CN115074772B - Electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide, preparation method and application - Google Patents
Electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide, preparation method and application Download PDFInfo
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Abstract
The invention discloses an electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide, a preparation method and application thereof, which are the electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide for electrocatalytically oxidizing 5-hydroxymethylfurfural, wherein the preparation method comprises the following steps: step 1, cutting foam nickel NF, and performing ultrasonic cleaning to obtain pretreated foam nickel; step 2, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 O and VCl 3 Mixing and dissolving in water, adding urea, and stirring uniformly to obtain a first mixed solution; and (3) placing the foam nickel into a high-pressure reaction kettle for reaction to obtain the high-efficiency electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide NiVCo-LDHs. The electrocatalyst can be used for preparing high-value FDCA by selectively electrocatalytically oxidizing HMF, and oxidized HMF at a low potential has high oxidation current density, and stable yield and Faraday efficiency of FDCA can be obtained in 10 continuous cycle electrolysis.
Description
Technical Field
The invention relates to the field of electrocatalysts, in particular to a high-efficiency electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide, a preparation method and application.
Background
5-Hydroxymethylfurfural (HMF) is widely used as a typical C6-based carbohydrate-derived biomass platform molecule for the production of pharmaceutical intermediates, polymer monomers and agrochemicals. The oxidation product 2, 5-furancarboxylic acid (FDCA) is an important polymer monomer, has a similar structure similar to petroleum-based terephthalic acid monomer, and can be used for synthesizing polyethylene furanate (PEF) to replace bulk polyethylene terephthalate (PET) plastics.
At present, the method used for converting 5-hydroxymethyl furfural (HMF) into 2, 5-furancarboxylic acid (FDCA) is mainly an aerobic oxidation method, and the method needs severe conditions such as high temperature, high pressure, toxic oxidant or noble metal catalyst, and the like, so that the green chemical concept is violated. Therefore, a more environment-friendly electrocatalytic method is generated, the electrocatalytic method can convert HMF into FDCA with high selectivity through electron transfer at normal temperature and normal pressure, and the method is a green and efficient conversion way. Among the reported electrocatalysts, ni and Co based catalysts perform optimally, almost quantitatively converting HMF to FDCA, unfortunately a high overpotential (1.423 v vs. rhe) is often required to drive efficient HMF conversion, and the stability of the catalyst is poor, in order to achieve an economical, efficient conversion of HMF to FDCA, it is highly desirable to construct an electrocatalyst with high activity, strong stability and inexpensive properties.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide an efficient electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide, a preparation method and application.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides an electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide which is an electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide for the efficient electrocatalytically oxidizing 5-hydroxymethylfurfural.
In a second aspect, the invention provides a method for preparing an electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide, comprising the steps of:
step 1, pretreatment of a carrier:
cutting foam nickel NF, ultrasonically cleaning to remove impurities, and drying at room temperature to obtain pretreated foam nickel;
step 2, preparation of NiVCo-LDHs catalyst:
(1) NiCl is added 2 ·6H 2 O、CoCl 2 ·6H 2 O and VCl 3 Mixing with water to form transparent solution, adding urea, stirringUniformly obtaining a first mixed solution;
(2) and (3) placing the pretreated foam nickel into a high-pressure reaction kettle, transferring the first mixed solution into the high-pressure reaction kettle, screwing the high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, performing high-pressure sealing reaction, washing the foam nickel by using water and ethanol after the reaction is cooled to room temperature, and drying overnight to obtain the high-efficiency electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide NiVCo-LDHs.
Preferably, in the step 1, the nickel foam NF is cut to a size of 1cm×3 cm.
Preferably, in the step 1, the ultrasonic cleaning is sequentially performed by using acetone, dilute hydrochloric acid, deionized water and ethanol.
Preferably, in the step 2, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 O and VCl 3 The molar ratio of (2) is 3:0-1:0-1.
Preferably, in the step 2, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 O and VCl 3 The molar ratio of (C) is 3:0.33:0.67, the water addition amount is 30mL, ni 2+ 、Co 2+ And V 3+ The total molar amount in the solution was 1.08mmol.
Preferably, in the step 2, the urea is added in an amount of 240.24mg and the stirring time is 30-60min.
