CN117535714A - Preparation method and application of NiFe LDH-loaded single-atom Ru catalyst - Google Patents
Preparation method and application of NiFe LDH-loaded single-atom Ru catalyst Download PDFInfo
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000006260 foam Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 21
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- 239000002028 Biomass Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- -1 NiOOH Chemical class 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical compound [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 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
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
-
- 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
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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
- C25B11/055—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
- C25B11/067—Inorganic compound e.g. ITO, silica or titania
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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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Abstract
The invention relates to the technical field of electrocatalytic electrode material preparation, in particular to a preparation method and application of a NiFe LDH loaded monoatomic Ru catalyst, and the preparation method comprises the following steps: s1, cutting foam nickel with the thickness of 0.5mm into a standard of 1 cm-2 cmSequentially ultrasonically washing the rectangle with deionized water and ethanol, and then drying in an oven; s2, ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water together, and the mixed solution is obtained by continuous stirring; according to the invention, ru monoatoms are introduced as Lewis acid sites to regulate the electronic structure of Ni in the NiFe LDH, and the generation of high-valence nickel active species is promoted under lower voltage, so that the performance of the NiFe LDH for electrocatalytically oxidizing biomass 5-hydroxymethylfurfural is improved, the hydrogen production at a cathode is promoted, the high-added-value oxidation product 2, 5-furandicarboxylic acid is obtained at an anode, the HMF conversion rate of the anode is close to 100%, the FDCA productivity is 96.2%, and the Faraday efficiency is 96%.
Description
Technical Field
The invention belongs to the technical field of preparation of electrocatalytic electrode materials, and particularly relates to a NiFe LDH-supported single-atom Ru catalyst, and a preparation method and application thereof.
Background
The excessive use of fossil fuels can lead to energy exhaustion and environmental pollution, so that the development of clean energy and the promotion of sustainable development strategy are of great importance, the electrolyzed water hydrogen production is considered to be the technology with the most development potential in the clean energy industry in the future due to mild conditions and sufficient raw materials, however, large-scale electrochemical decomposition water is limited by the slow-kinetics anode Oxygen Evolution Reaction (OER), so researchers try to replace the anode OER with the organic micromolecule oxidation reaction with more favorable thermodynamics and kinetics so as to realize the high-efficiency coupling hydrogen production.
The biomass derivative 5-Hydroxymethylfurfural (HMF) has small theoretical oxidation voltage, and the anode can obtain high-added-value chemical 2, 5-furandicarboxylic acid (FDCA), which is considered to be a good choice for replacing OER reaction, so that the development of an efficient catalytic oxidation 5-Hydroxymethylfurfural (HMFOR) electrocatalyst has important significance for promoting the cathode to produce hydrogen and the anode to obtain high-added-value products.
Currently, LDH, ni (OH) 2 Are considered to be effective catalysts for HMFOR reactions in which higher hydroxyl oxides, such as NiOOH, have been demonstrated to be the reactive sites, however, ni (OH) 2 The conversion to NiOOH requires the application of a higher potential, and competition between HMFOR and OER reactions is unavoidable in the anodic reaction, resulting in low faradaic efficiency of the anode and low FDCA formation rate of the product.
Disclosure of Invention
The invention aims to provide a preparation method and application of a NiFe LDH loaded single-atom Ru catalyst, so as to solve the problems in the background art.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a NiFe LDH loaded single-atom Ru catalyst is characterized by comprising the following steps of: the method comprises the following steps:
s1, cutting foam nickel with the thickness of 0.5mm into a standard rectangle with the thickness of 1cm and 2cm, sequentially ultrasonically washing the foam nickel with deionized water and ethanol, and then drying the foam nickel in an oven;
s2, ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water together, and is continuously stirred to obtain a mixed solution, and then RuCl is added 3 Adding the mixture into the mixed solution and stirring to obtain a uniform solution;
and S3, placing the clean foam nickel obtained in the step S1 into the uniform solution obtained in the step S2, adopting a three-electrode system to carry out electrodeposition, selecting a constant voltage mode for the deposition mode, taking out after deposition, washing and drying to obtain the NiFe LDH-loaded monoatomic Ru catalyst.
Preferably, in the step S1, the ultrasonic washing step with deionized water and ethanol is performed by alternately washing with water and ethanol for 3-5 times, and the washing time is 3-5min each time.
