CN117702163A - Large-scale preparation method and application of Ni-Mo-based heterojunction - Google Patents
Large-scale preparation method and application of Ni-Mo-based heterojunction Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910003296 Ni-Mo Inorganic materials 0.000 title claims abstract description 23
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 23
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 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 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 35
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 239000007772 electrode material Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000006260 foam Substances 0.000 claims description 17
- 239000002608 ionic liquid Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 150000002815 nickel Chemical class 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- -1 tetrafluoroborate Chemical compound 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 14
- 239000002028 Biomass Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910005809 NiMoO4 Inorganic materials 0.000 description 6
- 238000009776 industrial production Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 2
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XGBLLQBZRQMYNV-UHFFFAOYSA-N 1-butyl-3-methyl-2H-imidazole nitric acid Chemical group [N+](=O)(O)[O-].C(CCC)N1CN(C=C1)C XGBLLQBZRQMYNV-UHFFFAOYSA-N 0.000 description 1
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical group CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 description 1
- AABLGBMUTFDHTM-UHFFFAOYSA-N 1-methylimidazole;nitric acid Chemical group O[N+]([O-])=O.CN1C=CN=C1 AABLGBMUTFDHTM-UHFFFAOYSA-N 0.000 description 1
- QGKOZWJXEMFEOW-UHFFFAOYSA-N CN1CN(C=C1)CC.[N+](=O)(O)[O-] Chemical group CN1CN(C=C1)CC.[N+](=O)(O)[O-] QGKOZWJXEMFEOW-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- HNARNAHKCALHPG-UHFFFAOYSA-N [N+](=O)(O)[O-].C(C)N1CC=CC=C1 Chemical group [N+](=O)(O)[O-].C(C)N1CC=CC=C1 HNARNAHKCALHPG-UHFFFAOYSA-N 0.000 description 1
- PYBVIVSKAOAMAV-UHFFFAOYSA-N acetic acid;2-methyl-1h-imidazole Chemical group CC(O)=O.CC1=NC=CN1 PYBVIVSKAOAMAV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000015099 wheat brans Nutrition 0.000 description 1
Abstract
The invention discloses a preparation method and application of a Ni-Mo based heterojunction, wherein the preparation method comprises the steps of carrying metal in situ, combining and simply preparing anode materials for the heterojunction on a large scale by a hydrothermal method, oxidizing 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid at a lower potential, and realizing the yield of more than 99 percent, the recycling of more than 9 times, the good stability, the large-scale preparation and the yield of more than gram grade. The technology for producing hydrogen by coupling the high-added-value oxidation product electrolyzed water improves the hydrogen production efficiency of the cathode while the anode obtains high-added-value chemicals. The catalyst material has the advantages of simple preparation process, environmental protection and low cost, and has wide market application prospect in the field of industrial electrocatalytic organic synthesis and new energy.
Description
Technical Field
The invention belongs to the field of inorganic nano functional materials, and particularly relates to a simple and large-scale preparation method and application of a selective electrocatalytic oxidation furfural coupling hydrogen-producing electrode.
Background
Energy is the basis for survival of modern human society. Since the first industrial revolution, the demand for energy by the human society has increased. The current energy supply is mainly from fossil energy. After the 21 st century, with the rapid development of world economy, global energy consumption is increasing, so that fossil energy reserves are greatly reduced again. Fossil energy is a non-renewable resource, the global total amount is limited, and the massive consumption of fossil energy will lead to global resource shortages. And causes a great deal of environmental problems and also endangers human health. Therefore, the search for new, clean, renewable energy sources to alleviate the supply pressure of fossil resources is a necessary choice for sustainable development of human society. Renewable energy sources are of many kinds, including wind energy, solar energy, nuclear energy, geothermal energy, water energy, biomass energy, and the like. Among various renewable resources, biomass resources are the only renewable organic carbon source resources with neutral carbon, and chemical products with high added value can be obtained. The biomass source is abundant, the materials are convenient to obtain, the cost is low, and the biomass can be regenerated, for example, the biomass can be extracted from waste crops (corncobs, oat, wheat bran and the like). 5-Hydroxymethylfurfural (HMF), which is obtained from biomass resources such as cellulose, hemicellulose and lignin, is an important platform molecule, and its oxidation product 2, 5-furandicarboxaldehyde (DFF) is a very good biomass liquid fuel, and 2, 5-furandicarboxylic acid (FDCA) is the most likely compound to replace the petroleum-based product terephthalic acid for polyester production. In addition, the diethyl 2, 5-furandicarboxylate synthesized by FDCA can also be used in clinical medicine and can be used as a medical anesthetic; but also FDCA can be applied to the fire-fighting field because of the structure and stable chemical property of diacid carboxylic acid. Therefore, the electrocatalytic oxidation technology is utilized to convert into high-additional platform molecules, promote hydrogen production and promote the electrocatalytic synthesis technology to be applied to industrial production.
