CN114752962B - Preparation and application of spider-nest composite carbon nanomaterial @ ruthenium nanoparticle - Google Patents

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

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CN114752962B
CN114752962B CN202210438584.5A CN202210438584A CN114752962B CN 114752962 B CN114752962 B CN 114752962B CN 202210438584 A CN202210438584 A CN 202210438584A CN 114752962 B CN114752962 B CN 114752962B
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CN114752962A (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, in particular to a preparation method of spider nest composite carbon nanomaterial @ ruthenium nano particles, which comprises (1) synthesis of MOF derived spider nest composite carbon nanomaterial; (2) Preparation of MOF-derived spider nest-like composite carbon nanomaterial @ ruthenium nanoparticles. The application of the MOF derivative spider nest-shaped composite carbon nano material @ ruthenium nano particles as an electrochemical Hydrogen Evolution (HER) catalyst material can obviously enhance surface mass transfer, reduce the overpotential of the reaction and improve the performance and conductivity of the catalyst, and has lower overpotential and cost compared with platinum carbon in the HER reaction.

Description

Preparation and application of spider-nest composite carbon nanomaterial @ ruthenium nanoparticle
Technical Field
The invention belongs to the technical field of electrochemical hydrogen production, and particularly relates to spider nest-like composite carbon nanomaterial@ruthenium nanoparticles, a preparation method thereof and application thereof in electrochemical hydrogen production.
Background
With the increasing concern of global climate change caused by the crisis of traditional fossil fuel energy 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 (146 kJ g) -1 ) The advantages of abundant reserves, sustainability, zero emission after combustion and the like are recognized as the most promising fossil fuel substitute in the future. Currently, the main processes for industrial hydrogen production include Coal Gasification (CG), steam Methane Reforming (SMR), and Water Electrolysis (WE). CG and SMR are produced by converting methane and coal vapors to H 2 And CO 2 Throughout H 2 The production occupies more than 95 percent of market share, but both methods have low conversion efficiency and CO 2 Large discharge amount, water pollution and the like, reduces the yield and purity of products and accelerates global warming. The water electrolysis hydrogen production has been receiving more and more attention in research and industrial fields in recent years due to the advantages of mass production of high-purity hydrogen, no carbon emission, sustainability and abundant water resources. In particular for converting electrical energy into H 2 Fuel is an ideal way to store 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. Oxygen Evolution (OER) is the core reaction process that occurs at the anode. The theoretical thermodynamic voltage for the HER process is only 0V vs RHE. However, the energy barrier accumulated by the reaction of multiple elements results in slow kinetics of the reaction, and in practical applications, higher overpotential is typically required to trigger HER process. Thus, there is a need for efficient HER electrocatalysts to accelerate the kinetics of the reaction and to increase HER activity. Noble metal Pt has the best intrinsic catalytic activity for HER and has been considered as the standard electrocatalyst in Proton Exchange Membrane (PEM) water electrolysis. However, the low reserves, high cost and instability of Pt greatly hamper its large-scale industrial application. Therefore, it is highly desirable and important to find efficient, low cost, durable non-Pt electrocatalysts.
Non-noble metal-based catalysts for HER and OER have been studied more, such as transition metal-based compounds carbides, nitrides, phosphides, sulfides and selenides, however, their catalytic activity and durability remain worse than noble metal-based.
The cost of the metal Ru is about 4% of Pt, with 65kcal mol -1 The Pt-like hydrogen bond strength and strong corrosion resistance and the ignored water dissociation energy barrier make it a promising ion exchange membrane water electrolysis in both PEM and alkaline. To improve HER performance, various Ru-based catalysts were prepared by rational design of different nanostructures and modification of electronic properties. The carbon material doped with hetero atoms (N, P, S, B) also has hydrogen evolution activity, has close coordination with Ru-based catalyst, and not only promotes uniform loading of Ru-based particles, but also promotes hydrolytic dissociation under alkaline conditions.
Disclosure of Invention
The invention prepares the nanomaterial applied to the hydrogen evolution reaction electrode catalyst material by taking the spider nest-shaped iron-cobalt alloy nitrogen doped carbon nanomaterial with high specific surface area as a conductive network and ruthenium nanoparticles as a load.