In the step S1, the temperature of the oven is 40-80 ℃, and the drying time is 30-70 min.
In said step S2, ni (NO 3 ) 2 ·6H 2 The molar concentration of O is 0.1-0.3 mol/L, fe (NO) 3 ) 3 ·9H 2 The molar concentration of O is 0.1-0.3 mol/L, ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The molar ratio of O was 1:3, for Ni (NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The stirring speed of O is 30-80 r/min, and the stirring time is 15-45min.
In said step S2, ruCl 3 The concentration is 0.01 to 0.07mol/L, and the Ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The total molar concentration of O is RuCl 3 1 to 20 times of RuCl 3 Adding the above mixed solution, stirring at a stirring rate of 50-120min for 30-50min.
In the step S3, the voltage working range of the electrochemical workstation is-1V.
In the step S3, the electrodeposition time is 100 to 700 seconds.
In the step S3, the temperature of the oven is 40-85 ℃, and the drying time is 1-5 h.
A preparation method of a NiFe LDH loaded monoatomic Ru catalyst is provided, and the prepared NiFe LDH loaded monoatomic Ru catalyst is applied to electrocatalytic oxidation of biomass 5-hydroxymethylfurfural.
The invention has the beneficial effects that:
1. compared with the conventional hydrothermal method and calcination method, the method for preparing the NiFe LDH loaded monoatomic Ru catalyst by adopting the electrodeposition method is carried out at normal temperature and normal pressure, the operation condition is mild, the preparation time is short, and the self-supporting electrode material is formed by using the foam nickel as a substrate, so that the catalyst has a porous structure, good conductivity and electrochemical activity, and can promote charge transfer and accelerate electrode reaction.
2. The invention provides a method for stabilizing single atoms on the surface of NiFe LDH by utilizing metal-nonmetal bonding, wherein NiFe LDH is formed on foam nickel, ru is fixed on the NiFe LDH through ruthenium-oxygen coordination bonding, the noble metal atom utilization rate is improved, the instability of a single-atom catalyst is reduced, and compared with the single NiFe LDH, the single-atom Ru catalyst loaded by the NiFe LDH prepared by the method has smaller electrochemical impedance and larger double-layer capacitance, and meanwhile, ru single atoms can promote the adsorption of substrates, so that the catalytic activity is improved.
3. The invention provides the application of a NiFe LDH loaded single-atom Ru catalyst in an HMFOR electrocatalyst, and the electronic structure of Ni in the NiFe LDH is regulated by introducing Ru single atoms as Lewis acid sites, and the generation of high-valence nickel active species is promoted under lower voltage, so that the performance of the NiFe LDH for electrocatalytically oxidizing biomass 5-Hydroxymethylfurfural (HMF) is improved, the promotion of cathode hydrogen production and the obtainment of high-added-value oxidation product 2, 5-furandicarboxylic acid (FDCA) by an anode are facilitated, the anode HMF conversion rate is close to 100%, the FDCA productivity is 96.2%, and the Faraday efficiency is 96%
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained according to these drawings without inventive effort;
FIG. 1 is an XRD pattern of the products prepared in example 2 and comparative example 1;
FIG. 2 is a TEM image of a NiFe LDH supported monoatomic Ru catalyst prepared according to example 2;
FIG. 3 is a HRTEM diagram of a NiFe LDH supported monoatomic Ru catalyst prepared according to example 2;
FIG. 4 is a XAFS spectrum of a NiFe LDH supported single atom Ru catalyst prepared in example 2;
FIG. 5 is a graph comparing the linear sweep voltammograms of the samples prepared in example 2 and comparative example 1;
FIG. 6 is a graph comparing catalytic performance of samples prepared in example 2 and comparative example 1;
FIG. 7 is a graph of catalytic performance of the samples prepared in example 2 and comparative example 1 in a 5 cycle test.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Cutting 0.5mm thick nickel foam into standard rectangular shapes 1cm x 2cm, alternately ultrasonic washing with deionized water and ethanol for 3 times each for 5min, oven drying at 60deg.C for 30min, and collecting 6mmol Ni (NO 3 ) 2 ·6H 2 O (nickel nitrate hexahydrate) and 6mmol Fe (NO) 3 ) 3 ·9H 2 O (ferric nitrate nonahydrate) was dissolved in 50mL deionized water and stirred for 30minAfter that, a mixed solution was obtained, 1mmol of RuCl 3 Adding the nickel foam as a working electrode into the uniform solution, stirring to obtain a uniform solution, taking an Ag/AgCl electrode as a reference electrode, taking a graphite rod as a counter electrode to form a three-electrode system, selecting a constant voltage mode for deposition, setting the voltage to be-0.8V, performing electrodeposition for 300s, washing the product, and drying in a 60 ℃ oven for 5h to obtain a reddish brown NiFe LDH (layered NiFe double hydroxide) supported single-atom Ru catalyst, wherein XRD characterization proves that the NiFe LDH supported single-atom Ru catalyst is prepared in the embodiment 1.