Unlike noble metal catalysts, transition metal-based catalysts are widely studied because of their abundant reserves, low cost, easy availability, and a large number of adjustable d-orbital electrons. However, the transition metal-based catalyst, especially the first row transition metal, has the problems of poor electrocatalytic activity, lower conductivity, poor stability under alkaline conditions and the like, so that the corresponding current density is low under a certain voltage; in addition, at higher voltages the current density is high, but oxygen evolution reactions exist, resulting in low charge utilization; in production, large-scale synthesis of transition metal-based catalysts is difficult due to the limitations of the synthesis methods; these problems limit the application of this technology in the practical industry. Therefore, there is a need to develop a non-noble metal electrocatalyst for industrial production that is more efficient, high yield, high selectivity and stability to obtain high value-added platform compounds.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of a Ni-Mo-based heterojunction.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a Ni-Mo based heterojunction is characterized by comprising the following steps: comprising the steps of (a) a step of,
soaking a conductive substrate electrode in a nickel-containing source solution, preserving heat to obtain a substrate loaded with basic nickel salt, sequentially carrying out ultrasonic treatment on the substrate solution in water and absolute ethyl alcohol, and finally, putting the substrate solution loaded with basic nickel salt into a vacuum drying oven for drying;
transferring the substrate solution loaded with the basic nickel salt into a reaction kettle of molybdate water solution, uniformly stirring, naturally cooling to room temperature after reaction, cleaning with absolute ethyl alcohol and deionized water, and vacuum drying under a sample to obtain the prepared Ni-Mo-based heterojunction.
As a preferred embodiment of the preparation process according to the invention, there is provided: the nickel source solution is any one of an aqueous solution and low-temperature molten salt, wherein the low-temperature molten salt comprises at least one of nickel salt with a melting point lower than 400 ℃ or ionic liquid; the conductive base electrode material includes: one or more of carbon paper, nickel foam, copper foam, stainless steel mesh; the nickel source comprises at least one of nitrate, chloride, sulfate, phosphate, acetate and carbonate; the ionic liquid comprises molten salt in a liquid state at the temperature of lower than 100 ℃, and one or more of imidazole, ammonium salt and tetrafluoroborate.
As a preferred embodiment of the preparation process according to the invention, there is provided: the size of the foam nickel substrate is at least 4cm multiplied by 4cm, the foam nickel substrate is soaked in nickel source solution, the heat preservation temperature is 120-140 ℃, the time is 6-10h, the ultrasonic time is 10min, the vacuum drying temperature is 60 ℃, and the time is 6h.
As a preferred embodiment of the preparation process according to the invention, there is provided: the stirring time for transferring the basic nickel salt-loaded substrate solution into the molybdate water solution is 30min, the reaction temperature is 140-160 ℃, and the time is 6-10 h.
As a preferred embodiment of the preparation process according to the invention, there is provided: the times of washing with absolute ethyl alcohol and deionized water are more than 3 times, and the vacuum drying temperature of the washed sample is 60 ℃ and the time is 6 hours.
As a preferred embodiment of the preparation process according to the invention, there is provided: the Ni-Mo based heterogeneity wherein the ratio of the amounts of both Ni and Mo species is 0.01: 1-10, and the volume of the formed solution is 10-100 mL.
As a preferred embodiment of the preparation process according to the invention, there is provided: the working electrode electrolyte of the Ni-Mo-based heterogeneous battery is an aqueous solution containing 5-hydroxymethylfurfural, and the concentration is 5 mM-500 mM.
As a preferred embodiment of the preparation process according to the invention, there is provided: the application system is a three-electrode system, an H-type electrolytic cell is adopted, a stone mill rod sheet/platinum sheet is used as a counter electrode, a reference electrode is HgO/Hg, an electrolyte solution is KOH or NaOH aqueous solution, the pH is within the range of 10-14, the electrolysis voltage is 1.0V-2.0V, and the constant voltage reaction is carried out for more than 0.5H.