In order to achieve the above-mentioned object, the present invention provides a preparation method of a spider-nest composite carbon nanomaterial @ ruthenium nanoparticle, wherein the spider-nest composite carbon nanomaterial is a spider-nest iron-cobalt alloy nitrogen doped carbon nanomaterial derived from MOF, the spider-nest iron-cobalt alloy nitrogen doped carbon nanomaterial derived from MOF is a conductive network, and the ruthenium nanoparticle is a load, the preparation method specifically comprises the following steps:
step one, synthesizing a spider nest-shaped iron-cobalt alloy nitrogen doped carbon nanomaterial derived from MOF:
(1) Synthesis of zinc-based zeolitic imidazolate framework (ZIF-8) particles, a certain amount of Zn (NO) 3 ) 2 ·6H 2 Mixing O methanol solution, 1-methylimidazole and 2-methylimidazole together, stirring at room temperature for reaction, centrifuging, collecting, and washing with ethanol for several times;
(2) Synthesizing FeOOH nano rod, taking a certain amount of FeCl 3 ·6H 2 O is added into a round-bottom flask filled with deionized water and Polyethyleneimine (PEI), and heated and reacted for 2 hours at 65-90 ℃ to obtain uniform FeOOH nano rods;
(3) Preparation of polyvinylpyrrolidone (PVP) functionalized FeOOH nanorods: dispersing the FeOOH nano rod obtained in the step (2) in an ethanol solution of PVP, further stirring for 8-12 hours at room temperature to obtain PVP functionalized FeOOH nano rod, centrifugally separating, washing for a plurality of times by using ethanol, and dispersing in methanol for later use;
(4) Preparation of ZIF-8@FeOOH/cobalt-based zeolitic imidazolate framework (ZIF-67) hybrid particles comprising dispersing the prepared ZIF-8 particles of (1) and the PVP-functionalized FeOOH nanorod suspension prepared in (3) in Co (NO) by ultrasonic waves 3 ) 2 Adding a methanol solution of 2-methylimidazole into a 6H2O solution, stirring the mixture at room temperature for reaction, standing for 2 hours, centrifugally collecting, washing with methanol for several times, and vacuum drying to obtain ZIF-8@FeOOH/ZIF-67 hybrid particles;
(5) Synthesis of spider-nest type iron-cobalt alloy nitrogen doped carbon nanomaterial (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 mixed particles, filling nitrogen source organic matters in the ceramic boat, circulating argon and hydrogen in the whole process of a tube furnace, adopting a two-stage heating program, and cooling to room temperature after heating to obtain a spider-nest type iron-cobalt alloy nitrogen-doped carbon nanomaterial (FeCoSG/NCNT);
step two, preparing a spider nest-shaped iron-cobalt alloy nitrogen doped carbon nanomaterial @ ruthenium nanoparticle derived from MOF: by impregnating spider nest type iron-cobalt alloy nitrogen doped carbon nano material in RuCl 3 ·xH 2 And (3) in the ethanol solution of O, carrying out ultrasonic dispersion, standing for 5-8 hours, transferring the solution to a vacuum oven for drying, and placing the dried sample in a tube furnace for argon-hydrogen (7%) reduction to realize the loading of ruthenium nano particles.
Further, in the step (1) of the first step, the Zn (NO) 3 ) 2 ·6H 2 The O-methanol solution had a mass concentration of 20mM, zn (NO 3 ) 2 ·6H 2 The volume of the methanol solution of O is 180-250 mL; the mass fraction of the 1-methylimidazole is 99%, and the volume is 2-3 mL; the mass concentration of the substance of the 2-methylimidazole methanol solution is 100mM, and the volume of the 2-methylimidazole methanol solution is 180-230 mL. Further, in step (2) of the first step, the FeCl 3 ·6H 2 The mass of O is 5.46g, the volume of deionized water is 100mL, and the volume of Polyethylenimine (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 step (4), co (NO 3 ) 2 ·6H 2 The O-methanol solution has a mass concentration of 18 to 25mM, co (NO) 3 ) 2 ·6H 2 The volume of the O methanol solution is 100-150 mL; the mass concentration of the 2-methylimidazole methanol solution is 120-200 mM, and the volume is 160-240 mL.
Further, in step (5), the heating rate in the first stage of the two-stage heating program is 5 ℃ for min -1 Heating to 350 ℃ and preserving heat for 60min; the second stage is heating at 5 deg.C for min -1 The first stage is then heated to 800℃and incubated for 2h.
Further, the nitrogen source organic matter in the step (5) is one or two of melamine and dicyandiamide, and the nitrogen doped carbon nano tube grows by a chemical vapor deposition method and is in a spider nest shape.
Further, in the second step, the RuCl 3 ·xH 2 The amount of ruthenium in O is more than 37%, feCoSG/NCNT and RuCl 3 ·xH 2 O (O)The mass ratio is 3-4: 1. in the second step, the drying temperature in the vacuum oven is 50-60 ℃; the reduction temperature in the tube furnace is 350-450 ℃ and the time is 2-4 h.
The application of the spider nest-shaped iron-cobalt alloy nitrogen doped carbon nano material@ruthenium nano particles derived from the MOF as an electrochemical hydrogen evolution catalyst material is applied to catalyzing a HER reaction, the surface of the spider nest-shaped iron-cobalt alloy nitrogen doped carbon nano material is loaded with the ruthenium nano particles, so that the surface mass transfer is obviously enhanced, the overpotential of the reaction is reduced, the catalyst performance and the conductivity are improved, and the catalyst has lower overpotential compared with platinum carbon in the HER reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) The MOF material is used as a precursor, a complex carbon nano tube network is derived through chemical vapor deposition, the carbon nano tube presents a spider nest shape from the center to the outside, the spider nest-shaped iron-cobalt alloy nitrogen doped carbon nano material is 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-shaped iron-cobalt alloy nitrogen doped carbon nano material loaded ruthenium nano particles have high electrochemical active area ECSA and a highly stable carbon nano tube interweaved spider nest network structure, and the unique spider nest structure provides a highly loadable surface for the simple and uniform loading of the ruthenium nano particles, so that the flow is greatly simplified and the application is expanded compared with other loaded metal schemes.
