CN114752962A - Preparation and application of spider-nest-shaped composite carbon nanomaterial @ ruthenium nanoparticles - Google Patents

Preparation and application of spider-nest-shaped composite carbon nanomaterial @ ruthenium nanoparticles Download PDF

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CN114752962A
CN114752962A CN202210438584.5A CN202210438584A CN114752962A CN 114752962 A CN114752962 A CN 114752962A CN 202210438584 A CN202210438584 A CN 202210438584A CN 114752962 A CN114752962 A CN 114752962A
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CN114752962B (en
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蒋仲庆
郑辉
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Zhejiang Sci Tech University ZSTU
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Abstract

The invention belongs to the technical field of electrochemical hydrogen production, and particularly relates to a preparation method of a spider-nest-shaped composite carbon nano material @ ruthenium nano particle, which comprises (1) synthesis of an MOF-derived spider-nest-shaped composite carbon nano material; (2) preparation of MOF-derived spider-nest-shaped composite carbon nano-material @ ruthenium nano-particles. The MOF-derived spider-nest-shaped composite carbon nano material @ ruthenium nano particle prepared in the invention is applied as an electrochemical Hydrogen Evolution (HER) catalyst material, the ruthenium nano particle is loaded on the surface of the MOF-derived spider-nest-shaped composite carbon nano material, the surface mass transfer is obviously enhanced, the overpotential of the reaction is reduced, the catalyst performance and the electric conductivity are improved, and the overpotential and the cost are lower compared with platinum carbon in the HER reaction.

Description

Preparation and application of spider-nest-shaped composite carbon nanomaterial @ ruthenium nanoparticles
Technical Field
The invention belongs to the technical field of electrochemical hydrogen production, and particularly relates to a spider-nest-shaped composite carbon nano material @ ruthenium nano particle, a preparation method thereof and application thereof in electrochemical hydrogen production.
Background
With the growing concern over global climate change due to the traditional fossil fuel energy crisis and carbon emissions, efforts are being made to develop clean, environmentally friendly and sustainable energy sources. Hydrogen (H)2) The energy source has high weight energy density (146kJ g)-1) Rich in reserveThe advantages of sustainability, zero emission after combustion and the like are recognized as the most promising fossil fuel substitute in the future. Currently, the major methods of industrial hydrogen production include Coal Gasification (CG), Steam Methane Reforming (SMR), and Water Electrolysis (WE). CG and SMR conversion of methane and coal steam to H2And CO2In the whole H2The method has a market share of more than 95 percent in production, but the two methods have low conversion efficiency and CO2Large discharge amount, water pollution and the like, reduces the yield and purity of products and accelerates global warming. Hydrogen production by water electrolysis has the advantages of large-scale production of high-purity hydrogen, no carbon emission, sustainability, abundant water resources and the like, and therefore, the hydrogen production by water electrolysis receives more and more attention in the research and industrial fields in recent years. In particular for converting electrical energy into H2The fuel is an ideal way for storing intermittent renewable energy sources such as solar energy, wind energy and the like.
In water electrolysis, the Hydrogen Evolution Reaction (HER) is the key reaction that occurs at the cathode. The Oxygen Evolution Reaction (OER) is the core reaction process that occurs at the anode. The theoretical thermodynamic voltage of the HER process is only 0V vs RHE. However, the energy barrier accumulated by the reactions of various elements leads to slow reaction kinetics, and in practical applications higher overpotentials are often required to trigger the HER process. Thus, there is a need for highly efficient HER electrocatalysts to accelerate reaction kinetics and increase HER activity. The noble metal Pt has the best intrinsic catalytic activity on HER and has been considered as the benchmark electrocatalyst in Proton Exchange Membrane (PEM) water electrolysis. However, the low reserves, high costs and instability of Pt have greatly hindered its large-scale industrial application. Therefore, it is necessary and important to find efficient, low cost, durable non-Pt electrocatalysts.
Non-noble metal-based catalysts for HER and OER have been studied more extensively, such as carbides, nitrides, phosphides, sulfides and selenides of transition metal-based compounds, however, their catalytic activity and durability are still inferior to those of noble metal-based catalysts.
The cost of the metal Ru is about 4% of Pt, with 65kcal mol-1Has strong Pt-like hydrogen bond strength and strong corrosion resistance and neglected water dissociation energy barrier, so that the Pt-like hydrogen bond has PEM and alkaline performanceAnd (4) water electrolysis of the ion exchange membrane. To improve HER performance, various Ru-based catalysts were prepared by rational design of different nanostructures and modification of electronic properties. The heterogeneous heteroatom (N, P, S, B) doped carbon material also has hydrogen evolution activity, has close coordination with the Ru-based catalyst, and not only promotes the uniform loading of Ru-based particles, but also promotes water dissociation under alkaline conditions.
Disclosure of Invention
The invention prepares the nano material applied to the hydrogen evolution reaction electrode catalyst material by taking the spider-web-shaped iron-cobalt alloy nitrogen-doped carbon nano material with high specific surface area as a conductive network and taking ruthenium nano particles as a load.
