CN114525547A - Ru-ZnFexOyPreparation method and application of heterogeneous nanosheet modified porous carbon material - Google Patents

Ru-ZnFexOyPreparation method and application of heterogeneous nanosheet modified porous carbon material Download PDF

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CN114525547A
CN114525547A CN202210042433.8A CN202210042433A CN114525547A CN 114525547 A CN114525547 A CN 114525547A CN 202210042433 A CN202210042433 A CN 202210042433A CN 114525547 A CN114525547 A CN 114525547A
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carbon material
porous carbon
znfe
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CN114525547B (en
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刘苏莉
周峰
钱春竹
邵文倩
李亭亭
陈昌云
张星玥
顾祥耀
马李刚
李盛杰
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Nanjing Xiaozhuang University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
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    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention provides Ru-ZnFexOyA preparation method of a heterogeneous nanosheet modified porous carbon material adopts mushroom waste residues and low-toxicity metal salts (iron salts, zinc salts and ruthenium salts) as raw materials, and constructs a novel Ru-ZnFe material through optimization and regulation of the preparation method and strategyxOyThe heterogeneous nanosheet modifies the porous carbon material. The material develops a simple, green and enlargeable preparation method of the biomass-based carbon material loaded Ru nano catalyst by utilizing heteroatom sources (amino acid, protein and the like) which are rich in biomass mushroom dregs under the condition of not adding a template. Further research shows that Ru-ZnFexOyHeterogeneous nanosheet modified porous carbon material as electrocatalyst for alkaline pure water and seaThe catalyst shows excellent catalytic activity in the process of preparing hydrogen from water, and is superior to the current commercial 20% Pt/C catalyst.

Description

Ru-ZnFexOyPreparation method and application of heterogeneous nanosheet modified porous carbon material
Technical Field
The invention relates to the technical field of biomass porous carbon materials, in particular to Ru-ZnFexOyA preparation method and application of a heterogeneous nanosheet modified porous carbon material.
Background
Hydrogen is a promising alternative energy source due to its sustainability and environmental friendliness. Electrochemical water splitting is considered a clean, simple, high purity method of hydrogen production. The Hydrogen Evolution Reaction (HER) is one of the important reactions of electrochemical water splitting, the efficiency of which depends mainly on the electrocatalyst. Generally, Platinum Group Metals (PGMs) have proven to be the most effective HER electrocatalysts, but their widespread use is limited by the scarcity and high cost of precious metals. Precise control of the size and nanostructure of PGMs-based electrocatalysts is of great interest in order to reduce the use of platinum group metals, improve the utilization of atoms. To overcome the kinetics of the slow response of HER, achieving high current densities at low overpotentials, great efforts have been made to develop highly efficient PGMs-based electrocatalysts. In addition, electrocatalytic materials with low overpotentials in alkaline and seawater electrolytes are also essential for practical application of green hydrogen production technologies.
The electrolysis of seawater to produce hydrogen has been considered as one of the most promising methods due to the abundant seawater reserves on earth. Compared with fresh water electrolysis, the direct electrolysis of hydrogen by natural seawater is challenging. Firstly, the seawater is guidedPoor electrical properties, resulting in slow kinetics of HER reactions. Therefore, there is a need for a highly conductive electrocatalyst to accelerate charge transfer in seawater electrolysis processes. Secondly, insoluble precipitates generated on the surface of the electrode during the seawater cracking process, including Mg (OH)2And Ca (OH)2To solve this problem, an electrocatalyst having a large specific surface area and a rich catalytically active component is preferred. In addition, corrosion of the electrodes by corrosive anions in seawater also limits HER during seawater electrolysis. Therefore, it is highly desirable to develop a highly efficient electrocatalyst having high activity in alkaline seawater.
With the development of modern society, the large consumption of non-renewable fossil fuels poses serious environmental and energy problems. The development of sustainable technologies related to energy is beneficial to mitigate the threat of fossil fuel depletion. Nature uses carbon and other elements to create diverse organisms and provide a renewable approach to energy and matter conversion. The carbon-based natural resources or biomass are used as renewable precursors to controllably prepare the carbon material, so that the consumption of fossil reserves can be obviously reduced, and the sustainable development of the human society is promoted. Various biomass-derived carbon materials have been produced by carbonizing carbon-based precursors obtained from living bodies such as plants, animals, insects, and aquatic organisms.