As a preferred embodiment of the preparation process according to the invention, there is provided: the Ni-Mo based heterogeneous material is synthesized in situ on a Ni source load substrate, and a Ni source is not required to be added in the second step of synthesis.
As a preferred embodiment of the preparation process according to the invention, there is provided: the Ni-Mo-based heterogeneous material is used as an anode catalyst, and furfural can be converted into sodium salt, potassium salt and ammonium salt high-added-value chemicals corresponding to 2, 5-furandicarboxylic acid through electrocatalytic oxidation.
As a preferred embodiment of the preparation process according to the invention, there is provided: the application of the Ni-Mo based heterogeneity in electrocatalytic synthesis can realize the synthesis of a large amount of chemicals with high added value by continuously adding the raw material 5-hydroxymethylfurfural in the reaction process, and simultaneously, the cathode can continuously generate a large amount of hydrogen, thereby achieving the application in the fields of electrocatalytic organic synthesis, new energy conversion for hydrogen production, devices and the like.
It is still another object of the present invention to overcome the deficiencies of the prior art and to provide a product made by a method for making a Ni-Mo based heterojunction.
The invention further aims to overcome the defects in the prior art and provide an application of a product prepared by the preparation method of the Ni-Mo-based heterojunction in electrosynthesis of gram-grade 2, 5-furandicarboxylic acid.
The invention has the beneficial effects that:
(1) The invention provides a synthesis scheme of a heterojunction material with uniform petal shape of a nanorod by combining molybdate and nickel salt capable of being produced in a large scale, which realizes that transition metal basic salt capable of being simply prepared forms a heterojunction structure in the reaction process and improves the catalytic activity of the material. The method has the advantages of simple process, high yield, little environmental pollution, low raw material price and low production cost, can be used for large-scale production, and meets the industrial application requirements. The prepared material has excellent performance in the field of electrocatalytic oxidation of 5-hydroxymethylfurfural.
(2) The invention provides a preparation method of the electrode material, which is prepared by two steps of a nickel salt loading method and a hydrothermal method. Soaking the foam nickel in nickel nitrate aqueous solution, and preserving heat for 6-10 hours at 120-140 ℃ to obtain in-situ grown basic nickel nitrate (recorded as NiNH/NF); transferring the basic nickel nitrate and ammonium heptamolybdate solution with a certain concentration into a reaction kettle, and reacting for 6-10h at 140-160 ℃; naturally cooling to room temperature, washing with absolute ethanol and deionized water for more than 3 times, and vacuum drying the prepared sample at 60 ℃ for 10 hours to obtain the prepared electrode material. The synthesis method is simple and convenient, has mild conditions and is beneficial to realizing large-scale industrial production.
(3) The invention provides a nickel-molybdenum bimetal oxide mixture electrode material, which has the unique advantage of large-scale preparation, can have wide application prospect in the field of electrocatalytic oxidation of biomass small molecules, and particularly has excellent conversion rate, high selectivity of 2, 5-furandicarboxylic acid, high Faraday efficiency and good stability in the preparation of 2, 5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural. In the whole reaction process, the device and equipment are simple, so that the method has wide market application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
the electrode material is NiNH/NF and NiMoO 4 The heterojunction oxide material is simply called NiNH@NiMoO 4 /NF。
FIG. 1 is a schematic diagram of a typical NiNH@NiMoO as described in example 1 4 Powder X-ray diffraction pattern (a) of NF electrode material and EDX energy pattern (b) of NF electrode material.
FIG. 2 is a typical NiNH@NiMoO as described in example 1 4 Scanning electron microscope image of NF electrode material.
FIG. 3 is a chart of NiNH@NiMoO as described in example 1 4 XPS energy spectrum of NF electrode material.
FIG. 4 is a chart of NiNH@NiMoO as described in example 1 4 5mVs of/NF electrode material -1 Polarization curve of scanning rate of (c).
FIG. 5 is a chart of NiNH@NiMoO as described in example 1 4 Liquid phase of the product obtained from NF electrode materialAnd (5) a chromatogram.
FIG. 6 is a chart of NiNH@NiMoO as described in example 1 4 Yield, conversion and Faraday efficiency of NF electrode material.
