CN117983259A - Catalyst for electrochemical hydrogenation and preparation method and application thereof - Google Patents
Catalyst for electrochemical hydrogenation and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000002070 nanowire Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003607 modifier Substances 0.000 claims abstract description 27
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 63
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 45
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 44
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims description 40
- 230000009467 reduction Effects 0.000 claims description 31
- 238000001354 calcination Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 22
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 127
- 239000000243 solution Substances 0.000 description 39
- 229910052802 copper Inorganic materials 0.000 description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 26
- 239000006260 foam Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 239000003792 electrolyte Substances 0.000 description 21
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 description 20
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 16
- 239000002953 phosphate buffered saline Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000012018 catalyst precursor Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
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- 238000001075 voltammogram Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 238000012512 characterization method Methods 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- WBBANDSXKCNJLZ-UHFFFAOYSA-N (2-methyl-3h-furan-2-yl)methanol Chemical compound OCC1(C)CC=CO1 WBBANDSXKCNJLZ-UHFFFAOYSA-N 0.000 description 2
- WVHJBVPYIIBODU-UHFFFAOYSA-N 2-methyl-3h-furan-2-carbaldehyde Chemical compound O=CC1(C)CC=CO1 WVHJBVPYIIBODU-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- 239000000872 buffer Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to the field of electrochemical hydrogenation, in particular to a catalyst for electrochemical hydrogenation and a preparation method and application thereof. The catalyst for electrochemical hydrogenation comprises Cu nanowires and a modifier loaded on the Cu nanowires, wherein the modifier is Keggin type heteropolyacid and/or heteropolyacid salt. According to the invention, keggin type heteropolyacid and/or heteropolyacid salt is loaded on the Cu nanowire, and the Cu nanowire is modified by the type heteropolyacid and/or heteropolyacid salt, so that the overpotential of active hydrogen generated by the catalyst/hydrogen evolution can be greatly reduced, and the hydrogen coverage of the surface of the catalyst is improved, thereby improving the reactivity, selectivity and stability of the catalyst, and the catalyst provided by the invention can be suitable for higher substrate reaction concentration.
Description
Technical Field
The invention relates to the field of electrochemical hydrogenation, in particular to a catalyst for electrochemical hydrogenation and a preparation method and application thereof.
Background
The 5-Hydroxymethylfurfural (HMF) is an important platform compound derived from biomass, and can be used as a raw material for preparing high-added-value 2, 5-furandimethanol (BHMF) through selective hydrogenation. As diol compounds containing furan rings, BHMF can be applied to the synthesis of functionalized polyesters, polyethers, resins and pharmaceutical intermediates.
Because of the simultaneous existence of various hydrogenation functional groups in the HMF structure, such as aldehyde groups, furan rings, hydroxyl groups and the like, the HMF has active properties and complex hydrogenation products. The conventional method in thermocatalysis is a direct hydrogenation method using hydrogen as a hydrogen source and a hydrogen transfer method using lower alcohol as a hydrogen source. The direct hydrogen hydrogenation involves the use of noble metals, the selectivity is difficult to regulate and control, in addition, hydrogen has the property of inflammability and explosiveness, hydrogen used each time is excessive, the solubility in a solvent is low, the utilization rate is low, and certain potential safety hazards exist. The hydrogen transfer process of lower alcohols is a hotspot of current research, and although the process has higher selectivity, the use of lower alcohols and high temperature reaction conditions lead to higher costs.
The electrochemical hydrogenation can realize the selective hydrogenation of HMF by taking water as a solvent and protons in the water as a hydrogen source at room temperature, and is the method with the mildest reaction condition and environmental protection. However, the activity and selectivity of the currently developed electrocatalyst remain poor, and the use of a noble metal catalyst is required to increase the reactivity, resulting in high reaction costs.