Generally, the carbon nanomaterial of biomass has a unique three-dimensional structure, abundant surface functional groups, high specific surface area and high porosity, and has a good potential in the field of electrochemical industry. Pyrolysis method is commonly used for preparing activated carbon from biomass, but because the biomass has a complex structure, contains more heteroatoms except C and has strong chemical bonds, the carbon atoms in the biomass cannot be easily rearranged orderly and regularly by pyrolysis, so that carbon nano materials with high crystallinity can be rarely obtained, and related reports are few. Pretreatment of biomass, such as hydrothermal carbonization, is an effective method to reduce the difficulty of preparing carbon nanomaterials. However, there are inherent limitations to the strategy of hydrothermal carbonization that remain to be solved. For example, it must be performed in a relatively low temperature range (150-. In addition, various hydrolysates produced during the hydrothermal process of biomass have a negative impact on maintaining the original structure. Although various biomass precursors, carbonization methods, and other strategies have been developed to synthesize bio-based materials, there are still many challenges that need to be addressed for different application purposes. In particular, in the fields of energy conversion and electrocatalysis, a porous biomass carbon material with heteroatom doping, large specific surface area and high total pore volume is needed.
Disclosure of Invention
Aiming at the prior art, the invention provides Ru-ZnFexOyThe preparation method and the application of the heterogeneous nanosheet modified porous carbon material are characterized in that waste mushroom dregs are prepared into a biomass porous carbon material with excellent performance by a high-temperature carbonization method.
The invention provides Ru-ZnFexOyThe preparation method of the heterogeneous nanosheet modified porous carbon material comprises the following steps: cleaning mushroom waste residue with distilled water, drying in 90 deg.C oven, pre-carbonizing mushroom waste residue in inert atmosphere to obtain pre-carbonized product, and using ferric chloride hexahydrate (FeCl)3·6H2O) and zinc chloride (ZnCl)2) Preparation of ZnFe as activatorxOyModifying porous carbon material, and introducing ruthenium trichloride hydrate (RuCl) in situ3·xH2O), preparation of Ru-ZnFexOyThe heterogeneous nanosheet modifies the porous carbon material.
Preferably, the specific operations of pre-carbonization comprise: heating the mushroom waste residue in inert atmosphere preferably under argon, raising the temperature to 400 ℃, keeping the temperature for 0.5-1.5h at constant temperature, and reducing the temperature to obtain a pre-carbonized product.
Preferably, in the pre-carbonization, the temperature rising rate is 4-6 ℃/min.
Preferably, the preparation of ZnFexOyThe specific operation of modifying the porous carbon material comprises the following steps: 200-300mg of pre-carbonized product, 200-300mg of zinc chloride and 800-900mg of ferric chloride hexahydrate are ground and mixed uniformly, and then the mixture is carried out in an inert atmosphere, preferably under nitrogenAnd (4) high-temperature activation.
Preferably, the temperature of the high-temperature activation is 750-850 ℃, and the time is 1.5-2.5 h.
Preferably, in the high-temperature activation, the temperature rise rate is 4-6 ℃/min.
Preferably, the preparation of ZnFexOyThe specific operation of modifying the porous carbon material further comprises: washing and vacuum filtering the sample obtained after high-temperature activation until the sample is neutral, and drying to obtain ZnFexOyModifying the porous carbon material.
Preferably, the preparation of Ru-ZnFexOyThe specific operation of modifying the porous carbon material by the heterogeneous nanosheets comprises the following steps: 10-25mg ZnFexOyGrinding and mixing the modified porous carbon material and 10-15mg of hydrated ruthenium trichloride, heating the mixture in an inert atmosphere preferably under nitrogen, heating the mixture to 400-500 ℃, keeping the temperature at a constant temperature for 0.5-1.5h, and cooling the mixture to obtain Ru-ZnFexOyThe heterogeneous nanosheet modifies the porous carbon material.
