CN115537871A - Preparation method and application of nickel hydroxide electrode material - Google Patents

Preparation method and application of nickel hydroxide electrode material Download PDF

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CN115537871A
CN115537871A CN202211220382.XA CN202211220382A CN115537871A CN 115537871 A CN115537871 A CN 115537871A CN 202211220382 A CN202211220382 A CN 202211220382A CN 115537871 A CN115537871 A CN 115537871A
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nickel
electrode material
nickel hydroxide
hydroxide electrode
biomass
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王发楠
潘鑫晨
徐刚
李梦霞
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Fujian University of Technology
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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 discloses a preparation method of a nickel hydroxide electrode material and application thereof in electrocatalytic oxidation of a biomass-based platform compound; the invention adopts a simple and rapid chemical soaking method to obtain the in-situ growth self-supporting nickel hydroxide electrode material on the nickel substrate. The preparation method has the advantages of wide raw material sources, low price, simple operation, mild conditions, cleanness, environmental protection and easy scale up, can effectively reduce the preparation cost, and avoids environmental pollution and consumption of rare metals. Meanwhile, the prepared nickel hydroxide electrode material can efficiently catalyze and oxidize biomass-based platform compounds, greatly reduces the overall overpotential of the hydrogen production process by water electrolysis, improves the overall charge efficiency of the process, shows good stability and has good industrial application prospect.

Description

Preparation method and application of nickel hydroxide electrode material
Technical Field
The invention belongs to the fields of new energy technology and energy conservation and environmental protection, and particularly relates to a preparation method of a nickel hydroxide electrode and application of the nickel hydroxide electrode in efficient electrocatalytic oxidation of a biomass-based platform compound in an alkaline medium.
Background
The enormous consumption of fossil energy and the resulting serious environmental and climatic problems have prompted the energy structure of the world today to shift from a single fossil energy source to a diverse energy structure including renewable energy sources, nuclear energy. On the one hand, the technology of driving electrolysis water by using low-grade renewable electric energy has attracted extensive research attention in the aspect of producing clean and sustainable hydrogen energy. In the process of water electrolysis, the Oxygen Evolution Reaction (OER) of the anode relates to a complex four-electron transfer process, the reaction kinetics of the OER is slow, and the overall energy consumption of hydrogen production by water electrolysis is seriously influenced. The search for alternative anode reactions is of great significance for improving the overall charge efficiency of the water electrolysis hydrogen production process. On the other hand, biomass reserves are huge, and the biomass reserves are the only renewable carbon source on the earth, so that the biomass renewable carbon source has outstanding advantages in the aspects of green, sustainability and the like, and the clean and efficient conversion of the biomass into energy chemicals becomes an important development strategy of many countries. However, the traditional method for thermally catalyzing biomass conversion has severe reaction conditions, requires introduction of high-temperature and high-pressure gas and additional oxidant, and has certain limitations. The electrochemical mode is only driven by electrochemical potential, and has the advantages of controllability, cleanness and economy. Meanwhile, in a proper electro-catalysis system, the anode OER can be replaced by biomass electro-oxidation preparation, the reaction kinetics is faster, the overall energy consumption in the water electrolysis process can be reduced, the economic added value of the product is improved, and the wide application prospect is displayed.
