CN115928096A - Bimetallic alloy/nitride heterojunction structure catalyst and preparation method thereof - Google Patents

Bimetallic alloy/nitride heterojunction structure catalyst and preparation method thereof Download PDF

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CN115928096A
CN115928096A CN202111641105.1A CN202111641105A CN115928096A CN 115928096 A CN115928096 A CN 115928096A CN 202111641105 A CN202111641105 A CN 202111641105A CN 115928096 A CN115928096 A CN 115928096A
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nitride
alloy
transition metal
metal salt
catalyst
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曹澥宏
牛昕欣
刘文贤
毋芳芳
施文慧
尹瑞连
郑冬
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New Materials Research Institute Of Zhejiang University Of Technology Pinghu City
Zhejiang University of Technology ZJUT
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New Materials Research Institute Of Zhejiang University Of Technology Pinghu City
Zhejiang University of Technology ZJUT
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Abstract

The invention relates to the technical field of nano materials, in particular to a bimetallic alloy/nitride heterojunction structure catalyst and a preparation method thereof, wherein a MOF derived trimetal organic framework is subjected to high-temperature nitridation and etching treatment to obtain a bimetallic alloy/nitride heterojunction structure; setting M 1 M 2 The MOF-derived bimetallic alloy/nitride template is M, which is the metal in the bimetallic alloy/nitride heterojunction structure 1 M 2 The structure of the bimetal alloy-nitride heterojunction is Etch-M 1 M 2 and/MoN. The preparation process is simple, mild and universal, and has no special requirements on equipment; the bimetal alloy/nitride prepared by the method has the advantages of uniform size, stable structure and uniform component distribution, and shows better three-function catalytic activity.

Description

Bimetallic alloy/nitride heterojunction structure catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a bimetallic alloy/nitride heterojunction structure catalyst and a method for preparing a bimetallic alloy/nitride heterojunction structure by utilizing a MOF derived trimetal organic framework.
Background
Nanomaterials of heterojunction structure have attracted the attention of extensive research due to their excellent physicochemical properties. The construction of the heterostructure catalyst not only can improve the adsorption/activation speed of the interface active material, but also is beneficial to the transmission of electrons between different components, which is very beneficial to improving the electrocatalytic activity. To date, many studies have demonstrated that various heterostructure electrocatalysts exhibit better electrocatalytic activity.
Disclosure of Invention
The invention provides a method for preparing a bimetal alloy/nitride heterojunction structure by utilizing an MOF derived trimetal organic framework, aiming at overcoming the problem that the preparation process of the traditional heterojunction structure is complex, and the preparation process is simple, mild and universal.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a bimetal alloy/nitride heterojunction structure by utilizing an MOF derived trimetal organic framework is characterized in that the MOF derived trimetal framework structure is subjected to high-temperature nitridation and etching treatment to obtain the bimetal alloy/nitride heterojunction structure; setting M 1 M 2 Is the metal in the bimetal alloy-nitride heterojunction structure, the MOF derived bimetal alloy/nitride is M 1 M 2 /MoN。
Metal-organic frameworks (MOFs) are crystals with a porous network structure formed by combining Metal ions and organic ligands, have a highly ordered pore structure, have a larger specific surface area, and contact more active sites. The invention uses MOF to derive trimetal organic framework M 1 M 2 The Mo-MOF isPrecursor of, wherein M 1 M 2 Obtaining the Etch-M for the bimetal alloy in the target bimetal alloy/nitride heterojunction structure after high-temperature nitridation and acid etching treatment 1 M 2 and/MoN. The obtained bimetal alloy-nitride has uniform structure size, stable structure and uniform component distribution. The preparation method disclosed by the invention is simple to operate, mild in condition and capable of realizing large-scale preparation. The stability of the obtained bimetallic alloy/nitride heterojunction structure catalyst with the alloy phase is far superior to that of a catalyst prepared by a single metal.
