CN115198301A - Defect-rich transition metal nano-structure catalyst and preparation method thereof - Google Patents

Defect-rich transition metal nano-structure catalyst and preparation method thereof Download PDF

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CN115198301A
CN115198301A CN202210907545.5A CN202210907545A CN115198301A CN 115198301 A CN115198301 A CN 115198301A CN 202210907545 A CN202210907545 A CN 202210907545A CN 115198301 A CN115198301 A CN 115198301A
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transition metal
defect
rich
electrode
binder
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杜高辉
韩迪
苏庆梅
许并社
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier

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Abstract

The invention belongs to the field of nano material preparation, and discloses a preparation method of a defect-rich transition metal nanostructured catalyst, which comprises the following steps: weighing a transition metal compound and a binder, adding the transition metal compound and the binder into N-methylpyrrolidone, and mixing to form a black solution; dropwise adding the black solution onto a current collector, and carrying out vacuum drying to obtain a dried pole piece; the electrode plate is used as an electrode, the alkaline metal plate is used as a counter electrode, and a solution containing Li ions is used as an electrolyte and is assembled in a double-electrode electrolytic cell; connecting the double electrodes to two ends of a resistor, and driving electrons and ions to migrate by chemical energy of the double electrodes to carry out reduction reaction until the reaction is finished; and cleaning the reacted electrode, and drying in vacuum to obtain the defect-rich transition metal nano-structure catalyst. The prepared transition metal nano structure is composed of 2-8 nm metal nano crystals, the defect atom ratio is 30-50%, and the transition metal nano structure has high electro-catalytic activity and good stability.