(2) The nitrogen-doped spider-nest type iron-cobalt alloy carbon nano material provides more kinds of electrochemical reaction sites, and the nitrogen-doped surface is proved to have the functions of fixing, promoting dispersion and reducing agglomeration on ruthenium load, and is beneficial to improving the surface area and the utilization rate of ruthenium, so that the spider-nest type iron-cobalt alloy nitrogen-doped carbon nano material derived by MOF (metal oxide film) has higher surface area and utilization rate, uniform distribution reduces the common agglomeration phenomenon of supported nano metal ruthenium, ruthenium nano particles are uniformly supported in a spider-nest type iron-cobalt alloy carbon nano material three-dimensional network, good mass transfer and three-dimensional conductive network are realized, and various active sites promote the electrochemical performance.
(3) The MOF-derived spider nest type iron-cobalt alloy nitrogen doped carbon nano material @ ruthenium nano particles can be directly used for electrochemical hydrogen evolution electrode materials, and have the advantages of high catalytic effect, high stability and the like exceeding platinum carbon in an alkaline electrolytic cell.
Drawings
FIG. 1 is a microscopic morphology under a Scanning Electron Microscope (SEM) of MOF-derived spider-nest type iron-cobalt alloy nitrogen doped carbon nanomaterial @ ruthenium nanoparticle (FeCoSG/NCNT Ru-1) prepared in example 1;
FIG. 2 is a microscopic morphology of commercial carbon black @ ruthenium nanoparticles (Ru/C Ru) prepared according to comparative example 1 under a Scanning Electron Microscope (SEM);
FIG. 3 is a microscopic morphology of 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 voltammetric test plot (LSV) of Hydrogen Evolution Reactions (HERs) for the MOF-derived, nested, iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticle prepared in example 1, the commercial carbon black @ ruthenium nanoparticle prepared in comparative example 1, the iron-cobalt alloy nitrogen-doped carbon nanoshell material @ ruthenium nanoparticle prepared in comparative example 2, and a commercial 20wt.% Pt/C catalyst;
FIG. 5 is a linear scanning voltammetric plot (LSV) of a Hydrogen Evolution Reaction (HER) of a MOF-derived, nested, iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticle 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 20wt.% Pt/C catalyst;
fig. 6 is HER reaction potentials of MOF-derived spider-nest-like iron-cobalt alloy nitrogen doped carbon nanomaterial @ ruthenium nanoparticles prepared in example 1 at different current densities.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the following detailed description of the present invention is given with reference to the accompanying drawings and the specific embodiments, and the examples described in the present specification are only for explaining the present invention, and are not intended to limit the present invention, and parameters, proportions, etc. of the examples can be selected according to the local conditions without substantially affecting the results.
Example 1: the preparation and application of the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle specifically comprises the following steps:
(1) Synthesis of MOF-derived spider nest-like iron-cobalt alloy nitrogen doped carbon nanomaterial:
ZIF-8 particle Synthesis to synthesize ZIF-8 crystals, 200mL of 20mM Zn (NO 3 ) 2 ·6H 2 O (98%) in methanol, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) in methanol were mixed together, stirred at room temperature, and then allowed to stand for reaction and centrifugal collection, followed by washing with ethanol several times.
FeOOH nanorod Synthesis 5.46g FeCl 3 ·6H 2 O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethylenimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. Centrifugal separation, dispersing in 10mL PVP ethanol solution (0.5 g PVP, mw=40,000), and the mixture was stirred at room temperature for a further 12 hours. PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15ml of methanol for further use.
Preparation of ZIF-8@FeOOH/ZIF-67 hybrid particles the synthesized ZIF-8 particles and 1.6mL FeOOH nanorod suspension were first ultrasonically dispersed in 120mL 20mM Co (NO) 3 ) 2 ·6H 2 And O solution. Ultrasonic treatment, rapid addition of 200mL 160mM 2-methylimidazole (95%) methanol solution, stirring and mixing the mixture at room temperature, standing for 2h, centrifugal collection, methanol washing for several times, and vacuum drying to obtain ZIF-8@FeOOH/ZIF-67 hybrid particles.
4. Spider nest type iron-cobalt alloy nitrogen doped carbon nano material (FeCoSG/NCNT) is synthesized: the ZIF-8@FeOOH/ZIF-67 mixed particles obtained above were placed in a ceramic boat in an amount of 0.5g, and the other ceramic boat was placed above and filled with 3g of melamine. The whole argon/hydrogen (7%) mixed gas circulation of the tube furnace, the heating program is a two-stage heating mode, the first step is that the temperature is 5 ℃ for min at room temperature -1 Heating to 350 deg.C, and maintaining at this temperature for 60min. Then heated to 800℃and incubated for 2 hours. After that, the furnace was naturally cooled to room temperature.