The invention provides a bimetallic alloy/nitride heterojunction structure catalyst, which is prepared by the following method:
(1) Adding transition metal salt M 1 Transition metal salt M 2 Dissolving molybdate and 2-methylimidazole in deionized water, stirring and reacting for 6-12h (preferably for 8h at 120 ℃) in a Teflon reaction kettle at 100-160 ℃, and performing aftertreatment A on the obtained reaction liquid to obtain M 1 M 2 a/Mo-MOF material; the transition metal salt M 1 Transition metal salt M 2 The transition metals are different and are respectively and independently one of copper salt, zinc salt, iron salt, magnesium salt, aluminum salt, cobalt salt and nickel salt; the transition metal salt M 1 And transition metal salt M 2 In a ratio of 0.1 to 10:1 (preferably 1:1), the transition metal salt M 1 And transition metal salt M 2 Is in a ratio of 0.2 to 5:1 (preferably 1:1), the ratio of the amount of 2-methylimidazole to molybdate species is 1 to 5:1 (preferably 2.53;
(2) M prepared in the step (1) 1 M 2 Placing the/Mo-MOF material in a tube furnace, heating to 500-700 deg.C (preferably 600 deg.C) under protective atmosphere (such as inert gas or nitrogen atmosphere) at a rate of 2-10 deg.C (preferably 5 deg.C), adding melamine, and calcining for 1-3h (preferably 2 h) to obtain M 1 M 2 A MoN-derived bimetallic alloy-nitride precursor; the M is 1 M 2 The mass ratio of the/Mo-MOF material to melamine is 1:3-10 (preferably 1:5);
(3) Subjecting M described in step (2) 1 M 2 [ MoN ] derivationPutting the bimetal alloy-nitride precursor into 0.1-1M (preferably 0.5M) sulfuric acid solution for ultrasonic etching for 30s-90s (preferably 60 s), and carrying out post-treatment on the obtained mixture to obtain the bimetal alloy/nitride heterojunction structure catalyst, namely the final product Etch-M 1 M 2 /MoN。
Preferably, the molybdate in step (1) is sodium molybdate.
Preferably, the volume of the deionized water in the step (1) is 10 to 50L/mol (preferably 22L/mol) based on the amount of the molybdate substance.
Specifically, the post-treatment A in the step (1) is as follows: cooling the reaction solution to room temperature, centrifuging, centrifugally washing the obtained precipitate with deionized water, and drying (preferably vacuum drying at 60 ℃ for 12 h) to obtain the M 1 M 2 A/Mo-MOF material.
Preferably, the dissolving in step (1) is: adding transition metal salt M 1 And transition metal salt M 2 Dissolving in a portion of deionized water, dissolving molybdate and 2-methylimidazole in another portion of deionized water, and mixing the resulting aqueous solutions.
Further, the post-treatment B in the step (3) is: and centrifuging the mixture, centrifuging and washing the obtained precipitate with deionized water (3 times), and drying to obtain the bimetallic alloy/nitride heterojunction structure catalyst.
The invention also provides an application of the bimetallic alloy/nitride heterojunction structure catalyst in electrocatalytic reaction.
The MOFMOF-derived trimetal organic framework is prepared by simple hydrothermal method preparation of trimetal MOF through high-temperature nitridation and acid etching treatment. The MOF obtained by a hydrothermal method is stable in structure and uniform in size, and the bimetal alloy-nitride obtained after calcination and etching is uniform in size and stable in structure. Water soluble salt solution of M such as Co (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O, and other nitrates, and the like.
Therefore, compared with the prior art, the invention has the following beneficial effects:
(1) The preparation process is simple, mild and universal;
(2) The bimetal alloy-nitride heterojunction prepared by the method has the advantages of uniform size, stable structure and uniform component distribution, and shows excellent HER (hydrogen evolution), OER (oxygen evolution) and ORR (oxygen reduction) performances.
Drawings
FIG. 1 is an XRD spectrum of Etch-CoFe/MoN prepared in example 1.
FIG. 2 is a graph of HER performance testing of the Etch-CoFe/MoN multilevel structure prepared in example 1.
