CN117107275A - Method for synthesizing nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature with low energy consumption and application - Google Patents
Method for synthesizing nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature with low energy consumption and application Download PDFInfo
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- CN117107275A CN117107275A CN202310959423.5A CN202310959423A CN117107275A CN 117107275 A CN117107275 A CN 117107275A CN 202310959423 A CN202310959423 A CN 202310959423A CN 117107275 A CN117107275 A CN 117107275A
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- hydroxymethylfurfural
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 79
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000005265 energy consumption Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- -1 transition metal salt Chemical class 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000000047 product Substances 0.000 claims description 43
- 238000007254 oxidation reaction Methods 0.000 claims description 41
- 230000003647 oxidation Effects 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 239000004202 carbamide Substances 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 230000008901 benefit Effects 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000002243 furanoses Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
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- 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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- 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
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Abstract
The invention discloses a method for synthesizing a nickel-based electro-oxidation 5-hydroxymethylfurfural catalyst at room temperature with low energy consumption and application thereof. The transition metal salt consumed in the catalyst preparation process can be recycled through recovery, so that the catalyst preparation cost is further reduced. The prepared catalyst has high HMF catalytic activity, high FDCA selectivity and excellent stability.
Description
Technical Field
The invention belongs to the technical field of preparation of an electrooxidation 5-hydroxymethylfurfural catalyst, and particularly relates to a method for synthesizing a nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature with low energy consumption and application thereof.
Background
The utilization of renewable energy sources to replace non-renewable energy sources is an urgent need for human development, and biomass has the characteristics of renewable energy sources, is also an organic carbon resource, and can be used for synthesizing degradable biomass-based materials to replace non-degradable traditional petroleum-based materials. 2, 5-furandicarboxylic acid (FDCA) is one of important platform compounds in biomass, and derivatives thereof have wide application in medicine, chemical industry and the like, for example, polyethylene furanose (PEF) can replace polyethylene terephthalate (PET) plastic, and the problem of white pollution is relieved. Currently, FDCA is mainly produced by oxidation of 5-Hydroxymethylfurfural (HMF) by bio/enzyme catalytic oxidation, electrochemical catalytic oxidation, and thermochemical catalytic processes. The electrochemical catalytic oxidation method has the advantages of simple operation, accuracy and controllability, wide substrate selectivity, high safety and the like, and has important application potential.
The electrocatalytic oxidation of HMF mainly uses anode potential as driving force, promotes continuous oxidation of HMF through electron transfer, and finally converts to FDCA. Current research focuses mainly on achieving HMF electrooxidation in alkaline electrolytes, as FDCA tends to protonate under acidic conditions, adsorb at the electrode surface and hinder active site exposure. Alkaline electrooxidation HMF presents a reaction barrier and its oxidation process comprises a number of intermediate oxidation species, so there is a need to develop a highly efficient stable catalyst with high FDCA selectivity to promote the progress of the electrooxidation HMF reaction. Currently, the electro-oxidized HMF catalysts mainly include noble metal catalysts (Pt, pb, au, and Ru) and transition metal catalysts (Ni, cu, mn, and Co). The nickel-based catalyst has the advantages of abundant reserves, low price, strong structural adjustability and the like, and has higher economic value and potential application capability in the field of the electrooxidation HMF. In view of the above, the invention provides a method for conveniently synthesizing a nickel-based electrooxidation HMF catalyst with low energy consumption at room temperature, which takes foamed nickel as a reaction substrate, places the foamed nickel in an aqueous solution mixed with urea and transition metal salt (Ni, cu, mn or Co), stirs the substrate at room temperature to promote chemical reaction with the transition metal salt, and finally grows a transition metal hydroxide or oxyhydroxide active layer in situ on the surface of the foamed nickel as a self-supporting catalyst for promoting the electrocatalytic oxidation HMF reaction. The method has the outstanding advantages of simplicity, easiness, high controllability, low energy consumption, low cost and the like. The prepared catalyst has high catalytic activity, high FDCA selectivity and excellent stability, is cheap and easy to obtain, and can promote the high-selectivity oxidation of HMF to prepare FDCA under mild conditions. Therefore, the invention has wide market application prospect and commercialization potential. Currently, there is no report on this aspect.