The related art discloses a copper-based catalyst prepared by adopting a method of electrochemically reducing CuO nanowires, which is subjected to electrocatalytic hydrogenation for 2-3 hours under the voltage of-0.4V to-0.5V, and then the reaction of preparing BHMF by carrying out HMF electrochemical hydrogenation. However, the concentration of HMF in the reaction is only 50mM, which increases the use of solvents and the cost of separation; the stability test time of the copper-based catalyst in the electro-hydrogenation reaction is still shorter (within 10 hours); moreover, the technology does not disclose the selectivity of the above reaction to BHMF, and it is well known in the art that the electro-hydrogenation reaction of HMF not only produces BHMF, but also may produce by-products such as dimethylol bifurfuryl alcohol (BHH), 2-Methylfurfural (MF), 2-methylfurfuryl alcohol (MFA), etc., as shown in the following reaction formula:
Therefore, there is a need to develop a catalyst for electrochemical hydrogenation which does not contain noble metals, but still has high reactivity, and has high selectivity and stability at high concentrations.
Disclosure of Invention
In view of the above, the present invention provides a catalyst for electrochemical hydrogenation, which solves the problems of low reactivity, selectivity and stability of the existing electro-hydrogenation catalyst, and only being applicable to low reaction concentration.
In a first aspect, the present invention provides a catalyst for electrochemical hydrogenation comprising: the Cu nanowire and the modifier loaded on the Cu nanowire are Keggin type heteropolyacid and/or heteropolyacid salt.
By loading Keggin type heteropolyacid and/or heteropolyacid salt on the Cu nanowire and modifying the Cu nanowire by using the type heteropolyacid and/or heteropolyacid salt, the overpotential of active hydrogen generated by the catalyst and hydrogen evolution can be greatly reduced, and the hydrogen coverage of the surface of the catalyst is improved, so that the reactivity, selectivity and stability of the catalyst are improved, and the catalyst provided by the invention can be suitable for higher reaction concentration.
In the embodiment of the invention, the Keggin type heteropolyacid is at least one of phosphomolybdic acid, silicotungstic acid and phosphotungstic acid.
In the embodiment of the invention, the Keggin-type heteropolyacid salt is at least one of sodium phosphomolybdate and ammonium phosphotungstate.
In embodiments of the present invention, the Cu nanowires may be derived from Cu (OH) 2 nanowires and/or CuO nanowires.
In an embodiment of the present invention, the mass ratio of the modifier to the Cu nanowire is 0.1% to 10%, preferably 0.5% to 2%.
In an embodiment of the present invention, the length of the Cu nanowires is 0.5 to 12 μm and the width is 50 to 200nm.
In a second aspect, the present invention provides a method for preparing the catalyst for electrochemical hydrogenation, comprising the steps of:
S1, dissolving a modifier in an alcohol solvent to form a modifier solution, wherein the modifier is Keggin type heteropolyacid and/or heteropolyacid salt;
S2, placing the CuO nanowire and/or the Cu (OH) 2 nanowire in the modifier solution, soaking for the first time, taking out, drying, and calcining under the condition of existence of protective gas or air to obtain a precursor; or placing the Cu nanowire in the modifier solution, soaking for a first time, taking out, drying, and calcining under the condition of existence of protective gas or air to obtain a catalyst;
And S3, performing electrochemical reduction by taking the precursor as a cathode, taking out the reduced cathode, cleaning, and drying to obtain the catalyst.
In an embodiment of the invention, the concentration of the modifier solution is 0.3mmol/L to 2mmol/L.
In the embodiment of the invention, the Keggin type heteropolyacid is at least one of phosphomolybdic acid, silicotungstic acid and phosphotungstic acid.
In the embodiment of the invention, the Keggin-type heteropolyacid salt is at least one of sodium phosphomolybdate and ammonium phosphotungstate.
In an embodiment of the present invention, the alcohol solvent is a lower alcohol, and may be at least one of methanol, ethanol, and isopropanol, for example.