Preferably, in the step 2, the reaction temperature of the high-pressure reaction kettle is 120 ℃, and the reaction time is 12 hours; the washed nickel foam was dried in an oven at 60 c.
In a third aspect, the present invention provides a highly efficient electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide for use in the electrocatalytic conversion of 5-Hydroxymethylfurfural (HMF) to 2, 5-furancarboxylic acid (FDCA).
The beneficial effects of the invention are as follows:
1. the NiVCo-LDHs electrocatalyst prepared on the foam nickel substrate has the advantages that the electrocatalyst can be used for preparing high-value FDCA by selectively performing electrocatalytic oxidation on HMF in 1mol/LKOH, and the electrocatalyst can be used for oxidizing HMF at low potential and has high oxidation current density, so that stable FDCA yield and Faraday efficiency can be obtained in 10 continuous cycle electrolysis.
2. In the invention, niVCo-LDHs is synthesized by a simple hydrothermal method, and NiVCo-LDHs with optimal performance is screened out by simple initial raw material preparation and is used as an advanced electrocatalyst for the transformation of electrocatalytic oxidation of HMF into FDCA. NiVCo-LDHs has a wrinkled nano-sheet structure, and the current density of oxidized HMF can reach 100mA cm under the voltage of 1.37Vvs RHE -2 . In addition, the prepared NiVCo-LDHs have excellent durability, and the yield of FDCA is 93.2-99.7% and the FE is 86.5-97.8% in 10 continuous cycles, which are far superior to most reported LDHs and nickel-based oxide catalysts.
The present invention shows by characterization that the addition of V atoms can increase specific surface area by constructing a folded nano-sheet structure and enrich active sites by introducing oxygen vacancies. The invention prepares a ternary LDHs electrocatalyst with cost effectiveness, has satisfactory durability and conversion efficiency, and promotes the development of converting HMF into FDCA by a green electrochemical method.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a SEM image, TEM image (c) and energy dispersive X-ray element map (d-g) of an embodiment of the invention NiVCO-LDHs at low resolution (a) and high resolution (b);
FIG. 2 is a comparison of XRD spectra (a) of NiVCO-LDHs, niCo-LDHs, niV-LDHs and NiOOH, and XPS spectra (b) of Ni2p, (c) V2 p and (d) Co 2p of examples of the present invention;
FIG. 3 (a) shows LSV curves of a scan of NiVCo-LDHs at 10mV s-1 in 1M KOH with and without 10mM HMF; (b) LSV curves representing NiVCo-LDHs, niV-LDHs and NiCo-LDHs in 1M KOH containing 10mM HMF; (c) comparing the oxidized HMF current densities at different potentials;
FIG. 4 is a Tafel comparison plot (a) of NiVCO-LDHs, niV-LDHs and NiCo-LDHs and a plot (b) of capacitance current density versus scan rate at a potential of 0.95Vvs RHE in accordance with an embodiment of the present invention;
FIG. 5 (a) shows the HPLC spectra when different charges were passed; (b) Represents the concentration of HMF and its oxidation products as a function of passing charge at a potential of 1.376V vs RHE in 10ml of 1.0m koh containing 10mM HMF; (c) A comparison plot showing HMF conversion, FDCA yield and FE of FDCA on NiVCo-LDHs, niV-LDHs and NiCo-LDHs electrodes at a 1.376Vvs RHE voltage; (d) represent two routes for the oxidation of HMF to FDCA; (e) Representing the yield of FDCA and FE obtained by the NiVCo-LDHs electrode under the continuous 10-cycle electrolysis;
FIG. 6 shows XPS analysis of (a) Ni2p (b) V2 p and (c) Co 2p and (d) O1s of NiVCo-LDHs and NiVCo-LDHs after 10 cycles, which were newly prepared in the example of the present invention.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Examples
The invention provides an electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide, in particular to an electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide for efficiently electrocatalytically oxidizing 5-hydroxymethylfurfural.
The preparation method of the high-efficiency electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide for electrocatalytically oxidizing 5-hydroxymethylfurfural comprises the following steps of:
step 1, pretreatment of a carrier:
cutting foam Nickel (NF) into a size of 1cm multiplied by 3cm, respectively and sequentially carrying out ultrasonic cleaning treatment by using acetone, dilute hydrochloric acid, deionized water and ethanol to remove pollutants, blow-drying the surface by using nitrogen, and naturally drying a clean place at room temperature.