Disclosure of Invention
The invention solves the technical problem of providing a method for synthesizing a nickel-based electro-oxidation 5-hydroxymethylfurfural catalyst at room temperature with low energy consumption, which only needs to immerse foam nickel in a mixed solution of urea and transition metal salt, reacts at room temperature, does not need other energy consumption except stirring to promote the reaction, has obvious low energy consumption advantage, and grows an electro-oxidation HMF reaction catalytic active layer on the surface of the foam nickel in situ in the reaction process, so that the catalyst can effectively promote the electro-catalytic oxidation HMF reaction to prepare FDCA.
The invention adopts the following technical proposal to solve the technical problems, and the method for synthesizing the nickel-based electrooxidation 5-hydroxymethylfurfural catalyst with low energy consumption at room temperature is characterized by comprising the following specific steps:
step S1, cutting foam nickel, sequentially using ethanol and dilute hydrochloric acid to ultrasonically clean the foam nickel to remove organic pollutants and oxides on the surface, and sequentially using deionized water and ethanol to ultrasonically clean to remove residual acidic substances to obtain a material A;
step S2, dissolving urea and transition metal salt in deionized water, and fully and uniformly mixing to obtain a solution B, wherein the transition metal salt is MCl 2 、M(NO 3 ) 2 、MSO 4 Or M (Ac) 2 M is one of Ni, cu, mn or Co;
and S3, placing the material A obtained in the step S1 into the solution B obtained in the step S2, stirring and reacting at room temperature, taking out the material A after the reaction is stopped, cleaning the material A by using deionized water and ethanol in sequence, and drying to obtain a target product, namely a nickel-based electro-oxidation 5-hydroxymethylfurfural catalyst, wherein a transition metal hydroxide or hydroxyl oxide active layer generated on the surface of foam nickel in the catalyst is conducive to high-selectivity electro-catalytic oxidation of the 5-hydroxymethylfurfural to synthesize 2, 5-furandicarboxylic acid, the oxide active layer has a three-dimensional nano structure, rich active sites can be exposed, and further the electro-catalytic oxidation process of the 5-hydroxymethylfurfural is promoted, and the catalyst has a conversion rate of the 5-hydroxymethylfurfural of up to 99.63%, a yield of the 2, 5-furandicarboxylic acid of 99.25%, a selectivity of the 2, 5-furandicarboxylic acid of 99.62% and a Faraday efficiency of 99.36%.
Further defined, in the step S1, the thickness of the nickel foam is 1-5 mm, and the cutting size is (1-15) × (1-15) cm 2 。
Further limited, in the step S1, the ultrasonic cleaning time of the ethanol is 3-5 minutes, the ultrasonic cleaning time of the hydrochloric acid is 30 minutes, the ultrasonic cleaning time of the deionized water is 3-5 minutes, and the concentration of the hydrochloric acid is 1-2 mol/L.
Further limited, the concentration of urea and transition metal salt in the solution B in the step S2 is 50-100 mmol/L and 50-500 mmol/L respectively.
Further limited, in the step S3, the rotating speed of the magnetic stirrer in the stirring reaction process is 100-600 rpm, the stirring reaction time is 10 hours at room temperature, the drying temperature of the blast drying oven in the drying process is 60-90 ℃, and the drying time is 1-3 hours.
Further limiting, adding NaOH solution into the reaction solution after stopping the reaction in the step S3, and magnetically stirring to obtain M (OH) 2 And (3) filtering and separating the precipitate, completely dissolving the precipitate into an acid solution, filtering again, evaporating and concentrating the filtered filtrate, and sequentially cooling, filtering and drying to obtain a metal salt crystal, so that the recycling of metal salt is realized, and the utilization rate of metal atoms is improved.