(2) Synthesis of MOF-derived spider-nest-like iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticle:
MOF-derived spider nest type iron-cobalt alloy nitrogen doped carbon nano material is immersed in RuCl 3 ·xH 2 In the ethanol solution of O, the load of ruthenium nano particles is realized by the reduction of argon/hydrogen (7%) mixed gas through an ultrasonic and vacuum oven, and the specific process is as follows: grinding FeCoSG/NCNT0.1g, mixing with 0.03g RuCl 3 ·xH 2 O (ruthenium content more than 37%) is dispersed in 10mL ethanol solution, and the solution is put in a sample bottle, dispersed for 7 minutes by ultrasonic and then kept stand for 8 hours. And then transferring the liquid in the sample bottle into a culture dish, and quickly drying in a vacuum oven at 60 ℃, wherein liquid splashing phenomenon 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 3 hours at 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 Scanning Electron Microscopy (SEM), and as a result, ruthenium nanoparticles were uniformly loaded in the spider-nest type iron-cobalt alloy nitrogen-doped carbon nanomaterial shown in FIG. 1.
Evaluation of hydrogen evolution catalytic performance:
all electrochemical tests were performed at room temperature using an electrochemical workstation model CHI 760E and equipped with a PINE rotating disk electrode test system.
Preparation of working electrode: before using the Rotating Disk Electrode (RDE), i.e. the glassy carbon electrode (GCE, d=0.4 cm), al is first used 2 O 3 The powder is used for polishing the surface of the electrode to a mirror surface on polishing cloth, then distilled water is used for washing for a plurality of times, ultrasonic vibration is carried out for 10s, and the electrode is dried at room temperature for later use. Accurately weighing 5mg of MOF-derived spider nest-shaped iron-cobalt alloy nitrogen doped carbon nanomaterial @ ruthenium nano particles, 950 mu L of isopropanol and 50 mu L of Nafion solution (5 wt.%) and mixing, performing ultrasonic treatment on the mixture for 0.75h, finally taking 10 mu L of the prepared ink to uniformly drip and coat on the surface of GCE, and naturally drying to obtain the finished productThe working electrode used for the test was obtained. The loading of the electrode surface catalyst was about 0.35mg cm -2 . As a control experiment, a commercial 20wt.% Pt/C catalyst was also prepared and tested using the same electrode preparation method.
Electrochemical performance test: in the test process, a standard three-electrode electrochemical test system is adopted, wherein a counter electrode is a carbon rod, and a reference electrode is a Saturated Calomel Electrode (SCE) and the working electrode prepared by the method.
The FeCoSG/NCNT Ru-1 samples prepared in example 1 were tested with a commercial 20wt.% Pt/C catalyst using a Rotating Disk Electrode (RDE). Will N 2 The gas was continuously bubbled into a 1.0M KOH solution. All potentials were at 2mV s -1 Is 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 -2 The overpotential at current density was 21.11mV vs. RHE, which had an electrocatalytic activity exceeding that of the commercial Pt/C catalyst tested under the same conditions (10 mA cm -2 The overpotential at current density was 30.11mV vs. RHE). The material has excellent electrocatalytic performance in HER electrocatalytic process.
The FeCoSG/NCNT Ru-1 sample prepared in example 1 was tested in N using a Rotating Disk Electrode (RDE) 2 The gas was continuously bubbled into 1.0M KOH solution at different current densities without ohmic compensation, and the results are shown in FIG. 6. Has smaller overpotential even under larger current density, and has the same 10mA cm before and after reaction -2 Almost constant potential at current density indicates excellent stability of the material.
Comparative example 1: the preparation of the commercial carbon black@ruthenium nano particles (Ru/C Ru) specifically comprises the following steps:
grinding commercial carbon black 0.1g, mixing with RuCl 0.03g 3 ·xH 2 O (ruthenium content more than 37%) is dispersed in 10mL ethanol solution, and the solution is put in a sample bottle, dispersed for 7 minutes by ultrasonic and then kept stand for 8 hours. The liquid in the sample bottle was then transferred to a petri dish and dried rapidly in a vacuum oven at 60 ℃. Dried sample in tubeThe ruthenium metal salt was reduced with an argon/hydrogen (7%) mixture in a furnace for 3 hours at 400 ℃.
Carbon black @ ruthenium nanoparticle (Ru/C Ru) samples 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 -2 The overpotential at current density was 83.11mV vs. RHE, which had much lower electrocatalytic activity than the commercial Pt/C catalyst tested under the same conditions (10 mA cm -2 Over potential at current density of 30.11mV vs. RHE) and sample FeCoSG/NCNT Ru-1 prepared in example 1 (10 mA cm) -2 The overpotential at current density was 21.11mV vs. RHE). For further understanding of the reasons behind. Analysis of the morphology of the Ru/C Ru material obtained in comparative example 1 by Scanning Electron Microscopy (SEM) revealed that the ruthenium nanoparticles showed severe agglomeration as shown in fig. 2, which reduced the specific surface area of the ruthenium active ingredient and deteriorated the utilization of the material.
Comparative example 2: the preparation method of the iron-cobalt alloy nitrogen doped carbon nano-box material @ ruthenium nano-particles (FeCoNC Ru) specifically comprises the following steps:
(1) Synthesis of iron-cobalt alloy nitrogen doped carbon nano-box material (FeCoNC)
ZIF-8 particle Synthesis to synthesize ZIF-8 crystals, 200mL of 20mM Zn (NO 3 ) 2 ·6H 2 O (98%) in methanol, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) in methanol were mixed together, stirred at room temperature, and then allowed to stand for reaction and collected by centrifugation, and washed several times with ethanol.