Example 2
Cutting foam nickel with the thickness of 0.5mm into a standard rectangle with the thickness of 1cm and 2cm, alternately ultrasonically washing with deionized water and ethanol for 3 times, washing for 5min each time, and drying in a 60 ℃ oven for 30min. 6mmol Ni (NO) 3 ) 2 ·6H 2 O and 6mmol Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 50mL of deionized water, and after continuous stirring for 30 minutes, a mixed solution was obtained, and 2.5mmol of RuCl 3 Adding the nickel foam as a working electrode into the uniform solution, stirring to obtain a uniform solution, taking an Ag/AgCl electrode as a reference electrode, taking a graphite rod as a counter electrode to form a three-electrode system, selecting a constant voltage mode as a deposition mode, setting the voltage to be-0.8V, performing electrodeposition for 300 seconds, washing the product, and drying in a 60 ℃ oven for 5 hours to obtain a reddish brown NiFe LDH-supported single-atom Ru catalyst, wherein XRD characterization proves that the NiFe LDH-supported single-atom Ru catalyst prepared in the embodiment 2.
Example 3
Cutting foam nickel with the thickness of 0.5mm into a standard rectangle with the thickness of 1cm and 2cm, alternately ultrasonically washing with deionized water and ethanol for 3 times, washing for 5min each time, and drying in a 60 ℃ oven for 30min. 6mmol Ni (NO) 3 ) 2 ·6H 2 O and 6mmol Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 50mL of deionized water, and after continuous stirring for 30 minutes, a mixed solution was obtained, 3.5mmol of RuCl 3 Adding the mixture solution and stirring to obtain a uniform solutionThe preparation method comprises the steps of placing foam nickel serving as a working electrode into the uniform solution, using an Ag/AgCl electrode as a reference electrode and using a graphite rod as a counter electrode to form a three-electrode system, selecting a constant voltage mode in a deposition mode, setting the voltage to be-0.8V, performing electrodeposition for 300s, washing a product, placing the product in a 60 ℃ oven for drying for 5h, and obtaining a reddish brown NiFe LDH-supported single-atom Ru catalyst, wherein XRD characterization proves that the NiFe LDH-supported single-atom Ru catalyst is prepared in the embodiment 3.
Example 4
Cutting 0.5mm thick nickel foam into standard rectangular shapes 1cm x 2cm, alternately ultrasonic washing with deionized water and ethanol for 3 times each for 5min, oven drying at 60deg.C for 30min, and collecting 6mmol Ni (NO 3 ) 2 ·6H 2 O and 6mmol Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 50mL of deionized water, and after continuous stirring for 30 minutes, a mixed solution was obtained, and 2.5mmol of RuCl 3 Adding the nickel foam as a working electrode into the uniform solution, stirring to obtain a uniform solution, taking an Ag/AgCl electrode as a reference electrode, taking a graphite rod as a counter electrode to form a three-electrode system, selecting a constant voltage mode as a deposition mode, setting the voltage to be-0.8V, performing electrodeposition for 500 seconds, washing the product, and drying in a 60 ℃ oven for 5 hours to obtain a reddish brown NiFe LDH-supported single-atom Ru catalyst, wherein XRD characterization proves that the NiFe LDH-supported single-atom Ru catalyst is prepared in the embodiment 4.
