CN113186566A - Preparation and hydrogen evolution application of metal organic framework and graphene composite material - Google Patents

Preparation and hydrogen evolution application of metal organic framework and graphene composite material Download PDF

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CN113186566A
CN113186566A CN202110491142.2A CN202110491142A CN113186566A CN 113186566 A CN113186566 A CN 113186566A CN 202110491142 A CN202110491142 A CN 202110491142A CN 113186566 A CN113186566 A CN 113186566A
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composite material
metal organic
organic framework
hydrogen evolution
graphene
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聂明
刀学林
孙海
薛真洪
赵振鑫
董炜
廖建明
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Southwest University
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Southwest University
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention relates to preparation and hydrogen evolution application of a metal organic framework and graphene composite material, belonging to the field of electrochemistry; the composite material is prepared by a solvothermal method for 24 hours under the conditions of high temperature and high pressure, and the steps of washing, centrifugal collection, drying and the like are carried out. The metal organic framework and graphene composite material prepared by the invention has excellent hydrogen evolution performance under alkaline conditions: in N2Overpotential (i.e. current density of-10 mA cm) of the composite material in saturated 1M KOH solution‑2Potential) was only 268mV, plus shifted by 425mV compared to the original MOF (Ni).

Description

Preparation and hydrogen evolution application of metal organic framework and graphene composite material
Technical Field
The invention belongs to the field of preparation technology and application of a metal organic framework and graphene composite material, and particularly relates to a preparation method of a composite material and application of the composite material in hydrogen evolution catalysis under an alkaline condition.
Background
With the development of society, the energy problem is receiving more and more attention. The search for a novel energy source which is pollution-free, large in energy and wide in utilization rate is urgent nowadays. Hydrogen is a renewable energy source, is widely concerned because of the advantages of no toxicity, large heat released by combustion, no pollution and the like, and is an ideal clean and high-energy fuel. The electrolysis of water to produce hydrogen is now considered to be the most efficient method of hydrogen production, and the development and use of catalysts with high catalytic activity to improve the efficiency of industrial production of hydrogen is the primary task in the hydrogen production industry today. Pt is the most common hydrogen evolution electrocatalyst, and has the advantages of low hydrogen evolution overpotential, high catalytic activity and the like, but Pt belongs to a noble metal, and the application of Pt in the hydrogen evolution industry is limited due to low storage capacity, high cost and the like. In the large-scale preparation process of hydrogen, the selection of a catalyst with high catalytic activity, low price and rich content to improve the hydrogen evolution efficiency is the current research focus.
Metal Organic Frameworks (MOFs) have the excellent characteristics of porosity, large specific surface area, structural and functional diversity, high degree of order and the like, so that they are hot spots in the current research field and have great application and research potential. Although the electrochemical performance of pure MOFs as a catalytic material is not high, the composite material obtained by doping graphene with good conductivity and high stability into MOF (Ni) shows superiority in electrochemical hydrogen evolution. The doping of the graphene enhances the conductivity of the material, increases the specific surface area of the composite material, and provides more active sites for hydrogen evolution reaction, so that the hydrogen evolution performance of the composite material under an alkaline condition is superior.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a preparation method of a metal organic framework and graphene composite material, which has the advantages of simple process flow, simple operation and low cost, and hydrogen evolution catalysis application of the metal organic framework and graphene composite material under an alkaline condition.
In order to achieve the purpose, the invention provides the following technical scheme:
1) adding a certain amount of nickel sulfate hexahydrate (NiSO)4·6H2O) and 1, 3, 5-trimesic acid (C)9H6O6) Is dissolved into
In a mixed solvent of N, N-dimethylformamide, deionized water and absolute ethyl alcohol, carrying out ultrasonic treatment and magnetic stirring to obtain a uniformly dispersed solution;
2) transferring the mixed solution in the step 1) to a reaction kettle, and reacting in an oven at 200 ℃ for 24 hours;