FeOOH nanorod Synthesis 5.46g FeCl 3 ·6H 2 O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethylenimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. Centrifugal separation, dispersing in 10mL PVP ethanol solution (0.5 g, mw=40,000), the mixture was stirred at room temperature for a further 12h. PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15mL of methanol for further use.
3.ZIF-8@FeOOH/ZIF-67 hybrid particles were prepared by first dispersing the synthesized ZIF-8 particles and 1.6mL FeOOH nanorod suspension in 120mL 20mM Co (NO) using ultrasound 3 ) 2 ·6H 2 And O solution. Sonication was followed by rapid addition of 200mL of 160mM 2-methylimidazole (95%) methanol solution. The mixture was then allowed to stand for 2h after stirring and mixing at room temperature. And (3) centrifugally collecting, washing with methanol for several times, and drying in vacuum overnight to obtain ZIF-8@FeOOH/ZIF-67 hybrid particles.
4. Synthesizing an iron-cobalt alloy nitrogen doped carbon nano box material (FeCoNC): the ZIF-8@FeOOH/ZIF-67 mixed particles obtained above were placed in a ceramic boat in an amount of 0.5g, and a tube furnace was circulated with a mixed argon/hydrogen (7%) gas at room temperature for 5 min -1 Heating to 800 ℃, and preserving heat for 120min at the temperature. After that, the furnace was naturally cooled to room temperature.
(2) Synthesis of iron-cobalt alloy nitrogen doped carbon nano-box material @ ruthenium nano-particles (FeCoNC Ru):
grinding FeCoNC 0.1g, mixing with RuCl 0.03g 3 ·xH 2 O (containing more than 37 percent of ruthenium) is dispersed in 10mL of ethanol solution, and the mixture is put in a sample bottle, and is kept stand for 8 hours after ultrasonic dispersion for 7 minutes. The liquid in the sample bottle was then transferred to a petri dish and dried rapidly in a vacuum oven at 60 ℃. The dried sample was reduced with ruthenium metal salt in a tube furnace with an argon/hydrogen (7%) mixture for 3 hours at 400 ℃.
Samples of iron-cobalt alloy nitrogen doped carbon nano-box material @ ruthenium nano-particles (feconnc Ru) were tested using a Rotating Disk Electrode (RDE). The results are shown in FIG. 4. The iron-cobalt alloy nitrogen doped carbon nano box material @ ruthenium nano particle (FeCoNC Ru) sample shows low hydrogen evolution catalytic effect, and 10mA cm -2 The overpotential at current density was 68.11mV vs. RHE, which had much lower electrocatalytic activity than the commercial Pt/C catalyst tested under the same conditions (10 mA cm -2 Over potential at current density of 30.11mV vs. RHE) and FeCoSG/NCNT Ru-1 (10 mA cm) prepared in example 1 -2 The overpotential at current density was 21.11mV vs. RHE). For further understanding of the reasons behind. The morphology of the feconnc Ru material obtained in comparative example 1 was analyzed by Scanning Electron Microscopy (SEM), and the result showed that ruthenium nanoparticles appeared as shown in fig. 3The partial agglomeration phenomenon is due to the lack of the specific surface area and conductivity of the generated spider-like carbon nanotube material to decrease.
Example 2: the preparation and application of the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle specifically comprises the following steps:
(1) Synthesis of MOF-derived spider nest-like iron-cobalt alloy nitrogen doped carbon nanomaterial:
ZIF-8 particle Synthesis to synthesize ZIF-8 crystals, 200mL of 20mM Zn (NO 3 ) 2 ·6H 2 O (98%) in methanol, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) in methanol were mixed together, stirred at room temperature, and then allowed to stand for reaction and centrifugal collection, followed by washing with ethanol several times.
FeOOH nanorod Synthesis 5.46g FeCl 3 ·6H 2 O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethylenimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. Centrifugal separation, dispersing in 10mL PVP ethanol solution (0.5 g PVP, mw=40,000), and the mixture was stirred at room temperature for a further 12 hours. PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15ml of methanol for further use.
Preparation of ZIF-8@FeOOH/ZIF-67 hybrid particles the synthesized ZIF-8 particles and 1.6mL FeOOH nanorod suspension were first ultrasonically dispersed in 120mL 20mM Co (NO) 3 ) 2 ·6H 2 And O solution. Ultrasonic treatment, rapid addition of 200mL 160mM 2-methylimidazole (95%) methanol solution, stirring and mixing the mixture at room temperature, standing for 2h, centrifugal collection, methanol washing for several times, and vacuum drying to obtain ZIF-8@FeOOH/ZIF-67 hybrid particles.
4. Spider nest type iron-cobalt alloy nitrogen doped carbon nano material (FeCoSG/NCNT) is synthesized: the ZIF-8@FeOOH/ZIF-67 mixed particles obtained above were placed in a ceramic boat in an amount of 0.5g, and the other ceramic boat was placed above and filled with 3g of melamine. The whole argon/hydrogen (7%) mixed gas of the tube furnace circulates, the heating temperature program is a two-section heating mode, the first oneStep at room temperature for 5℃min -1 Heated to 350℃and incubated at this temperature for 60 minutes. Then heated to 800℃and incubated for 2 hours. After that, the furnace was naturally cooled to room temperature.