In the embodiment of the invention, the first time is 20 min-4 h, preferably 30 min-1 h. The soaking time is too short, and the modifier cannot be fully loaded; the soaking time is too long and more modifier cannot be loaded, so that the soaking is only needed for 20min to 4h, and particularly, the soaking is more suitable for 30min to 1h.
In an embodiment of the present invention, the temperature of the drying in step S2 is 25 ℃ to 80 ℃. Too low a drying temperature can extend the drying time, while too high a drying temperature can result in too fast volatilization of the modifier solution, reducing the uniformity of the modifier clusters on the surface of the material. Therefore, it is most preferable to dry at 25℃to 80 ℃.
In the embodiment of the invention, the calcination temperature is 200-350 ℃, the temperature rising speed is 1-5 ℃/min, and the time is 1-5 h. The effect of calcination is to anchor the modifier by forming chemical bonds with the support, so that the calcination temperature cannot be too low, which would otherwise result in the formation of stable chemical bonds, but the calcination temperature cannot be too high, which would otherwise result in thermal decomposition of the modifier. The temperature rising speed cannot be too high, otherwise, temperature overshoot is caused, the temperature rising speed cannot be too low, and the preparation time is increased.
In an embodiment of the present invention, the shielding gas is at least one of nitrogen and argon.
In the embodiment of the invention, the Cu nanowire can be prepared by high-temperature reduction of the Cu (OH) 2 nanowire, wherein the reducing atmosphere is at least one of hydrogen, hydrogen-argon mixed gas containing at least 5% by volume of hydrogen and hydrogen-nitrogen mixed gas containing at least 5% by volume of hydrogen, and the reducing condition is about 300 ℃ for 3 hours.
In the embodiment of the invention, in the step S3, the reduction potential is-0.2V to-0.7V, and the reduction time is 20min to 1h. The purpose of electrochemical reduction is to convert CuO to metallic Cu, and if the reduction potential is too high, too many hydrogen bubbles are generated, leading to the shedding of the modifier on the Cu surface, and if the reduction potential is too low, the reduction time is prolonged. Correspondingly, the reduction time needs to be controlled between 20min and 1h, the reduction is incomplete due to too short time, and the catalytic effect is further affected, and the reduction time only wastes time and resources due to too long time.
In the embodiment of the invention, in the step S3, ag/AgCl is adopted as a reference electrode, a platinum electrode is a counter electrode, a cathode and an anode electrolyte in an H-type electrolytic cell are both 0.5M PBS (phosphate buffered saline) solution with pH=7, and the cathode and the anode electrolyte are separated by a Nafion 212 proton exchange membrane; the catholyte uses PBS buffer solution as electrolyte, and can keep the pH value relatively constant.
In a third aspect, the invention also provides the catalyst for electrochemical hydrogenation or the application of the catalyst for electrochemical hydrogenation prepared by the preparation method in the preparation of 2, 5-furandimethanol by catalyzing the electro-hydrogenation of 5-hydroxymethylfurfural.
In a fourth aspect, the present invention also provides a process for preparing 2, 5-furandimethanol, comprising the steps of:
A catalyst is adopted as a cathode, the cathode is placed in a catholyte solution in which 5-hydroxymethylfurfural is dissolved, and negative voltage is applied to perform electrochemical hydrogenation reaction;
the catalyst is a catalyst for electrochemical hydrogenation provided according to the first aspect of the present invention or a catalyst for electrochemical hydrogenation prepared according to the preparation method provided according to the second aspect of the present invention.
The electrochemical hydrogenation reaction of 5-hydroxymethylfurfural is carried out by adopting the catalyst, the reaction activity is improved due to the great reduction of the overpotential of the catalyst, the selectivity of 2, 5-furandimethanol is also improved, the higher Faraday efficiency is still maintained even under the concentration of 1M HMF, and the operation is still stable for nearly 80 hours under the condition of larger current density.
In an embodiment of the invention, the electrode area of the cathode is 1cm 2.