Currently, research on electrochemical oxidation processes of biomass-based platform compounds is receiving much attention. Noble metal materials such as palladium and the like show high activity, however, the selectivity of the catalyst to a target product is relatively low, and the wide application of the catalyst is severely restricted by the high price and low storage amount of the noble metal. Therefore, there is an urgent need to find an inexpensive and efficient electrocatalyst to replace the noble metals. Research shows that the nickel-based compound has higher activity and stability in reaction. For example, chinese patent CN111472020B discloses a method for preparing 2, 5-furandicarboxylic acid (FDCA) by electrocatalytic oxidation of 5-Hydroxymethylfurfural (HMF) with hydrotalcite-based layered catalyst, which uses nickel-based hydrotalcite layered catalyst loaded on carbon paper by hydrothermal method and shows better catalytic performance (FDCA selectivity reaches 84.8%). In addition, patent CN114318404A discloses a preparation method and application of a cobalt-nickel-based electrocatalytic material, wherein a nickel-containing electrode substrate is prepared by hydrothermal-calcination, and then a cobalt-nickel electrode is obtained by electrodeposition. Patent CN114481203A reports a nickel foam-loaded nanometer flower-shaped nickel sulfide-molybdenum sulfide catalyst, a preparation method and application thereof, and the method is also used for preparing an electrode material by a high-temperature hydrothermal method. However, the electrochemical activity is still to be improved due to the limitation of poor intrinsic activity of the transition metal-based material; by loading heterogeneous catalytic materials on the electrode substrate, the bonding strength of the heterogeneous catalytic materials and the substrate is weak, which often results in poor stability of the electrode. More importantly, the preparation method generally adopts a high-temperature hydrothermal method to prepare the electrode catalyst, has high energy consumption and high danger, is influenced by the amplification effect of a hydrothermal kettle, and is difficult to realize large-scale batch production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing a high-efficiency nickel hydroxide electrocatalytic oxidation electrode at normal temperature and normal pressure in situ. The electrocatalytic oxidation electrode of the cheap metal nickel-based hydroxide prepared by the preparation method shows very high electrocatalytic oxidation activity of a biomass-based platform compound in an alkaline medium and long-term chemical and performance stability, and can be suitable for an industrial electrolyzed water hydrogen production system so as to reduce the energy consumption of the system and improve the economic added value. In addition, the method also has the advantages of clear and novel process design thought, mature and stable process, simple operation, mild condition and strong controllability, and is suitable for large-scale production.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a nickel hydroxide electrode material grows nickel hydroxide on a nickel substrate in situ by a step-by-step chemical immersion method, and specifically comprises the following steps:
1) Dissolving oxalic acid in ethanol/water solution, obliquely placing a conductive substrate material in the solution, standing for reaction, and cleaning and drying after the reaction is finished;
2) And obliquely placing the dried material in an alkali solution, standing for reaction, and cleaning and drying after the reaction is finished.
Further, the conductive substrate material is a pure nickel substrate. The pure nickel substrate is any one of a nickel plate, foamed nickel and a nickel felt.
Preferably, the conductive substrate material is subjected to oxygen and oil removing pretreatment by adopting a conventional acidification treatment manner before use.
Preferably, the concentration of the Chinese herbal acid solution in the step 1) is 0.1-10 mol/L, and the volume fraction of ethanol in the ethanol/water solution is 0-100%.
Preferably, the pH of the alkali solution in the step 2) is 11-15; the alkali source in the alkali solution is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.
Preferably, the standing reaction time in the step 1) is 10-200 min; the standing reaction time in the step 2) is 1-60 min.
The invention provides application of the prepared nickel hydroxide electrode material, and the nickel hydroxide electrode material is applied to electrocatalytic oxidation of a biomass-based platform compound.
Preferably, the nickel hydroxide electrode material is applied to electrocatalytic oxidation of a biomass-based platform compound in an alkaline medium, and the specific steps include:
forming a two-electrode/three-electrode system by using the nickel hydroxide electrode material, and adding a certain amount of biomass-based platform compound into electrolyte;
the biomass-based platform compound is one or more of 5-hydroxymethyl furfural (HMF), furfural, glycerol, glucose and other biomass-based platform compounds; the pH value of the electrolyte is 11-15, and the concentration of the biomass-based platform compound is 5-500 mmol/L.
And respectively carrying out a linear sweep voltammetry curve test and a cyclic stability test during performance test. During the circulation stability test, certain voltage is applied to the electrode, the reaction is circularly carried out for multiple times, a current-time curve is recorded, and products in the reaction process are analyzed through high performance liquid chromatography.