Step 2, preparation of NiVCo-LDHs catalyst:
NiCl was stirred with moderate intensity 2 ·6H 2 O、CoCl 2 ·6H 2 O and VCl 3 In 30mL of water at a ratio of 3:0.33:0.67, wherein Ni 2+ 、Co 2+ And V 3+ The total amount of (2) was 1.08mmol. Due to VCl 3 The moisture is easy to absorb, and the instant use is required; after a clear solution was formed, 240.24mg of urea was further added to the solution and stirred for 30 minutes at medium intensity; placing fresh clean foam nickel into a 50mL high-pressure reaction kettle with the wall inclined, and placing the Ni into a reactor 2+ 、Co 2+ And V 3+ Transferring the mixed solution into a reaction kettle; screwing up the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, and performing high-pressure sealing reaction for 12 hours at 120 ℃; after the reaction is cooled to room temperature, washing foam nickel with a large amount of water and ethanol, and drying at 60 ℃ overnight to obtain the catalyst NiVCo-LDHs.
Comparative example 1
The electrocatalyst NiV-LDHs is prepared by the same method as the example, except that in the step 2, coCl is not added 2 ·6H 2 O,NiCl 2 ·6H 2 O and VCl 3 The molar ratio of (2) is 3:1.
Comparative example 2
The preparation method of the electrocatalyst NiCo-LDHs is the same as that of the embodiment, and is characterized in that in the step 2, VCl is not added 3 ,NiCl 2 ·6H 2 O and CoCl 2 ·6H 2 The molar ratio of O was 3:1.
Comparative example 3
An electrocatalyst NiOOH was prepared in the same manner as in the examples, except that in step 2, no CoCl was added 2 ·6H 2 O and VCl 3 。
Experimental example
(1) Electrochemical performance test of oxidized HMF:
cutting nickel foam loaded with NiVCo-LDHs into a size of 1cm×0.5cm, clamping and exposing 0.5cm×0.5cm by using an electrode as a working electrode, and using a saturated Ag/AgCl electrode as a reference electrodeThe carbon rod is used as a counter electrode; electrochemical workstation with CHI 920E in 1mol/L KOH solution at 10mV s in the potential interval 0.2V-0.65V -1 Performing a Linear Sweep Voltammetry (LSV) technique to test the performance of the oxidized water; fresh 10mmol/L HMF was added to 1mol/L KOH solution and the performance of selectively oxidizing HMF was tested by the same linear sweep voltammetry; in the above LSV test, solution resistance was tested by CHI 920e and an iR compensation of 85% was applied to all LSV tests.
(2) Cycling stability test of electrochemically oxidized HMF:
in an H-type cell separated by an N117 proton exchange membrane (Sigma-Aldrich), 10mL of 1M KOH solution was injected into the cathode chamber, and 10mL of 1M KOH solution containing 10mM HMF was injected into the anode chamber; cutting 1.5cm multiplied by 1cm of nickel foam loaded with NiVCo-LDHs, clamping the nickel foam with a Pt electrode clamp, exposing the nickel foam with the size of 1cm multiplied by 1cm, placing the nickel foam in an anode chamber as a working electrode, and placing a carbon rod in a cathode chamber as a counter electrode; adding a stirrer into an anode chamber, and carrying out electrocatalytic oxidation on HMF by using a constant potential electrolysis technology of a DC-EC 1200 electrochemical analyzer (vinca dingcheng science and technology Co., ltd.) under mild stirring until the primary electrolysis is completed after the electric charge of 57.89 ℃ below zero is passed; after one round of electrolysis is finished, the electrolyte in the electrode chamber is reconfigured, and the same working electrode is washed by a large amount of deionized water and dried, and then is continuously used as the working electrode to carry out the next round of electrolysis reaction, so that 10 times of electrolysis experiments are repeatedly carried out.