3) placing the mixed solution after the reaction in the step 2) into a centrifuge tube for centrifugation, taking a precipitate, washing the obtained precipitate by using absolute ethyl alcohol and deionized water, and then centrifugally collecting the precipitate;
4) drying the product obtained by centrifugation in the step 3) to obtain metal organic framework MOF (Ni);
5) ultrasonically dispersing a certain amount of graphene into the mixed solution obtained in the step 1), transferring the obtained mixed solution into a reaction kettle, and reacting in an oven at 200 ℃ for 24 hours;
6) placing the mixed solution after the reaction in the step 5) into a centrifuge tube for centrifugation, taking a precipitate, washing the obtained precipitate by using absolute ethyl alcohol and deionized water, and then centrifugally collecting the precipitate;
7) drying the product obtained by centrifuging in the step 6) to obtain the metal organic framework and graphene composite material;
8) the synthesized material was subjected to a hydrogen evolution test.
Preferably, the ratio of the mixed solvent of the N, N-dimethylformamide, the deionized water and the absolute ethyl alcohol in the step 1) is 1: 1: 1 (V: V: V).
Preferably, the centrifugation in the step 3) and the step 6) is specifically performed at a speed of 8000-12000r/min for 3 min.
Preferably, the drying in the step 4) and the step 7) is specifically drying at 60 ℃ for 6-12 h.
Preferably, the hydrogen evolution test in the step 8) is to use an electrochemical workstation to place the prepared material in N by adopting a three-electrode system2The linear sweep voltammetry test was performed in a saturated 1M KOH solution.
The invention has the beneficial effects that: the invention provides a preparation method of a metal organic framework and graphene composite material and application of the metal organic framework and graphene composite material in hydrogen evolution catalysis under an alkaline condition. When the metal organic framework is synthesized in the first step, the metal organic framework with a spherical state is synthesized by regulating and controlling the amount of the adopted raw materials, the reaction temperature, the reaction time and the composition of the solvent. According to the invention, when the metal organic framework and graphene composite material is prepared, graphene with a determined mass fraction is added into a mixed solution before the metal organic framework is synthesized through accurate calculation, so that the composite material is synthesized. Due to the fact that the graphene has the advantages of being good in conductivity and high in stability, the conductivity of the material can be effectively enhanced by doping the graphene with a proper mass fraction into the metal organic framework, and the transmission rate of electrons in the reaction process of the material is effectively improved. In addition, doping of graphene may improve the composite material
The specific surface area of the material is increased, so that more active sites are provided for the hydrogen evolution reaction, and the hydrogen evolution reaction is facilitated. Meanwhile, the interaction between graphene and metal organic framework mof (ni) particles in the composite material can also affect the properties of the material. Therefore, the composite material has excellent hydrogen evolution performance under alkaline conditions. The hydrogen evolution performance of the material can be known through a test of a linear sweep voltammetry curve (LSV), and the more positive the hydrogen evolution potential of the electrode is, the higher the hydrogen evolution activity is under the same condition. The metal organic framework and graphene composite material prepared by the invention is N2Overpotential of the composite material (i.e., current density of-10 mA cm) in saturated 1M KOH solution-2Potential) is 268mV, which is shifted forward by 425mV compared with a pure metal organic framework (693mV), and the hydrogen evolution performance is improved by 2.6 times.
In conclusion, the composite material of the metal organic framework and the graphene prepared by the invention has good hydrogen evolution performance under an alkaline condition, and a feasible scheme is provided for the design of a hydrogen evolution catalyst.
Drawings
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings, in which:
FIG. 1 is an X-ray powder diffraction pattern (XRD) of example 1(MOF (Ni) -GR (4%)) and comparative example 1(MOF (Ni));
FIG. 2 is a Scanning Electron Microscope (SEM) image of example 1 and comparative example 1;
FIG. 3 is an X-ray spectral analysis (EDS) of example 1;
fig. 4 is a Linear Sweep Voltammogram (LSV) of example 1 and comparative example 1.
FIG. 1 is an X-ray powder diffraction (XRD) pattern of example 1(MOF (Ni) -GR (4%)) and comparative example 1(MOF (Ni)). The diffraction peaks of example 1 and comparative example 1 were sharp, and no impurity peak was observed. In addition, in the embodiment 1, only the position at 26.3 degrees of 2 θ is added with one more characteristic peak of graphene relative to the comparative example 1, and the positions of the rest diffraction peaks are consistent. The invention can be demonstrated that the composite material of the metal organic framework and the graphene is successfully synthesized.