In order to achieve the above object, the present invention provides a method for preparing a spider-nest-shaped composite carbon nanomaterial @ ruthenium nanoparticle, wherein the spider-nest-shaped composite carbon nanomaterial is a MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nanomaterial, the MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nanomaterial is a conductive network, and the ruthenium nanoparticle is a load, the method specifically comprises the following steps:
step one, synthesizing an MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material:
(1) synthesis of zinc-based zeolitic imidazolate framework (ZIF-8) particles by reacting a quantity of Zn (NO)3)2·6H2Mixing O methanol solution, 1-methylimidazole and 2-methylimidazole, stirring at room temperature for reaction, centrifuging and collecting, and washing with ethanol for several times;
(2) synthesizing FeOOH nano rod by taking a certain amount of FeCl3·6H2Adding O into a round-bottom flask filled with deionized water and Polyethyleneimine (PEI), and heating and reacting for 2 hours at 65-90 ℃ to obtain a uniform FeOOH nanorod;
(3) preparation of polyvinylpyrrolidone (PVP) functionalized FeOOH nano-rod: dispersing the FeOOH nano rod obtained in the step (2) in an ethanol solution of PVP, further stirring for 8-12 h at room temperature to obtain a PVP functionalized FeOOH nano rod, washing the PVP functionalized FeOOH nano rod for several times after centrifugal separation, and dispersing in methanol for later use;
(4) ZIF-8@ FeOOH/cobalt basePreparing zeolite imidazole ester framework material (ZIF-67) hybrid particles, namely dispersing the ZIF-8 particles prepared in the step (1) and PVP functionalized FeOOH nanorod suspension prepared in the step (3) in Co (NO) by ultrasonic waves3)2Quickly adding a methanol solution of 2-methylimidazole into a 6H2O solution, then stirring the mixture at room temperature for reaction, standing for 2 hours, centrifugally collecting, washing with methanol for several times, and drying in vacuum to obtain ZIF-8@ FeOOH/ZIF-67 hybrid particles;
(5) synthesizing a spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material (FeCoSG/NCNT): placing a certain amount of ZIF-8@ FeOOH/ZIF-67 mixed particles obtained in the step (4) in a ceramic boat, placing another ceramic boat above the ceramic boat and containing a nitrogen source organic matter, enabling argon and hydrogen to flow through the whole tube furnace, adopting a two-stage heating program, and cooling to room temperature after heating to obtain a spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material (FeCoSG/NCNT);
step two, preparing the MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material @ ruthenium nano particles: by immersing the spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material in RuCl3·xH2And (3) in the ethanol solution of O, standing for 5-8 hours after ultrasonic dispersion, transferring the ethanol solution to a vacuum oven for drying, and putting the dried sample in a tubular furnace to be reduced by introducing argon and hydrogen (7%) to realize the loading of the ruthenium nanoparticles.
Further, in the step (1) of the first step, the Zn (NO)3)2·6H2The substance concentration of O methanol solution is 20mM, Zn (NO)3)2·6H2The volume of the methanol solution of O is 180-250 mL; the mass fraction of the 1-methylimidazole is 99%, and the volume of the 1-methylimidazole is 2-3 mL; the mass concentration of the 2-methylimidazole methanol solution is 100mM, and the volume of the 2-methylimidazole methanol solution is 180-230 mL. Further, in the step (2) of the first step, the FeCl is3·6H2The mass of O is 5.46g, the volume of the deionized water is 100mL, and the volume of the Polyethyleneimine (PEI) is 0.1-0.5 mL.
Further, in the step (3), the volume of the PVP ethanol solution is 6-12 mL, wherein the mass fraction of PVP is 2% -8%; the volume of the methanol is 10-20 mL.
Further, in the step one (4), Co (NO)3)2·6H2The O methanol solution has a concentration of 18-25 mM of Co (NO)3)2·6H2The volume of the O methanol solution is 100-150 mL; the amount concentration of the 2-methylimidazole methanol solution is 120-200 mM, and the volume is 160-240 mL.
Further, in the step (5) of the first step, the heating rate in the first step of the two-step temperature-raising heating process is 5 ℃ for min-1Heating to 350 deg.C and maintaining for 60 min; the second stage is heating at a rate of 5 deg.C for min-1Then the first stage is heated to 800 ℃ and the temperature is kept for 2 h.
Further, the organic nitrogen source in step (5) is one or two of melamine or dicyandiamide, and the nitrogen-doped carbon nanotube grows by using a chemical vapor deposition method and is in a spider shape.
Further, in the second step, the RuCl is added3·xH2The content of ruthenium in O is more than 37 percent, FeCoSG/NCNT and RuCl3·xH2The mass ratio of O is 3-4: 1. further, in the second step, the drying temperature in the vacuum drying oven is 50-60 ℃; the reduction temperature in the tubular furnace is 350-450 ℃, and the time is 2-4 h.
The application of the MOF-derived spider-web-shaped iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticles as an electrochemical hydrogen evolution catalyst material is applied to catalysis of HER reaction, the ruthenium nanoparticles are loaded on the surface of the spider-web-shaped iron-cobalt alloy nitrogen-doped carbon nanomaterial, so that surface mass transfer is remarkably enhanced, the overpotential of the reaction is reduced, the performance and the conductivity of the catalyst are improved, and the catalyst has lower overpotential in the HER reaction compared with platinum carbon.
Compared with the prior art, the invention has the following beneficial effects:
(1) the complex carbon nanotube network is derived by taking an MOF material as a precursor through chemical vapor deposition, the carbon nanotubes grow outwards from the center and are in a spider-nest shape, the spider-nest iron-cobalt alloy nitrogen-doped carbon nanomaterial is not only used as a catalyst conductive carrier, the surface area and the utilization rate of ruthenium are improved, more hydrogen evolution active substances are directly exposed on the surface, the spider-nest iron-cobalt alloy nitrogen-doped carbon nanomaterial loaded ruthenium nanoparticles have high electrochemical activity area ECSA and a highly stable carbon nanotube interweaving spider-nest network structure, but also the unique spider-nest structure provides a highly loadable surface for simple and uniform loading of the ruthenium nanoparticles, and compared with other metal loading schemes, the process is greatly simplified, and the application is expanded.