In an embodiment of the invention, the negative voltage is-0.15V to-0.4V (vs RHE). In electrochemical hydrogenation, a certain negative voltage is applied to overcome hydrogenation overpotential, but if the absolute value of the potential is too low, hydrogenation reaction or too low current density cannot be realized, and if the absolute value of the potential is too high, serious hydrogen evolution side reaction may occur.
In an embodiment of the invention, the coulomb number of the electrochemical hydrogenation reaction is 101% of the theoretical coulomb number required for assuming complete conversion of 5-hydroxymethylfurfural. This provides a sufficient amount of charge to ensure as complete a reaction as possible.
In an embodiment of the invention, the molar concentration of 5-hydroxymethylfurfural in the catholyte is 100mM to 1000mM.
In an embodiment of the invention, the catholyte further comprises 0.5M PBS having ph=7.
In the embodiment of the invention, ag/AgCl is used as a reference electrode, and platinum is used as a counter electrode.
In an embodiment of the invention, the anolyte is a 0.5M H 2SO4 solution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a transmission electron microscope image of the PMA/Cu catalyst prepared in example 1 of the present invention.
FIG. 2 is a graph showing the high angle annular dark field image (HAADF) of a transmission electron microscope and its elemental distribution of the PMA/Cu catalyst prepared in example 1 of the present invention.
FIG. 3 is a linear sweep voltammogram of the PMA/Cu catalyst prepared in example 1 of the present invention and the Cu catalyst prepared in comparative example 2.
FIG. 4 shows the Faraday efficiency of HMF hydrogenation products and the rate of BHMF formation at various potentials for the PMA/Cu catalyst prepared in example 1 of the present invention.
Fig. 5 is a graph showing the faradaic efficiency of HMF hydrogenation products and the BHMF formation rate at various potentials for the Cu catalyst prepared in comparative example 2 of the present invention.
Figure 6 shows the faraday efficiency of the hydrogenation product and the BHMF formation rate for the PMA/Cu catalyst prepared in example 1 of the present invention at different HMF concentrations.
FIG. 7 is a linear sweep voltammogram of the PMA/Cu-2 catalyst prepared in example 2 of the present invention and the Cu catalyst prepared in comparative example 2.
FIG. 8 is a linear sweep voltammogram of the PMA/Cu-3 catalyst prepared in example 3 of the present invention and the Cu catalyst prepared in comparative example 2.
FIG. 9 is a linear sweep voltammogram of the PMA/Cu-4 catalyst prepared in example 4 of the present invention and the Cu catalyst prepared in comparative example 2.
FIG. 10 is a linear sweep voltammogram of the SWA/Cu catalyst prepared in example 5 of the present invention and the Cu catalyst prepared in comparative example 2.
FIG. 11 is a stability test of the PMA/Cu catalyst prepared in example 1 of the present invention at a potential of-0.3V and a concentration of 0.25 MHMF.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In the present invention, the unit "M" represents mol/L, the unit "mM" represents mmol/L, PBS represents phosphate buffer solution, and the pH value of the PBS buffer used in the present invention is 7. The Cu (OH) 2 nanowire, the CuO nanowire and the Cu nanowire can be prepared by referring to the related prior art, and the Cu (OH) 2 nanowire, the CuO nanowire and the Cu nanowire can be loaded on foam copper, carbon paper or activated carbon, or Cu (OH) 2 nanowire, cuO nanowire and Cu nanowire powder can be directly adopted without a carrier. It is understood that the present invention is not particularly limited with respect to the existence form of Cu (OH) 2 nanowires, cuO nanowires, and Cu nanowires, and any loaded or unloaded Cu (OH) 2 nanowires, cuO nanowires, and Cu nanowires can be applied to the present invention.