The invention prepares the nickel hydroxide catalyst by a step-by-step chemical immersion method, and applies the nickel hydroxide catalyst to electrocatalytic oxidation preparation reaction. The high-valence nickel is a main active site of electrocatalytic oxidation, namely NiOOH, and the formation and the stability of the high-valence nickel have important significance for improving the catalytic activity of the nickel-based material.
In the invention, the oxalic acid solution with weak acidity can be used for controllably ionizing the metallic nickel substrate (H) + (ag.)+Ni(s)→Ni 2+ (ag.)) and nickel ions in ionic state can be matched with oxalate to generate nickel oxalate precipitate (Ni) 2+ (ag.)+C 2 O 4 2- (ag.)→NiC 2 O 4 (s)). Different solvent compositions can affect precipitation nucleation and growth due to different polarities, geometrical configurations and ionization degrees, so that the final nano-structure morphology is affected. Wherein, the ethanol/water solution with 95 percent of volume ratio can form an ultrafine nanowire structure, thereby greatly improving the specific surface area. Further soaking in alkaline solution due to Ni (OH) 2 Solubility product less than NiC 2 O 4 And thus may be in NiC 2 O 4 In-situ formation of ultra-thin Ni (OH) on the surface of nanowires 2 Nanosheet structure (NiC) 2 O 4 (s)+OH - (ag.)→Ni(OH) 2 (s)+C 2 O 4 2- (ag.)) to ultimately form Ni (OH) 2 NiC coated by nanosheets 2 O 4 And (4) a nanowire composite structure.
The structure has extremely high specific surface area and can be fully contacted with electrolyte, so that a large number of high-valence nickel active centers are easily formed in the electrooxidation process. In addition, the NiC of the inner layer 2 O 4 Because of having certain electron-withdrawing effect, can stabilize the high valence state nickel active center on the surface. Thus, the nanocomposite structure is very intrinsic to electrocatalytic oxidationAnd (4) activity.
In addition, because no nickel source or other heterogeneous raw materials are additionally added in the preparation process, the nickel substrate is used as the nickel source to grow the nickel hydroxide in situ to form the integrated electrode, so that the integrated electrode has extremely high bonding strength with the substrate and has good cycle stability in the long-term reaction process.
Compared with the prior art, the invention has the following beneficial effects:
1) The method utilizes a simple step-by-step chemical immersion method, takes a nickel substrate as a nickel source, does not need to add an additional nickel source, and grows nickel hydroxide in situ on the substrate to form an integrated electrode. The preparation method has the advantages of cheap and easily-obtained raw materials, simple process, mild conditions and controllable process, can avoid the problem of weak combination of the catalyst and the substrate, and is easy for large-scale production.
2) The nickel hydroxide electrode prepared by the invention has excellent activity of electrocatalytic oxidation of a biomass-based platform compound and long-term stability in an alkaline medium. The method has the advantages of mild reaction process conditions, greenness, no pollution, higher raw material conversion rate, higher target product selectivity, high Faraday efficiency and industrial application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic flow chart of the production method of the present invention.