(2) The nitrogen-doped cobweb-shaped iron-cobalt alloy carbon nano material provides more types of electrochemical reaction sites, and the nitrogen-doped surface is proved to have fixed functions of promoting dispersion and reducing agglomeration on ruthenium load, so that the surface area and the utilization rate of ruthenium are improved, therefore, the MOF-derived cobweb-shaped iron-cobalt alloy nitrogen-doped carbon nano material @ ruthenium nano particles have higher surface area and utilization rate, the common agglomeration phenomenon of loaded nano metal ruthenium is reduced due to uniform distribution, the ruthenium nano particles are uniformly loaded in a cobweb-shaped iron-cobalt alloy carbon nano material three-dimensional network, a good mass transfer and three-dimensional conductive network are formed, and various active sites improve the electrochemical performance of the carbon nano material.
(3) The spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material @ ruthenium nano particle derived from the MOF can be directly used for an electrochemical hydrogen evolution electrode material, and has the advantages of high catalytic effect, high stability and the like in an alkaline electrolytic cell over platinum carbon.
Drawings
FIG. 1 is a microscopic morphology under a Scanning Electron Microscope (SEM) of MOF-derived, spidery, iron-cobalt alloy nitrogen-doped carbon nanomaterials @ ruthenium nanoparticles (FeCoSG/NCNT Ru-1) prepared in example 1;
FIG. 2 is a microscopic morphology under a Scanning Electron Microscope (SEM) of commercial carbon black @ ruthenium nanoparticles (Ru/C Ru) prepared in comparative example 1;
FIG. 3 is a microscopic morphology of the iron-cobalt alloy nitrogen doped carbon nano-box material @ ruthenium nano-particles (FeCoNC Ru) prepared in comparative example 2 under a Scanning Electron Microscope (SEM);
FIG. 4 is a Linear Sweep Voltammetry (LSV) plots of Hydrogen Evolution (HER) for the MOF-derived, spider-web iron-cobalt alloy nitrogen-doped carbon nanomaterials @ ruthenium nanoparticles prepared in example 1, commercial carbon black @ ruthenium nanoparticles prepared in comparative example 1, iron-cobalt alloy nitrogen-doped carbon nanocapsule materials @ ruthenium nanoparticles prepared in comparative example 2, and a commercial 20 wt.% Pt/C catalyst;
FIG. 5 is a linear sweep voltammetry test plot (LSV) of Hydrogen Evolution Reaction (HER) of the MOF-derived, spidery iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticles prepared in example 1, example 2(FeCoSG/NCNT Ru-2), example 3(FeCoSG/NCNT Ru-3), example 4(FeCoSG/NCNT Ru-4), and a commercial 20 wt.% Pt/C catalyst;
fig. 6 is the HER reaction potential of MOF-derived, spidery, iron-cobalt alloy, nitrogen-doped carbon nanomaterials @ ruthenium nanoparticles prepared in example 1 at different current densities.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention clearer, the following detailed description of the present invention is made with reference to the accompanying drawings and the detailed description, the embodiments described in the present specification are only for explaining the present invention and are not intended to limit the present invention, and the parameters, ratios and the like of the embodiments may be selected according to circumstances without substantially affecting the result.
Example 1: preparation and application of a spider-nest-shaped composite carbon nanomaterial @ ruthenium nanoparticle specifically comprise the following steps:
(1) synthesis of MOF-derived spidery iron-cobalt alloy nitrogen-doped carbon nano-materials:
ZIF-8 particle Synthesis for the synthesis of ZIF-8 crystals, 200mL of 20mM Zn (NO)3)2·6H2O (98%) methanol solution, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) methanol solution were mixed together, stirred and mixed at room temperature, and then the mixture was left to stand for reaction and collected by centrifugation, and washed with ethanol several times.
2, synthesizing FeOOH nano-rod by using 5.46g of FeCl3·6H2O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethyleneimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. After centrifugation, the mixture was dispersed in 10mL of an ethanol solution of PVP (0.5g of PVP, Mw 40000) and the mixture was further stirred at room temperatureThe mixture was stirred for 12 hours. The PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15ml of methanol for further use.
3, preparing ZIF-8@ FeOOH/ZIF-67 hybrid particles, namely firstly, dispersing the synthesized ZIF-8 particles and 1.6mL of FeOOH nanorod suspension into 120mL of 20mM Co (NO) by ultrasonic waves3)2·6H2In O solution. And (3) carrying out ultrasonic treatment, then quickly adding 200mL of 160mM 2-methylimidazole (95%) methanol solution, then stirring and mixing the mixture at room temperature, standing for reaction for 2 hours, centrifugally collecting, washing with methanol for several times, and drying in vacuum to obtain the ZIF-8@ FeOOH/ZIF-67 hybrid particles.
4. Synthesizing a spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material (FeCoSG/NCNT): 0.5g of the ZIF-8@ FeOOH/ZIF-67 mixed particles obtained above was placed in a ceramic boat, and another ceramic boat was placed above the boat and charged with 3g of melamine. The whole process of the tubular furnace is that argon/hydrogen (7%) mixed gas circulates, the heating temperature-rising procedure is a two-stage heating mode, and the first step is 5 ℃ for min at room temperature-1The temperature was raised to 350 ℃ and the temperature was maintained for 60 minutes. Followed by heating to 800 ℃ and holding for 2 hours. After that, the furnace is naturally cooled to room temperature.
