CN112591754A - Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite - Google Patents

Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite Download PDF

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CN112591754A
CN112591754A CN202011562320.8A CN202011562320A CN112591754A CN 112591754 A CN112591754 A CN 112591754A CN 202011562320 A CN202011562320 A CN 202011562320A CN 112591754 A CN112591754 A CN 112591754A
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molybdenum
molybdenum carbide
quantum dot
carbide quantum
carbon
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CN112591754B (en
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杜建平
赵瑞花
杜倩倩
郭天宇
李晋平
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Taiyuan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Abstract

The invention discloses a preparation method of a carbon nanocage coupled molybdenum carbide quantum dot nanocomposite, which comprises the following steps: (1) dissolving acid and ammonium molybdate in a mass ratio of 100 (14-25) in deionized water to form 26-45 g/L ammonium molybdate solution, stirring for 3-4 h to obtain molybdenum-containing hydrogel, and then drying in an oven at 80-120 ℃ for 0.5-5 h to obtain a molybdenum xerogel precursor; (2) and placing the precursor in a tube furnace, heating at the speed of 5 ℃/min, and carrying out constant-temperature treatment for 2 hours at the temperature of 850-950 ℃ in an inert atmosphere to obtain the composite material of the carbon nanocage dispersed molybdenum carbide quantum dots. The composite material of the carbon nano cage dispersed molybdenum carbide quantum dots prepared by the invention has the advantages of simple preparation process, convenient operation and easy control of process parameters, and the novel carbide composite material is obtained and can be applied to the field of hydrogen production catalysis.

