CN114904505A - For KBH 4 Composite catalyst for hydrogen production and preparation method thereof - Google Patents

For KBH 4 Composite catalyst for hydrogen production and preparation method thereof Download PDF

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CN114904505A
CN114904505A CN202210512131.2A CN202210512131A CN114904505A CN 114904505 A CN114904505 A CN 114904505A CN 202210512131 A CN202210512131 A CN 202210512131A CN 114904505 A CN114904505 A CN 114904505A
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hydrogen
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kbh
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CN114904505B (en
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王贵领
王显超
高一民
赵婧
温青
殷金玲
李峻青
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Heilongjiang Hachang Carbon Material Technology Co ltd
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Abstract

The invention provides a method for KBH 4 A composite catalyst for hydrogen production and a preparation method thereof belong to the technical field of catalyst preparation. The catalyst of the present invention comprises Ti 3 C 2 T x rGO support, carbon nanotubes and Co-N compounds, Ti 3 C 2 T x the/rGO carrier can anchor Co-N nano particles, and the defect-rich structure can effectively inhibit the agglomeration of metal nano particles and increase the active sites of the catalyst; n doping can play a role of an atom barrier, the surface area of the Co catalyst can be obviously increased by avoiding agglomeration, N can also be used as an electron donor to increase the electron density of Co, and thus the catalytic activity of Co is further improvedAnd (4) sex. Co-N/CNT/Ti 3 C 2 The open porous structure formed by Tx/rGO has good conductivity, which is beneficial to the diffusion of aqueous solution and the timely desorption and release of generated hydrogen.

Description

For KBH 4 Composite catalyst for hydrogen production and preparation method thereof
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a catalyst for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 Tx/rGO composite catalyst.
Background
The hydrogen energy source is wide, the energy density is high, and the product is green and environment-friendly, so the hydrogen energy source is considered as an effective substitute for solving the energy shortage, however, the development and the utilization of the hydrogen energy source still have many unsolved problems, such as the lack of a low-cost preparation method for the hydrogen gas, low prepared density and the flammability and explosiveness of the hydrogen gas. Among the numerous hydrogen storage materials, KBH 4 The characteristics of safe preservation, high hydrogen storage capacity and easy hydrogen production are widely concerned.
KBH 4 The solution is very stable in alkaline solutions, but under neutral acidic conditions, very slow hydrolysis can occur to release hydrogen. The solution is usually stored under alkaline conditions and, if desired, rapidly releases H 2 However, this requires a suitable catalyst. As early as the 50's of the 20 th century, cobalt chloride was found to accelerate NaBH 4 Hydrolysis of (2). In recent years, a novel graphene-like material MXene attracts great attention, the material can anchor metal nanoparticles due to the fact that the surface of the material is rich in a large number of-OH and-F functional groups, and the MXene has good surface hydrophilicity and is a very promising carrier material. Preparation of KBH by using material with Mxene structure as carrier 4 The catalyst for hydrogen production is the problem to be solved by the present application.
Disclosure of Invention
In view of the above, the present invention provides a method for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 Tx/rGO composite catalyst. The Co-N catalyst taking the Mxene graphene surface carbon nanotube array as the matrix makes up the defects that catalytic particles are easy to agglomerate and reactThe catalyst has the advantages of overcoming the defects of insufficient active sites, poor material conductivity and the like, solving the problems of slow hydrogen evolution rate and the like, being cheaper than the commonly used noble metal catalyst, and being widely used for realizing KBH in a controllable manner under mild conditions 4 And (4) hydrolyzing to prepare hydrogen.
The invention is used for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 Tx/rGO composite catalysts comprising Ti 3 C 2 T x a/rGO support, carbon nanotubes and Co-N compounds.