Description

Defect-rich transition metal nano-structure catalyst and preparation method thereof
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a defect-rich transition metal nano structure catalyst and a preparation method thereof.
Background
With the continuous consumption of fossil energy and the increasing environmental pollution, it is necessary to find efficient clean energy. Hydrogen gas is an ideal choice as both a clean energy source and an energy storage carrier due to its excellent energy density, high energy conversion efficiency, renewability, and zero pollution characteristics. At present, platinum (Pt) based materials are ideal and efficient catalysts for electrolyzing water to generate hydrogen. However, the low reserves and high costs of precious metal materials limit their further widespread use.
The transition metal-based catalyst is used as a potential water electrolysis catalyst material, and has the advantages of low cost, environmental friendliness, rich resources, various types, rich electronic layer structures, variable valence states and the like, and the like. Among the numerous transition metal-based catalysts, single metals or transition metal alloys have incomparable electrical conductivity and excellent intrinsic activity. However, metal elements are inevitably oxidized, and it is difficult to obtain uniform-sized nanocrystals by high-temperature synthesis, so that the catalytic activity of the transition metal nanostructure is reduced.
In order to solve the problem, the synthesis of the transition metal nanocrystalline with metal defects can increase active sites, and the metal defects can improve the electronic structure of the nanostructure, accelerate electron transfer, improve the catalytic activity of the catalyst and enhance the stability of the structure. However, it is difficult to prepare a catalyst containing many metal defects by hydrothermal growth, etching, dealloying, ion intercalation, etc., and the synthesis process requires high cost and causes some environmental pollution.
Disclosure of Invention
The invention aims to provide a defect-rich transition metal nanostructured catalyst and a preparation method thereof, and solves the problems that the existing preparation method cannot synthesize a catalyst containing a plurality of metal defects and cannot obtain nanocrystals with uniform size easily.
In order to realize the purpose, the invention is realized by the following technical scheme:
a method for preparing a defect-rich transition metal nanostructured catalyst comprising the steps of:
1) Weighing a transition metal compound and a binder, adding the transition metal compound and the binder into N-methylpyrrolidone, and mixing and stirring to form a black solution; wherein, the mass percentage of the transition metal compound is 70 percent to 98 percent, and the mass percentage of the binder is 2 percent to 30 percent;
2) Dropwise adding the black solution onto a current collector, and carrying out vacuum drying for 6-24 h at the temperature of 60-120 ℃ to obtain a dried pole piece;
3) The dried pole piece is used as an electrode, the alkaline metal piece is used as a counter electrode, and a solution containing Li ions is used as an electrolyte and is assembled in a double-electrode electrolytic cell;
4) Connecting the double electrodes to two ends of a resistor of 500-3000 omega, and driving electrons and ions to migrate by chemical energy of the double electrodes to carry out reduction reaction until the reaction is finished;
5) And cleaning the reacted electrode, and drying in vacuum to obtain the defect-rich transition metal nano-structure catalyst.
Further, in step 1), the transition metal compound is a transition metal oxide, a transition metal sulfide, a transition metal hydroxide, or a transition metal halide.
Further, the transition metal is Fe, co, ni, cu, mo or Zn element.
Further, in the step 1), the binder is polyvinylidene fluoride, polyacrylic acid, carboxymethyl chitosan, polypropylene or polyvinyl alcohol.
Further, in the step 1), stirring is carried out for 5-48 h.
Further, in the step 2), the current collector is a foam metal, a metal sheet or a carbon cloth.
Further, in the step 3), the alkali metal sheet is a lithium sheet, a sodium sheet or a potassium sheet.
The invention also discloses a transition metal nanostructured catalyst rich in defects, which is prepared by the preparation method, wherein the interior of the transition metal nanostructured catalyst is composed of uniform metal nanocrystals, the size of the metal nanocrystals is 2-8 nm, and the atomic proportion of the defects in the transition metal nanostructured catalyst is 30-50%.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a defect-rich transition metal nanostructure, which is obtained by carrying out reduction reaction between an electrode plate made of a transition metal compound and a binder and an alkaline metal plate electrode through self-driven electron and ion migration of chemical energy. The size of the transition metal nanocrystalline prepared by chemical energy self-driving is uniformly distributed at 3-8 nm, and the electrode slice is cleaned after reaction to remove alkaline metal, so that a clean metal surface can be obtained without an oxide layer; the transition metal nano structure has 30 to 50 percent of defect atoms, which can optimize the electronic structure and the electro-catalysis performance of the material; the obtained metal nano structure is attached to a current collector, can be directly applied to electrocatalytic water decomposition, and avoids the problem that the performance is reduced due to oxidation of the active surface of metal or organic matter wrapping in the electrode preparation process of the traditional powder