution and aggregation of the noble metal Pt in corrosive solutions can lead to poor stability and catalytic activity. This requires the use of large amounts of Pt to achieve and maintain the required power density for operating conditions. These dilemmas have continually prompted researchers to develop more efficient solutions to rationally design Pt-based catalysts with high platinum atom utilization, high activity, and stability for various electrocatalytic reactions.
To reduce the Pt content of the catalyst and to increase its activity and stability, pt may be "alloyed" with a 3d transition metal M (Fe, co, ni, mn, zn, cu, etc.) or a non-metal. The method not only can reduce the Pt consumption to reduce the cost, but also can exert the electronic effect of alloying to improve the catalytic activity and the stability. Pt-based (Pt-M) intermetallic compounds and platinum biphosphide (PtP) 2 ) As a multifunctional electrocatalyst, attention has been paid to the high catalytic activity and long-term durability in both ORR and HER/HOR of fuel cells, water splitting and the like. Wherein Pt-M gold is synthesizedThe most common method for the intermetallic compounds is co-reduction by a reducing agent in a liquid phase system and subsequent high temperature annealing under a hydrogen atmosphere. In general, the transition of the structure from disordered to ordered requires a heat treatment higher than 600 ℃, which inevitably causes nanoparticle aggregation and an increase in particle size, resulting in a decrease in catalytic performance.
Disclosure of Invention
Based on the problems of the prior art, the present application provides a Pt-based intermetallic compound and PtP supported on nitrogen-doped carbon 2 Composite nano catalyst, preparation method and application thereof, and PtP (PtP) preparation in ordering process of Pt-M alloy 2 Doping of the carbon support is completed at the same time. This strategy not only inhibits Pt-M and PtP 2 Growth of nanoparticles, also skillfully combining Pt-M with PtP 2 The catalyst is compounded into a whole and is used as a high-efficiency electrocatalyst in electrochemical reactions.
The invention adopts the specific technical scheme that:
the application provides a composite nano catalyst loaded on nitrogen-doped carbon, which takes nitrogen-doped carbon as a carrier, and loads Pt-M intermetallic compound and PtP of cubic structure on the carrier 2 Wherein M is a transition metal atom; the Pt-M intermetallic compound and PtP 2 The molar ratio of total platinum atoms to transition metal M atoms in the complex of (a) is 0.3 to 3, and the molar ratio of carbon in the carrier to transition metal M atoms is 1.7 to 37.5.
Further, the M includes one of Fe, co, ni, mn, zn, cu, ti, in, pd, mo, ir, ru and Au.
Further, the carbon material in the carrier comprises one of carbon black, graphene, carbon nanotube, graphene-carbon nanotube composite material, carbon nanotube cup, annealed polypyrrole tube, carbon aerogel, mesoporous carbon, carbon nanospheres, carbon nanocages, carbon nanocapsules and carbon nanofibers.
Further, the complex is in the shape of truncated octahedron, and the complex is highly uniformly dispersed on the nitrogen-doped carbon carrier.
The invention also provides a preparation method of the composite nano catalyst loaded on the nitrogen-doped carbon, which comprises the following steps:
(1) Grinding and mixing adenine phosphate and the dried carbon-supported Pt-M alloy according to the mass ratio of 0.2-1.0, sintering and annealing in a hydrogen-argon mixed atmosphere, wherein the sintering temperature is 600-1000 ℃, the heating rate is 5-10 ℃/min, the annealing time is 0.5-3 h, and taking out a sample after naturally cooling to room temperature;
(2) Carrying out acid washing treatment on the sample in an inert atmosphere;
the method comprises the following steps: firstly, pouring a sample into 0.1-1.0 mol/L diluted acid, uniformly mixing under the ultrasonic action, and then stirring for 12-24 hours at 50-80 ℃ under the protection of inert gas;
(3) After the pickling, cooling to room temperature, centrifuging (10000 rpm) and cleaning (ultrapure water) the sample, and drying in a vacuum freeze dryer.