The Co-N/CNT/Ti 3 C 2 The preparation method of the Tx/rGO composite catalyst comprises the following steps:
(1) weighing Ti 3 C 2 T x And GO (graphene oxide) powder, respectively dissolving in deionized water, performing ultrasonic treatment under argon gas for 2 hours, centrifuging, collecting precipitate, freeze-drying, and adding Ti 3 C 2 T x And placing GO powder in a tube furnace porcelain boat, heating to 200 ℃ at a heating rate of 2 ℃/min under the atmosphere of hydrogen-argon mixed gas, preserving heat for 1h, and naturally cooling to room temperature to obtain Ti 3 C 2 T x a/rGO support;
(2) weighing the Ti prepared in the step (1) 3 C 2 T x dissolving/rGO carrier in methanol, and performing ultrasonic treatment for 1-2 h in argon atmosphere to obtain Ti 3 C 2 T x a/rGO suspension;
(3) weighing a Co-N compound, dissolving the Co-N compound in methanol, and stirring for 1h for dispersion to obtain a Co-N compound solution; dissolving 2-methylimidazole in methanol, adding CNT, and stirring until the CNT is completely dispersed to obtain a 2-methylimidazole solution;
(4) adding a Co-N compound solution to the Ti prepared in the step (2) 3 C 2 T x Stirring the rGO suspension for 1 hour, then quickly pouring a 2-methylimidazole solution, stirring for 7-8 hours under an argon atmosphere, centrifuging by using methanol, putting the suspension into a watch glass, and drying in vacuum at 70-80 ℃ to obtain black purple powder;
(5) heating the black purple powder in the step (4) to 700-800 ℃ at a heating rate of 2-3 ℃/min in the atmosphere of hydrogen-argon mixed gas, and preserving heat for 2-5 hours to obtain the Co-N/CNT/Ti 3 C 2 T x a/rGO catalyst.
Preferably, said Ti of step (1) 3 C 2 T x The mass ratio of the carbon to GO is 1-4: 1-3; the Ti 3 C 2 T x The mass volume ratio of the deionized water to the deionized water is 2: 1 mg/mL.
Preferably, the temperature of the freeze drying in the step (1) is-10 ℃ and the time is 48 hours.
Preferably, H in the hydrogen-argon mixture gas in the step (1) 2 :Ar＝1：9。
Preferably, said Ti of step (2) 3 C 2 T x The mass-to-volume ratio of/rGO to methanol is 8: 4-5 mg/mL.
Preferably, the Co-N compound in step (3) is Co (NO) 3 ) 2 ·6H 2 O, the mass volume ratio of the Co-N compound to the methanol is 2.5-3: 30-40 g/mL.
Preferably, the mass-to-volume ratio of the 2-methylimidazole to the methanol in the step (3) is 3-3.2: 30-40 g/mL, wherein the mass ratio of the 2-methylimidazole to the CNT is (300-310): 2 to 3.
Preferably, said Ti of step (4) 3 C 2 T x The volume ratio of the/rGO suspension to the Co-N compound solution to the 2-methylimidazole solution is 4-5: 3-4: 3 to 4.
Said for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 Tx/rGO composite catalyst with 3% KOH concentration, KBH 4 Hydrogen is catalytically produced in 2-5% concentration water solution.
The reaction equation is as follows:
KBH 4 +2H 2 O→KBO 2 +4H 2
the invention uses Co-N/CNT/Ti 3 C 2 T x catalyst/rGO in KOH and KBH 4 Hydrolyzing in the aqueous solution to obtain stable hydrogen gas, and separating out the hydrogen gas with high purity.