catalytic material. Therefore, compared with the metal nano structure synthesized by other methods, the product of the invention has higher catalytic activity and good electrocatalytic stability. The preparation method of the transition metal nano structure disclosed by the invention has the advantages of controllable material structure, simple process, no need of conventional synthesis equipment and no need of external energy for exciting reaction, and is easy for large-scale production and application. The invention provides a chemical energy-driven reduction method which has low cost and energy consumption and is convenient for batch production, and the synthesized transition metal nano structure not only has uniform and fine size, but also has high proportion of metal defect atoms, namely the electrochemical specific surface area is increased, and the catalytic activity is improved.
The advantages and the characteristics of the invention are as follows: 1) The reaction at room temperature can prevent the metal crystal grains from rapidly aggregating and growing up at high temperature, thereby obtaining the superfine metal nano structure with uniform size; 2) By utilizing the characteristic of slow crystallization kinetics at room temperature, abundant surface and interface defects can be formed, so that the coordination number is changed, the surface stress is formed, the electronic structure and the hydrogen adsorption Gibbs free energy of metal are changed, and the excellent electro-catalysis characteristic is created; 3) The direct products of the reduction reaction are superfine metal nanocrystalline and alkaline oxide, the alkaline oxide can prevent the oxidation of the metal surface from reducing the performance during storage, and the fresh and clean metal surface and active sites can be exposed only by washing to remove the alkaline oxide during use; 4) Although similar to conventional electrochemical preparation on a reaction apparatus, the mechanism is different; the reaction driving force is potential difference formed by different chemical energy of the reaction driving force and is not external potential; the inherent chemical energy driving force diminishes as the reaction proceeds, which has the advantage of spontaneously slowing the reaction rate (ion mobility and metal growth rate) and promoting the formation of ultra-fine nanocrystals and a large number of defect atoms.
The size of the nanocrystalline in the transition metal prepared by the method is about 2-8 nm, the transition metal has a large electrochemical surface area and 30-50% of surface interface defect atoms, and the transition metal has high catalytic activity and good electrochemical stability. The preparation method has the advantages of simple and convenient process, no need of using conventional synthesis equipment and external energy, easy mass production, low energy consumption and low cost.
Drawings
FIG. 1 is an XRD pattern of iron nanostructures prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of cobalt nanostructures made in example 2 of the present invention;
FIG. 3 is an XRD pattern of nickel nanostructures made in example 3 of the present invention;
FIG. 4 is an XRD pattern of copper nanostructures made in example 4 of the present invention;
FIG. 5 is an XRD pattern of molybdenum nanostructures made in example 5 of the present invention;
FIG. 6 is a TEM image of iron nanostructures prepared in example 1 of the present invention;
FIG. 7 is a TEM image of cobalt nanostructures prepared in example 2 of the present invention;
FIG. 8 is a TEM image of nickel nanostructures prepared in example 3 of the present invention;
FIG. 9 is a TEM image of a copper nanostructure prepared in example 4 of the present invention;
FIG. 10 is a TEM image of a molybdenum nanostructure prepared in example 5 of the present invention;
FIG. 11 shows the result of the electro-catalytic hydrogen evolution performance test of the metal nanostructure prepared by the method of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The invention discloses a preparation method of a defect-rich transition metal nano structure, which comprises the following steps:
(1) 0.21g of iron oxide Fe was weighed out separately 2 O 3 0.09g of PVDF, 5mL of NMP was added, and the mixture was stirred for 5 hours to form a black solution.
(2) Dropwise adding the black solution onto the foamed nickel, and controlling the loading amount to be 5mg/cm 2 And vacuum drying for 12h at 80 ℃.
(3) Cutting the dried electrode plate into a circular sheet with the radius of 0.8cm to be used as a positive electrode, taking a lithium sheet as a counter electrode, and taking 1M LiPF 6 The bipolar cell was assembled as an electrolyte.
(4) The chemical energy self-driven reaction was started by connecting the two electrodes with a 3000 Ω resistor.
(5) And after the reaction is finished, taking out the electrode slice, cleaning the electrode slice by using deionized water, and finally drying the electrode slice in vacuum for 12 hours at the temperature of 60 ℃ to obtain the iron nanostructure rich in defects.
As shown in FIG. 1, fe after discharge corresponds exactly to the PDF card of Fe in jade (PDF # 85-1410), indicating Fe 2 O 3 Has been completely reduced.
FIG. 6 is Fe 2 O 3 In the TEM image after discharge, the particle diameter is about 2nm, and it is obvious that there are many defects between particles, and the atom ratio of the defects inside is about 50%.
The reaction equation of the present invention is M x O y +Li→y/2Li 2 O + xM, wherein M x O y Represents a transition metal oxide.
Example 2
The invention discloses a preparation method of a defect-rich transition metal nano structure, which comprises the following steps:
(1) 0.225g of cobalt oxide CoO and 0.075g of polyvinyl alcohol PVA were weighed out separately and 5.5mL of N-methylpyrrolidone NMP were added, after which stirring was carried out for 48h to give a black solution.
(2) Dripping black solution on the copper foil, and controlling the loading amount to be 5mg/cm 2 And vacuum drying for 12h at 80 ℃.
(3) Cutting the dried pole piece into a circular sheet with the radius of 0.8cm to be used as a positive electrode, taking a lithium piece as a counter electrode, and taking 1M LiPF 6 The bipolar cell was assembled as an electrolyte.
(4) The chemical energy self-driven reaction was started by connecting the two electrodes with a resistance of 2500 Ω.
(5) And after the reaction is finished, taking out the pole piece, cleaning the pole piece by using deionized water, and finally drying the pole piece in vacuum for 12 hours at the temperature of 80 ℃ to obtain the cobalt nanostructure rich in defects.
As shown in FIG. 2, the discharged Co completely corresponds to the PDF card (PDF # 89-4307) of Co in jade, indicating that the CoO has been completely reduced.
FIG. 7 is a TEM image of CoO reaction, and the particle diameter is about 4nm, and it is clear that there are many defects between particles, and the atomic ratio of the internal defects is about 42%.
Example 3
The invention discloses a preparation method of a defect-rich transition metal nano structure, which comprises the following steps:
(1) 0.24g of nickel oxide NiO and 0.06g of polyacrylic acid PAA were weighed, respectively, and 6mL of N-methylpyrrolidone NMP was added, followed by stirring for 10 hours to form a black solution.
(2) Dripping black solution on carbon cloth, and controlling the loading amount to be 3mg/cm 2 And vacuum drying for 6h at 120 ℃.
(3) Taking the dried pole piece as an electrode, taking a lithium piece as a counter electrode and taking 1M LiPF 6 The bipolar electrolytic cell was assembled as an electrolyte.
(4) The chemical energy self-driven reaction was started by connecting the two electrodes with a 2000 Ω resistor.
(5) And after the reaction is finished, taking out the pole piece, cleaning the pole piece by using deionized water, and finally drying the pole piece in vacuum for 12 hours at the temperature of 70 ℃ to obtain the nickel nanostructure rich in defects.
As shown in FIG. 3, the discharged Ni corresponds exactly to the PDF card (PDF # 70-1849) of Ni in jade, indicating that NiO has been completely reduced.
FIG. 8 is a TEM image after NiO reaction, and the particle diameter is about 6nm, and it is clear that there are many defects between particles, and the atom ratio of the internal defects is about 40%.
Example 4
The invention discloses a preparation method of a defect-rich transition metal nano structure, which comprises the following steps:
(1) 0.255g of copper oxide (CuO) and 0.045g of carboxymethyl chitosan were weighed, respectively, and 6.5mL of N-methylpyrrolidone NMP was added, followed by stirring for 12 hours to form a black solution.
(2) Dropwise adding the black solution onto the foamed nickel, and controlling the loading amount to be 7mg/cm 2 And vacuum drying for 12h at 80 ℃.
(3) Taking the dried pole piece as an electrode, taking a lithium piece as a counter electrode and taking 1M LiPF 6 The bipolar cell was assembled as an electrolyte.
(4) The chemical energy self-driven reaction was started by connecting the two electrodes with a 1500 Ω resistor.
(5) And after the reaction is finished, taking out the pole piece, cleaning the pole piece by using deionized water, and finally drying the pole piece in vacuum for 12 hours at the temperature of 80 ℃ to obtain the copper nano structure rich in defects.
As shown in FIG. 4, the discharged Cu corresponds exactly to the PDF card (PDF # 70-3038) of Cu in jade, indicating that CuO has been completely reduced.
FIG. 9 is a TEM image of CuO after reaction, and the particle diameter is about 7nm, and it is apparent that there are many defects between particles and the atomic ratio of the internal defects is about 35%.
Example 5
The invention discloses a preparation method of a defect-rich transition metal nano structure, which comprises the following steps:
(1) 0.294g of molybdenum oxide MoO is weighed out separately 3 0.006g polyacrylonitrile PAN, 7.5mL N-methylpyrrolidone NMP was added followed by stirring for 12h to form a black solution.
(2) Dropwise adding the black solution onto the foamed nickel, and controlling the loading amount to be 5mg/cm 2 Vacuum drying for 24h at 70 deg.C.
(3) Taking the dried pole piece as an electrode, taking a lithium piece as a counter electrode and taking 1M LiPF 6 The bipolar cell was assembled as an electrolyte.
(4) The chemical energy self-driven reaction was started by connecting the two electrodes with a 500 Ω resistor.
(5) And after the reaction is finished, taking out the pole piece, cleaning the pole piece by using deionized water, and finally drying the pole piece in vacuum for 12 hours at the temperature of 80 ℃ to obtain the defect-rich molybdenum nanostructure.
As shown in FIG. 5, mo after discharge corresponds exactly to the PDF card of Mo in jade (PDF # 89-5023), which illustrates MoO 3 Has been completely reduced.
FIG. 10 is a MoO 3 The TEM image after reaction has a particle diameter of about 8nm, and obviously shows that many defects exist among particles, and the atom ratio of the defects inside the particles is about 30%.
As shown in FIG. 11a, ni has the highest performance compared to the over-point potentials of the five metals at high current densities, followed by Co, mo, cu, fe.
As shown in FIG. 11b, the concentration of Co, ni, fe, cu and Mo was 100mA/cm 2 The over-point potentials of (A) are 208mV, 152mV, 329mV, 315mV and 294mV, respectively.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.