Further, the synthesis of the carbon-supported Pt-M alloy is carried out under the protection of inert atmosphere, and comprises the following steps:
(1) Adding a platinum precursor and a transition metal M precursor into an alcohol solution, and stirring at room temperature;
(2) Adding a carbon material into an alcohol solution, and carrying out reflux reaction;
(3) Dropwise adding the solution obtained in the step (1) into the solution obtained in the step (2), stirring at the reflux reaction temperature, adding alkali to adjust the pH to be more than 11, and continuously stirring at the reflux reaction temperature to form a pasty suspension containing metal salt;
(4) Adding NaBH to the suspension obtained in the step (3) 4 Stirring the alcohol solution for 10-30 min at the reflux reaction temperature, then raising the temperature to 120-200 ℃, and stirring for 0.5-4 h;
(5) Cooling to room temperature after the reaction is finished, adding acid to adjust the pH to be less than 2, and stirring; centrifuging (10000 rpm), cleaning (ethanol and then ultrapure water), and drying (vacuum freeze dryer).
Further, the molar ratio of the platinum precursor to the transition metal M precursor is 0.15:0.05 to 0.45, wherein the stirring time in the step (1) is 1 to 3 hours;
the concentration of the carbon material in the alcohol solution in the step (2) is 2-5 mg/mL, and the reaction time is 1-3 h;
in the step (3), the stirring time is 15-60 min before adding alkali to adjust the pH value, and the stirring time is 1-3 h after adding alkali to adjust the pH value; the concentration of the alkali is 0.1-1.0 mol/L;
the temperature of the reflux reaction in the step (2), the step (3) and the step (4) is 60-100 ℃;
NaBH in step (4) 4 The concentration in the solution is 2-4 mmol/mL;
the concentration of the acid in the step (5) is 1-5 mol/L, and the stirring time is 10-60 min.
Further, the alcohol solution comprises at least one of ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and glycerol;
the platinum precursor comprises one of potassium chloroplatinate, chloroplatinic acid, potassium chloroplatinite, hexahydroxyplatinate, platinum acetylacetonate and the like;
the transition metal M precursor comprises one of nitrate, chloride, sulfate, acetate, acetylacetonate, oxalate and carbonate of transition metal M;
the alkali comprises at least one of KOH, naOH and ammonia water.
Further, the inert atmosphere comprises at least one of nitrogen, argon and helium.
Further, the pickling solution comprises at least one of perchloric acid, sulfuric acid, nitric acid and hydrochloric acid with the concentration of 0.1-1.0 mol/L.
The invention also provides application of the composite nano catalyst or the composite nano catalyst prepared by the preparation method, and the composite nano catalyst is applied to catalysts of hydrogen-oxygen fuel cells, metal-air cells or electrolytic water cells.
The invention has the beneficial effects that:
(1) Pt-M intermetallic compound with truncated octahedral structure and PtP 2 The composite nano-particles and the doped carbon carrier can be used as active ingredients to further promote catalytic reaction, wherein the doped carbon carrier can also play a role in anchoring the composite nano-catalyst particles, so that the stability is enhanced.
The nitrogen-doped carbon loads Pt-M and PtP 2 The composite nano catalyst is applied to catalysts of oxyhydrogen fuel cells, metal-air cells and electrolytic water cells, has higher catalytic activity and stability, improves the catalytic activity and stability, solves the defect that metal nano particles are easy to agglomerate, and has simple preparation process, convenient operation and low cost.
(2) Aiming at the problem that the Pt-M alloy particles become large due to heat treatment, the method carries out high-temperature treatment after fully and uniformly ball-milling the Pt-M alloy and adenine phosphate. After the adenine phosphate is added, ptP is synthesized 2 The method comprises the steps of carrying out a first treatment on the surface of the On the other hand, the formed heteroatom N-doped carbon carrier not only provides a protective barrier, effectively inhibits migration and aggregation of metal nano particles, improves the problem of growth of particles due to heat treatment, promotes conductivity and charge/mass transmission of materials in an electrochemical process, and can also synergistically improve the overall catalytic activity as a part of a catalyst.