FIG. 3 is an OER performance test chart of the Etch-CoFe/MoN multilevel structure prepared in example 1.
FIG. 4 is an ORR performance test chart of the Etch-CoFe/MoN multilevel structure prepared in example 1.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Adding 25ml deionized water into a dry Teflon reaction kettle, and weighing 0.4545g Fe (NO) 3 ) 3 ·9H 2 O
(0.001125 mol) and 0.327g Co (NO) 3 ) 2 ·6H 2 O (0.001125 mol) was poured into deionized water and dissolved by sonication. Another clean beaker is taken and added into 25ml of deionized water, and 0.544g of Na is weighed 2 MoO 4 (0.00225 mol) and 0.468g of 2-methylimidazole (0.0057 mol) were poured into deionized water and dissolved by sonication. Adding the solution in the beaker into the solution in the Teflon reaction kettle. And raising the temperature to 120 ℃ by a forced air oven, stirring and reacting for 8 hours, and naturally cooling to room temperature after the reaction is stopped. Centrifugally washing with deionized water, repeating for three times, and performing vacuum drying at 60 ℃ for 12 hours to obtain CoFe/Mo-MOF;
(2) Taking 0.1g of CoFe/Mo-MOF, placing the CoFe/Mo-MOF in a boat-shaped crucible, placing the crucible in the middle of a quartz tube, and then adding the mixture of melamine: weighing 0.5g of melamine, placing the melamine in a boat-shaped crucible, placing the crucible at the front end of a quartz tube, heating the crucible to 600 ℃ in a tube furnace in a nitrogen atmosphere, pushing melamine powder in the crucible, and nitriding the melamine powder at the high temperature of 600 ℃ for 2 hours at the heating rate of 5 ℃/min to obtain CoFe/MoN crystal powder, wherein the mass ratio of the CoFe/Mo-MOF is 5:1;
(3) 20mg of CoFe/MoN crystal powder was put in a clean container, and 2ml of 0.5mol/L H was added 2 SO 4 And (3) reacting the solution in an ultrasonic pool for 1min, transferring the product into a centrifuge tube after the reaction is finished, centrifugally washing the product by using deionized water, repeating the washing for 3 times, and then drying the product in a vacuum oven at 60 ℃ for 12h to obtain the catalyst with the Etch-CoFe/MoN heterojunction structure.
The CoFe/MoN crystalline powder obtained in example 1, the Etch-CoFe/MoN heterojunction structure, was characterized as follows:
(1) Wide angle XRD analysis:
the XRD test was performed on an X' Pert Pro X-ray diffractometer, and the samples to be tested were prepared as follows: coFe/MoN crystal powder and Etch-CoFe/MoN heterojunction structure powder in example 1 were respectively spread in square frosted grooves on a quartz plate, and the powder was pressed and flattened by a glass slide for testing.
FIG. 1 shows the wide-angle XRD spectra of CoFe/MoN crystal powder and Etch-CoFe/MoN heterojunction structure powder prepared in example 1, and shows that the obtained CoFe/MoN crystal material and the obtained Etch-CoFe/MoN crystal material both have good crystallinity, and diffraction peaks and Fe in the images 11 Co 5 The alloy standard card (PDF # 04-014-6030) is consistent, and the successful synthesis of Fe is proved 11 Co 5 And (3) an alloy material. Diffraction peak and Mo in the figure 1.67 N 2 The standard card (PDF # 04-007-3359) is consistent, and the successful synthesis of Mo is proved 1.67 N 2 The materials prove that the CoFe/MoN crystal structure is successfully synthesized, and the Etch-CoFe/MoN material still has consistent composition after etching.
(2) And (3) testing hydrogen evolution performance:
as can be seen from FIG. 2, the hydrogen evolution performance test was conducted in 1M KOH at a current density of 10mA/cm 2 In this case, the overpotential of commercial Pt/C is 15mV, whereas that of the Etch-CoFe/MoN multi-stage structure obtained in example 1 is 162mV, which is inferior to that of commercial materialsCan, but exhibit better hydrogen evolution performance than reported trifunctional catalyst materials.