Compared with the prior art, the invention has the following beneficial effects:
prepared Co-N/CNT/Ti 3 C 2 T x catalyst/rGOWith Ti 3 C 2 T x the/rGO is used as a carrier, a CNT (carbon nano tube) array is grown on the surface, and Co-N (cobalt nitrogen) nano particles are uniformly distributed on the CNT/Ti 3 C 2 T x PerGO surface, Ti 3 C 2 T x The material is of an Mxene structure, the surface of the material is rich in a large number of-OH and-F functional groups, the surface of rGO and CNT is rich in a large number of-OH and-O functional groups, and Co-N nano particles can be anchored, and the defect-rich structure can effectively inhibit the agglomeration of metal nano particles and increase the active sites of a catalyst; the N doping can play a role of an atom barrier, the surface area of the Co catalyst can be obviously increased by avoiding agglomeration, and the N can also be used as an electron donor to increase the electron density of Co, so that the catalytic activity of Co is further improved. Co-N/CNT/Ti 3 C 2 T x The open porous structure formed by/rGO has good conductivity, and is beneficial to the diffusion of aqueous solution and the timely desorption and release of generated hydrogen.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
For KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 The Tx/rGO composite catalyst is prepared by the following steps:
(1) weighing 40mg of Ti 3 C 2 T x And 40mg of GO (graphene oxide), dissolving in 20mL of deionized water, performing ultrasonic treatment for 2 hours under argon gas, centrifuging, collecting precipitate, performing freeze drying at-10 ℃ for 48 hours, and adding Ti 3 C 2 T x And GO powder in a tube furnace porcelain boat in hydrogen-argon mixture (H) 2 Ar is 1: 9) heating to 200 ℃ at a heating rate of 2 ℃/min in the atmosphere, keeping for 1h, and naturally cooling to room temperature to obtain Ti 3 C 2 T x /rGO。
(2) Weighing 80mg of Ti in the step (1) 3 C 2 T x dissolving/rGO in 40mL of methanol, and performing ultrasonic treatment for 1h in argon atmosphere to obtain Ti 3 C 2 T x a/rGO suspension;
(3) mixing 2.91gCo (NO) 3 ) 2 ·6H 2 O solutionStirring in 30mL of methanol for 1h for dispersion; dissolving 3.08g of 2-methylimidazole in 30mL of methanol for complete dispersion, adding 20mg of CNT, and stirring until complete dispersion is achieved;
(4) mixing Co (NO) 3 ) 2 ·6H 2 Adding O solution into the Ti obtained in the step (2) 3 C 2 T x Stirring the rGO suspension for 1h, then quickly pouring a 2-methylimidazole solution, stirring for 8h under an argon atmosphere, centrifuging by using methanol, putting the suspension into a watch glass, and drying in vacuum for 24 h at 70 ℃ to obtain black purple powder;
(5) raising the temperature to 800 ℃ at the temperature rise rate of 2 ℃/min under the atmosphere of hydrogen-argon mixed gas, and preserving the temperature for 2 hours to obtain Co-N/CNT/Ti 3 C 2 T x a/rGO catalyst.
Application of the catalyst prepared in example 1 of the present invention to KBH 4 The method for preparing hydrogen by catalysis comprises the following steps: KBH at a KOH concentration of 3% 4 Adding Co-N/CNT/Ti when the concentration is 3% and the reaction temperature is 30 DEG C 3 C 2 T x The rGO is subjected to catalytic reaction to obtain the hydrogen evolution rate of 5400 mL-min -1 ·g -1 The activation energy of the reaction was 40.0 kJ. mol -1 。
Example 2
For KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 The Tx/rGO composite catalyst is prepared by the following steps:
(1) weighing 40mg of Ti 3 C 2 T x And 40mg of GO (graphene oxide), dissolving in 20mL of deionized water, performing ultrasonic treatment for 2 hours under argon gas, centrifuging, collecting precipitate, performing freeze drying at-10 ℃ for 48 hours, and adding Ti 3 C 2 T x And GO powder in a tube furnace porcelain boat in hydrogen-argon mixture (H) 2 Ar is 1: 9) heating to 200 ℃ at a heating rate of 2 ℃/min in the atmosphere, keeping for 1h, and naturally cooling to room temperature to obtain Ti 3 C 2 T x /rGO。
(2) Weighing 80mg of Ti in the step (1) 3 C 2 T x dissolving/rGO in 40mL of methanol, and performing ultrasonic treatment for 1h in argon atmosphere to obtain Ti 3 C 2 T x a/rGO suspension;
(3) mixing 2.91gCo (NO) 3 ) 2 ·6H 2 Dissolving O in 40mL of methanol, and stirring for 1h for dispersion; dissolving 3.08g of 2-methylimidazole in 40mL of methanol to completely disperse; then 30mgCNT is added and stirred until complete dispersion;
(4) mixing Co (NO) 3 ) 2 ·6H 2 Adding the solution of O into the Ti in the step (2) 3 C 2 T x Stirring the rGO suspension for 1h, then quickly pouring a 2-methylimidazole solution, stirring for 8h under the argon atmosphere, centrifuging by using methanol, putting the suspension into a watch glass, and drying in vacuum for 12 h at the temperature of 80 ℃ to obtain black purple powder;
(5) raising the temperature to 800 ℃ at the temperature rise rate of 2 ℃/min under the atmosphere of hydrogen-argon mixed gas, and preserving the temperature for 2 hours to obtain Co-N/CNT/Ti 3 C 2 T x a/rGO catalyst.