FIG. 2 shows nickel hydroxide/nickel foam (Ni (OH) 2 The activity and stability of the/NF) and foam Nickel (NF) electrodes are tested;
in FIG. 2, FIG. (a) shows Ni (OH) 2 The activity of the NF electrode is compared with that of the NF electrode in 1mol/L potassium hydroxide solution and 1mol/L potassium hydroxide solution added with 20mmol/L HMF solution; FIG. b shows Ni (OH) 2 /NThe activity of the F electrode at different concentrations of HMF is compared; FIG. c shows Ni (OH) with sulfuric acid or oxalic acid as an activator 2 Comparative activity plots of/NF electrodes at different concentrations of HMF; FIG. d shows Ni (OH) 2 Potential-time diagram of the NF electrode at constant current; FIG. (e) shows Ni (OH) 2 A graph showing the change of raw materials and reaction products along with the charge quantity in the process of the HMF electrooxidation reaction of the NF electrode; FIG. f shows Ni (OH) 2 The result of 5 times of circulation of time-varying current density of HMF electrooxidation reaction of NF electrode; FIG. g shows Ni (OH) 2 5-cycle results of HMF conversion (conv.) in the/NF electrode HMF electrooxidation, FDCA yield (yield) and Faraday Efficiency (FE).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The invention provides a preparation method of a nickel hydroxide electrode material, which grows nickel hydroxide on a nickel substrate in situ by a step-by-step chemical immersion method and specifically comprises the following steps:
1) Pretreatment: before the pure nickel conductive substrate material is used, the pure nickel conductive substrate material is subjected to deoxidization and oil removal by adopting a conventional acidification treatment mode;
2) Dissolving oxalic acid in an ethanol/water solution, wherein the concentration of the oxalic acid solution is 0.1-10 mol/L, and the volume fraction of ethanol in the ethanol/water solution is 0-100%; obliquely placing the pure nickel substrate material in the solution, standing for reaction for 10-200 min, and cleaning and drying after the reaction is finished;
3) And obliquely placing the dried material in an alkaline solution with the pH value of 11-15, standing for reaction for 1-60 min, and cleaning and drying after the reaction is finished to obtain the nickel hydroxide electrode material. Wherein, the alkali source in the alkali solution is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.
The nickel hydroxide electrode material is used to form a two-electrode/three-electrode system, and a certain amount of biomass-based platform compound with the concentration of 5-500 mmol/L is added into electrolyte with the pH of 11-15; wherein the biomass-based platform compound is one or more of 5-Hydroxymethylfurfural (HMF), furfural, glycerol, glucose and other biomass-based platform compounds. Then, a linear sweep voltammetry test and a cyclic stability test are respectively carried out. During the circulation stability test, certain voltage is applied to the electrode, the reaction is circularly carried out for multiple times, a current-time curve is recorded, and products in the reaction process are analyzed through high performance liquid chromatography.
Example 1
Nickel hydroxide electrode in this example (Ni (OH) 2 The preparation method of/NF) and the electrochemical performance test thereof are specifically operated as follows:
(1) Pretreatment of foamed nickel: sequentially carrying out ultrasonic washing in absolute ethyl alcohol, deionized water, dilute hydrochloric acid and deionized water for later use;
(2) Weighing 5.0428g of oxalic acid, dissolving in 40ml of ethanol/water (v/v = 95. Obliquely placing the pretreated substrate material in the solution, standing for 90min, washing with absolute ethyl alcohol after the reaction is finished, and drying in the air.
(3) And obliquely placing the dried material in 40ml of 1mol/L potassium hydroxide solution, standing for 5min, washing with absolute ethyl alcohol after the reaction is finished, and drying in the air to obtain the nickel hydroxide/foamed nickel electrode material.
(4) The oxygen evolution and HMF oxidation performance tests of the prepared electrode were carried out as follows: a three-electrode system is adopted, the working electrode is the prepared nickel hydroxide/foamed nickel electrode, the counter electrode is a platinum sheet electrode, and the reference electrode is a mercury/mercury oxide electrode. Electrochemical testing was performed on an admiral electrochemical workstation. Oxygen evolution reaction test: the electrolyte is 1mol/L potassium hydroxide solution; the linear sweep voltammetry test has a sweep rate of5mV/s, electrode potentials are all iR corrected and converted to electrode potentials relative to the Reversible Hydrogen Electrode (RHE); when the stability is tested, 50mA/cm is added on the electrode 2 The potential-time curve was recorded for 24 hours, after which the current density was further increased to 100mA/cm 2 And recorded for 24 hours. HMF oxidation test: the electrolyte is a mixed solution of 1mol/L potassium hydroxide solution and 10-50 mmol/L HMF solution. When the linear sweep voltammetry curve is tested, the sweep rate is 5mV/s, the electrode potentials are all subjected to iR correction, and the iR correction is converted into the electrode potential relative to RHE; for the cycling stability test, a voltage of 1.37V (relative to RHE) was applied to the electrodes, the reaction was cycled five times, current-time curves were recorded, and the products during the reaction were analyzed by high performance liquid chromatography.