Claims (8)

1. A method for preparing a defect-rich transition metal nanostructured catalyst, comprising the steps of:
1) Weighing a transition metal compound and a binder, adding the transition metal compound and the binder into N-methylpyrrolidone, and mixing and stirring to form a black solution; wherein, the mass percentage of the transition metal compound is 70-98 percent, and the mass percentage of the binder is 2-30 percent;
2) Dropwise adding the black solution onto a current collector, and performing vacuum drying at the temperature of 60-120 ℃ for 6-24 hours to obtain a dried pole piece;
3) The dried pole piece is used as an electrode, an alkaline metal piece is used as a counter electrode, a solution containing Li ions is used as an electrolyte, and the two-electrode electrolytic cell is assembled;
4) Connecting the double electrodes to two ends of a resistor of 500-3000 omega, and driving electrons and ions to migrate by chemical energy of the double electrodes to carry out reduction reaction until the reaction is finished;
5) And cleaning the reacted electrode, and drying in vacuum to obtain the defect-rich transition metal nano-structure catalyst.
2. The method of preparing a defect-rich transition metal nanostructured catalyst according to claim 1, wherein in step 1), the transition metal compound is a transition metal oxide, a transition metal sulfide, a transition metal hydroxide, or a transition metal halide.
3. The method of preparing a defect-rich transition metal nanostructured catalyst according to claim 2, wherein the transition metal is an element of Fe, co, ni, cu, mo or Zn.
4. The method of claim 1, wherein in step 1), the binder is polyvinylidene fluoride, polyacrylic acid, carboxymethyl chitosan, polypropylene or polyvinyl alcohol.
5. The method of claim 1, wherein the step 1) is performed by stirring for 5 to 48 hours.
6. The method of preparing a defect-rich transition metal nanostructured catalyst according to claim 1, wherein in step 2), the current collector is a metal foam, a metal sheet or a carbon cloth.
7. The method of preparing a defect-rich transition metal nanostructured catalyst according to claim 1, wherein in step 3), the alkali metal sheet is a lithium sheet, a sodium sheet, or a potassium sheet.
8. The transition metal nanostructured catalyst rich in defects prepared by the preparation method of any one of claims 1 to 7, characterized in that the interior of the transition metal nanostructured catalyst is composed of uniform metal nanocrystals, the size of the metal nanocrystals is 2 to 8nm, and the atomic proportion of defects in the interior is 30 to 50%.
CN202210907545.5A 2022-07-29 2022-07-29 Defect-rich transition metal nano-structure catalyst and preparation method thereof Pending CN115198301A (en)

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