FIG. 7 is a chart of NiNH@NiMoO as described in example 1 4 Cycling stability profile of NF electrode materials.
Fig. 8 is a mass produced electrode material.
Fig. 9 is an electrosynthesis gram grade FDCA product.
Fig. 10 is an HPLC diagram of an electrosynthesis reaction electrolyte solution.
Fig. 11 is an SEM image of the synthesized electrode material.
FIG. 12 shows the preparation of electrode materials described in examples 2 to 10 at 5mVs -1 Polarization curve of scanning rate of (c).
Fig. 13 is an LSV graph of comparative example 1.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Preparation of Ni-Mo bimetallic oxide heterojunction electrode material: (Nickel source: molybdenum source mass ratio is 1:2, ionic liquid is 100ml aqueous solution)
(1) 10g of nickel nitrate was dissolved in a glass beaker containing 100mL of aqueous ionic liquid solution, then placed in an oven and the nickel foam was placed in the beaker with a 4x4cm lay down, immersed in the nickel nitrate solution and incubated for 6 hours at 140 ℃, and basic nickel nitrate (noted as NiNH/NF) grown in situ on the nickel foam obtained.
(2) The obtained basic nickel nitrate (recorded as NiNH/NF) grown on the foam nickel in situ is sequentially treated by ultrasonic in water and absolute ethyl alcohol for 10min, and finally the NiNH/NF is put into a vacuum drying oven for drying at 60 ℃ for 6h.
(3) Dissolving 20g of ammonium heptamolybdate into water, and uniformly stirring; transferring the solution and NiNH/NF into a reaction kettle, and preserving heat for 6 hours at 140 ℃; naturally cooling to room temperature, washing with absolute ethanol and deionized water for more than 3 times, and vacuum drying the prepared sample at 60 ℃ for 6 hours to obtain the prepared electrode material.
Analysis of the Crystal Structure of example 1
Powder X-ray diffraction was performed on an X-ray powder diffractometer model D8 from Bruker, germany, under the test conditions of fixed target monochromatic light source Cu-K alpha, wavelengthThe scanning range is 5-50 degrees, and the scanning step length is 0.02 degrees. Sample 1# is a typical electrode material prepared in example 1, as shown in fig. 1. Comparing the X-ray diffraction pattern obtained by fitting with the pattern obtained by X-ray diffraction test of the scraped powder of sample No. 1 in FIG. 1, the heterojunction prepared contains Ni2 (NO 3) 2 (OH) 2.2H2O (PDF: 27-0939), niMoO 4( PDF: 86-0362) and NiMoO 4 ·xH 2 O (PDF: 13-0128) shows that the alkali nickel nitrate can be simply grown on the foam nickel in a large scale in the form of molten salt under the simple, mild and environment-friendly conditions, and then a Mo source is introduced by a mild hydrothermal method to smoothly form a regular Ni-Mo bimetallic oxide heterojunction electrode material on a substrate. In addition, as can be seen from the EDX spectrum in fig. 2, the main components in the material are Ni, mo, O, N, and it is further proved that the obtained material is a ni—mo oxide heterojunction material.
Characterization test of example 1 morphology
Characterization testing was performed on the prepared sample # 1 morphology by SEM. The prepared precursor material has a regular nano-flake structure, has a nano-scale length and a more uniform morphology, and has a thinner thickness than the material reported in the prior literature, as shown in fig. 3 (a); after the Mo source is introduced to form oxide, a large number of uniform rod-shaped structures are covered and grown on the original sheet layers, and petal-shaped branches are arranged at the tail ends of the rod-shaped structures, as shown in fig. 3 (b), a heterojunction structure is formed, the contact surface of the catalyst and a reaction substrate is increased, more reactive sites are exposed, and therefore the catalytic activity of the catalyst can be improved.