Preferably, the preparation of Ru-ZnFexOyIn the porous carbon material modified by the heterogeneous nanosheets, the heating rate is 1-3 ℃/min.
The invention also discloses Ru-ZnFexOyThe application of the heterogeneous nanosheet modified porous carbon material is to apply the porous carbon material to a catalyst in the hydrogen evolution reaction of electrolytic alkaline pure water and seawater.
According to the invention, the drying temperature and time ensure complete volatilization of water in the biomass porous carbon material, and the stability of the biomass porous carbon material is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes cheap and easily available mushrooms with stable sources as raw materials, has wide sources, high yield, low price, easy obtaining and sustainable obtaining, can be directly produced in factories, is suitable for large-scale application, realizes waste recycling, saves resources and makes up for the defect of high cost of carbon materials.
2. The preparation method provided by the invention has the advantages of simple process and short flow, reduces the production cost and time, improves the preparation efficiency, effectively solves the problems of low capacity and complex production process of the existing carbon material, has low requirement on equipment, and is easy to implement.
3. The invention takes mushroom as a carbon source, and the elements contained in the mushroom are mainly C, N and O, thus not influencing the determination of the active site of the catalyst. In addition, the mushroom is porous after carbonization and activation treatment, which is beneficial to modification of metal precursor and exposure of active sites, thereby effectively improving the overall catalytic activity of the catalyst.
4. The invention adopts FeCl3·6H2O and ZnCl2The reaction of the active agent and carbon promotes the increase of pores and pore structures in the carbon material, improves the specific surface area and pore structures of the biomass porous carbon material, and is beneficial to HER reaction under the condition of alkaline seawater.
5. The invention can also improve the catalytic activity and selectivity of the metal nanoparticles by modulating the interaction between the carrier and the metal nanoparticles, thereby improving the use efficiency and the recycling capability of the metal nanoparticles, and Ru which is a member of Pt group has the hydrogen evolution activity similar to Pt, and the price of Ru is only 4 percent of Pt, so the invention has very wide application prospect.
Drawings
FIG. 1 is a TEM image of a pre-carbonized product in example 1 of the present invention.
FIG. 2 shows ZnFe in example 1 of the present inventionxOyTEM images of modified porous carbon materials.
FIG. 3 shows Ru-ZnFe in example 1 of the present inventionxOyAnd (4) TEM image of the heterogeneous nanosheet modified porous carbon material.
FIG. 4 shows the pre-carbonized product, ZnFe, in example 1 of the present inventionxOyModified porous carbon material and Ru-ZnFexOyAnd (3) modifying an XRD pattern of the porous carbon material by using the heterogeneous nanosheets.
FIG. 5 shows the pre-carbonized product, ZnFe, in example 1 of the present inventionxOyModified porous carbon material and Ru-ZnFexOyXPS (X spectrum of X-ray diffraction) diagram of heterogeneous nanosheet modified porous carbon material.
FIG. 6 shows the pre-carbonization in example 1 of the present inventionConversion product, ZnFexOyBET profile of the modified porous carbon material.
FIG. 7 ZnFe, a pre-carbonized product in an example of the present inventionxOyModified porous carbon material and Ru-ZnFexOyAnd (3) a hydrogen evolution performance comparison graph of the heterogeneous nanosheet modified porous carbon material.
FIG. 8 shows Ru-ZnFe in Experimental example 1 of the present inventionxOyA comparison graph of hydrogen evolution performance of the heterogeneous nanosheet modified porous carbon material and catalysts reported in other related documents in seawater is shown.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below by combining the specific drawings.