(3) Qualitative and quantitative analysis of oxidation products:
the reaction product was separated by using a Tech comp LC2000A high performance liquid chromatograph and a BioRadAlminex HPX-87H column (300X 7.8 mm), and the detection wavelength of the ultraviolet-visible detector was set to 265nm. Periodically extracting reaction samples from the reactor, filtering the reaction liquid by using a filter head with the thickness of 0.22 mu m, diluting 10 mu L of filtrate by 50 times with deionized water, and injecting the diluted filtrate into a chromatographic column for analysis; using 5mM sulfuric acid as the mobile phase, at 60℃at 0.5ml min -1 Is subjected to constant flow rate isocratic separation; and (3) carrying out qualitative and quantitative analysis on the separated samples according to the retention time of the standard samples and standard curves drawn by different concentrations.
The experimental results and their analysis are as follows:
(1) as shown in fig. 1 (a) and (b), scanning Electron Microscopy (SEM) showed that NiVCo-LDHs nanoplatelets were grown vertically on the surface of NF substrate, whose nanoplatelets were of a micrometer-sized lateral length and a nanometer-sized ultra-thin thickness.
The transmission electron microscope image (TEM) in fig. 1 (c) further shows that NiVCo-LDHs nanoplatelets have rich folds.
The scanning transmission electron microscope energy dispersive X-ray spectroscopy (STEM-EDX) element map image in fig. 1 (d) shows that Ni, V, co and O elements are uniformly distributed and superimposed on NiVCo-LDHs nanoplatelets. The Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) characterization in fig. 1 shows that the addition of V atoms can increase the specific surface area of NiVCo-LDHs by building up a folded nano-sheet structure.
(2) In FIG. 2 (a) X-ray diffraction (XRD) shows that NiOOH is hexagonal alpha-Ni (OH) 2 NiCo-LDHs and NiV-LDHs are nickel cobalt hydroxide (JCPDS: 33-0429) and nickel vanadium hydroxide (JCPDS: 052-1627), respectively, indicating the formation of a typically pure LDH phase during doping. XRD spectra of NiVCo-LDHs are consistent with those of NiV-LDHs, which shows that NiVCo-LDHs are isomorphic with NiV-LDH.
In FIG. 2 (b), the high resolution XPS spectrum of Ni2p is that of Ni2p 3/2 (854.4 eV) and Ni2p 1/2 The two characteristic peaks (872.3 eV), and the satellite peaks at 878.4eV and 860.1eV, are Ni 2+ Is a characteristic peak of (2).
In FIG. 2 (c), V2 p is shown in the high resolution XPS spectrum of V2 p 3/2 Three peaks, i.e., V, can be fitted at 516.2eV, 517.1eV, and 518.0eV 3+ 、V 4+ And V 5+ Indicating V 3+ Oxidized to a higher valence state under hydrothermal treatment.
In FIG. 2 (d), the high resolution XPS of Co 2p has two main peaks at 780.6eV and 796.2eV, corresponding to Co 2p, respectively 3/2 And Co 2p 1/2 Is a combination of the binding energy of the above-mentioned materials.
The XPS spectrum of FIG. 2 shows that the binding energies of Ni2p, co 2p and V2 p of NiVCo-LDHs are slightly negative shifted compared to NiV-LDHs and NiCo-LDHs, indicating a synergistic electron interaction between Ni, co and V.
(3) As shown in FIG. 3, niVCo-LDHsOxidizing water at a potential higher than 1.55V vs RHE, increasing LSV sharply after adding HMF, and oxidizing HMF at a current density of 100mA cm at 1.37V vs RHE -2 . The lower initial oxidation potential and increased oxidation current density of HMF indicate that NiVCo-LDHs favor the oxidation of HMF. Comparing the oxidation current densities of HMF at different potentials obtained from LSV curves of NiV-LDHs, niCo-LDHs and NiVCo-LDHs oxidized HMF, the NiVCo-LDHs are found to have higher current densities and lower initial potentials than the NiV-LDHs and the NiCo-LDHs, and the good performance of the NiVCo-LDHs in the oxidation of HMF is further emphasized.
(4) As shown in FIG. 4, tafel slope values of NiVCo-LDHs (18.05 mV.dec -1 ) Is lower than NiV-LDH (19.14 mV. Dec -1 ) And NiCo-LDH (21.59 mV.dec) -1 ) It is shown that Co-doping of V and Co plays a key role in promoting HMF oxidation kinetics and increasing intrinsic activity. The electrochemical activity specific surface area (ECSR) of the catalyst is shown by a Cyclic Voltammetry (CV) measurement curve collected in the non-Faraday region of 0.90-1.00V vs RHE, niVCo-LDHs (1.56 mF cm -2 ) And NiV-LDHs (1.49 mF.cm) -2 ) ECSR of (C) is almost equivalent but higher than that of NiCo-LDHs (1.13 mF.cm) -2 ) The addition of V was shown to be critical to increasing the specific surface area of NiVCo-LDHs to build multi-folded nanoplatelet structures.