Fig. 2 is a Scanning Electron Microscope (SEM) image of example 1 and comparative example 1. It can be seen from the figure that the metal organic framework prepared in comparative example 1 is a spherical substance (fig. 2, a), and the graphene in the composite material prepared in example 1 has a sheet-like structure and is uniformly distributed around the metal organic framework (fig. 2, b).
FIG. 3 is an X-ray spectral analysis (EDS) chart of example 1. The elemental composition of the prepared sample can be analyzed through an energy spectrum, and the composite material is mainly composed of C, O and Ni, so that the prepared composite material is pure, and graphene is successfully compounded with a metal organic framework.
Fig. 4 is a graph of the scanning linear voltammograms (LSV) of example 1 and comparative example 1. In N2Overpotential of the composite material (i.e., current density of-10 mA cm) in saturated 1M KOH solution-2Potential) is 268mV, which is shifted forward by 425mV compared with a pure metal organic framework (693mV), and the hydrogen evolution performance is improved by 2.6 times.
Detailed Description
The following examples are further elaborated on the invention and are not to be understood as limiting the technical solutions.
Example 1
The preparation method and the hydrogen evolution application of the metal organic framework MOF (Ni) and graphene composite material in the embodiment 1 comprise the following specific steps:
1) 0.8g of nickel sulfate hexahydrate (NiSO)4·6H2O) is dissolved in 10ml of deionized water and is subjected to ultrasonic treatment for 20 min;
2) 0.3162g of trimesic acid (C)9H6O6) Dissolving in a mixed solvent of 10ml ethanol and 10ml N, N-dimethylformamide, and subjecting to ultrasonic treatment for 20 min;
3) slowly dripping the solution obtained in the step 2) into the solution obtained in the step 1) under the stirring of a magnetic stirrer, and keeping stirring for 10-20min to uniformly mix the solution;
4) transferring the mixed solution obtained in the step 3) to a reaction kettle, and reacting in an oven at 200 ℃ for 24 hours;
5) centrifugally washing the product obtained in the step 4) by using absolute ethyl alcohol and deionized water, repeating for 2-3 times, and centrifuging for 3min at a speed of 8000 r/min;
6) putting the product obtained in the step 5) in a drying oven at 60 ℃ for drying for 12h to obtain metal organic framework MOF (Ni);
7) subjecting the mof (ni) to a hydrogen evolution electrochemical test;
8) adding 0.0465g of graphene into the mixed solution in the step 3), and performing ultrasonic treatment for 20min to uniformly disperse the graphene;
9) transferring the mixed solution obtained in the step 8) to a reaction kettle, and reacting in an oven at 200 ℃ for 24 hours;
10) centrifugally washing the product obtained in the step 9) by using absolute ethyl alcohol and deionized water, repeating for 2-3 times, and centrifuging for 3min at a speed of 8000 r/min;
11) drying the product obtained in the step 10) in an oven at 60 ℃ for 12h to obtain a composite material MOF (Ni) -GR (4%) of the metal organic framework MOF (Ni) and the graphene;
12) MOF (Ni) -GR (4%) was subjected to hydrogen evolution electrochemical tests.
Comparative example 1
The preparation method and the hydrogen evolution application of the metal organic framework mof (ni) in the comparative example 1 comprise the following specific steps:
1) 0.8g of nickel sulfate hexahydrate (NiSO)4·6H2O) is dissolved in 10ml of deionized water and is subjected to ultrasonic treatment for 20 min;
2) 0.3162g of trimesic acid (C)9H6O6) Dissolving in a mixed solvent of 10ml ethanol and 10ml N, N-dimethylformamide, and subjecting to ultrasonic treatment for 20 min;
3) slowly dripping the solution obtained in the step 2) into the solution obtained in the step 1) under the stirring of a magnetic stirrer, and keeping stirring for 10-20min to uniformly mix the solution;
4) transferring the mixed solution obtained in the step 3) to a reaction kettle, and reacting in an oven at 200 ℃ for 24 hours;
5) centrifugally washing the product obtained in the step 4) by using absolute ethyl alcohol and deionized water, repeating for 2-3 times, and centrifuging for 3min at a speed of 8000 r/min;
6) putting the product obtained in the step 5) in a drying oven at 60 ℃ for drying for 12h to obtain metal organic framework MOF (Ni);
7) mof (ni) was subjected to hydrogen evolution electrochemical test.
Various advantages and effects of the present invention can be easily understood by those skilled in the art from the content of the present specification, and the above-mentioned embodiments are only for further detailed description of the present invention and should not be understood as a limitation to the technical solution, and modifications or equivalent substitutions of the technical solution of the present invention within the spirit and scope of the present invention should be included in the protection scope of the claims of the present invention.
The invention is not the best known technology.