Further limited, the concentration of the NaOH solution is 1mol/L, the rotating speed of the magnetic stirrer is 100-600 rpm, and the acid solution is HCl solution and HNO 3 Solution, H 2 SO 4 One of the solution or HAc solution, wherein the concentration of the acid solution is 0.1-1 mol/L, the evaporation temperature is 80 ℃, and the evaporation time is 1-3 hours; cooling temperature is 0 ℃, and cooling time is 0.5 hour; the drying temperature is 80 ℃, and the drying time is 6-12 hours; the metal salt crystal is corresponding MCl 2 、M(NO 3 ) 2 、MSO 4 Or M (Ac) 2 One or more of the following.
The nickel-based electro-oxidation 5-hydroxymethylfurfural catalyst is used as a working electrode to form a three-electrode system to realize electro-catalytic oxidation of 5-hydroxymethylfurfural in alkaline electrolyte to synthesize 2, 5-furandicarboxylic acid.
Further limited, the platinum sheet and the mercury/mercury oxide electrode in the three-electrode system are a counter electrode and a reference electrode, the alkaline electrolyte is a KOH or NaOH solution with the concentration of 1M, the concentration of dissolved 5-hydroxymethylfurfural is 10-20 mmol/L, the applied external potential is 1.35-1.6V, and the nickel-based electrooxidation 5-hydroxymethylfurfural catalyst is used for preparing 2, 5-furandicarboxylic acid by high-selectivity electrocatalytic oxidation of 5-hydroxymethylfurfural in the alkaline electrolyte.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention has the advantages that the catalyst can prepare FDCA by high-selectivity electrocatalytic oxidation of HMF in alkaline electrolyte, and the optimal catalyst has FDCA selectivity as high as 99.25% and Faraday efficiency of 99.36% in the HMF oxidation process.
2. The invention synthesizes the nickel-based electrooxidation HMF catalyst mainly through stirring at room temperature, has the advantages that the synthesis process does not need high temperature and high pressure environment, can be carried out at room temperature, does not need noble metal participation, has low cost, and can synthesize 10 multiplied by 10cm in a laboratory 2 The bulk catalyst has excellent catalytic activity of the electrooxidative HMF, which shows that the preparation method has potential of industrial production.
3. The transition metal waste liquid after reaction related in the invention extracts and purifies the transition metal salt from the reaction waste liquid into the recyclable reaction raw material through a simple recovery mechanism, thereby realizing the reutilization of the transition metal, reducing the production cost and reducing the environmental pollution. Therefore, the invention has the double advantages of economic benefit and environmental protection benefit.
4. The transition metal hydroxide or hydroxyl oxide active layer generated by the reaction is favorable for the selective oxidation of the HMF, and the oxidation active layer presents a three-dimensional nano structure, so that a large number of HMF oxidation active sites can be provided, and the catalytic activity of the catalyst is obviously improved. The prepared nickel-based HMF oxidation electrocatalyst has high oxidation current density under low potential of 1.45V, still maintains high FDCA yield and Faraday efficiency after 5 times of cyclic electrolysis, and has excellent recycling stability.
Drawings
FIG. 1 is a scanning electron microscope image of the target product C1 prepared in example 1;
FIG. 2 is a plot of HMF oxidation linear sweep voltammograms for target products C1-C5 prepared in examples 1-5;
FIG. 3 is an electrochemical impedance diagram of the target products C1-C4 prepared in examples 1-4;
FIG. 4 is a linear sweep voltammogram of HMF oxidation and oxygen evolution for target product C1 prepared in example 1;
FIG. 5 is a sample of the target product C5 prepared in example 5;
FIG. 6 is a scanning electron microscope image of the target product C5 prepared in example 5;
FIG. 7 is a plot of HMF oxidation linear sweep voltammograms of target products C3, C6-C7 prepared in examples 3, 6-7;
fig. 8 is a high performance liquid chromatography analysis chart of the target product C1 prepared in example 1 during oxidation.