KBH of catalyst prepared in example 2 of the present invention 4 The method for preparing hydrogen by catalysis comprises the following steps: KBH at a KOH concentration of 3% 4 Adding Co-N/CNT/Ti when the concentration is 3% and the reaction temperature is 30 DEG C 3 C 2 T x The catalytic reaction is carried out on/rGO, and the obtained hydrogen evolution rate is 5261 mL-min -1 ·g -1 The activation energy of the reaction was 45.0 kJ. mol -1 。
Example 3
For KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 The Tx/rGO composite catalyst is prepared by the following steps:
(1) weighing 40mg of Ti 3 C 2 T x And 30mg of GO (graphene oxide), dissolving in 20mL of deionized water, performing ultrasonic treatment for 2 hours under argon gas, centrifuging, collecting precipitate, performing freeze drying at-10 ℃ for 48 hours, and adding Ti 3 C 2 T x And GO powder in a tube furnace porcelain boat in hydrogen argon gas (H) 2 Ar is 1: 9) heating to 200 ℃ at a heating rate of 2 ℃/min in the atmosphere, keeping for 1h, and naturally cooling to room temperature to obtain Ti 3 C 2 T x /rGO。
(2) Weighing 80mg of Ti in the step (1) 3 C 2 T x /rGO, dissolved in 50mL of methanol,performing ultrasonic treatment for 2 hours in argon atmosphere to obtain Ti 3 C 2 T x a/rGO suspension;
(3) mixing 2.91gCo (NO) 3 ) 2 ·6H 2 Dissolving O in 30mL of methanol, and stirring for 1h for dispersion; dissolving 3.08g of 2-methylimidazole in 30mL of methanol to completely disperse; then adding 20mgCNT and stirring to completely disperse;
(4) mixing Co (NO) 3 ) 2 ·6H 2 Adding the solution of O into the Ti in the step (2) 3 C 2 T x Stirring the rGO suspension for 1h, then quickly pouring a 2-methylimidazole solution, stirring for 8h under an argon atmosphere, centrifuging by using methanol, putting the suspension into a watch glass, and drying in vacuum for 24 h at 70 ℃ to obtain black purple powder;
(5) raising the temperature to 700 ℃ at the temperature rise rate of 2 ℃/min under the atmosphere of hydrogen-argon mixed gas, and preserving the temperature for 5 hours to obtain Co-N/CNT/Ti 3 C 2 T x a/rGO catalyst.
KBH of catalyst prepared in inventive example 3 4 The method for preparing hydrogen by catalysis comprises the following steps: KBH at a KOH concentration of 3% 4 Adding Co-N/CNT/Ti when the concentration is 3% and the reaction temperature is 30 DEG C 3 C 2 T x The catalytic reaction is carried out on the/rGO to obtain the hydrogen evolution rate of 5095 mL-min -1 ·g -1 The activation energy of the reaction was 47.5 kJ. mol -1 。
Comparative example 1
KBH at a KOH concentration of 3% 4 When the concentration is 3 percent and the reaction temperature is 30 ℃, adding Co 3 O 4 Carrying out catalytic reaction to obtain the hydrogen evolution rate of 3447 mL/min -1 ·g -1 The activation energy of the reaction was 65.0 kJ. mol -1 。
Comparative example 2
KBH at a KOH concentration of 3% 4 When the concentration is 3% and the reaction temperature is 30 ℃, adding Fe-B alloy (boron content is 1-5%) to perform catalytic reaction, and obtaining the hydrogen evolution rate of 1590 mL/min -1 ·g -1 The activation energy of the reaction was 87.0 kJ. mol -1 。
Comparative example 3
At a KOH concentration of 3%，KBH 4 When the concentration is 3% and the reaction temperature is 30 ℃, adding RuNi (ruthenium content is 1-5%) of ruthenium-nickel alloy to perform catalytic reaction, and obtaining the hydrogen evolution rate of 4321 mL/min -1 ·g -1 The activation energy of the reaction was 48.0 kJ. mol -1 。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. For KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 Tx/rGO composite catalyst, characterized in that it comprises Ti 3 C 2 T x a/rGO support, carbon nanotubes and Co-N compounds.