(2) Synthesis of MOF-derived spider-nest-like iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticle:
MOF-derived spider nest type iron-cobalt alloy nitrogen doped carbon nano material is immersed in RuCl 3 ·xH 2 In the ethanol solution of O, the load of ruthenium nano particles is realized by the reduction of argon/hydrogen (7%) mixed gas through an ultrasonic and vacuum oven, and the specific process is as follows: grinding FeCoSG/NCNT0.1g, mixing with 0.03g RuCl 3 ·xH 2 O (ruthenium content more than 37%) is dispersed in 10mL ethanol solution, and the solution is put in a sample bottle, dispersed for 7 minutes by ultrasonic and then kept stand for 8 hours. And then transferring the liquid in the sample bottle into a culture dish, and quickly drying in a vacuum oven at 60 ℃, wherein liquid splashing phenomenon 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 3 hours 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). At N 2 The gas was continuously bubbled into a 1.0M KOH solution. All potentials were at 2mV s -1 Is 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 shows very high HER electrocatalytic activity, 10mA cm -2 The overpotential at current density was 24.1mV vs. RHE, which had an electrocatalytic activity exceeding that of the commercial Pt/C catalyst tested under the same conditions (10 mA cm -2 The overpotential at current density was 30.11mV vs. RHE). The material has excellent electrocatalytic performance in the HER electrocatalytic process, and the catalytic effect is superior to that of commercial Pt/C but slightly lower than that of a FeCoSG/NCNT Ru-1 sample.
Example 3: the preparation and application of the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle specifically comprises the following steps:
(1) Synthesis of MOF-derived spider nest-like iron-cobalt alloy nitrogen doped carbon nanomaterial:
ZIF-8 particle Synthesis to synthesize ZIF-8 crystals, 200mL of 20mM Zn (NO 3 ) 2 ·6H 2 O (98%) in methanol, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) in methanol were mixed together, stirred at room temperature, and then allowed to stand for reaction and centrifugal collection, followed by washing with ethanol several times.
FeOOH nanorod Synthesis 5.46g FeCl 3 ·6H 2 O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethylenimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. Centrifugal separation, dispersing in 10mL PVP ethanol solution (0.5 g PVP, mw=40,000), and the mixture was stirred at room temperature for a further 12 hours. PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15ml of methanol for further use.
Preparation of ZIF-8@FeOOH/ZIF-67 hybrid particles the synthesized ZIF-8 particles and 1.6mL FeOOH nanorod suspension were first ultrasonically dispersed in 120mL 20mM Co (NO) 3 ) 2 ·6H 2 And O solution. Ultrasonic treatment, rapid addition of 200mL 160mM 2-methylimidazole (95%) methanol solution, stirring and mixing the mixture at room temperature, standing for 2h, centrifugal collection, methanol washing for several times, and vacuum drying to obtain ZIF-8@FeOOH/ZIF-67 hybrid particles.
4. Spider nest type iron-cobalt alloy nitrogen doped carbon nano material (FeCoSG/NCNT) is synthesized: the ZIF-8@FeOOH/ZIF-67 mixed particles obtained above were placed in a ceramic boat in an amount of 0.5g, and the other ceramic boat was placed above and filled with 3g of melamine. The whole argon/hydrogen (7%) mixed gas circulation of the tube furnace, the heating program is a two-stage heating mode, the first step is that the temperature is 5 ℃ for min at room temperature -1 Heated to 350℃and incubated at this temperature for 60 minutes. Then heated to 800℃and incubated for 2 hours. After that, the furnace was naturally cooled to room temperature.
(2) Synthesis of spider-nest-shaped iron-cobalt alloy nitrogen doped carbon nanomaterial @ ruthenium nanoparticles:
MOF-derived spider nest type iron-cobalt alloy nitrogen doped carbon nano material is immersed in RuCl 3 ·xH 2 In the ethanol solution of O, the load of ruthenium nano particles is realized by the reduction of argon/hydrogen (7%) mixed gas through an ultrasonic and vacuum oven, and the specific process is as follows: grinding FeCoSG/NCNT0.1g, mixing with 0.03g RuCl 3 ·xH 2 O (ruthenium content more than 37%) is dispersed in 10mL ethanol solution, and the solution is put in a sample bottle, dispersed for 7 minutes by ultrasonic and then kept stand for 8 hours. And then transferring the liquid in the sample bottle into a culture dish, and quickly drying in a vacuum oven at 60 ℃, wherein liquid splashing phenomenon 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 3 hours 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). At N 2 The gas was continuously bubbled into a 1.0M KOH solution. All potentials were at 2mV s -1 Is converted to a Reversible Hydrogen Electrode (RHE). The results obtained for all Linear Sweep Voltammetry (LSV) curves at 1600rpm are shown in FIG. 5. FeCoSG/NCNT RU-3 samples showed very high HER electrocatalytic activity, 10mA cm -2 The overpotential at current density was 44.1mV vs. RHE, which had slightly lower electrocatalytic activity than the commercial Pt/C catalyst tested under the same conditions (10 mA cm -2 The overpotential at current density was 30.11mV vs. RHE). The material has faster reaction kinetics in the HER electrocatalytic process, and the catalytic effect is slightly lower than that of commercial Pt/C and FeCoSG/NCNT RU-1 samples. Exhibits low catalytic activity at higher reduction temperatures, possibly due to agglomeration of ruthenium nanoparticles.