(3) The application adopts the isopropanol modified at high temperature to stabilize NaBH 4 The method prepares the nitrogen-doped high-activity carbon-loaded Pt-M nano intermetallic compound catalyst by a polyol reduction method. The reduction of the metal precursor at high temperatures is chosen because the polyol can act not only as a solvent but also as a stabilizer and dispersant in high temperature environments.
Drawings
FIG. 1 is an XRD pattern of a sample heat treated with an adenine phosphate and a commercial 20% Pt/C (JM) catalyst without addition of 0.06mmol of the cobalt precursor in example 1.
FIG. 2 shows a sample (Pt) after heat treatment without addition of adenine phosphate when the cobalt precursor was 0.06mmol in example 1 3 Co) EDX mapping graph.
FIG. 3 is a sample (Pt) after heat treatment with adenine phosphate added when the cobalt precursor was 0.06mmol in example 1 3 Co+PtP 2 ) EDX mapping graph of (c).
FIG. 4 shows a sample (Pt) obtained by heat treatment with adenine phosphate at a cobalt precursor of 0.06mmol in example 1 3 Co+PtP 2 ) With commercial 20% Pt/C (JM) catalystLinear scan profile of the chemical agent.
FIG. 5 shows a sample (Pt) obtained by heat treatment with adenine phosphate added when the manganese precursor was 0.10mmol in example 2 3 Mn+PtP 2 ) Linear scan plot with commercial 20% Pt/C (JM) catalyst.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Example 1
Co-supported Pt-based intermetallic compound and PtP on nitrogen-doped carbon 2 The preparation method of the composite nano catalyst comprises the following steps:
the following steps (2) to (5) and (7) were all carried out under nitrogen protection with magnetic stirring.
(1) 0.15mmol of platinum precursor and 0.06mmol of transition metal Co precursor are added into 10mL of ethylene glycol solvent, and magnetically stirred for 1h at room temperature;
(2) 70mg of BP2000 carbon black is added into 30mL of ethylene glycol solvent, the temperature is increased to 80 ℃ after a reflux device is arranged, and the mixture is magnetically stirred for 1h at the temperature;
(3) Dropwise adding the solution obtained in the step (1) into the solution obtained in the step (2), stirring for 20min, adding 0.3mol/L alkaline substance (NaOH is used in the embodiment) to adjust the pH value of the mixture to be more than 11, and continuously stirring for 1h at 80 ℃ under the protection of inert gas to form slurry carbon black suspension containing metal salt;
(4) To the suspension obtained in step (3) was added rapidly (within 30-60 s) NaBH at a concentration of 2.5mmol/mL 4 Glycol solution, after reacting for 15min, heating the temperature to 180 ℃ and reacting for 1.5h at the temperature;
(5) After the reaction, cooling to room temperature, adding 3mol/L HCl to adjust the pH of the reaction solution to be less than 2, and stirring for 30min. Then centrifuging (10000 rpm) and cleaning (ethanol and ultrapure water) the sample, and finally drying in a vacuum freeze dryer for standby;
(6) Grinding adenine phosphate and a dried product in a ball mill according to a mass ratio of 0.5 to be uniformly mixed, then placing the mixture in a porcelain boat, carrying out high-temperature annealing in a quartz tube filled with mixed gas of 5% hydrogen and 95% argon, setting the temperature at 850 ℃, setting the heating rate at 5 ℃/min, fixing the annealing time at 1h, and naturally cooling to room temperature and taking out a sample;
(7) And carrying out acid washing treatment on the sample. The annealed sample was poured into 30mL of 0.5mol/L H 2 SO 4 Uniformly mixing under the ultrasonic action, and stirring in an oil bath at 60 ℃ for 18 hours under the protection of nitrogen;
(8) After the pickling was completed, the sample was centrifuged (10000 rpm) and washed (ultra-pure water) by cooling to room temperature, followed by drying in a vacuum freeze-dryer.
FIG. 1 is an XRD pattern of samples heat treated without and with adenine phosphate and with commercial 20% Pt/C (JM) catalyst at 0.06mmol of cobalt precursor in example 1. As can be seen from the figure, pt was produced when adenine phosphate was not added 3 Co intermetallic compounds; when adenine phosphate has been added, the resulting product is PtP 2 With Pt 3 The Co-existing composite catalyst can also be seen in fig. 3.