(2) Synthesis of an MOF-derived spider-web-shaped iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticle:
the nitrogen-doped carbon nano material of the MOF-derived spider-nest-shaped iron-cobalt alloy is impregnated in RuCl3·xH2In an ethanol solution of O, the load of ruthenium nanoparticles is realized by ultrasonic and vacuum drying oven and reduction of argon/hydrogen (7%) mixed gas, and the specific process is as follows: taking FeCoSG/NCNT0.1g, grinding and mixing with 0.03g RuCl3·xH2O (ruthenium content is more than 37 percent) is co-dispersed in 10mL of ethanol solution, filled in a sample bottle, ultrasonically dispersed for 7 minutes and then kept stand for 8 hours. Then transferring the liquid in the sample bottle into a culture dish, and quickly drying in a vacuum oven at 60 ℃, wherein the phenomenon of liquid splashing can not occur due to the effect of the salt solution and FeCoSG/NCNT on ethanol. The dried sample was subjected to reduction of the ruthenium metal salt in a tube furnace with an argon/hydrogen (7%) gas mixture for 3h at a temperature of 400 ℃. The resulting sample was designated FeCoSG/NCNT Ru-1.
The morphology of the FeCoSG/NCNT Ru-1 material obtained in example 1 was analyzed by a Scanning Electron Microscope (SEM), and as a result, ruthenium nanoparticles were uniformly loaded in the spider-like nitrogen-doped iron-cobalt alloy carbon nanomaterial shown in FIG. 1.
Evaluation of hydrogen evolution catalytic performance:
all electrochemical tests were performed using an electrochemical workstation model CHI 760E equipped with a PINE rotating disk electrode test system and were performed at room temperature.
Preparation of a working electrode: before using the Rotating Disk Electrode (RDE), i.e. the glassy carbon electrode (GCE, d ═ 0.4cm), Al was used first2O3Grinding the surface of the electrode on polishing cloth to a mirror surface by using powder, then washing the electrode with distilled water for several times, ultrasonically oscillating for 10s, and drying the electrode at room temperature for later use. Accurately weighing 5mg of MOF-derived spider-web-shaped iron-cobalt alloy nitrogen-doped carbon nano material @ ruthenium nano particles, 950 mu L of isopropanol and 50 mu L of Nafion solution (5 wt.%), mixing, carrying out ultrasonic treatment on the mixture for 0.75h, finally uniformly dripping 10 mu L of prepared ink on the surface of GCE, and naturally drying to obtain the working electrode used for testing. The loading amount of the catalyst on the surface of the electrode is about 0.35mg cm-2. As a control experiment, a commercial 20 wt.% Pt/C catalyst was also prepared and tested using the same electrode preparation method.
And (3) electrochemical performance testing: in the testing process, a standard three-electrode electrochemical testing system is adopted, wherein the counter electrode is a carbon rod, and the reference electrode is a Saturated Calomel Electrode (SCE) and the prepared working electrode.
The FeCoSG/NCNT Ru-1 sample prepared in example 1 was tested with a commercial 20 wt.% Pt/C catalyst using a Rotating Disk Electrode (RDE). Will N2Gas was continuously bubbled into 1.0M KOH solution. All potentials are given in 2mV s-1Is recorded and converted to a Reversible Hydrogen Electrode (RHE). The results obtained for all Linear Sweep Voltammetry (LSV) curves at 1600rpm are shown in fig. 4. The FeCoSG/NCNT Ru-1 sample shows very high HER electrocatalytic activity, 10mA cm-2An overpotential at current density of 21.11mV vs. RHE with electrocatalytic activity exceeding that of a commercial Pt/C catalyst tested under the same conditionsReagent (10mA cm)-2Overpotential at current density was 30.11mV vs. rhe). The material has excellent electrocatalytic performance in HER electrocatalytic process.
FeCoSG/NCNT Ru-1 samples prepared in example 1 were tested in N using a Rotating Disk Electrode (RDE)2The gas was continuously bubbled into the 1.0M KOH solution at different current densities without ohmic compensation, the results are shown in FIG. 6. Has small overpotential even under large current density, and the same 10mA cm before and after reaction-2The almost constant potential at the current density indicates that the material has excellent stability.
Comparative example 1: the preparation method of the commercial carbon black @ ruthenium nanoparticle (Ru/C Ru) comprises the following steps:
grinding 0.1g of commercial carbon black with 0.03g of RuCl3·xH2O (ruthenium content is more than 37 percent) is co-dispersed in 10mL of ethanol solution, filled in a sample bottle, ultrasonically dispersed for 7 minutes and then kept stand for 8 hours. The liquid in the sample bottle was then transferred to a petri dish and quickly dried in a vacuum oven at 60 ℃. The dried sample was reduced to the ruthenium metal salt in a tube furnace with an argon/hydrogen (7%) mixture for 3h at 400 ℃.
Samples of carbon black @ ruthenium nanoparticles (Ru/C Ru) were tested using a Rotating Disk Electrode (RDE). The results are shown in FIG. 4. Commercial carbon black @ ruthenium nanoparticle (Ru/C Ru) samples exhibited the lowest hydrogen evolution catalytic effect, 10mA cm-2RHE at a current density with an overpotential of 83.11mV vs. C, the electrocatalytic activity of which is much lower than that of a commercial Pt/C catalyst (10mA cm)-2RHE) at a current density of 30.11mV vs. RHE and sample FeCoSG/NCNT Ru-1(10mA cm) prepared in example 1-2Overpotential at current density 21.11mV vs. rhe). To further understand the reasons behind. The morphology of the Ru/C Ru material obtained in comparative example 1 was analyzed by Scanning Electron Microscope (SEM), and as a result, the ruthenium nanoparticles showed severe agglomeration as shown in fig. 2, which decreased the specific surface area of the active ingredient ruthenium worsened the material utilization.
Comparative example 2: a preparation method of an iron-cobalt alloy nitrogen-doped carbon nano-box material @ ruthenium nano-particle (FeCoNC Ru) specifically comprises the following steps:
(1) synthesis of iron-cobalt alloy nitrogen-doped carbon nano box material (FeCoNC)
ZIF-8 particle Synthesis for the synthesis of ZIF-8 crystals, 200mL of 20mM Zn (NO)3)2·6H2O (98%) methanol solution, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) methanol solution were mixed together, mixed with stirring at room temperature, left to react and collected by centrifugation, and washed several times with ethanol.