Polarization diagram of electrode material
NiNH@NiMoO4/NF electrode material was used as the working electrode, then Hg/HgO electrode and Pt plate were used as the reference electrode and counter electrode, respectively, and 1M sodium hydroxide solution and 20mM 5-Hydroxymethylfurfural (HMF) were used as the electrolyte and electrolyte, respectively. The polarization curve test of LSV was performed at a rate of 5 mV.s-1 at the electrochemical workstation of Shanghai Chen Hua 760E, and the test was performed by scanning 20 cycles at 100mV/s to reach a steady state before the Linear Sweep Voltammetry (LSV) test, and then at a scanning rate of 5 mV/s. The potential value was calculated according to the equation evs rhe=evs Hg/hgo+0.098+0.059ph, where evs RHE is the relative reversible hydrogen electrode potential (V) and evs Hg/HgO is the relative Hg/HgO electrode potential (V). The polarization curve is shown in FIG. 4, from which it can be seen that NiNH@NiMoO 4 the/NF heterojunction electrode material has excellent performance on HMF catalytic oxidation, and the current density can exceed 200mA/cm under 1.6V (vs RHE) 2 Meets the requirement of industrial current density and can be used in industrial production application.
The catalytic reaction path is used for detecting an intermediate product, HMF is converted into 5-formyl-2-furancarboxylic acid (FFCA) through an intermediate 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) under the condition of the invention, and 2 electrons are further transferred to obtain 2, 5-furandicarboxylic acid (FDCA), so that 6 electrons are transferred in the whole process, 1mol of FDCA can be obtained after 1mol of HMF is converted, and 3mol of H2 is obtained.
Liquid chromatogram of electrode material
The products obtained during the different reaction times were characterized by liquid chromatography using NiNH@NiMoO4/NF electrocatalytic 1M sodium hydroxide solution containing 20mM HMF, as shown in FIG. 5 for the residence time of the individual products in the high performance liquid chromatography during the different reaction times.
Yield, faraday efficiency and cycle stability of 5-hydroxymethylfurfural of the prepared material
The NiNH@NiMoO4/NF electrode was placed in an H-type electrolytic cell and used as a working electrode, a mercury oxide electrode as a reference electrode, a Pt plate as a counter electrode, a membrane as a Nafion proton exchange membrane, and a 1M sodium hydroxide solution containing 20mM HMF as an electrolyte. As shown in FIG. 7, the bar graph shows the yield, faraday efficiency and FDCA selectivity from left to right, and the abscissa indicates the number of cycles, and as shown in FIG. 7, the prepared NiNH@NiMoO4/NF electrode has high electrocatalytic activity and stability to benzyl alcohol, and the electrode material has the characteristics of high yield and high catalytic stability to electrocatalytic oxidation HMF as shown by higher FDCA yield and high Faraday efficiency after multiple cycles under the same voltage.
At a RHE voltage of 1.52Vvs, the catalyst still maintains excellent HMF oxidative conversion efficiency (95% or more) and high FDCA selectivity (95% or more) after 9 cycles as shown in FIG. 7, when the recycling property of NiNH@NiMoO4/NF electrode material is tested in a 1M sodium hydroxide solution. The stability and the cyclic practicability of the prepared catalyst are illustrated, the catalyst is favorable for industrial application and popularization, and the technology has certain guiding significance for the material synthesis of electrocatalytic biomass small molecules.
Realize mass production of electrode material and make the reaction scale reach gram-scale
First, large-scale synthesis of 4x4cm 2 The NiNH@NiMoO4/NF of the size is shown in a physical diagram of FIG. 8; 7.5g of HMF reaction raw material was charged at 4X4cm 2 After 42h of reaction, the reaction solution is completely acidified by hydrochloric acid, precipitated solids are separated, 8.8g of the reaction solution is weighed, the yield can reach 94.8%, as shown in FIG. 9, and the liquid phase diagram after the reaction is shown in FIG. 10, so that the product is proved to be FDCA basically. From the SEM image of the electrode material after reaction (shown in FIG. 11), it can be seen that the morphology of the material is substantially unchangedThe electrode material has good stability under the electrosynthesis condition, and shows the recycling practicability.
Example 2
The type of the ion liquid is H except that the low Wen Nieyuan is nickel nitrate 2 The source of O, mo is (NH) 4 ) 2 Mo 4 O 13 ·2H 2 O, nickel source and molybdenum source in the mass ratio of 1:5, liquid H 2 The other experimental setup was the same as in example 1 except that 10ml of O was used, the substrate was carbon paper, the reaction temperature was 130℃and the time was 0.5 h.