FIGS. 2 and 3 show the cobalt precursor of example 1 at 0.06mmol (Pt) 3 Co) and added (Pt 3 Co+PtP 2 ) EDX mapping graph of samples after adenine phosphate heat treatment. As can be seen from the figure, the catalyst of the present invention has good dispersibility and relatively uniform size, and has a particle diameter of about 10 nm.
FIG. 4 shows a sample (Pt) obtained by heat treatment with adenine phosphate at a cobalt precursor of 0.06mmol in example 1 3 Co+PtP 2 ) Linear scan plots with commercial 20% Pt/C (JM) catalysts, from which it is seen that the catalytic activity of the prepared samples is better than commercial 20% Pt/C (JM) catalysts.
Example 2
Co-supported Pt-based intermetallic compound and PtP on nitrogen-doped carbon 2 The preparation method of the composite nano catalyst comprises the following steps:
the following steps (2) to (5) and (7) were all carried out under argon atmosphere with magnetic stirring.
(1) 0.15mmol of platinum precursor and 0.10mmol of transition metal Mn precursor are added into 10mL of propylene glycol solvent, and magnetically stirred for 1h at room temperature;
(2) 100mg of ECP600JD carbon black was added to 30mL of propylene glycol solvent, and after the reflux apparatus was installed, the temperature was raised to 60℃and magnetically stirred at this temperature for 1h;
(3) Dropwise adding the solution obtained in the step (1) into the solution obtained in the step (2), stirring for 40min, adding 0.8mol/L alkaline substance (KOH is used in the embodiment) to adjust the pH value of the mixture to be more than 11, and continuously stirring for 1h at 60 ℃ under the protection of inert gas to form slurry carbon black suspension containing metal salt;
(4) To the suspension obtained in step (3) was added rapidly NaBH at a concentration of 3mmol/mL 4 Propylene glycol solution, after reacting for 25min, heating the temperature to 130 ℃, and reacting for 1h at the temperature;
(5) After the reaction, cooling to room temperature, adding 3mol/L HCl to adjust the pH of the reaction solution to be less than 2, and stirring for 30min. Then centrifuging (10000 rpm) and cleaning (ethanol and ultrapure water) the sample, and finally drying in a vacuum freeze dryer for standby;
(6) Grinding adenine phosphate and a dried product in a ball mill according to a mass ratio of 0.3 to be uniformly mixed, then placing the mixture in a porcelain boat, carrying out high-temperature annealing in a quartz tube filled with mixed gas of 5% hydrogen and 95% argon, setting the temperature to 750 ℃, setting the heating rate to 5 ℃/min, fixing the annealing time to 1h, and naturally cooling to room temperature and taking out a sample;
(7) And carrying out acid washing treatment on the sample. The annealed sample is poured into 30mL of 0.1mol/L HClO 4 Uniformly mixing under the ultrasonic action, and stirring in an oil bath at 60 ℃ for 24 hours under the protection of nitrogen;
(8) After the pickling was completed, the sample was centrifuged (10000 rpm) and washed (ultra-pure water) by cooling to room temperature, followed by drying in a vacuum freeze-dryer.
FIG. 5 shows a sample (Pt) obtained by heat treatment with adenine phosphate added when the manganese precursor was 0.10mmol in example 2 3 Mn+PtP 2 ) With commercial 20% Pt/C (JM) catalystLinear scan plot of the catalyst from the plot it is seen that the catalytic activity of the prepared samples is better than the commercial 20% Pt/C (JM) catalyst.

Claims (10)

1. A composite nano catalyst loaded on nitrogen-doped carbon is characterized in that nitrogen-doped carbon is used as a carrier, and Pt-M intermetallic compound and PtP are loaded on the carrier 2 Wherein M is a transition metal atom; the Pt-M intermetallic compound and PtP 2 The molar ratio of total platinum atoms to transition metal M atoms in the complex of (a) is 0.3 to 3, and the molar ratio of carbon in the carrier to transition metal M atoms is 1.7 to 37.5.