Comparative example 1
The copper foam loaded with Cu nanowires was prepared according to the method described in example 1 of China patent document CN113430559A, concretely:
(1) Pretreating a foam copper sheet with the length of 1cm multiplied by 2 cm: sequentially and respectively ultrasonically treating the foam copper in 3mol/L hydrochloric acid, acetone and deionized water for 10 minutes, and then washing with deionized water;
(2) And respectively carrying out electrochemical etching on the pretreated foamy copper serving as a cathode and an anode in a sodium hydroxide solution of 3mol/L, and carrying out current etching for 10 minutes under the condition that the current density is 20mA/cm 2, thereby obtaining the Cu (OH) 2 nanowire loaded on the foamy copper.
(3) And (3) placing the Cu (OH) 2 nanowire in a square boat, calcining in a muffle furnace, heating to 300 ℃ at a speed of 1 ℃/min, and preserving heat for 2 hours to obtain the CuO nanowire loaded on the foam copper.
(4) In an H-type three-electrode system electrolytic cell, directly taking the CuO nanowire loaded on the foam copper, which is prepared in the step (3), as a working electrode, ag/AgCl as a reference electrode, a platinum electrode as a counter electrode, 0.5mol/L Na 2SO4 solution as an anode chamber electrolyte, 0.05 mol/L5 hydroxymethyl furfural and 0.5mol/L Na 2SO4 solution as a cathode chamber electrolyte, and separating the chambers by using a DuPont 117 cation exchange membrane; electrochemical reduction is carried out for 10 minutes under the voltage of 0.4V to obtain the Cu nanowire loaded on the foam copper, namely the Cu catalyst.
Comparative example 2
The comparative example provides a method for preparing copper foam loaded with Cu (OH) 2 nanowire, copper foam loaded with CuO nanowire and copper foam loaded with Cu nanowire, which is as follows:
Step 1: copper foam 1mm thick was cut to 1x2cm, then ultrasonically washed with 3mol/L hydrochloric acid, acetone, deionized water, respectively, and dried in air.
Step 2: a mixed aqueous solution of 2.5mol/L NaOH and 50mmol/L (NH 4)2S2O8) was prepared.
Step 3: soaking the foam copper obtained in the step 1 in 3ml of the solution prepared in the step 2 for 20-30min.
Step 4: the copper foam grown with Cu (OH) 2 nanowires was removed, washed with deionized water, and dried in an oven at 80 ℃.
Step 5: calcining the prepared Cu (OH) 2 nanowire in a muffle furnace at the temperature of 250 ℃ at the speed of 5 ℃/min for 2 hours to obtain the copper foam loaded with the CuO nanowire.
Step 6: and 5, carrying out electrochemical reduction on the CuO nanowire prepared in the step5 serving as a cathode, wherein the cathode electrolyte and the anode electrolyte are respectively 0.5M PBS solution with pH=7, the reduction potential is-0.4V, and the reduction time is 40 minutes. And taking out the reduced cathode, washing with deionized water, and drying to obtain the Cu nanowire catalyst growing on the foam copper.
Example 1
The preparation method of the PMA/Cu catalyst provided by the embodiment is as follows:
Step 1: a solution of 0.8mmol/L PMA was prepared by dissolving 4.4mg phosphomolybdic acid (PMA) in 3ml ethanol.
Step 2: copper foam (1 x2cm, preparation method same as comparative example 2) loaded with CuO nanowires was immersed in the PMA solution prepared in step 1 for 30min.
Step 3: and taking out the soaked CuO nanowire, and drying in an oven at 80 ℃.
Step 4: calcining the dried catalyst precursor in nitrogen atmosphere, wherein the calcining temperature is 300 ℃, the heating speed is 2 ℃/min, and the calcining time is 2 hours.
Step 5: and (3) using an H-type electrolytic cell, carrying out electrochemical reduction by taking the calcined catalyst precursor as a cathode, wherein the cathode electrolyte and the anode electrolyte are respectively 0.5M PBS solution with pH=7, the reduction potential is-0.3V, and the reduction time is 30 minutes. And taking out the reduced cathode, washing with deionized water, and drying to obtain the PMA/Cu catalyst.