2, synthesizing FeOOH nano-rod by using 5.46g of FeCl3·6H2O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethyleneimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. After centrifugation, the mixture was dispersed in 10mL of PVP ethanol solution (0.5g, Mw 40000) and the mixture was further stirred at room temperature for 12 hours. The PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15mL methanol for further use.
3, ZIF-8@ FeOOH/ZIF-67 hybrid particle preparation, namely, firstly, dispersing the synthesized ZIF-8 particles and 1.6mL of FeOOH nanorod suspension liquid in 120mL of 20mM Co (NO) by ultrasonic waves3)2·6H2In O solution. Sonication was followed by the rapid addition of 200mL of 160mM 2-methylimidazole (95%) in methanol. The mixture was then allowed to stir and mix at room temperature and allowed to stand for 2 h. Centrifugally collecting, washing with methanol for several times, and vacuum-drying overnight to obtain ZIF-8@ FeOOH/ZIF-67 hybrid particles.
4. Synthesizing an iron-cobalt alloy nitrogen-doped carbon nano box material (FeCoNC): placing 0.5g of the ZIF-8@ FeOOH/ZIF-67 mixed particles in a ceramic boat, circulating argon/hydrogen (7%) mixed gas in the whole tube furnace, and keeping the temperature at room temperature for 5 min-1The temperature is raised to 800 ℃, and the temperature is kept for 120 min. After that, the furnace is naturally cooled to room temperature.
(2) Synthesizing an iron-cobalt alloy nitrogen-doped carbon nano-box material @ ruthenium nano-particle (FeCoNC Ru):
taking 0.1g of FeCoNC, grinding the FeCoNC and 0.03g of RuCl3·xH2O (ruthenium content is more than 37 percent) is co-dispersed in 10mAnd (3) putting the L ethanol solution into a sample bottle, performing ultrasonic dispersion for 7min, and standing for 8 h. The liquid in the sample bottle was then transferred to a petri dish and quickly dried in a vacuum oven at 60 ℃. The dried sample was reduced with a ruthenium metal salt in a tube furnace with an argon/hydrogen (7%) mixture for 3h at 400 ℃.
Samples of iron-cobalt alloy nitrogen-doped carbon nano-box material @ ruthenium nano-particles (feconn Ru) were tested using a Rotating Disk Electrode (RDE). The results are shown in FIG. 4. The sample of the iron-cobalt alloy nitrogen-doped carbon nano-box material @ ruthenium nano-particle (FeCoNC Ru) shows low hydrogen evolution catalysis effect, 10mA cm-2RHE at a current density with an overpotential of 68.11mV vs. much lower electrocatalytic activity than the commercial Pt/C catalyst (10mA cm) tested under the same conditions-2RHE at an overpotential of 30.11mV vs. E) and FeCoSG/NCNT Ru-1(10mA cm) prepared in example 1-2Overpotential at current density was 21.11mV vs. rhe). To further understand the reasons behind. The morphology of the feconnc Ru material obtained in comparative example 1 was analyzed by a Scanning Electron Microscope (SEM), and as a result, as shown in fig. 3, partial agglomeration of the ruthenium nanoparticles occurred, and the specific surface area and conductivity of the spider-like carbon nanotube material generated by the material were decreased.
Example 2: preparation and application of a spider-nest-shaped composite carbon nanomaterial @ ruthenium nanoparticle specifically comprise the following steps:
(1) synthesizing an MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material:
ZIF-8 particle Synthesis for the synthesis of ZIF-8 crystals, 200mL of 20mM Zn (NO)3)2·6H2O (98%) methanol solution, 1.6mL of 1-methylimidazole (99%), and 200mL of 100mM 2-methylimidazole (95%) methanol solution were mixed together, mixed with stirring at room temperature, left to stand for reaction and collected by centrifugation, and washed several times with ethanol.
2, synthesizing FeOOH nano-rod by using 5.46g of FeCl3·6H2O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethyleneimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. Centrifuging, dispersing in 10mLTo a PVP ethanol solution (0.5g PVP, Mw 40000), the mixture was further stirred at room temperature for 12 hours. The PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15ml of methanol for further use.
3, preparing ZIF-8@ FeOOH/ZIF-67 hybrid particles, namely firstly dispersing the synthesized ZIF-8 particles and 1.6mL of FeOOH nanorod suspension in 120mL of 20mM Co (NO) by using ultrasonic waves3)2·6H2In O solution. And (3) performing ultrasonic treatment, then quickly adding 200mL of 160mM 2-methylimidazole (95%) methanol solution, then stirring and mixing the mixture at room temperature, standing for reaction for 2 hours, centrifugally collecting, washing with methanol for several times, and performing vacuum drying to obtain the ZIF-8@ FeOOH/ZIF-67 hybrid particles.
4. Synthesizing a spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material (FeCoSG/NCNT): 0.5g of the ZIF-8@ FeOOH/ZIF-67 mixed particles obtained above was placed in a ceramic boat, and another ceramic boat was placed above the boat and charged with 3g of melamine. The argon/hydrogen (7%) mixed gas circulates in the whole process of the tubular furnace, the heating temperature-rise procedure is a two-stage heating mode, and the first step is carried out at room temperature for 5 ℃ for min-1The temperature was raised to 350 ℃ and the temperature was maintained for 60 minutes. Followed by heating to 800 ℃ and holding for 2 hours. After that, the furnace is naturally cooled to room temperature.