Comparative example 1
Cutting 0.5mm thick nickel foam into standard rectangular shapes 1cm x 2cm, alternately ultrasonic washing with deionized water and ethanol for 3 times each for 5min, oven drying at 60deg.C for 30min, and collecting 6mmol Ni (NO 3 ) 2 ·6H 2 O and 6mmol Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 50mL of deionized water together, after continuous and sufficient stirring is carried out for 30 minutes, a mixed solution is obtained, foam nickel is taken as a working electrode and is placed in the mixed solution, an Ag/AgCl electrode is taken as a reference electrode, a graphite rod is taken as a counter electrode to form a three-electrode system, a constant voltage mode is selected for the deposition mode, the voltage is set to be minus 0.8V, and electric power is carried outDeposition, deposition time of 300s, washing the product, and drying in an oven at 60 ℃ for 5h to obtain a dark yellow NiFe LDH catalyst, wherein XRD characterization proves that the NiFe LDH catalyst is prepared in comparative example 1.
FIG. 1 is an X-ray diffraction pattern (XRD) of the products prepared in example 2 and comparative example 1, and it is understood from the XRD results of FIG. 1 that the diffraction peak of the NiFe LDH-supported single-atom Ru catalyst prepared in example 2 corresponds to that of the NiFe LDH (JCPDS: 40-0215) of comparative example 1, indicating successful preparation of the NiFe LDH, no new diffraction peak appears compared with pure NiFe LDH, indicating that the original phase structure of the NiFe LDH is not changed after Ru is doped in example 2, indicating that Ru atoms are not doped in the crystal lattice of Ni or Fe, no new phase is formed, and evidence is provided for bonding of Ru atoms to form single atoms on the surface of the NiFe LDH.
Fig. 2 is a transmission electron microscope (TEM image) of a NiFe LDH-supported single-atom Ru catalyst, fig. 3 is a high-resolution transmission electron microscope (HRTEM image) of a NiFe LDH-supported single-atom Ru catalyst, and as can be seen from fig. 2, the sample has a two-dimensional layered structure with a size of 200nm to 300nm, clear lattice fringes can be observed from the high-resolution image of the sample of fig. 3, and the crystal planes corresponding to the (012) and (015) planes of NiFe LDH can be determined according to the lattice spacing, corresponding to the XRD result.
FIG. 4 is an X-ray absorption fine structure spectrum (XAFS) of the Ru K edge of a NiFe LDH-supported single-atom Ru catalyst prepared in example 2,is Ru-O bond, < >>Is Ru-Cl bond->For Ru-Ru bonds, it can be seen from FIG. 3 that no Ru-Ru coordination and Ru-Cl coordination occur in the NiFe LDH supported single-atom Ru catalyst, and that Ru-O peaks occur only in the first shell layer, indicating that Ru atoms are supported on the NiFe LDH surface and form bonds with oxygen on the LDH surface, further indicating successful loading of single-atom Ru.
To evaluate the activity of the NiFe LDH supported monoatomic Ru catalyst of example 2 and the NiFe LDH catalyst of comparative example 1 in OER (oxygen evolution reaction) and HMFOR (oxidation with 5-hydroxymethylfurfural) under alkaline conditions, electrocatalytic performance tests were performed on them, respectively, with the following specific test procedures and results:
1. the test was performed in a three electrode mode with a graphite rod as a counter electrode, a silver/silver chloride electrode as a reference electrode, and example 2 and comparative example 1 as working electrodes, respectively, in a 1M KOH solution, with an anodic linear voltammetric scan rate of 5mV s -1 The IR compensation was 90%.
2. The test was performed in a three electrode mode with a graphite rod as a counter electrode, a silver/silver chloride electrode as a reference electrode, and example 2 and comparative example 1 as working electrodes, respectively, in a 1M KOH+10mM HMF solution, with an anodic linear voltammetric scan rate of 5mV s -1 The IR compensation was 90%.
The test results are shown in fig. 5, in which fig. 5 is a linear sweep voltammogram of the products of example 2 and comparative example 1 in 1M KOH and 1M koh+10mm HMF solutions, respectively, at a sweep rate of 5mV/s and 90% ir compensation, it can be seen from the graph that, in KOH solution, the NiFe LDH-loaded single-atom Ru catalyst prepared in example 2 has a better alkaline OER activity, a higher current density than NiFe LDH, and in KOH solution containing 10mM HMF, both the current densities of the NiFe LDH-loaded single-atom Ru catalyst and NiFe LDH are improved, indicating that HMFOR reaction kinetics is superior to OER process, and that the NiFe LDH-loaded single-atom Ru catalyst has a good catalytic effect on HMF.