As determined by ICP-MS and SEM, in the PMA/Cu catalyst prepared by the embodiment, the mass ratio of PMA to Cu nanowire is 1%, the length of the Cu nanowire is 0.5-1 μm, and the width is about 100 nm.
As shown in fig. 1, the PMA/Cu catalyst prepared in this example exhibited a porous rod-like structure due to shrinkage of the structure after electro-reduction of CuO to Cu. From FIG. 2, it can be seen that three elements Cu, mo and O exist in PMA/Cu at the same time, thereby indicating that the phosphomolybdic acid modifier is successfully loaded on the Cu surface.
Example 2
The preparation method of the PMA/Cu-2 catalyst provided by the embodiment is as follows:
Step 1: 5.5mg of phosphomolybdic acid (PMA) was dissolved in 3ml of ethanol to prepare a 1mmol/L PMA solution.
Step 2: copper foam (1 x2cm, preparation method similar to comparative example 2) loaded with Cu (OH) 2 nanowires was immersed in the PMA solution prepared in step 1 for 60min.
Step 3: taking out the soaked Cu (OH) 2 nanowire, and drying in an oven at 60 ℃.
Step 4: and (3) calcining the dried catalyst precursor in an argon atmosphere at a temperature of 300 ℃ at a heating rate of 3 ℃/min for 3 hours.
Step 5: and (3) using an H-type electrolytic cell, carrying out electrochemical reduction by taking the calcined catalyst precursor as a cathode, wherein the cathode electrolyte and the anode electrolyte are respectively 0.5M PBS solution with pH=7, the reduction potential is-0.4V, and the reduction time is 30 minutes. And taking out the reduced cathode, washing with deionized water, and drying to obtain the PMA/Cu-2 catalyst.
As determined by SEM characterization, the length of the Cu nanowire in the PMA/Cu-2 catalyst prepared by the embodiment is 0.5-2 mu m, and the width is 100-200 nm.
Example 3
The preparation method of the PMA/Cu-3 catalyst provided by the embodiment is as follows:
Step 1: 4.5mg of sodium phosphomolybdate (NaPMA) was dissolved in 3ml of ethanol to prepare a solution of NaPMA at 0.8 mmol/L.
Step 2: copper foam (1 x2cm, preparation method same as comparative example 2) loaded with CuO nanowires was immersed in NaPMA solution prepared in step 1 for 60min.
Step 3: and taking out the soaked CuO nanowire, and drying in an oven at 80 ℃.
Step 4: calcining the dried catalyst precursor in nitrogen atmosphere, wherein the calcining temperature is 300 ℃, the heating speed is 2 ℃/min, and the calcining time is 2 hours.
Step 5: and (3) using an H-type electrolytic cell, carrying out electrochemical reduction by taking the calcined catalyst precursor as a cathode, wherein the cathode electrolyte and the anode electrolyte are respectively 0.5M PBS solution with pH=7, the reduction potential is-0.3V, and the reduction time is 30 minutes. And taking out the reduced cathode, washing with deionized water, and drying to obtain the PMA/Cu catalyst.
As determined by SEM characterization, in the PMA/Cu-3 catalyst prepared by the embodiment, the length of the Cu nanowire is 0.5-1 mu m, and the width is about 100 nm.
Example 4
The preparation method of the PMA/Cu-4 catalyst provided by the embodiment is as follows:
Step 1: and (3) placing the copper foam loaded with the Cu (OH) 2 nanowire (the preparation method is the same as that of the comparative example 2) in a hydrogen-argon mixed atmosphere (the hydrogen volume concentration is 5% in the hydrogen-argon mixed atmosphere), calcining at the temperature of 300 ℃ for 3 hours at the heating speed of 1 ℃ per minute, and obtaining the copper foam loaded with the Cu nanowire.
Step 2: 2.8mg of phosphomolybdic acid (PMA) was dissolved in 3ml of ethanol to prepare a 0.5mmol/L PMA solution.