(2) Synthesis of an MOF-derived spider-web-shaped iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticle:
the nitrogen-doped carbon nano material of the MOF-derived spider-nest-shaped iron-cobalt alloy is impregnated in RuCl3·xH2In an ethanol solution of O, the load of ruthenium nanoparticles is realized by ultrasonic and vacuum drying oven and reduction of argon/hydrogen (7%) mixed gas, and the specific process is as follows: taking FeCoSG/NCNT0.1g, grinding and mixing with 0.03g RuCl3·xH2O (ruthenium content is more than 37 percent) is co-dispersed in 10mL of ethanol solution, filled in a sample bottle, ultrasonically dispersed for 7 minutes and then kept stand for 8 hours. Then transferring the liquid in the sample bottle into a culture dish, and quickly drying in a vacuum oven at 60 ℃, wherein the phenomenon of liquid splashing can not occur due to the effect of the salt solution and FeCoSG/NCNT on ethanol. The dried sample is put into a tube furnace to reduce ruthenium metal salt by argon/hydrogen (7 percent) mixed gas, the reaction time is 3 hours, and the temperature is highSet at 300 ℃. The resulting sample was designated FeCoSG/NCNT Ru-2.
Evaluation of hydrogen evolution catalytic performance:
FeCoSG/NCNT Ru-2 samples were tested using a Rotating Disk Electrode (RDE). In N2Gas was continuously bubbled into the 1.0M KOH solution. All potentials are given in 2mV s-1Is recorded and converted to a Reversible Hydrogen Electrode (RHE). The results obtained for all Linear Sweep Voltammetry (LSV) curves at 1600rpm are shown in fig. 5. The FeCoSG/NCNT Ru-2 sample showed very high HER electrocatalytic activity, 10mA cm-2Overpotential at current density of 24.1mV vs. RHE, which exceeds the electrocatalytic activity of a commercial Pt/C catalyst (10mA cm) tested under the same conditions-2Overpotential at current density 30.11mV vs. rhe). The material is proved to have excellent electrocatalytic performance in a HER electrocatalytic process, and the catalytic effect is superior to that of commercial Pt/C but slightly lower than that of FeCoSG/NCNT Ru-1 sample.
Example 3: preparation and application of a spider-nest-shaped composite carbon nanomaterial @ ruthenium nanoparticle specifically comprise the following steps:
(1) synthesizing an MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material:
ZIF-8 particle Synthesis for the synthesis of ZIF-8 crystals, 200mL of 20mM Zn (NO)3)2·6H2O (98%) methanol solution, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) methanol solution were mixed together, stirred and mixed at room temperature, and then the mixture was left to stand for reaction and collected by centrifugation, and washed with ethanol several times.
2, synthesizing FeOOH nano-rod by using 5.46g of FeCl3·6H2O (98%) was added to a round bottom flask containing 100mL of deionized water and 0.3mL of Polyethyleneimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. After centrifugation, the mixture was dispersed in 10mL of an ethanol solution of PVP (0.5g of PVP, Mw 40000) and the mixture was further stirred at room temperature for 12 hours. The PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15ml of methanol for further use.
ZIF-8@ FeOOH/ZIF-67 hybrid particlesThe preparation method comprises the steps of firstly dispersing synthesized ZIF-8 particles and 1.6mL of FeOOH nanorod suspension in 120mL of 20mM Co (NO) by ultrasonic waves3)2·6H2In O solution. And (3) carrying out ultrasonic treatment, then quickly adding 200mL of 160mM 2-methylimidazole (95%) methanol solution, then stirring and mixing the mixture at room temperature, standing for reaction for 2 hours, centrifugally collecting, washing with methanol for several times, and drying in vacuum to obtain the ZIF-8@ FeOOH/ZIF-67 hybrid particles.
4. Synthesizing a spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material (FeCoSG/NCNT): 0.5g of the ZIF-8@ FeOOH/ZIF-67 mixed particles obtained above was placed in a ceramic boat, and another ceramic boat was placed above the boat and charged with 3g of melamine. The whole process of the tubular furnace is that argon/hydrogen (7%) mixed gas circulates, the heating temperature-rising procedure is a two-stage heating mode, and the first step is 5 ℃ for min at room temperature-1The temperature was raised to 350 ℃ and the temperature was maintained for 60 minutes. Followed by heating to 800 ℃ and holding for 2 hours. After that, the furnace is naturally cooled to room temperature.
(2) The synthesis of the spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material @ ruthenium nano particles comprises the following steps:
the nitrogen-doped carbon nano material of the MOF-derived spider-nest-shaped iron-cobalt alloy is impregnated in RuCl3·xH2In an ethanol solution of O, the load of ruthenium nanoparticles is realized by ultrasonic and vacuum drying oven and reduction of argon/hydrogen (7%) mixed gas, and the specific process is as follows: taking FeCoSG/NCNT0.1g, grinding and mixing with 0.03g RuCl3·xH2O (ruthenium content is more than 37 percent) is co-dispersed in 10mL of ethanol solution, filled in a sample bottle, ultrasonically dispersed for 7 minutes and then kept stand for 8 hours. Then transferring the liquid in the sample bottle into a culture dish, and quickly drying in a vacuum oven at 60 ℃, wherein the phenomenon of liquid splashing can not occur due to the effect of the salt solution and FeCoSG/NCNT on ethanol. The dried sample was subjected to reduction of ruthenium metal salt in a tube furnace with an argon/hydrogen (7%) mixture for 3h at 500 ℃. The resulting sample was designated FeCoSG/NCNT RU-3.