Example 3
Except for the low Wen Nieyuan, the ion liquid type is nickel nitrate, the ion liquid type is 1-ethyl-3-methylimidazole acetate, and the Mo source is (NH) 4 ) 2 Mo 4 O 13 ·2H 2 The other experimental settings were the same as in example 1 except that the mass ratio of O, ni source to Mo source was 1:10, the liquid was 20ml, the substrate was foam nickel, the reaction temperature was 150℃and the time was 0.5 h.
Example 4
The type of the low-level Wen Nieyuan is nickel carbonate, the ionic liquid type is N-ethylpyridine nitrate, and the Mo source is (NH) 4 ) 2 MoO 4 The other experimental settings were the same as example 1 except that the mass ratio of nickel source to molybdenum source was 0.5:10, the liquid was 5ml, the substrate was copper foam, the reaction temperature was 160 ℃ and the time was 1 h.
Example 5
Except that the low Wen Nieyuan type is nickel sulfate, the ionic liquid type is 3-methylimidazole nitrate, and the Mo source is Na 2 MO 4 ·2H 2 The other experimental settings were the same as in example 1 except that the mass ratio of O, ni source to Mo source was 0.5:20, the liquid was 10ml, the substrate was a stainless steel mesh, the reaction temperature was 170℃and the time was 2 hours.
Example 6
Except that the low Wen Nieyuan type is nickel nitrate, the ionic liquid type is 2-methylimidazole acetate, and the Mo source is (NH) 4 ) 2 MoO 4 The other experimental settings were the same as example 1 except that the mass ratio of nickel source to molybdenum source was 0.1:10, the liquid was 5ml, the substrate was foamed nickel, the reaction temperature was 80 ℃ and the time was 3 hours.
Example 7
The type of the removed low Wen Nieyuan is nickel nitrate, the ionic liquid type is N-ethylpyridine tetrafluoroborate, and the Mo source is Na 2 MO 4 ·2H 2 The other experimental settings were the same as example 1 except that the mass ratio of O, nickel source to molybdenum source was 0.2:15, the liquid was 1.5ml, the substrate was foamed nickel, the reaction temperature was 60℃and the time was 12 hours.
Example 8
The low Wen Nieyuan type is nickel chloride, the ionic liquid type is 1-butyl-3-methylimidazole nitrate, and the Mo source is (NH) 4 ) 2 MoO 4 The other experimental settings were the same as in example 1 except that the mass ratio of nickel source to molybdenum source was 0.5:15, the liquid was 2.0ml, the substrate was copper foam, the reaction temperature was 100 ℃ and the time was 6 hours.
Example 9
Except for the low Wen Nieyuan, the ion liquid type is 1-ethyl-3-methylimidazole nitrate, and the Mo source is Na 2 MO 4 ·2H 2 The mass ratio of O, nickel source and molybdenum source is 0.2:8, the ionic liquid is 2.0ml, the substrate is stainless steel, the reaction temperature is 120 ℃, the reaction time is 4 hours, and other experimental settings are the same as those of the example 1.
Example 10
The type of the removed low Wen Nieyuan is nickel nitrate, the ionic liquid type is N-ethylpyridine hexafluorophosphate, and the Mo source is (NH) 4 ) 2 MoO 4 The mass ratio of the nickel source to the molybdenum source is 1:50, the ionic liquid is 8ml, the substrate is carbon paper, the reaction temperature is 110 ℃, the time is 36 hours, and other experimental settings are the same as those of the example 1.
The electrocatalytic properties of the materials prepared in examples 2 to 10 are shown in FIG. 12, and at most 1.45V (vs RHE) voltage needs to be applied, and the prepared different electrodes can reach 50mA/cm 2 The current density of the electrode can reach 100mA/cm when the voltage of 1.80V (vs RHE) is applied to the electrode 2 The industrial current density requirements of the electrode materials prepared by different methods are shown to be applicable to industrial production applications.
Comparative example 1
The electrochemical catalytic reaction was carried out using a commercial foam nickel electrode material as the working electrode, and Hg/HgO electrode and a stone mill rod piece as the reference electrode and the counter electrode, respectively, placed in 50mL of an aqueous solution containing 1.0M NaOH and 20mM HMF.
The results of comparative example 1 are shown in FIG. 13, in which LSV curves show that 50mA cm was reached in the electrolyte without HMF -2 The current density, which is 1.87V (vs. RHE), reaches 50mA cm after HMF is added -2 The current density is 1.72V (vs. RHE), which is much higher than the electrode material prepared according to the present invention, although the applied voltage is reduced after HMF is added. It can be seen that the heterojunction material prepared by the method has significant advantages over the existing commercial electrode materials.