Step 3: and (3) immersing the copper foam (1 x2 cm) loaded with the Cu nanowires obtained in the step (1) in the PMA solution prepared in the step (2) for 30min.
Step 4: and taking out the soaked Cu nanowire, and drying at room temperature.
Step 5: calcining the dried catalyst precursor in nitrogen atmosphere at the temperature of 200 ℃ and the heating speed of 2 ℃/min for 3 hours to obtain the PMA/Cu-4 catalyst.
Example 5
The preparation method of the SWA/Cu catalyst provided by the embodiment is as follows:
step 1: 8.6mg of silicotungstic acid (SWA) was dissolved in 3ml of methanol to prepare a SWA solution of 1.5 mmol/L.
Step 2: copper foam (1 x2cm, preparation method same as comparative example 2) loaded with CuO nanowires was immersed in the SWA solution prepared in step 1 for 2 hours.
Step 3: and taking out the soaked CuO nanowire, and drying in an oven at 40 ℃.
Step 4: calcining the dried catalyst precursor in nitrogen atmosphere, wherein the calcining temperature is 200 ℃, the heating speed is 2 ℃/min, and the calcining time is 2 hours.
Step 5: and (3) using an H-type electrolytic cell, carrying out electrochemical reduction by taking the calcined catalyst precursor as a cathode, wherein the cathode electrolyte and the anode electrolyte are respectively 0.5M PBS solution with pH=7, the reduction potential is-0.5V, and the reduction time is 20 minutes. And taking out the reduced cathode, washing with deionized water, and drying to obtain the SWA/Cu catalyst.
As determined by SEM characterization, the length of the Cu nanowire in the SWA/Cu catalyst prepared in the embodiment is 0.1-0.5 mu m, and the width is about 100 nm.
Example 6
Using Metrohm Vionic electrochemical workstation and H-type electrolytic cell, PMA/Cu catalyst prepared in example 1 of the present invention or Cu catalyst prepared in comparative example 2 was used as cathode (electrode area 1cm 2), ag/AgCl was used as reference electrode, platinum mesh was used as counter electrode, 0.5M PBS or 0.5M PBS solution with 0.1M HMF dissolved therein was used as catholyte 20ml, anolyte was 0.5M H 2SO4 solution, and the two were separated by Nafion 212 proton exchange membrane, and Linear Sweep Voltammetry (LSV) was performed in the range of applying 0.05 to-0.5V relative to standard hydrogen electrode, to obtain the results shown in FIG. 3.
As can be seen from FIG. 3, the PMA/Cu catalyst has a hydrogen evolution reaction overpotential of only 225mV at a current density of-100 mAcm -2, which is reduced by nearly 200mV compared to the Cu catalyst. The HMF hydrogenation current density of the PMA/Cu catalyst at-200 mA cm -2 only needs to apply a potential of-0.273V, compared with the Cu catalyst which needs to apply a potential of-0.450V.
The electrochemical performance of the Cu catalyst prepared in comparative example 1 was tested in the same manner as in this example, and the result showed that the Cu catalyst of comparative example 2 required lower overpotential to reach the corresponding current (HMF hydrogenation current density of-120 mA cm -2 required to be applied with a potential of about-0.6V for comparative example 1, and HMF hydrogenation current density of-120 mA cm -2 required to be applied with a potential of-0.4V for comparative example 2) compared to comparative example 1.
Experimental example 7
The method for preparing 2, 5-furandimethanol by catalyzing the electric hydrogenation of 5-hydroxymethylfurfural provided by the embodiment comprises the following steps:
An H-type electrolytic cell is selected, the PMA/Cu catalyst prepared in the embodiment 1 of the invention or the Cu catalyst prepared in the comparative example 2 is used as a cathode (the electrode area is 1cm 2), ag/AgCl is used as a reference electrode, a platinum net is used as a counter electrode, a 0.5M PBS solution of 100mmolHMF is dissolved in catholyte solution, the anolyte solution is 0.5M H 2SO4 solution, the two solutions are separated by a Nafion 212 proton exchange membrane, a certain negative potential is applied to carry out HMF electrochemical hydrogenation reaction, and the reaction product is subjected to high performance liquid chromatography analysis after 150 coulombs, and the results are shown in tables 1-2 and figures 4-5.