Example 1
Ru-ZnFexOyThe preparation method of the heterogeneous nanosheet modified porous carbon material comprises the following steps: cleaning mushroom waste residues with distilled water, drying the mushroom waste residues in a 90 ℃ drying oven, putting part of the mushroom waste residues into a clean alumina porcelain boat, putting the boat in a tubular furnace, heating the boat to 350 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, keeping the temperature for 1h at the temperature, cooling the boat to a certain temperature, taking out the boat, and grinding the boat into powder to obtain a pre-carbonized product. The morphology of the nano-porous carbon nano-film is seen from the TEM characterization result shown in FIG. 1. From the XRD characterization result of fig. 4, it is shown that a distinct C peak appears at a diffraction angle of 22 degrees, which is composed mainly of carbon element on the surface. From the XPS characterization results of fig. 5, it can be seen that the pre-carbonized product is mainly composed of C and O, with 4 peaks in total appearing in the C1s orbit, at binding energies 284.68eV, 285.64eV, 288.68eV and 292.87eV, respectively, which correspond to the stretching shock peaks of C C, C-O, C ═ 0 and pi → pi ═ respectively; the 3 peaks in the O1s orbital, located at binding energies 530.97eV, 532.28eV and 533.61eV respectively, are associated with the M-O peak and the oxygen vacancy (O) respectivelyvac) Peak and C-OH adsorption and desorption peaks on the surface of the carbon material. The BET characterization result of FIG. 6 shows that the specific surface area of the pre-carbonized product obtained after direct calcination with mushroom waste residue is only 6.51m2/g。
Further, 250mg of the pre-carbonized product and 250mg of ZnCl were weighed at room temperature2And 850mg FeCl3·6H2O, fully grinding and mixing, transferring to an alumina square boat, placing in a tubular furnace protected by nitrogen atmosphere, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 2h, cooling to a certain temperature, collecting a sample, repeatedly washing and vacuum-filtering the collected sample for 3 times until the sample is neutral, and drying a filter cake in a vacuum drying box at the temperature of 60 ℃ to obtain ZnFexOyModifying the porous carbon material. The morphology is ZnFe as shown by the TEM representation of FIG. 2xOyA modified porous carbon material. From the XRD characterization result of FIG. 4, it was shown that its main component was ZnFe2O4(JCPDS # 22-1012). From the XPS characterization results of fig. 5, it can be seen that the composite structure composition is mainly composed of C, O, Fe and Zn, and 3 peaks occur together in the C1s orbital, respectively at the binding energies of 284.69eV, 285.81eV and 289.12eV, which correspond to the C C, C-O, C-0 peak, respectively; the 3 peaks in the O1s orbital, located at binding energies 531.58eV, 532.99eV and 534.14eV respectively, are associated with the M-O peak and the oxygen vacancy (O) respectivelyvac) Peaks and C-OH adsorption and desorption peaks on the surface of the carbon material; in the Fe 2p orbit, 3 groups of peaks occur together, and the first group of peaks is located at 711.16eV binding energy (Fe 2 p)3/2)、724.80eV(Fe 2p1/2) Here, the set of peaks indicates ZnFexOyFe in the modified porous carbon material is mainly Fe2+, the second set of peaks at 715.09eV, 729.10eV, indicating ZnFexOyModified porous carbon material containing Fe3+, the third set of peaks at binding energies 719.09eV, 733.64eV is a set of satellite peaks; the common 1 group peak in the Zn 2p orbital is located at the binding energy of 1021.70eV and 1044.86eV, respectively, and represents ZnFexOyThe valence state of Zn element in the modified porous carbon material is mainly Zn2+. The BET characterization result in FIG. 6 shows that ZnFe is obtained after activation by the activator and high temperature calcinationxOyThe specific surface area of the modified porous carbon material is 393.06m2The specific surface area is increased by 60 times compared with that of the pre-carbonized product, and the pores on the surface are mesopores.
Further, 20mg of ZnFe was weighed at room temperaturexOyModified porous carbon Material and 12mg RuCl3·xH2O, fully grinding and mixing, transferring to an alumina square boat, heating to 450 ℃ at the speed of 2 ℃/min in a tube furnace in the nitrogen atmosphere, preserving heat for 1h, cooling to a certain temperature to obtain a final product Ru-ZnFexOyThe heterogeneous nanosheet modifies the porous carbon material. The morphology of the material is shown to be provided with Ru-ZnFe through the TEM representation result of FIG. 3xOyThe heterogeneous nanosheet is modified with a porous carbon nanomaterial. From the XRD characterization result of FIG. 4, it was shown that its main component was ZnFe2O4(JCPDS #22-1012) and Ru simple substance (JCPDS # 65-1863). From the XPS characterization result of FIG. 5, it can be seen that the composite material is mainly composed of C, O, Fe, Zn and Ru, and the 01 s, Fe 2p and Zn 2p orbitals thereof and ZnFexOyThe modified porous carbon materials are substantially similar in that the Ru 3p orbital consists of a set of peaks, each being Ru 3p at a binding energy of 462.60eV2/3Orbitals and the Ru 3p1/2 orbit at 484.66eV, which indicates that the doped Ru element is mainly a 0-valent Ru simple substance.