Evaluation of hydrogen evolution catalytic performance:
FeCoSG/NCNT RU-3 samples were tested using a Rotating Disk Electrode (RDE). In N2Gas was continuously bubbled into the 1.0M KOH solution. All potentials are given in 2mV s-1Is recorded and converted to a Reversible Hydrogen Electrode (RHE). The results obtained for all Linear Sweep Voltammetry (LSV) curves at 1600rpm are shown in fig. 5. The FeCoSG/NCNT RU-3 sample exhibited very high HER electrocatalytic activity, 10mA cm-2Overpotential at current density of 44.1mV vs. RHE, with slightly lower electrocatalytic activity than the commercial Pt/C catalyst (10mA cm)-2Overpotential at current density was 30.11mV vs. rhe). The material is proved to have faster reaction kinetics in a HER electrocatalytic process, and the catalytic effect is slightly lower than that of commercial Pt/C and FeCoSG/NCNT RU-1 samples. Low catalytic activity at higher reduction temperatures, probably due to agglomeration of the ruthenium nanoparticles.
Example 4: preparation and application of a spider-nest-shaped composite carbon nanomaterial @ ruthenium nanoparticle specifically comprise the following steps:
(1) synthesizing an MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material:
ZIF-8 particle Synthesis for the synthesis of ZIF-8 crystals, 200mL of 20mM Zn (NO)3)2·6H2O (98%) methanol solution, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) methanol solution were mixed together, stirred and mixed at room temperature, and then the mixture was left to stand for reaction and collected by centrifugation, and washed with ethanol several times.
2, synthesizing FeOOH nano-rod by using 5.46g of FeCl3·6H2O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethyleneimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. After centrifugation, the mixture was dispersed in 10mL of a PVP ethanol solution (0.5g of PVP, Mw 40000) and the mixture was further stirred at room temperature for 12 hours. The PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15ml of methanol for further use.
3, preparing ZIF-8@ FeOOH/ZIF-67 hybrid particles, namely firstly dispersing the synthesized ZIF-8 particles and 1.6mL of FeOOH nanorod suspension in 120mL of 20mM Co (NO) by using ultrasonic waves3)2·6H2In O solution. Sonicate and then add 200mL 160 quicklyAnd (2) mixing the mixture with a mM 2-methylimidazole (95%) methanol solution under stirring at room temperature, standing for reacting for 2 hours, centrifugally collecting, washing with methanol for a plurality of times, and drying in vacuum to obtain the ZIF-8@ FeOOH/ZIF-67 hybrid particles.
4. Synthesizing a spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material (FeCoSG/NCNT): 0.5g of the ZIF-8@ FeOOH/ZIF-67 mixed particles obtained above was placed in a ceramic boat, and another ceramic boat was placed above the boat and charged with 3g of melamine. The argon/hydrogen (7%) mixed gas circulates in the whole process of the tubular furnace, the heating temperature-rise procedure is a two-stage heating mode, and the first step is carried out at room temperature for 5 ℃ for min-1The temperature was raised to 350 ℃ and the temperature was maintained for 60 minutes. Followed by heating to 800 ℃ and holding for 2 hours. After that, the furnace is naturally cooled to room temperature.
(2) Synthesis of an MOF-derived spider-web-shaped iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticle:
the nitrogen-doped carbon nano material of the MOF-derived spider-nest-shaped iron-cobalt alloy is impregnated in RuCl3·xH2In an ethanol solution of O, the load of ruthenium nanoparticles is realized by ultrasonic and vacuum drying oven and reduction of argon/hydrogen (7%) mixed gas, and the specific process is as follows: taking FeCoSG/NCNT0.1g, grinding and mixing with 0.03g of RuCl3·xH2O (ruthenium content is more than 37 percent) is co-dispersed in 10mL of ethanol solution, filled in a sample bottle, ultrasonically dispersed for 7 minutes and then kept stand for 8 hours. Then transferring the liquid in the sample bottle into a culture dish, and quickly drying in a vacuum oven at 60 ℃, wherein the phenomenon of liquid splashing can not occur due to the effect of the salt solution and FeCoSG/NCNT on ethanol. The dried sample was subjected to reduction of the ruthenium metal salt in a tube furnace with an argon/hydrogen (7%) gas mixture for 3h at a temperature set at 700 ℃. The resulting sample was designated FeCoSG/NCNT Ru-4.
Evaluation of hydrogen evolution catalytic performance:
FeCoSG/NCNT Ru-4 samples were tested using a Rotating Disk Electrode (RDE). In N2Gas was continuously bubbled into the 1.0M KOH solution. All potentials are given in 2mV s-1Is recorded and converted to a Reversible Hydrogen Electrode (RHE). The results obtained for all Linear Sweep Voltammetry (LSV) curves at 1600rpm are shown in fig. 5. The FeCoSG/NCNT Ru-4 sample shows very highHER electrocatalytic activity of 10mA cm-2An overpotential at current density of 61.1mV vs. RHE with electrocatalytic activity lower than that of a commercial Pt/C catalyst (10mA cm) tested under the same conditions-2Overpotential at current density was 30.11mV vs. rhe). The material is proved to have serious loss of HER electrocatalytic performance at higher reduction temperature, and the catalytic effect is lower than that of commercial Pt/C and FeCoSG/NCNT Ru-1 samples. The catalyst shows low catalytic activity at a higher reduction temperature of 700 ℃, and the agglomeration of ruthenium nanoparticles is serious. Nevertheless, at large current densities (e.g., over 100mA cm)-2) The FeCoSG/NCNT Ru-4 shows advantages of inverse ultra-platinum carbon, and mass transfer and conductivity are accelerated due to the unique three-dimensional spider structure.
Finally, it should also be mentioned that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The preparation method of the spider-nest-shaped composite carbon nano material @ ruthenium nano particle is characterized in that the spider-nest-shaped composite carbon nano material is an MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material, the MOF-derived spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material is a conductive network, the ruthenium nano particle is a load, and the growth of the spider-nest-shaped composite carbon nano material adopts a chemical vapor deposition method.