(5) As shown in FIG. 5, niVCo-LDHs underwent electrochemical conversion of HMF at an applied potential of 1.376Vvs RHE, resulting in a yield of 99.7% FDCA and a Faraday Efficiency (FE) of 97.0% FDCA, indicating successful conversion of HMF to FDCA. Whereas FDCA with NiV-LDHs (92.1%) and NiCo-LDHs (90.3%) had poor FE. In addition, the prepared NiVCo-LDHs have excellent stability, and the yield of FDCA is 93.2-99.7% and the FE is 86.5-97.8% in 10 continuous cycles, which are far superior to most reported LDHs and nickel-based oxide catalysts (as shown in the following Table 1).
TABLE 1 Performance of different catalysts
(6) In fig. 6, the X-ray photoelectron spectrum (XPS) of the catalyst before and after the reaction further shows that after cyclic testing a slight blue shift is observed in the Ni2p region of NiVCo-LDH (fig. 6 a), indicating that high valence Ni is formed during the reaction and has been involved in the oxidation process of HMF. No V2 p signal was detected in NiVCo-LDHs after cyclic testing, which may be due to dissolution of the higher V element (fig. 6 c). In fig. 6d, the X-ray photoelectron spectrum (XPS) of the catalyst before and after the reaction further shows that active oxygen vacancies are generated during the reaction, providing rich active sites. In the O1s spectrum, three peaks at 530.8eV (O1), 531.4eV (O2) and 532.2eV (O3) are consistent with fresh catalyst and can be respectively attributed to the binding energy of metal-oxygen bond, hydroxyl group and adsorbed water. In addition, O4 at 533.5eV is attributed to surface oxygen defect species, and it can be speculated that dissolution of V species during the reaction induces oxygen vacancies, the formation of which provides rich active sites, facilitating the electrocatalytic oxidation process of HMF.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. The application of the nickel-vanadium-cobalt ternary layered double hydroxide as an electrocatalyst in the reaction of oxidizing 5-hydroxymethylfurfural into 2, 5-furancarboxylic acid is characterized in that the preparation method of the nickel-vanadium-cobalt ternary layered double hydroxide comprises the following steps:
step 1, pretreatment of a carrier:
cutting foam nickel NF, ultrasonically cleaning to remove impurities, and drying at room temperature to obtain pretreated foam nickel;
step 2, preparation of NiVCo-LDHs catalyst:
21: niCl is added 2 ·6H 2 O、CoCl 2 ·6H 2 O and VCl 3 Mixing and dissolving in water to form a transparent solution, and adding urea and stirring uniformly to obtain a first mixed solution;
22, placing the pretreated foam nickel into a high-pressure reaction kettle, transferring the first mixed solution into the high-pressure reaction kettle, screwing the high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, performing high-pressure sealing reaction, washing the foam nickel by using water and ethanol after the reaction is cooled to room temperature, and drying to obtain the high-efficiency electrocatalyst nickel-vanadium-cobalt ternary layered double hydroxide NiVCo-LDHs.
2. The use according to claim 1, wherein in step 1, the nickel foam NF is cut to a size of 1cm x 3 cm.
3. The use according to claim 1, wherein in step 1, the ultrasonic cleaning is performed by sequentially using acetone, 3mol/L dilute hydrochloric acid, deionized water and ethanol.
4. The use according to claim 1, wherein in step 2, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 O and VCl 3 The molar ratio of (C) is 3:0.33:0.67, the water addition amount is 30mL, ni 2+ 、Co 2+ And V 3+ The total molar amount in the solution was 1.08mmol.
5. The use according to claim 1, wherein urea is added in step 2 in an amount of 240.24mg and the stirring time is 30min.
6. The use according to claim 1, wherein in step 2, the reaction temperature of the autoclave is 120 ℃ and the reaction time is 12 hours; the washed nickel foam after the reaction was dried at 60 ℃.
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