2. The composite nanocatalyst of claim 1 wherein the M comprises one of Fe, co, ni, mn, zn, cu, ti, in, pd, mo, ir, ru and Au.
3. The composite nanocatalyst of claim 1 wherein the carbon material in the support comprises one of carbon black, graphene, carbon nanotubes, graphene-carbon nanotube composites, carbon nanotube cups, annealed polypyrrole tubes, carbon aerogels, mesoporous carbon, carbon nanospheres, carbon nanocapsules, and carbon nanofibers.
4. The preparation method of the composite nano catalyst loaded on the nitrogen-doped carbon is characterized by comprising the following steps of:
(1) Grinding and mixing adenine phosphate and the dried carbon-supported Pt-M alloy according to the mass ratio of 0.2-1.0, sintering and annealing in a hydrogen-argon mixed atmosphere, wherein the sintering temperature is 600-1000 ℃, the heating rate is 5-10 ℃/min, the annealing time is 0.5-3 h, and taking out a sample after the temperature is reduced to room temperature;
(2) Carrying out acid washing treatment on the sample in an inert atmosphere;
(3) And after the pickling is finished, cooling to room temperature, centrifuging, cleaning and drying to obtain the finished product.
5. The method according to claim 4, wherein the synthesis of the carbon-supported Pt-M alloy is performed under the protection of an inert atmosphere, comprising the steps of:
(1) Adding a platinum precursor and a transition metal M precursor into an alcohol solution, and stirring at room temperature;
(2) Adding a carbon material into an alcohol solution, and carrying out reflux reaction;
(3) Dropwise adding the solution obtained in the step (1) into the solution obtained in the step (2), stirring at the reflux reaction temperature, adding alkali to adjust the pH to be more than 11, and continuously stirring at the reflux reaction temperature to form a suspension containing metal salt;
(4) Adding NaBH to the suspension obtained in the step (3) 4 Stirring the alcohol solution for 10-30 min at the reflux reaction temperature, then raising the temperature to 120-200 ℃, and stirring for 0.5-4 h;
(5) Cooling to room temperature after the reaction is finished, adding acid to adjust the pH to be less than 2, and stirring; centrifuging, cleaning, and drying.
6. The method of claim 5, wherein the molar ratio of the platinum precursor to the transition metal M precursor is 0.15:0.05 to 0.45, wherein the stirring time in the step (1) is 1 to 3 hours;
the concentration of the carbon material in the alcohol solution in the step (2) is 2-5 mg/mL, and the reaction time is 1-3 h;
in the step (3), the stirring time is 15-60 min before adding alkali to adjust the pH value, and the stirring time is 1-3 h after adding alkali to adjust the pH value; the concentration of the alkali is 0.1-1.0 mol/L;
the temperature of the reflux reaction in the step (2), the step (3) and the step (4) is 60-100 ℃;
NaBH in step (4) 4 The concentration in the solution is 2-4 mmol/mL;
the concentration of the acid in the step (5) is 1-5 mol/L, and the stirring time is 10-60 min.
7. The method according to claim 5, wherein the alcohol solution comprises at least one of ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerol;
the platinum precursor comprises one of potassium chloroplatinate, chloroplatinic acid, potassium chloroplatinite, hexahydroxyplatinate and platinum acetylacetonate;
the transition metal M precursor comprises one of nitrate, chloride, sulfate, acetate, acetylacetonate, oxalate and carbonate of transition metal M;
the alkali comprises at least one of KOH, naOH and ammonia water.
8. The method of claim 5, wherein the inert atmosphere comprises at least one of nitrogen, argon and helium.
9. The method according to claim 4, wherein the acid-washing solution comprises at least one of perchloric acid, sulfuric acid, nitric acid and hydrochloric acid.
10. Use of the composite nanocatalyst according to any of claims 1-3 or the composite nanocatalyst prepared by the method of preparation according to any of claims 4-9, characterized in that it is applied to catalysts for hydrogen oxygen fuel cells, metal-air cells or electrolyzed water cells.
CN202211584753.2A 2022-12-09 2022-12-09 Composite nano catalyst loaded on nitrogen-doped carbon and preparation method and application thereof Pending CN116093351A (en)

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