Fig. 9 is a graph of HMF conversion, FDCA yield, FDCA selectivity, and faraday efficiency for the target product C1 five cycles of electrooxidation HMF prepared in example 1.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Examples
Step S1: cutting foam nickel to 2X 2cm 2 Ultrasonically cleaning in ethanol for 3-5 minutes, then ultrasonically cleaning in 1mol/L hydrochloric acid for 30 minutes, and finally ultrasonically cleaning with deionized water and ethanol for 3-5 minutes in sequence to obtain a material A1;
step S2: dissolving urea and nickel chloride into 30mL of deionized water, and uniformly stirring and mixing to obtain a solution B1, wherein the concentration of the urea is 100mmol/L and the concentration of the nickel chloride is 50mmol/L;
step S3: and (2) putting the material A1 in the step (S1) into the solution B1 in the step (S2), stirring and reacting for 10 hours at a speed of 100rpm by using a magnetic stirrer, washing the A1 after the reaction is finished by using deionized water and ethanol, and then drying in a blast drying oven at 80 ℃ for 2 hours to obtain a target product C1.
Examples
Step S1: cutting foam nickel to 2×2cm 2 Ultrasonically cleaning in ethanol for 3-5 minutes, then ultrasonically cleaning in 1mol/L hydrochloric acid for 30 minutes, and finally ultrasonically cleaning with deionized water and ethanol for 3-5 minutes in sequence to obtain a material A2;
step S2: dissolving urea and nickel sulfate into 30mL of deionized water, and uniformly stirring and mixing to obtain a solution B2, wherein the concentration of the urea is 100mmol/L and the concentration of the nickel sulfate is 50mmol/L;
step S3: and (2) putting the material A2 in the step (S1) into the solution B2 in the step (S2), stirring and reacting for 10 hours at a speed of 100rpm by using a magnetic stirrer, washing the A2 after the reaction is finished by using deionized water and ethanol, and then drying in a blast drying oven at 80 ℃ for 2 hours to obtain a target product C2.
Examples
Step S1: cutting foam nickel to 2X 2cm 2 Ultrasonically cleaning in ethanol for 3-5 minutes, then ultrasonically cleaning in 1mol/L hydrochloric acid for 30 minutes, and finally ultrasonically cleaning with deionized water and ethanol for 3-5 minutes in sequence to obtain a material A3;
step S2: dissolving urea and nickel nitrate into 30mL of deionized water, and uniformly stirring and mixing to obtain a solution B3, wherein the concentration of the urea is 100mmol/L and the concentration of the nickel nitrate is 50mmol/L;
step S3: and (3) putting the material A3 in the step (S1) into the solution B3 in the step (S2), stirring and reacting for 10 hours at a speed of 100rpm by using a magnetic stirrer, washing the A3 after the reaction with deionized water and ethanol, and then drying in a blast drying oven at 80 ℃ for 2 hours to obtain a target product C3.
Examples
Step S1: cutting foam nickel to 2X 2cm 2 Ultrasonically cleaning in ethanol for 3-5 minutes, then ultrasonically cleaning in 1mol/L hydrochloric acid for 30 minutes, and finally ultrasonically cleaning with deionized water and ethanol for 3-5 minutes in sequence to obtain a material A4;
step S2: dissolving urea and nickel acetate into 30mL of deionized water, and uniformly stirring and mixing to obtain a solution B4, wherein the concentration of urea is 100mmol/L and the concentration of nickel acetate is 50mmol/L;
step S3: and (2) putting the material A4 in the step (S1) into the solution B4 in the step (S2), stirring and reacting for 10 hours at a speed of 100rpm by using a magnetic stirrer, washing the A4 after the reaction is finished by using deionized water and ethanol, and then drying in a blast drying oven at 80 ℃ for 2 hours to obtain a target product C4.