In contrast to the prior art similar to the present invention, my preparation was made as basic nickel nitrate NiMoO 4 The heterojunction material has excellent electrocatalytic performance due to different compositions, and in the preparation method, the preparation method does not need high-temperature sintering or flammable and explosive gas, the reaction temperature is below 200 ℃, the energy consumption in the preparation process is low, the process is simple, and the industrial production is more convenient. In addition, unlike electrocatalytic reduction hydrogen production in the comparative example, the method realizes the scale preparation of the metal oxide heterojunction, and the prepared metal oxide heterojunction can be used in electrosynthesis of gram-grade fine chemicals, and the catalyst has excellent catalytic activity and stability, and shows the innovation and industrial applicability of the invention.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, 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 the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, and it should be covered in the scope of the present invention.
Claims (10)
1. A preparation method of a Ni-Mo based heterojunction is characterized by comprising the following steps: comprising the steps of (a) a step of,
soaking a conductive substrate electrode in a nickel-containing source solution, preserving heat to obtain a substrate loaded with basic nickel salt, sequentially carrying out ultrasonic treatment on the substrate solution in water and absolute ethyl alcohol, and finally, putting the substrate solution loaded with basic nickel salt into a vacuum drying oven for drying;
transferring the substrate solution loaded with the basic nickel salt into a reaction kettle of molybdate water solution, uniformly stirring, naturally cooling to room temperature after reaction, cleaning with absolute ethyl alcohol and deionized water, and vacuum drying under a sample to obtain the prepared Ni-Mo-based heterojunction.
2. The method of manufacturing according to claim 1, wherein: the conductive base electrode material includes: one or more of carbon paper, nickel foam, copper foam, stainless steel mesh; the nickel source solution is any one of nickel salt aqueous solution, nickel salt ionic liquid solution and nickel salt low-temperature molten salt, wherein the low-temperature molten salt comprises at least one of nickel salt or ionic liquid with a melting point lower than 400 ℃; the ionic liquid comprises molten salt which is in a liquid state at the temperature of lower than 100 ℃, and one or more of imidazole, ammonium salt and tetrafluoroborate; the nickel source comprises at least one of nitrate, chloride, sulfate, phosphate, acetate and carbonate.
3. The method of manufacturing according to claim 1, wherein: the size of the foam nickel substrate is at least 4cm multiplied by 4cm, the foam nickel substrate is soaked in nickel source solution, the heat preservation temperature is 120-140 ℃, the time is 6-10h, the ultrasonic time is 10min, the vacuum drying temperature is 60 ℃, and the time is 6h.
4. The method of manufacturing according to claim 1, wherein: the stirring time for transferring the basic nickel salt-loaded substrate solution into the molybdate water solution is 30min, the reaction temperature is 140-160 ℃, and the time is 6-10 h.
5. The method of manufacturing according to claim 1, wherein: the times of washing with absolute ethyl alcohol and deionized water are more than 3 times, and the vacuum drying temperature of the washed sample is 60 ℃ and the time is 6 hours.
6. The Ni-Mo based heterogeneity produced by the production method of claim 1 to 5.
7. The Ni-Mo based heterogeneous mass of claim 6, wherein: the Ni-Mo based heterogeneity wherein the ratio of the amounts of both Ni and Mo species is 0.01: 1-10, and the volume of the formed solution is 10-100 mL.
8. The Ni-Mo based heterogeneous mass of claim 7, wherein: the working electrode electrolyte of the Ni-Mo-based heterogeneous battery is an aqueous solution containing 5-hydroxymethylfurfural, and the concentration is more than 5 mM.
9. Use of the Ni-Mo based heterogeneity according to claim 6 for the electrosynthesis of gram grade 2, 5-furandicarboxylic acid.
10. The use according to claim 9, wherein: the application system is a three-electrode system, an H-type electrolytic cell is adopted, a stone mill rod sheet/platinum sheet is used as a counter electrode, a reference electrode is HgO/Hg, an electrolyte solution is KOH or NaOH aqueous solution, the pH is within the range of 10-14, the electrolysis voltage is 1.0V-2.0V, and the constant voltage reaction is carried out for more than 0.5H.
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