Example 4: the preparation and application of the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle specifically comprises the following steps:
(1) Synthesis of MOF-derived spider nest-like iron-cobalt alloy nitrogen doped carbon nanomaterial:
ZIF-8 particle Synthesis to synthesize ZIF-8 crystals, 200mL of 20mM Zn (NO 3 ) 2 ·6H 2 O (98%) in methanol, 1.6mL of 1-methylimidazole (99%) and 200mL of 100mM 2-methylimidazole (95%) in methanol were mixed together, stirred at room temperature, and then allowed to stand for reaction and centrifugal collection, followed by washing with ethanol several times.
FeOOH nanorod Synthesis 5.46g FeCl 3 ·6H 2 O (98%) was added to a round bottom flask containing 100mL deionized water and 0.3mL Polyethylenimine (PEI). The reaction mixture was heated at 80 ℃ for 2h with stirring to obtain uniform FeOOH nanorods. Centrifugal separation, dispersing in 10mL PVP ethanol solution (0.5 g PVP, mw=40,000), and the mixture was stirred at room temperature for a further 12 hours. PVP functionalized FeOOH nanorods were collected by centrifugation, washed several times with ethanol, and dispersed in 15ml of methanol for further use.
Preparation of ZIF-8@FeOOH/ZIF-67 hybrid particles the synthesized ZIF-8 particles and 1.6mL FeOOH nanorod suspension were first ultrasonically dispersed in 120mL 20mM Co (NO) 3 ) 2 ·6H 2 And O solution. Ultrasonic treatment, rapid addition of 200mL 160mM 2-methylimidazole (95%) methanol solution, stirring and mixing the mixture at room temperature, standing for 2h, centrifugal collection, methanol washing for several times, and vacuum drying to obtain ZIF-8@FeOOH/ZIF-67 hybrid particles.
4. Spider nest type iron-cobalt alloy nitrogen doped carbon nano material (FeCoSG/NCNT) is synthesized: the ZIF-8@FeOOH/ZIF-67 mixed particles obtained above were placed in a ceramic boat in an amount of 0.5g, and the other ceramic boat was placed above and filled with 3g of melamine. The whole argon/hydrogen (7%) mixed gas circulation of the tube furnace, the heating program is a two-stage heating mode, the first step is that the temperature is 5 ℃ for min at room temperature -1 Heated to 350℃and incubated at this temperature for 60 minutes. Then heated to 800℃and incubated for 2 hours. After that, the furnace was naturally cooled to room temperature.
(2) Synthesis of MOF-derived spider-nest-like iron-cobalt alloy nitrogen-doped carbon nanomaterial @ ruthenium nanoparticle:
MOF-derived spider nest type iron-cobalt alloy nitrogen doped carbon nano material is immersed in RuCl 3 ·xH 2 O in ethanol solution, argon/hydrogen (7%) was mixed by ultrasonic and vacuum ovenThe gas reduction realizes the loading of ruthenium nano particles, and the specific process is as follows: grinding FeCoSG/NCNT0.1g, mixing with 0.03g RuCl 3 ·xH 2 O (ruthenium content more than 37%) is dispersed in 10mL ethanol solution, and the solution is put in a sample bottle, dispersed for 7 minutes by ultrasonic and then kept stand for 8 hours. And then transferring the liquid in the sample bottle into a culture dish, and quickly drying in a vacuum oven at 60 ℃, wherein liquid splashing phenomenon 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 3 hours 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). At N 2 The gas was continuously bubbled into a 1.0M KOH solution. All potentials were at 2mV s -1 Is 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 high HER electrocatalytic activity, 10mA cm -2 The overpotential at current density was 61.1mV vs. RHE, which had lower electrocatalytic activity than the commercial Pt/C catalyst tested under the same conditions (10 mA cm -2 The overpotential at current density was 30.11mV vs. RHE). The material is proved to be seriously lost under the condition of higher reduction temperature of HER electrocatalytic performance, 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 nano-particles is serious. Nevertheless, at large current densities (e.g. in excess of 100mA cm -2 ) The FeCoSG/NCNT Ru-4 presents the advantage of anti-super platinum carbon, and the mass transfer and conductivity improvement are accelerated due to the unique three-dimensional spider nest structure.