Example 2
The preparation method of the foam nickel electrode (NF) and the electrochemical performance test thereof are specifically operated as follows:
(1) Pretreatment of foamed nickel: sequentially carrying out ultrasonic washing in absolute ethyl alcohol, deionized water, dilute hydrochloric acid and deionized water for later use;
(2) The oxygen evolution and HMF oxidation performance tests of the prepared electrode are carried out according to the following methods: a three-electrode system is adopted, the working electrode is the prepared nickel hydroxide/foamed nickel electrode, the counter electrode is a platinum sheet electrode, and the reference electrode is a mercury/mercury oxide electrode. Electrochemical testing was performed on an admiral electrochemical workstation. Oxygen evolution reaction test: the electrolyte is 1mol/L potassium hydroxide solution; for the linear sweep voltammogram test, the sweep rate was 5mV/s, and the electrode potentials were all iR corrected and converted to electrode potentials relative to the Reversible Hydrogen Electrode (RHE). HMF oxidation test: the electrolyte is a mixed solution of 1mol/L potassium hydroxide solution and 20mmol/L HMF solution. For the linear sweep voltammogram test, the sweep rate was 5mV/s and the electrode potentials were all iR corrected and converted to electrode potentials relative to RHE.
Example 3
In order to embody the key role of oxalic acid as weak acid in activating NF substrate, strong acid sulfuric acid was used to perform comparative experiments, and the immersion time was optimized to 7min in consideration of the strong corrosive effect of strong acid on the substrate. The preparation method and the electrochemical performance test thereof specifically operate as follows:
(1) Pretreatment of foamed nickel: sequentially carrying out ultrasonic washing in absolute ethyl alcohol, deionized water, dilute hydrochloric acid and deionized water for later use;
(2) 2.2mL of concentrated sulfuric acid was measured, diluted to 40mL with ethanol/water (v/v = 95) to prepare a sulfuric acid ethanol solution having a concentration of 1 mol/L. Obliquely placing the pretreated substrate material in the solution, standing for 7min, washing with absolute ethyl alcohol after the reaction is finished, and drying in the air.
(3) And obliquely placing the dried material in 40ml of potassium hydroxide solution with the concentration of 1mol/L, standing for 5min, washing with absolute ethyl alcohol after the reaction is finished, and drying in the air to obtain the nickel hydroxide/foamed nickel-sulfuric acid electrode material.
(4) The HMF oxidation performance of the prepared electrode was tested as follows: a three-electrode system is adopted, the working electrode is the prepared nickel hydroxide/foamed nickel electrode, the counter electrode is a platinum sheet electrode, and the reference electrode is a mercury/mercury oxide electrode. Electrochemical testing was performed on an admiral electrochemical workstation. HMF oxidation test: HMF oxidation test: the electrolyte is a mixed solution of 1mol/L potassium hydroxide solution and 10-50 mmol/L HMF solution. For the linear sweep voltammogram test, the sweep rate was 5mV/s and the electrode potentials were all iR corrected and converted to electrode potentials relative to RHE.