2. The method of claim 1 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 The preparation method of the Tx/rGO composite catalyst is characterized by comprising the following steps:
(1) weighing Ti 3 C 2 T x And GO powder, respectively dissolving in deionized water, performing ultrasonic treatment under argon gas for 2 hours, centrifuging, collecting precipitate, freeze drying, and adding Ti 3 C 2 T x And placing GO powder in a tube furnace porcelain boat, heating to 200 ℃ at a heating rate of 2 ℃/min under the atmosphere of hydrogen-argon mixed gas, preserving heat for 1h, and naturally cooling to room temperature to obtain Ti 3 C 2 T x a/rGO support;
(2) weighing the Ti prepared in the step (1) 3 C 2 T x dissolving/rGO carrier in methanol, and performing ultrasonic treatment for 1-2 h in argon atmosphere to obtain Ti 3 C 2 T x a/rGO suspension;
(3) weighing a Co-N compound, dissolving the Co-N compound in methanol, and stirring for 1h for dispersion to obtain a Co-N compound solution; dissolving 2-methylimidazole in methanol, adding CNT, and stirring until the CNT is completely dispersed to obtain a 2-methylimidazole solution;
(4) adding Co-N compound solution into the step (2) to prepareTi of (A) 3 C 2 T x Stirring the rGO suspension for 1 hour, then quickly pouring a 2-methylimidazole solution, stirring for 7-8 hours under an argon atmosphere, centrifuging by using methanol, putting the suspension into a watch glass, and drying in vacuum for 12-24 hours at 70-80 ℃ to obtain black purple powder;
(5) heating the black purple powder in the step (4) to 700-800 ℃ at a heating rate of 2-3 ℃/min in the atmosphere of hydrogen-argon mixed gas, and preserving heat for 2-5 hours to obtain the Co-N/CNT/Ti 3 C 2 T x a/rGO catalyst.
3. Use according to claim 2 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 T x The preparation method of the/rGO composite catalyst is characterized in that the Ti in the step (1) is 3 C 2 T x The mass ratio of the carbon to GO is 1-4: 1-3; the Ti 3 C 2 T x The mass volume ratio of the deionized water to the deionized water is 2: 1 mg/mL.
4. Use according to claim 2 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 T x The preparation method of the/rGO composite catalyst is characterized in that the temperature of the freeze drying in the step (1) is-10 ℃ and the time is 48 hours.
5. Use according to claim 2 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 T x The preparation method of the/rGO composite catalyst is characterized in that the H in the hydrogen-argon mixed gas in the step (1) 2 :Ar＝1：9。
6. The method of claim 2 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 T x The preparation method of the/rGO composite catalyst is characterized in that the Ti in the step (2) is 3 C 2 T x The mass-to-volume ratio of/rGO to methanol is 8: 4-5 mg/mL.
7. Use according to claim 2 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 T x The preparation method of the/rGO composite catalyst is characterized in that the Co-N compound in the step (3) is Co (NO) 3 ) 2 ·6H 2 O, the mass volume ratio of the Co-N compound to the methanol is 2.5-3: 30-40 g/mL.
8. Use according to claim 2 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 T x The preparation method of the/rGO composite catalyst is characterized in that the mass-volume ratio of the 2-methylimidazole to the methanol in the step (3) is 3-3.2: 30-40 g/mL, wherein the mass ratio of the 2-methylimidazole to the CNT is (300-310): 2 to 3.
9. Use according to claim 2 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 T x The preparation method of the/rGO composite catalyst is characterized in that the Ti in the step (4) is 3 C 2 T x The volume ratio of the/rGO suspension to the Co-N compound solution to the 2-methylimidazole solution is 4-5: 3-4: 3 to 4.
10. The method of claim 1 for KBH 4 Hydrogen-producing Co-N/CNT/Ti 3 C 2 T x The application of the/rGO composite catalyst is characterized in that the KBH with the KOH concentration of 3 percent 4 Hydrogen is catalytically produced in 2-5% concentration water solution.
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