Finally, it should also be stated that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (9)

1. The preparation method of the spider nest composite carbon nano material @ ruthenium nano particle is characterized in that the spider nest composite carbon nano material is MOF derived spider nest iron-cobalt alloy nitrogen doped carbon nano material, the MOF derived spider nest iron-cobalt alloy nitrogen doped carbon nano material is a conductive network, and the ruthenium nano particle is a load; the preparation method specifically comprises the following steps:
step one, synthesizing an MOF derived spider nest type composite carbon nano material:
(1) Synthesis of zinc-based Zeolite imidazole ester skeleton Material ZIF-8 particles, a certain amount of Zn (NO) 3 ) 2 ⋅6H 2 Mixing O methanol solution, 1-methylimidazole and 2-methylimidazole together, stirring at room temperature for reaction, centrifuging, collecting, and washing with ethanol for several times;
(2) Synthesizing FeOOH nano rod, taking a certain amount of FeCl 3 ·6H 2 O is added into a round-bottom flask filled with deionized water and Polyethyleneimine (PEI), and heated to react at 65-90 ℃ for 2h to obtain uniform FeOOH nano rods;
(3) Preparation of polyvinylpyrrolidone (PVP) functionalized FeOOH nanorods: dispersing the FeOOH nano rod obtained in the step (2) in PVP ethanol solution, further stirring for 8-12 hours at room temperature to obtain PVP functionalized FeOOH nano rod, centrifugally separating, washing for a plurality of times by ethanol, and dispersing in methanol for later use;
(4) Preparation of ZIF-8@FeOOH/cobalt-based zeolitic imidazolate framework material ZIF-67 hybrid particles comprising dispersing the prepared ZIF-8 particles of (1) and the PVP-functionalized FeOOH nanorod suspension prepared in (3) in Co (NO) by ultrasonic waves 3 ) 2 ⋅6H 2 Adding a methanol solution of 2-methylimidazole into the O solution, stirring and mixing the mixture at room temperature, standing for reaction 2h, centrifugally collecting, washing with methanol for several times, and vacuum drying to obtain ZIF-8@FeOOH/ZIF-67 hybrid particles;
(5) Synthesis of spider nest type iron-cobalt alloy nitrogen doped carbon nanomaterial 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 mixed particles, filling nitrogen source organic matters in the ceramic boat, circulating argon and hydrogen in the whole process of a tube furnace, adopting a two-stage heating program, and cooling to room temperature after heating to obtain the spider-nest type iron-cobalt alloy nitrogen-doped carbon nanomaterial FeCoSG/NCNT;
step two, preparing MOF derived spider nest composite carbon nano material @ ruthenium nano particles: by impregnating spider nest type iron-cobalt alloy nitrogen doped carbon nano material in RuCl 3 ·xH 2 And (3) in the ethanol solution of O, carrying out ultrasonic dispersion, standing for 5-8 hours, transferring the solution to a vacuum oven for drying, and placing the dried sample in a tube furnace for reducing by introducing 7% of argon-hydrogen mixed gas to realize the loading of ruthenium nano particles.
2. The method for producing a spider-nest-like composite carbon nanomaterial @ ruthenium nanoparticle according to claim 1, wherein in step (1), the Zn (NO 3 ) 2 ⋅6H 2 The amount of O substance was 20mM, zn (NO 3 ) 2 ⋅6H 2 The volume of the O methanol solution is 180-250 mL; the mass fraction of the 1-methylimidazole is 99%, and the volume 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.
3. The method for preparing a spider-nest-like composite carbon nanomaterial @ ruthenium nanoparticle according to claim 1, wherein in step one (2), the feci 3 ·6H 2 The mass of O is 5.46-g, the volume of deionized water is 100mL, and the volume of Polyethylenimine (PEI) is 0.1-0.5 mL.
4. The preparation method of the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle according to claim 1, wherein in the first step (3), the volume of the PVP ethanol solution is 6-12 mL, and the mass fraction of PVP is 2% -8%; the volume of the methanol is 10-20 mL.
5. The method for preparing a spider-nest-like composite carbon nanomaterial @ ruthenium nanoparticle according to claim 1, wherein in step one (4), co (NO 3 ) 2 ⋅6H 2 The amount of O is 18-25 mM, co (NO 3 ) 2 ⋅6H 2 The 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.
6. The method for preparing the spider-nest composite carbon nanomaterial @ ruthenium nanoparticle according to claim 1, wherein the nitrogen source organic matter in the step one (5) is one or two of melamine and dicyandiamide; the heating rate of the first section of the two-section heating program is 5 ℃ min −1 Heating to 350 ℃ and preserving heat for 60min; the heating rate of the second stage program is 5 ℃ min −1 The first stage is then heated to 800 ℃ and incubated 2h.
7. The method for preparing a spider-nest-like composite carbon nanomaterial @ ruthenium nanoparticle according to claim 1, wherein in the second step, the Rucl 3 ·xH 2 The amount of ruthenium in O is more than 37%, feCoSG/NCNT and RuCl 3 ·xH 2 The mass ratio of O is 3-4: 1.
8. the method for preparing the spider-nest-like composite carbon nanomaterial @ ruthenium nanoparticles according to claim 1, wherein the drying temperature in the vacuum oven is 50-60 ℃; the reduction temperature in the tube furnace is 350-450 ℃ and the time is 2-4 hours.
9. The application of the MOF-derived composite carbon nanomaterial @ ruthenium nanoparticle according to any one of 1-8, which is characterized in that the MOF-derived composite carbon nanomaterial is applied to HER reaction, and the surface of the MOF-derived spider-nest-like composite carbon nanomaterial is loaded with ruthenium nanoparticle, so that the surface mass transfer is obviously enhanced, the overpotential of the reaction is reduced, and the performance and the conductivity of the catalyst are improved.
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