Example 2
Ru-ZnFexThe preparation method of the Oy heterogeneous nanosheet modified porous carbon material comprises the following steps: cleaning mushroom waste residues with distilled water, drying in a 90 ℃ oven, putting part of the mushroom waste residues into a clean alumina porcelain boat, putting the boat in a tubular furnace, heating to 400 ℃ at the heating rate of 4 ℃/min in the argon atmosphere, preserving heat for 0.5h at the temperature, cooling to a certain temperature, taking out, grinding into powder, and obtaining a pre-carbonized product.
Further, 300mg of the pre-carbonized product and 200mg of ZnCl were weighed at room temperature2And 900mg FeCl3·6H2O, fully grinding and mixing, transferring to an alumina square boat, placing in a tubular furnace protected by nitrogen atmosphere, heating to 850 ℃ at the speed of 4 ℃/min, preserving heat for 1.5h, cooling to a certain temperature, collecting a sample, repeatedly washing and carrying out vacuum filtration on the collected sample for 3 times until the sample is neutral, and placing a filter cake in a vacuum drying oven at 60 ℃ for drying to obtain ZnFexOyModifying the porous carbon material.
Further, 25mg of ZnFe was weighed at room temperaturexOyModified porous carbon Material and 10mg RuCl3·xH2O, fully grinding and mixing, transferring to an alumina square boat, heating to 400 ℃ at the speed of 3 ℃/min in a tube furnace in the nitrogen atmosphere, preserving heat for 1.5h, cooling to a certain temperature to obtain a final product Ru-ZnFexOyThe heterogeneous nanosheet modifies the porous carbon material.
Example 3
Ru-ZnFexOyThe preparation method of the heterogeneous nanosheet modified porous carbon material comprises the following steps: cleaning mushroom waste residues with distilled water, drying the mushroom waste residues in a 90 ℃ oven, putting part of the mushroom waste residues into a clean alumina porcelain boat, putting the boat in a tubular furnace, heating the boat to 300 ℃ at the heating rate of 6 ℃/min in the argon atmosphere, preserving the heat for 1.5h at the temperature, cooling the boat to a certain temperature, taking out the boat, and grinding the boat into powder to obtain a pre-carbonized product.
Further, 200mg of the pre-carbonized product and 300mg of ZnCl were weighed at room temperature2And 800mg FeCl3·6H2O, fully grinding and mixing, transferring to an alumina square boat, placing in a tubular furnace protected by nitrogen atmosphere, heating to 750 ℃ at the speed of 6 ℃/min, preserving heat for 2.5h, cooling to a certain temperature, collecting a sample, repeatedly washing and carrying out vacuum filtration on the collected sample for 3 times until the sample is neutral, and placing a filter cake in a vacuum drying oven at 60 ℃ for drying to obtain ZnFexOyModifying the porous carbon material.
Further, 10mg of ZnFe was weighed at room temperaturexOyModified porous carbon Material and 15mg RuCl3·xH2O, fully grinding and mixing, transferring to an alumina square boat, heating to 500 ℃ at the speed of 1 ℃/min in a tube furnace in the nitrogen atmosphere, preserving heat for 0.5h, cooling to a certain temperature to obtain a final product Ru-ZnFexOyThe heterogeneous nanosheet modifies the porous carbon material.