Claims (5)

1. The preparation and hydrogen evolution application of the metal organic framework and graphene composite material are characterized in that: the preparation method comprises the following steps:
1) adding a certain amount of nickel sulfate hexahydrate (NiSO)4·6H2O) and 1, 3, 5-trimesic acid (C)9H6O6) Dissolving the mixture into a mixed solvent of N, N-dimethylformamide, deionized water and absolute ethyl alcohol, and obtaining a uniformly dispersed solution through ultrasonic treatment and magnetic stirring;
2) transferring the mixed solution obtained in the step 1) to a reaction kettle, and reacting in an oven at 200 ℃ for 24 hours;
3) placing the mixed solution after the reaction in the step 2) into a centrifuge tube, centrifuging, taking a precipitate, washing the obtained precipitate, and drying to obtain the metal organic framework MOF (Ni);
4) ultrasonically dispersing a certain amount of graphene into the mixed solution obtained in the step 1), transferring the obtained mixed solution into a reaction kettle, and reacting in an oven at 200 ℃ for 24 hours;
5) placing the mixed solution after the reaction in the step 4) in a centrifuge tube, centrifuging to obtain a precipitate, washing the obtained precipitate, and drying to obtain the metal organic framework and graphene composite material;
6) the synthesized material was subjected to a hydrogen evolution test.
2. The method according to claim 1, wherein the ratio of the mixed solvent of N, N-dimethylformamide, deionized water and absolute ethyl alcohol in step 1) is 1: 1: 1 (V: V: V).
3. The method as claimed in claim 1, wherein the centrifugation in step 3) and step 5) is performed at a speed of 8000-.
4. The method according to claim 1, wherein the drying in step 3) and step 5) is carried out at 60 ℃ for 6-12 h.
5. The method according to claim 1, wherein the hydrogen evolution test in step 6) is carried out by placing the prepared material in a three-electrode system using an electrochemical workstation under N2Carrying out linear sweep voltammetry curve test in saturated 1M KOH solution; the prepared composite material of the metal organic framework and the graphene has excellent hydrogen evolution performance under alkaline conditions: in N2Overpotential of the composite material (i.e., current density of-10 mA cm) in saturated 1M KOH solution-2Of the hourPotential) was only 268mV, plus shifted by 425mV compared to the original MOF (Ni).
CN202110491142.2A 2021-05-06 2021-05-06 Preparation and hydrogen evolution application of metal organic framework and graphene composite material Pending CN113186566A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114614032A (en) * 2022-03-18 2022-06-10 江苏索普化工股份有限公司 Anode composite nano catalyst material of methanol fuel cell and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114614032A (en) * 2022-03-18 2022-06-10 江苏索普化工股份有限公司 Anode composite nano catalyst material of methanol fuel cell and preparation method and application thereof

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