FIG. 6 is a graph showing the performance of the catalytic oxidation of HMF from the products prepared in example 2 and comparative example 1, using graphite rod as the counter electrode, silver/silver chloride electrode as the reference electrode, and example 2 and comparative example 1 as the working electrode, respectively, in a 1MKOH+100mM HMF solution, using constant voltage mode electrolysis, and quantitatively analyzing the anode product by liquid nuclear magnetism, it can be seen from the graph that the HMF conversion rate of the NiFe LDH supported single atom Ru catalyst is close to 100%, the FDCA generation rate is 96.2%, and the Faraday efficiency is 96%, which is significantly better than that of the NiFe LDH prepared in comparative example 1.
FIG. 7 is a graph showing the cycling stability of the catalytic oxidation HMF prepared in example 2, wherein a graphite rod is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and example 2 is used as a working electrode in a 1M KOH+100mM HMF solution, the electrochemical reaction is carried out for 5 times in a constant voltage mode, and the anode product is quantitatively analyzed through liquid nuclear magnetism, so that the HMF conversion rate and the FDCA generation rate of the NiFe LDH-supported single-atom Ru catalyst are maintained above 90%, and the catalyst stability is good.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (9)
1. A preparation method of a NiFe LDH loaded single-atom Ru catalyst is characterized by comprising the following steps of: the method comprises the following steps:
s1, cutting foam nickel with the thickness of 0.5mm into a standard rectangle with the thickness of 1cm and 2cm, sequentially ultrasonically washing the foam nickel with deionized water and ethanol, and then drying the foam nickel in an oven;
s2, ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water together, and is continuously stirred to obtain a mixed solution, and then RuCl is added 3 Adding the mixture into the mixed solution and stirring to obtain a uniform solution;
s3, placing the clean foam nickel obtained in the step S1 into the uniform solution obtained in the step S2, taking the foam nickel as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a graphite rod as a counter electrode to form a three-electrode system, performing electrodeposition, selecting a constant voltage mode for the deposition mode, taking out after the deposition, washing and drying to obtain the NiFe LDH-loaded single-atom Ru catalyst.
2. The method for preparing the NiFe LDH-supported single-atom Ru catalyst according to claim 1, wherein in the step S1, ultrasonic washing with deionized water and ethanol is performed for 3-5 times by alternately washing with water and ethanol, and the washing time is 3-5min each time.
3. The method according to claim 2, wherein in the step S1, the oven temperature is 40-80 ℃ and the drying time is 30-70 min.
4. The method for preparing a NiFe LDH-supported single-atom Ru catalyst according to claim 1, wherein in said step S2, ni (NO 3 ) 2 ·6H 2 The molar concentration of O is 0.1-0.3 mol/L, fe (NO) 3 ) 3 ·9H 2 The molar concentration of O is 0.1-0.3 mol/L, ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The molar ratio of O was 1:3, for Ni (NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The stirring speed of O is 30-80 r/min, and the stirring time is 15-45min.
5. The method for preparing a NiFe LDH-supported single-atom Ru catalyst according to claim 4, wherein in said step S2, ruCl 3 The concentration is 0.01 to 0.07mol/L, and the Ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The total molar concentration of O is RuCl 3 1 to 20 times of RuCl 3 Adding the above mixed solution, stirring at a stirring rate of 50-120min for 30-50min.
6. The method for preparing a NiFe LDH-supported monoatomic Ru catalyst according to claim 1, wherein in step S3, the voltage operating range of the electrochemical workstation is-1 to 1V.
7. The method for preparing a NiFe LDH-supported monoatomic Ru catalyst according to claim 6, wherein in step S3, the electrodeposition time is 100 to 700S.
8. The method according to claim 7, wherein in the step S3, the oven temperature is 40-85 ℃ and the drying time is 1-5 h.
9. A method for preparing a NiFe LDH-supported monoatomic Ru catalyst as claimed in any of claims 1 to 8, the NiFe LDH-supported monoatomic Ru catalyst prepared being used in electrocatalytic oxidation of biomass 5-hydroxymethylfurfural.
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