Examples of the experiments
For the pre-carbonized product obtained in example 1, ZnFexOyModified porous carbon material, Ru-ZnFexOyThe heterogeneous nanosheet modified porous carbon material and a commercial 20% Pt/C catalyst are respectively subjected to an alkaline seawater hydrogen evolution performance (HER) test, and the test method comprises the following steps: before the experiment, 3mg of the substance to be detected is weighed and dispersed in 200 mu L of absolute ethyl alcohol, 370 mu L of secondary distilled water is added after uniform dispersion, and 5mg/mL suspension is obtained. The glassy carbon electrode with the diameter of 5mm adopts Al2O3Grinding to a mirror surface, rinsing with secondary distilled water, and drying in a 45 ℃ oven for later use. And dripping 10 mu L of the suspension on the surface of the electrode in one time, and finally dispersing 3 mu L of 0.1 wt% naphthol solution on the surface of a glassy carbon electrode with the diameter of 5mm and drying in an oven to obtain the modified electrode.
Before HER test, high-purity N is firstly introduced into the solution for 30min2To remove dissolved other gases from the solution and continue to feed N during the experiment2To remove dissolved oxygen. LSV test is also at N2The scanning is carried out in the atmosphere, and the corresponding electrochemical scanning rate is 5mV/s, and the scanning range is-1.2V to-0.5V.
Referring to FIG. 7, HER Performance testing may result in Ru-ZnFe in 1M KOH pure waterxOyThe current density of the heterogeneous nanosheet modified porous carbon material can reach 200mA/cm2. When the current density is 10, 50, 100, 150, 200mA/cm2When the catalyst is used, the overpotential is respectively 18, 48, 77, 102 and 126mV, which is much less than 31, 113, 187 and 261mV of the current density corresponding to the commercial Pt/C catalyst; simultaneous Ru-ZnFexOyThe Tafel slope of the heterogeneous nanosheet modified porous carbon material in 1M KOH pure water is 22mV/dec, which is less than 39mV/dec of a commercial Pt/C catalyst. In addition, Ru-ZnFe is contained in 1M KOH seawaterxOyThe current density of the heterogeneous nanosheet modified porous carbon material can also reach 200mA/cm2. When the current density is 10, 50, 100, 150, 200mA/cm2When the catalyst is used, the overpotentials are respectively 27, 71, 106, 135 and 164mV, which are greatly superior to that of the commercial Pt/C catalyst (the current density is 10 mA/cm)2The overpotential is 29.1mV, and the device cannot work under high current density); simultaneous Ru-ZnFexOyThe Tafel slope of the heterogeneous nano-sheet modified porous carbon material in 1M KOH seawater is 33mV/dec, and is also less than48mV/dec for a commercial Pt/C catalyst. The test result shows that the catalyst performance (overpotential) and the reaction rate (Tafel slope) of the catalyst in 1M KOH and seawater are both superior to those of commercial 20% Pt/C, and the catalyst has the potential of replacing the commercial Pt/C.
Referring to FIG. 8, Ru-ZnFe was preparedxOyThe HER performance of the heterogeneous nanosheet modified porous carbon material in seawater is greatly superior to that of a plurality of materials reported in the literature at present, and the performance parameters are shown in the following table:
Figure BDA0003470859570000091
Figure BDA0003470859570000101
the invention takes mushroom waste residue as a material and realizes Ru-ZnFe through a simple hydrothermal carbonization processxOyAnd (3) green preparation of the biomass carbon material modified by the heterogeneous nanosheets. The invention takes mushroom as carbon source, the elements contained in the mushroom are mainly C, N and O, which can not affect the determination of the active site of the catalyst, moreover, the mushroom presents porous characteristic after carbonization and activation treatment, which is beneficial to the load of metal precursor and the exposure of the active site, thereby effectively improving the whole catalytic activity of the catalyst. Using FeCl3·6H2O and ZnCl2The activated carbon material is calcined at high temperature of about 800 ℃ and then reacts with carbon to promote the increase of pores and pore structures in the carbon material, so that the specific surface area and pore structures of the biomass porous carbon material are improved, and meanwhile, the conductivity of the biomass porous carbon material is greatly increased, so that the biomass porous carbon material has high current density, and the activated carbon material is very beneficial to HER reaction under the condition of alkaline seawater. In addition, the catalytic activity and selectivity of the metal nanoparticles can be improved by modulating the interaction between the carrier and the metal nanoparticles, so that the use efficiency and the recycling capability of the metal nanoparticles are improved, Ru, as a member of the Pt family, has the hydrogen evolution activity similar to Pt, has the price of only 4 percent of Pt, and has very wide application prospect。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures made by using the contents of the present specification and the drawings can be directly or indirectly applied to other related technical fields, and are within the scope of the present invention.