2. The method for preparing the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle according to claim 1, wherein the method specifically comprises the following steps:
step one, synthesizing an MOF-derived spider-nest-shaped composite carbon nano material:
(1) synthetic zinc-base zeolite imidazole ester framework materialMaterial (ZIF-8) particles prepared by adding a certain amount of Zn (NO)3)2·6H2Mixing the O methanol solution, the 1-methylimidazole and the 2-methylimidazole together, stirring at room temperature for reaction, centrifuging and collecting, and washing with ethanol for several times;
(2) synthesizing FeOOH nano rod by taking a certain amount of FeCl3·6H2Adding O into a round-bottom flask filled with deionized water and Polyethyleneimine (PEI), and heating and reacting for 2 hours at 65-90 ℃ to obtain a uniform FeOOH nanorod;
(3) preparation of polyvinylpyrrolidone (PVP) functionalized FeOOH nano-rod: dispersing the FeOOH nano rod obtained in the step (2) in a PVP ethanol solution, further stirring for 8-12 h at room temperature to obtain a PVP functionalized FeOOH nano rod, washing with ethanol for several times after centrifugal separation, and dispersing in methanol for later use;
(4) preparing ZIF-8@ FeOOH/cobalt-based zeolite imidazolate framework material (ZIF-67) hybrid particles by dispersing the ZIF-8 particles prepared in the step (1) and PVP functionalized FeOOH nanorod suspension prepared in the step (3) in Co (NO) through ultrasonic waves3)2·6H2Adding a methanol solution of 2-methylimidazole into the O solution quickly, stirring and mixing the mixture at room temperature, standing for reacting for 2 hours, centrifugally collecting, washing with methanol for several times, and drying in vacuum to obtain ZIF-8@ FeOOH/ZIF-67 hybrid particles;
(5) synthesizing a spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material (FeCoSG/NCNT): placing a certain amount of ZIF-8@ FeOOH/ZIF-67 mixed particles obtained in the step (4) in a ceramic boat, placing another ceramic boat above the ceramic boat and containing a nitrogen source organic matter, enabling argon and hydrogen to flow through the whole tube furnace, adopting a two-stage heating program, and cooling to room temperature after heating to obtain a spider-nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material (FeCoSG/NCNT);
step two, preparing the MOF derived spider-nest-shaped composite carbon nano material @ ruthenium nano particle: by dipping the spider nest-shaped iron-cobalt alloy nitrogen-doped carbon nano material in RuCl3·xH2In the ethanol solution of O, standing for 5-8 hours after ultrasonic dispersion, transferring the solution to a vacuum oven for drying, placing the dried sample in a tube furnace, and introducing argon-hydrogen (7%) mixed gas for reduction to realize ruthenium nanoparticlesThe load of (2).
3. The method for preparing spider-nest composite carbon nanomaterial @ ruthenium nanoparticles of claim 2, wherein in step one (1), the Zn (NO) is3)2·6H2The amount of substance O is 20mM, Zn (NO)3)2·6H2The volume of the O methanol solution is 180-250 mL; the mass fraction of the 1-methylimidazole is 99%, and the volume of the 1-methylimidazole is 2-3 mL; the amount of the 2-methylimidazole substance is 100mM, and the volume of the 2-methylimidazole methanol solution is 180-230 mL.
4. The method for preparing spider-web composite carbon nanomaterial @ ruthenium nanoparticles according to claim 2, wherein in the step one (2), the FeCl is3·6H2The mass of O is 5.46g, the volume of the deionized water is 100mL, and the volume of the Polyethyleneimine (PEI) is 0.1-0.5 mL.
5. The method for preparing the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle according to claim 2, wherein in the step one (3), the volume of the PVP ethanol solution is 6-12 mL, wherein the mass fraction of PVP is 2% -8%; the volume of the methanol is 10-20 mL.
6. The method for preparing the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle according to claim 2, wherein in the step one (4), Co (NO) is used3)2·6H2The amount of O is 18-25 mM, Co (NO)3)2·6H2The volume of the O methanol solution is 100-150 mL; the amount of the 2-methylimidazole substance is 120-200 mM, and the volume of the 2-methylimidazole methanol solution is 160-240 mL.
7. The method for preparing the spider-nest composite carbon nanomaterial @ ruthenium nanoparticles according to claim 2, wherein the nitrogen source organic in the step one (5) is one or two of melamine or dicyandiamide; the two-stage heatingThe heating rate of the first stage of the procedure was 5 ℃ min-1Heating to 350 deg.C and maintaining for 60 min; the second stage of the process has a heating rate of 5 deg.C for min-1Then the first stage is heated to 800 ℃ and the temperature is kept for 2 h.
8. The method for preparing spider-nest composite carbon nanomaterial @ ruthenium nanoparticles of claim 2, wherein in step two, the RuCl3·xH2The content of ruthenium in O is more than 37 percent, FeCoSG/NCNT and RuCl3·xH2The mass ratio of O is 3-4: 1.
9. the method for preparing the spider-web composite carbon nanomaterial @ ruthenium nanoparticles according to claim 2, wherein the drying temperature in the vacuum oven is 50-60 ℃; the reduction temperature in the tubular furnace is 350-450 ℃, and the time is 2-4 h.
10. The application of the MOF-derived composite carbon nanomaterial @ ruthenium nanoparticle is characterized in that the MOF-derived composite carbon nanomaterial @ ruthenium nanoparticle is applied to HER reaction, and the ruthenium nanoparticle is loaded on the surface of the MOF-derived spider-nest-shaped composite carbon nanomaterial, so that the surface mass transfer is remarkably enhanced, the over-potential of the reaction is reduced, and the performance and the conductivity of a catalyst are improved.
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CN116334676A (en) * 2023-06-01 2023-06-27 中石油深圳新能源研究院有限公司 Oxygen evolution catalyst, preparation method thereof and electrolysis device
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