Description

Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a preparation method of a carbon nanocage-coupled molybdenum carbide quantum dot nanocomposite.
Background
Metal carbides are a new class of functional materials with high hardness, high melting point, good thermal stability and corrosion resistance, and have found applications in many fields. In the 90 s of the 20 th century, Ledoux et al reported that metal carbides have noble metal-like properties, and it is believed that in metal carbides, carbon atoms fill in the metal lattice, causing a change in electron density, leading to an increase in lattice parameter and lattice spacing, resulting in a contraction of the d-band and an increase in electron density in the fermi state, and thus have surface properties and absorption properties similar to those of noble metals. In recent years, carbides, particularly molybdenum carbide, have attracted much attention as a new class of catalytic materials. In terms of catalytic activity, molybdenum carbide is similar to a Pt group noble metal in many respects, and particularly, is equivalent to a noble metal such as Pt or Pd in terms of hydrogen evolution activity, and is expected to be a substitute for the noble metal.
With the progress of research, new methods for preparing molybdenum carbide are continuously proposed and verified. At present, the preparation methods of molybdenum carbide mainly comprise the following steps: 1. a temperature programmed reaction method, molybdenum oxide precursors are added into light hydrocarbon or light hydrocarbon/H2The mixed gas is heated and carbonized. The method is simple and easy to empty and the product is purer, but the method is easy to cause catalysisCarbonizing the surface area of the reagent, wherein the specific surface area of the obtained molybdenum carbide is smaller; 2. the method comprises the following steps of (1) carrying out a carbothermic reduction method, wherein molybdenum oxide and a proper amount of carbon carriers react in a protective atmosphere or a reducing atmosphere, and the obtained product has a large specific surface area, but the reaction temperature is usually high; 3. a solvent thermal reduction method, which adopts a substance (KBH) with strong reducing power4) The method is simple and easy to control, the temperature is low, but the product is impure; 4. the metal precursor cracking method is prepared by using a metal organic compound and a mixture of ammonium molybdate and hexamethylenetetramine for high-temperature cracking, but the precursor is complex to prepare, and the prepared particles are large. In addition, there are reports of CVD, hydrothermal method, ultrasonic method, microwave method, etc., but these methods also have problems of small yield, insufficient reaction, large product particles, and impure product. The above methods have limitations and inherent characteristics and have great disadvantages in practical applications, particularly in mass production of catalysts.
Disclosure of Invention
The invention aims to provide a novel composite catalytic material, and particularly relates to a preparation method of a carbon nanocage coupled molybdenum carbide quantum dot nanocomposite.
The invention is realized by adopting the following technical scheme:
a preparation method of a carbon nano cage coupling molybdenum carbide quantum dot nano composite material comprises the following steps:
(1) dissolving acid and ammonium molybdate in a mass ratio of 100 (14-25) in deionized water to form 26-45 g/L ammonium molybdate solution, stirring for 3-4 h to obtain molybdenum-containing hydrogel, and then drying in an oven at 80-120 ℃ for 0.5-5 h to obtain a molybdenum xerogel precursor;
(2) and placing the precursor in a tube furnace, heating at the speed of 5 ℃/min, and carrying out constant-temperature treatment for 2 hours at the temperature of 850-950 ℃ in an inert atmosphere to obtain the composite material of the carbon nanocage dispersed molybdenum carbide quantum dots.
Preferably, in step (1), the acid is tartaric acid or ascorbic acid.
The method utilizes the structural characteristic of polycarboxyl of organic acid, and molecules of the organic acid are connected by hydrogen bonds to form a three-dimensional network structure while coordinating with molybdate ions, so that bubbles are promoted to overflow by drying, the chain breaking of the hydrogen bonds is stabilized, and the three-dimensional fluffy precursor is obtained by reaction under mild conditions; under the condition of high-temperature treatment, the acid substance provides a carbon source to form a nano carbon cage, and molybdenum is carbonized in situ on the carbon cage to obtain the nano carbon quantum dot composite material.
The method avoids the formation of molybdenum oxide in the carbonization process by regulating and controlling the coordination of acid and molybdenum ions and optimizing the process.
The invention has reasonable design, the prepared composite material of the carbon nano cage dispersed molybdenum carbide quantum dots has simple preparation process, convenient operation and easy control of process parameters, and the novel carbide composite material is obtained, can be applied to the field of hydrogen production catalysis, and has good practical application and popularization prospect.
Drawings
Fig. 1a shows a scanning electron micrograph (500 nm) of a sample (three-dimensional carbon nanocage-dispersed molybdenum carbide quantum dot composite) prepared in example 1.
Fig. 1b shows a scanning electron micrograph (20 nm) of the sample (three-dimensional carbon nanocage dispersed molybdenum carbide quantum dot composite) prepared in example 1.
Fig. 2 shows an XRD pattern of the sample (three-dimensional carbon nanocage dispersed molybdenum carbide quantum dot composite) prepared in example 1.
Detailed Description
The following detailed description of specific embodiments of the invention refers to the accompanying drawings.
Example 1
A preparation method of a carbon nanocage coupled molybdenum carbide quantum dot nanocomposite material comprises the following steps:
1. 2.7g of tartaric acid and 0.68g of ammonium molybdate are dissolved in 15mL of deionized water to form 45g/L of ammonium molybdate solution, the solution is stirred for 3h to obtain molybdenum-containing hydrogel, and then the molybdenum-containing hydrogel is placed in an 80 oven to be dried for 0.5 to obtain a molybdenum xerogel precursor.
2. And (3) placing the precursor in a tube furnace, heating at the speed of 5 ℃/min, and carrying out constant-temperature treatment for 2 hours at the temperature of 850 ℃ in an inert atmosphere to obtain the composite material of the carbon nanocage dispersed molybdenum carbide quantum dots.
As can be seen from fig. 1a and 1b, the resulting composite material is composed of nano-particles of uniform particle size in the form of carbon nanocages.
As can be seen from fig. 2, the composite material in which the molybdenum carbide quantum dots are dispersed on the carbon nanocages having a size of about 100 nm is obtained.
The sample prepared in example 1 shows high catalytic activity in the alkaline medium of the electrochemical hydrogen evolution reaction, at 10mA/cm2The overpotential of (3) is 157 mV.
Example 2
A preparation method of a carbon nanocage coupled molybdenum carbide quantum dot nanocomposite material comprises the following steps:
1. 2.7g of tartaric acid and 0.5g of ammonium molybdate are dissolved in 15mL of deionized water to form 33g/L of ammonium molybdate solution, the solution is stirred for 3.5h to obtain molybdenum-containing hydrogel, and then the molybdenum-containing hydrogel is placed in an oven at 100 ℃ to be dried for 2.5 to obtain a molybdenum xerogel precursor.
2. And (3) placing the precursor in a tube furnace, heating at the speed of 5 ℃/min, and carrying out constant-temperature treatment for 2 hours at the temperature of 900 ℃ in an inert atmosphere to obtain the composite material of the carbon nanocage dispersed molybdenum carbide quantum dots.
The sample prepared in example 2 shows high catalytic activity in the alkaline medium of the electrochemical hydrogen evolution reaction, at 10mA/cm2The overpotential of (2) is 160 mV.
Example 3
A preparation method of a carbon nanocage coupled molybdenum carbide quantum dot nanocomposite material comprises the following steps:
1. 2.7g of tartaric acid and 0.39g of ammonium molybdate are dissolved in 15mL of deionized water to form 26g/L of ammonium molybdate solution, the solution is stirred for 4 hours to obtain molybdenum-containing hydrogel, and then the molybdenum-containing hydrogel is placed in an oven at 120 ℃ to be dried for 5 hours to obtain a molybdenum xerogel precursor.
2. And (3) placing the precursor in a tube furnace, heating at the speed of 5 ℃/min, and carrying out constant-temperature treatment for 2 hours at the temperature of 950 ℃ in an inert atmosphere to obtain the composite material of the carbon nanocage dispersed molybdenum carbide quantum dots.
The sample prepared in example 3 shows high catalytic activity in the alkaline medium of the electrochemical hydrogen evolution reaction, at 10mA/cm2The overpotential of (3) was 164 mV.
It should be noted that modifications and applications may occur to those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (5)