Examples
Step S1: cutting foam nickel to 10X 10cm 2 Ultrasonically cleaning in ethanol for 3-5 minutes, then ultrasonically cleaning in 1mol/L hydrochloric acid for 30 minutes, and finally sequentially ultrasonically treating with deionized water and ethanol for 3-5 minutes to obtain a material A5;
step S2: dissolving urea and nickel chloride into 750mL of deionized water, and uniformly stirring and mixing to obtain a solution B5, wherein the concentration of the urea is 100mmol/L and the concentration of the nickel chloride is 50mmol/L;
step S3: and (2) putting the material A5 in the step (S1) into the solution B5 in the step (S2), stirring and reacting for 10 hours at a speed of 100rpm by using a magnetic stirrer, washing the A5 after the reaction with deionized water and ethanol, and then drying in a blast drying oven at 80 ℃ for 2 hours to obtain a target product C5.
Examples
Step S1: cutting foam nickel to 2X 2cm 2 Ultrasonically cleaning in ethanol for 3-5 minutes, then ultrasonically cleaning in 1mol/L hydrochloric acid for 30 minutes, and finally ultrasonically cleaning with deionized water and ethanol for 3-5 minutes in sequence to obtain a material A6;
step S2: dissolving urea, nickel nitrate and copper nitrate into 30mL of deionized water, and uniformly stirring and mixing to obtain a solution B6, wherein the concentration of urea is 100mmol/L, the concentration of nickel nitrate is 37.5mmol/L, and the concentration of copper nitrate is 12.5mmol/L;
step S3: and (3) putting the material A6 in the step S1 into the solution B6 in the step S2, stirring and reacting for 10 hours at a speed of 100rpm by using a magnetic stirrer, washing the A6 after the reaction is finished by using deionized water and ethanol, and then drying in a blast drying oven at 80 ℃ for 2 hours to obtain a target product C6.
Examples
Step S1: cutting foam nickel to 2X 2cm 2 Ultrasonic cleaning in ethanol for 3-5 min, ultrasonic cleaning in 1mol/L hydrochloric acid for 30 min, and sequentially using deionized waterUltrasonically cleaning with ethanol for 3-5 minutes to obtain a material A7;
step S2: dissolving urea, nickel nitrate and manganese nitrate into 30mL of deionized water, and uniformly stirring and mixing to obtain a solution B7, wherein the concentration of urea is 100mmol/L, the concentration of nickel nitrate is 37.5mmol/L, and the concentration of manganese nitrate is 12.5mmol/L;
step S3: the material A7 in the step S1 is put into the solution B7 in the step S2, the reaction is stirred for 10 hours at the speed of 100rpm by using a magnetic stirrer, the A7 after the reaction is washed by deionized water and ethanol, and then the washed material A7 is placed into a blast drying oven at the temperature of 80 ℃ for drying for 2 hours, so that the target product C7 is obtained.
Electrochemical performance test of electrocatalytic oxidation HMF:
three electrode systems were assembled using H-type cells, separated using proton exchange membranes (Nafion-117, duPont), and the target product C1 was cut to 1X 1.5cm 2 Size, fixed with platinum sheet electrode clip, exposed to 1X 1cm 2 The effective area of the dimensions was used as working electrode, mercury/mercury oxide electrode and platinum sheet (effective area 1X 1cm 2 ) The electrodes serve as a reference electrode and a counter electrode, respectively. The working electrode and the reference electrode were inserted into the anode chamber, the counter electrode was inserted into the cathode chamber, 30mL of 1mol/L KOH solution was added to each of the anode chamber and the cathode chamber, and 10mmol/L HMF was additionally added to the anode chamber as an electrolyte. Working electrodes of the target products C2, C3, C4 and C5 were prepared in the same manner as a control group of the target product C1. The scanning speed of the Linear Sweep Voltammetry (LSV) test was 5mV s –1 The scanning range is 1-1.8V (vs. RHE), and the impedance of the target product is measured at 1.5V (vs. RHE). A magneton was added to the anode chamber and the anode was gently stirred to promote the mass transfer process as the electrochemical test was performed.