(3) And (3) oxygen evolution performance test:
as can be seen from FIG. 3, the oxygen evolution performance test was performed in 1M KOH, and the current density reached 10mA/cm 2 Commercial RuO 2 The potential of (1) was 1.627V, while that of the Etch-CoFe/MoN multi-stage structure obtained in example 1 was 1.569V, which is comparable to commercial RuO 2 The low concentration of 58mV shows excellent oxygen evolution performance.
(4) And (3) testing oxygen reduction performance:
as can be seen from FIG. 4, the oxygen reduction performance test in 0.1M KOH showed superior oxygen reduction performance with the peak start potential of 1.02V and the half-wave potential of 0.89V for commercial Pt/C, while the peak start potential of 0.909V and the half-wave potential of 0.824V for the Etch-CoFe/MoN multi-stage structure obtained in example 1.
Example 2
(1) Adding 25ml deionized water into a dry Teflon reaction kettle, and weighing 0.4545g Fe (NO) 3 ) 3 ·9H 2 O (0.001125 mol) and 0.327g Ni (NO) 3 ) 2 ·6H 2 O (0.001125 mol) was poured into deionized water and dissolved by sonication. Another clean beaker is taken and added into 25ml of deionized water, and 0.544g of Na is weighed 2 MoO 4 (0.00225 mol) and 0.468g (0.0057 mol) of 2-methylimidazole are poured into deionized water and dissolved by ultrasound. Adding the solution in the beaker into the solution in the Teflon reaction kettle. And raising the temperature to 120 ℃ by using a blast oven, stirring and reacting for 8 hours, and naturally cooling to room temperature after the reaction is stopped. Centrifugally washing with deionized water, repeating for three times, and vacuum drying at 60 ℃ for 12h to obtain NiFe/Mo-MOF
(2) Taking 0.13g of NiFe/Mo-MOF, placing the NiFe/Mo-MOF in a boat-shaped crucible, placing the crucible in the middle of a quartz tube, and then adding melamine: weighing 0.65g of melamine, placing the melamine in a boat-shaped crucible, placing the crucible at the front end of fluorescence, heating to 600 ℃ in a tube furnace in a nitrogen atmosphere, pushing melamine powder in the boat-shaped crucible, and nitriding at 600 ℃ for 2h at the high temperature at the heating rate of 5 ℃/min to obtain NiFe/MoN crystal powder, wherein the mass ratio of NiFe/Mo-MOF is 5:1;
(3) Putting 20mg of NiFe/MoN crystal powder into a clean container2ml of H with a concentration of 0.5mol/L are added to a vessel 2 SO 4 And (3) reacting the solution in an ultrasonic pool for 1min, transferring the product into a centrifuge tube after the reaction is finished, centrifugally washing the product by using deionized water, repeating the washing for 3 times, and then drying the product in a vacuum oven at 60 ℃ for 12h to obtain the catalyst with the Etch-NiFe/MoN heterojunction structure.
The NiFe/MoN crystalline powder obtained in example 1, the Etch-NiFe/MoN heterojunction structure, was characterized as follows:
(1) Wide angle XRD analysis
The XRD test was performed on an X' Pert Pro X-ray diffractometer, and the samples to be tested were prepared as follows: niFe/MoN crystal powder and Etch-NiFe/MoN heterojunction structure powder in example 1 were spread in square frosted grooves on a quartz plate, and the test was performed by pressing and flattening with a glass slide.
FIG. 1 shows the wide-angle XRD spectra of the NiFe/MoN crystal powder and the Etch-NiFe/MoN heterojunction structure powder prepared in example 1, and shows that the obtained NiFe/MoN crystal material and the Etch-NiFe/MoN crystal material both have good crystallinity, and diffraction peaks in the images are consistent with NiCo alloy standard cards (PDF # 21-0868), thereby proving that the NiCo alloy material is successfully synthesized. Diffraction peak and Mo in the figure 1.67 N 2 The standard card (PDF # 45-0031) is consistent, and the successful synthesis of Mo is proved 1.67 N 2 The materials prove that the NiFe/MoN crystal structure is successfully synthesized, and the Etch-NiFe/MoN material still has consistent composition after etching.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the scope of the present invention as set forth in the claims.