Claims (10)

1. Ru-ZnFexOyThe preparation method of the heterogeneous nanosheet modified porous carbon material is characterized by comprising the following steps: pre-carbonizing mushroom waste residue in inert atmosphere to obtain pre-carbonized product, and activating with ferric chloride hexahydrate and zinc chloride to prepare ZnFexOyModified porous carbon material, and Ru-ZnFe prepared by introducing hydrated ruthenium trichloridexOyThe heterogeneous nanosheet modifies the porous carbon material.
2. The method according to claim 1, characterized in that said pre-carbonization comprises, in particular: heating the mushroom waste residue in an inert atmosphere, raising the temperature to 300-400 ℃, keeping the temperature for 0.5-1.5h at constant temperature, and reducing the temperature to obtain a pre-carbonized product.
3. The production method according to claim 2, wherein in the preliminary carbonization, the temperature increase rate is 4 to 6 ℃/min.
4. The method according to claim 1 or 2, wherein the preparation of ZnFe is carried outxOyThe specific operation of modifying the porous carbon material comprises the following steps: 200-300mg of the pre-carbonized product, 200-300mg of zinc chloride and 800-900mg of ferric trichloride hexahydrate are ground and mixed uniformly, and then activated at high temperature.
5. The method as claimed in claim 4, wherein the temperature for the high temperature activation is 750-850 ℃ and the time is 1.5-2.5 h.
6. The method according to claim 5, wherein in the high-temperature activation, the temperature increase rate is 4 to 6 ℃/min.
7. The method of claim 4, wherein the preparation of ZnFe is carried outxOyThe specific operation of modifying the porous carbon material further comprises: washing and vacuum filtering the sample obtained after high-temperature activation until the sample is neutral, and drying to obtain ZnFexOyModifying the porous carbon material.
8. The production method according to claim 1 or 2, wherein the production of Ru-ZnFexOyThe specific operation of modifying the porous carbon material by the heterogeneous nanosheets comprises the following steps: 10-25mg ZnFexOyGrinding and mixing the modified porous carbon material and 10-15mg of ruthenium trichloride hydrate, heating in an inert atmosphere, raising the temperature to 400-plus-one 500 ℃, keeping the temperature at a constant temperature for 0.5-1.5h, and cooling to obtain Ru-ZnFexOyThe heterogeneous nanosheet modifies the porous carbon material.
9. The method of claim 8, wherein the preparation of Ru-ZnFexOyIn the porous carbon material modified by the heterogeneous nanosheets, the heating rate is 1-3 ℃/min.
10. Ru-ZnFexOyUse of a heterogeneous nanosheet modified porous carbon material, characterized in that the porous carbon material of any one of claims 1 to 9 is applied as a catalyst in an electrolytic alkaline pure water and seawater hydrogen evolution reaction.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780952A (en) * 2010-03-26 2010-07-21 上海交通大学 Method for preparing loading functional oxide porous carbon
WO2011117657A2 (en) * 2010-03-26 2011-09-29 Shanghai Jiao Tong University Carbon materials comprising nano structures
CN113571719A (en) * 2021-07-29 2021-10-29 云南大学 Biomass carbon material derived transition metal-based catalyst, preparation method and application thereof, and solid zinc-air battery
CN113774425A (en) * 2021-09-18 2021-12-10 南京晓庄学院 Preparation method and application of Ru-modified FeCo @ NF electrocatalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780952A (en) * 2010-03-26 2010-07-21 上海交通大学 Method for preparing loading functional oxide porous carbon
WO2011117657A2 (en) * 2010-03-26 2011-09-29 Shanghai Jiao Tong University Carbon materials comprising nano structures
CN113571719A (en) * 2021-07-29 2021-10-29 云南大学 Biomass carbon material derived transition metal-based catalyst, preparation method and application thereof, and solid zinc-air battery
CN113774425A (en) * 2021-09-18 2021-12-10 南京晓庄学院 Preparation method and application of Ru-modified FeCo @ NF electrocatalyst

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