Analysis of the properties of the catalyst obtained:
the properties of the target product in all examples are characterized as follows: FIG. 1 is a scanning electron microscope image of the target product C1 prepared in example 1, showing that the target product C1 has a nano-sheet structure; FIG. 2 shows the linear sweep voltammograms of the target products C1 to C5 prepared in examples 1 to 5, from which it can be seen that the target products C1 and C5 are compared with other targetsThe products have a lower starting potential and a higher current density, which indicates that the target products C1 and C5 have good properties in terms of HMF oxidation, wherein the target product C1 has more excellent properties. FIG. 3 is an electrochemical impedance plot of the target products C1-C4 prepared in examples 1-4, with a smaller radius for product C1, indicating that product C1 has a lower impedance, which facilitates charge transfer during oxidation of HMF. FIG. 4 is a graph showing the polarization curves of HMF oxidation and oxygen evolution for target product C1 prepared in example 1, showing that target product C1 has similar initial potential during HMF oxidation and oxygen evolution, but the oxidation current density during HMF oxidation is significantly higher than that during oxygen evolution, when the current density is 50mV cm –2 The HMF oxidation overpotential of the target product C1 is 215mV lower than the oxygen evolution potential, which indicates that the target product C1 is more prone to promote the HMF oxidation and inhibit the oxygen evolution reaction. Fig. 5 and 6 are a sample view and a scanning electron microscope view, respectively, of the target product C5 prepared in example 5, fig. 6 shows that C5 has the same nano-sheet structure as the target product C1 of example 1, and fig. 5 and 6 show that the preparation of a bulk catalyst is possible. Fig. 7 shows linear sweep voltammetry curves of target products C3, C6-C7 prepared in examples 3, 6-7, which show that the introduction of Cu metal can effectively promote the catalytic activity of the electrooxidized HMF, and the introduction of Mn metal can reduce the reaction barrier of the electrooxidized HMF, indicating that both Cu metal and Mn metal are favorable for the HMF oxidation reaction. Fig. 8 is a graph of the change in oxide of the target product C1 prepared in example 1 during the process of preparing FDCA by the electrooxidation of HMF, showing that HMF and FDCA are mainly present during the oxidation, which indicates that FDCA is rapidly formed by the conversion of HMF to intermediate product, and that the catalyst has excellent catalytic performance as well as 99.25% HMF conversion and 98.87% FDCA yield. Fig. 9 is a graph of HMF conversion, FDCA yield, FDCA selectivity, and faraday efficiency of five consecutive cycles of preparing FDCA from HMF, which is the target product C1 prepared in example 1, showing that the performance of HMF, which is the target product C1, remains stable during the cycle and that 99.63% HMF conversion, 99.25% FDCA yield, 99.62% FDCA selectivity, and 99.36% faraday efficiency can be achieved, indicating that the catalyst has excellent catalytic activity and excellent stability.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (9)
1. A method for synthesizing a nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature with low energy consumption is characterized by comprising the following specific steps:
step S1, cutting foam nickel, sequentially using ethanol and dilute hydrochloric acid to ultrasonically clean the foam nickel to remove organic pollutants and oxides on the surface, and sequentially using deionized water and ethanol to ultrasonically clean to remove residual acidic substances to obtain a material A;
step S2, dissolving urea and transition metal salt in deionized water, and fully and uniformly mixing to obtain a solution B, wherein the transition metal salt is MCl 2 、M(NO 3 ) 2 、MSO 4 Or M (Ac) 2 M is one of Ni, cu, mn or Co;
and S3, placing the material A obtained in the step S1 into the solution B obtained in the step S2, stirring and reacting at room temperature, taking out the material A after the reaction is stopped, cleaning the material A by using deionized water and ethanol in sequence, and drying to obtain a target product, namely a nickel-based electro-oxidation 5-hydroxymethylfurfural catalyst, wherein a transition metal hydroxide or hydroxyl oxide active layer generated on the surface of foam nickel in the catalyst is conducive to high-selectivity electro-catalytic oxidation of the 5-hydroxymethylfurfural to synthesize 2, 5-furandicarboxylic acid, the oxide active layer has a three-dimensional nano structure, rich active sites can be exposed, and further the electro-catalytic oxidation process of the 5-hydroxymethylfurfural is promoted, and the catalyst has a conversion rate of the 5-hydroxymethylfurfural of up to 99.63%, a yield of the 2, 5-furandicarboxylic acid of 99.25%, a selectivity of the 2, 5-furandicarboxylic acid of 99.62% and a Faraday efficiency of 99.36%.