1. A preparation method of a carbon nano cage coupling molybdenum carbide quantum dot nano composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving acid and ammonium molybdate in a mass ratio of 100 (14-25) in deionized water to form 26-45 g/L ammonium molybdate solution, stirring for 3-4 h to obtain molybdenum-containing hydrogel, and then drying in an oven at 80-120 ℃ for 0.5-5 h to obtain a molybdenum xerogel precursor;
(2) and placing the precursor in a tube furnace, heating at the speed of 5 ℃/min, and carrying out constant-temperature treatment for 2 hours at the temperature of 850-950 ℃ in an inert atmosphere to obtain the composite material of the carbon nanocage dispersed molybdenum carbide quantum dots.
2. The method for preparing a carbon nanocage-coupled molybdenum carbide quantum dot nanocomposite material according to claim 1, wherein the method comprises the following steps: in the step (1), the acid is tartaric acid or ascorbic acid.
3. The method for preparing a carbon nanocage-coupled molybdenum carbide quantum dot nanocomposite material according to claim 1 or 2, wherein the method comprises the following steps: in the step (1), the mass ratio of tartaric acid to ammonium molybdate is 4: 1.
4. The method for preparing a carbon nanocage-coupled molybdenum carbide quantum dot nanocomposite material according to claim 3, wherein the method comprises the following steps: in the step (1), the concentration of the ammonium molybdate solution is 45 g/L.
5. The use of the carbon nanocage-coupled molybdenum carbide quantum dot nanocomposite prepared according to any one of claims 1 to 4 in electrochemical hydrogen evolution reactions.
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CN115029153A (en) * 2022-06-14 2022-09-09 湘潭大学 Method for preparing aviation kerosene by catalyzing biomass derivatives

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Publication number Priority date Publication date Assignee Title
CN115029153A (en) * 2022-06-14 2022-09-09 湘潭大学 Method for preparing aviation kerosene by catalyzing biomass derivatives
CN115029153B (en) * 2022-06-14 2023-08-15 湘潭大学 Method for preparing aviation kerosene by catalyzing biomass derivative

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