Claims (10)

1. A bimetallic alloy/nitride heterojunction structure catalyst, characterized in that the catalyst is prepared as follows:
(1) Adding transition metal salt M 1 Transition metal salt M 2 Dissolving molybdate and 2-methylimidazole in deionized water, stirring and reacting for 6-12h in a Teflon reaction kettle at 100-160 ℃, and carrying out aftertreatment A on the obtained reaction liquid to obtain M 1 M 2 /Mo-a MOF material; the transition metal salt M 1 Transition metal salt M 2 The transition metals are different and are respectively and independently one of copper salt, zinc salt, iron salt, magnesium salt, aluminum salt, cobalt salt and nickel salt; the transition metal salt M 1 And transition metal salt M 2 In an amount of 0.1 to 10:1, the transition metal salt M 1 And transition metal salt M 2 Of the total amount of substances to molybdate in a ratio of 0.2 to 5:1, the mass ratio of the 2-methylimidazole to molybdate is 1-5:1;
(2) The M prepared in the step (1) is 1 M 2 Putting the/Mo-MOF material in a tube furnace, heating to 500-700 ℃ at the speed of 2-10 ℃ in a protective atmosphere, adding melamine, and continuously calcining for 1-3h to obtain the M 1 M 2 A MoN-derived bimetallic alloy-nitride precursor; the M is 1 M 2 The mass ratio of the/Mo-MOF material to the melamine is 1:3-10;
(3) Subjecting M described in step (2) 1 M 2 Putting the/MoN derived bimetallic alloy-nitride precursor into 0.1-1M sulfuric acid solution for ultrasonic etching for 30-90 s, and carrying out aftertreatment B on the obtained mixture to obtain the bimetallic alloy/nitride heterojunction structure catalyst.
2. The bimetallic alloy/nitride heterostructure catalyst of claim 1, wherein: the molybdate in the step (1) is sodium molybdate.
3. The bimetallic alloy/nitride heterostructure catalyst of claim 1, wherein: the volume of the deionized water in the step (1) is 10-50L/mol based on the amount of molybdate substances.
4. The bimetal alloy/nitride heterojunction structure catalyst of claim 1, wherein: the protective atmosphere is inert gas or nitrogen.
5. The bimetallic alloy/nitride heterostructure catalyst of claim 1, wherein:the transition metal salt M 1 And transition metal salt M 2 The ratio of the amounts of substances (1): 1.
6. the bimetallic alloy/nitride heterostructure catalyst of claim 1, wherein: the transition metal salt M 1 And transition metal salt M 2 Is in a ratio of 1:1.
7. the bimetallic alloy/nitride heterostructure catalyst of claim 1, wherein: the mass ratio of 2-methylimidazole to molybdate was 2.53.
8. The bimetallic alloy/nitride heterostructure catalyst of claim 1, wherein: the post-treatment A in the step (1) is as follows: cooling the reaction solution to room temperature, centrifuging, centrifugally washing the obtained precipitate with deionized water, and drying to obtain the M 1 M 2 A/Mo-MOF material.
9. The bimetal alloy/nitride heterojunction structure catalyst of claim 1, wherein said post-treatment B in step (3) is: and centrifuging the mixture, centrifuging and washing the obtained precipitate with deionized water, and drying to obtain the bimetallic alloy/nitride heterojunction structure catalyst.
10. Use of the bimetal alloy/nitride heterojunction structure catalyst of claim 1 in electrocatalytic reactions.
CN202111641105.1A 2021-12-29 2021-12-29 Bimetallic alloy/nitride heterojunction structure catalyst and preparation method thereof Pending CN115928096A (en)

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