As shown in FIG. 2 (a), ni (OH) 2 the/NF has better HMF oxidation activity than NF. The addition of 20mmol/L HMF in 1mol/L potassium hydroxide solution greatly increased the current density, especially before the lower aqueous Oxidation (OER) potential (. About.1.55V). FIG. 2 (b) is a linear sweep voltammogram after addition of 10-50 mmol/L HMF, showing that the increase in current density is positively correlated with the concentration of added HMF, indicating that the increased current density is due to oxidation of HMF. The results further demonstrate that anodic HMF electrooxidation can increase the efficiency of electrical energy utilization, and thus has the potential to replace OER. Meanwhile, from FIG. 2 (c), the results of the activation by a strong acid (sulfuric acid) are comparedIt can be seen that the catalyst prepared using oxalic acid, which is less acidic, has a significantly higher HMF oxidation activity. In terms of stability, as can be seen from FIG. 2 (d), the electrode was charged with 100mA/cm in 1mol/L potassium hydroxide solution 2 After the current density reaction of the electrode material is carried out for 10 hours, the voltage is almost not obviously changed, even is slightly reduced, and the electrode material is proved to have excellent electrochemical stability. Fig. 2 (e) shows the results of the product test by hplc on the reaction process, and it can be seen that the conversion of HMF and the yield of FDCA increase with the increase of the transferred charge amount, and about 80% conversion and yield can be achieved with 60C charge amount. Fig. 2 (f) and (g) show the results of cycle tests of HMF oxidation, in 5 cycle reactions, HMF can be completely converted within about 40min, and both the FDCA yield and FE can be stabilized at more than 90%, which proves that the electrode material has good cycle stability for selective oxidation of HMF into FDCA.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a nickel hydroxide electrode material is characterized in that nickel hydroxide grows in situ on a nickel substrate by a step-by-step chemical immersion method, and the method specifically comprises the following steps:
1) Dissolving oxalic acid in ethanol/water solution, obliquely placing a conductive substrate material in the solution, standing for reaction, and cleaning and drying after the reaction is finished;
2) And obliquely placing the dried material in an alkali solution, standing for reaction, and cleaning and drying after the reaction is finished.
2. The method of claim 1, wherein the conductive substrate material is a pure nickel substrate.
3. The method for preparing a nickel hydroxide electrode material as claimed in claim 2, wherein the pure nickel substrate is selected from any one of a nickel plate, a nickel foam and a nickel felt.
4. The method for preparing a nickel hydroxide electrode material according to claim 1, wherein the conductive substrate material is pretreated for removing oxygen and oil by conventional acidification treatment before use.
5. The method for preparing a nickel hydroxide electrode material as claimed in claim 1, wherein the concentration of the oxalic acid solution in step 1) is 0.1-10 mol/L, and the volume fraction of ethanol in the ethanol/aqueous solution is 0-100%.
6. The method for preparing a nickel hydroxide electrode material according to claim 1, wherein the pH of the alkali solution in the step 2) is 11 to 15; the alkali source in the alkali solution is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.
7. The method for preparing a nickel hydroxide electrode material according to claim 1, wherein the standing reaction time in the step 1) is 10-200 min; the standing reaction time in the step 2) is 1-60 min.
8. Use of a nickel hydroxide electrode material prepared according to the preparation method of any one of claims 1 to 7, characterized in that the nickel hydroxide electrode material is used for electrocatalytic oxidation of biomass-based platform compounds.
9. The use of a nickel hydroxide electrode material according to claim 8, wherein the nickel hydroxide electrode material is used for electrocatalytic oxidation of a biomass-based platform compound in an alkaline medium.
10. The use of the nickel hydroxide electrode material according to claim 8, comprising the steps of:
forming a two-electrode/three-electrode system by using a nickel hydroxide electrode material, and adding a biomass-based platform compound into an electrolyte;
the biomass-based platform compound is one or more of 5-hydroxymethylfurfural, furfural, glycerol and glucose; the pH value of the electrolyte is 11-15, and the concentration of the biomass-based platform compound is 5-500 mmol/L.
CN202211220382.XA 2022-10-08 2022-10-08 Preparation method and application of nickel hydroxide electrode material Pending CN115537871A (en)

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