2.The method for synthesizing the nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature and low energy consumption according to claim 1, which is characterized in that: the thickness of the foam nickel in the step S1 is 1-5 mm, and the cutting size is (1-15) × (1-15) cm 2 。
3. The method for synthesizing the nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature and low energy consumption according to claim 1, which is characterized in that: in the step S1, the ultrasonic cleaning time of the ethanol is 3-5 minutes, the ultrasonic cleaning time of the hydrochloric acid is 30 minutes, the ultrasonic cleaning time of the deionized water is 3-5 minutes, and the concentration of the hydrochloric acid is 1-2 mol/L.
4. The method for synthesizing the nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature and low energy consumption according to claim 1, which is characterized in that: and in the step S2, the concentration of urea and the concentration of transition metal salt in the solution B are respectively 50-100 mmol/L and 50-500 mmol/L.
5. The method for synthesizing the nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature and low energy consumption according to claim 1, which is characterized in that: and in the step S3, the rotating speed of the magnetic stirrer in the stirring reaction process is 100-600 rpm, the stirring reaction time is 10 hours at room temperature, the drying temperature of the blast drying oven in the drying process is 60-90 ℃, and the drying time is 1-3 hours.
6. The method for synthesizing the nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature and low energy consumption according to claim 1, which is characterized in that: adding NaOH solution into the reaction solution after stopping the reaction in the step S3, and magnetically stirring to obtain M (OH) 2 And (3) filtering and separating the precipitate, completely dissolving the precipitate into an acid solution, filtering again, evaporating and concentrating the filtered filtrate, and sequentially cooling, filtering and drying to obtain a metal salt crystal, so that the recycling of metal salt is realized, and the utilization rate of metal atoms is improved.
7. The method for synthesizing nickel-based electrooxidation 5-hydroxymethylfurfural catalyst at room temperature and low energy consumption according to claim 6The method is characterized in that: the concentration of the NaOH solution is 1mol/L, the rotating speed of the magnetic stirrer is 100-600 rpm, and the acid solution is HCl solution and HNO 3 Solution, H 2 SO 4 One of the solution or HAc solution, wherein the concentration of the acid solution is 0.1-1 mol/L, the evaporation temperature is 80 ℃, and the evaporation time is 1-3 hours; cooling temperature is 0 ℃, and cooling time is 0.5 hour; the drying temperature is 80 ℃, and the drying time is 6-12 hours; the metal salt crystal is corresponding MCl 2 、M(NO 3 ) 2 、MSO 4 Or M (Ac) 2 One or more of the following.
8. The room-temperature low-energy-consumption synthetic nickel-based electrooxidation 5-hydroxymethylfurfural catalyst prepared by the method according to any one of claims 1-7 is used as a working electrode to form a three-electrode system, and electrocatalytic oxidation of 5-hydroxymethylfurfural in alkaline electrolyte is realized to synthesize 2, 5-furandicarboxylic acid.
9. The use according to claim 8, characterized in that: the platinum sheet and the mercury/mercury oxide electrode in the three-electrode system are a counter electrode and a reference electrode, the alkaline electrolyte is a KOH or NaOH solution with the concentration of 1M, the concentration of dissolved 5-hydroxymethylfurfural is 10-20 mmol/L, the applied potential is 1.35-1.6V, and the nickel-based electrooxidation 5-hydroxymethylfurfural catalyst is used for preparing 2, 5-furandicarboxylic acid by high-selectivity electrocatalytic oxidation of 5-hydroxymethylfurfural in the alkaline electrolyte.
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