TABLE 1 PMA/Cu conversion and Selectivity after 150 coulombs of the catalyst at different reaction potentials
TABLE 2 Cu conversion and Selectivity of the catalysts after 150 coulombs of reaction at different reaction potentials
From tables 1-2, it can be seen that the PMA/Cu catalyst still maintains extremely high selectivity to BHMF with increasing potential, but the selectivity of Cu catalyst to BHMF with increasing potential is greatly reduced, which indicates that the Cu catalyst has higher BHMF selectivity after PMA modification (i.e., PMA/Cu catalyst).
As can be seen from fig. 4, the main conversion product of the hydrogenation reaction of PMA/Cu catalyst against HMF in the corresponding potential range is BHMF, the hydrogen evolution faraday efficiency is only about 15%, and the BHMF production rate is as high as 5.5mmol cm -2h-1 at-0.4V, with little coupling byproduct BHH generated only at more negative potential. Thus, the Cu loaded PMA modifier has excellent selectivity and extremely high catalytic activity for preparing BHMF through hydrogenation (i.e. PMA/Cu catalyst).
As can be seen from fig. 5, the Cu catalyst, although the reaction rate was gradually increased with increasing potential, the reaction rate was much lower than that of the PMA/Cu catalyst, and the HMF hydrogenation by-product (especially the coupling product BHH) was greatly increased, and the selectivity of BHMF showed a decrease, thus indicating that the faraday efficiency of the Cu catalyst for BHMF was lower.
Example 8
The method for preparing 2, 5-furandimethanol by catalyzing the electric hydrogenation of 5-hydroxymethylfurfural provided by the embodiment comprises the following steps:
An H-type electrolytic cell is selected, the PMA/Cu catalyst prepared in the embodiment 1 of the invention is used as a cathode (the electrode area is 1cm 2), ag/AgCl is used as a reference electrode, a platinum mesh is used as a counter electrode, a 0.5M PBS solution with HMF dissolved in the catholyte is 20ml, the anolyte is a 0.5M H 2SO4 solution, the two solutions are separated by a Nafion 212 proton exchange membrane, an electrochemical hydrogenation reaction of HMF is carried out by applying a negative potential of 0.3V compared with a reversible hydrogen electrode, the coulomb number of the reaction is set to be 101% of the theoretical coulomb number required by assuming full conversion of HMF, and the result is shown in a table 3 and a figure 6 after the reaction is subjected to high performance liquid chromatography analysis.
TABLE 3 conversion and Selectivity of PMA/Cu catalysts after reacting a specific charge at different HMF concentrations
As can be seen from Table 3, at-0.3V (vs RHE) voltage, the PMA/Cu catalyst is able to maintain high HMF conversion and BHMF selectivity at high concentrations of 1M HMF.
As can be seen from fig. 6, the PMA/Cu catalyst further increased in faradaic efficiency of BHMF with increasing HMF concentration and suppressed the faradaic efficiency of hydrogen evolution reaction, and the faradaic efficiency of the coupling by-product BHH was as low as 2.5% even at HMF concentration of 1M. This demonstrates that the hydrogenation selectivity of PMA/Cu catalysts for BHMF is extremely tolerant to HMF concentrations.
The PMA/Cu-2, PMA/Cu-3, PMA/Cu-4 and SWA/Cu catalysts prepared in examples 2-5 of the present invention also exhibit substantially the same reaction laws and effects as those of example 6 (see FIGS. 7-10), and thus are not described in detail herein.
Example 9
The stability test of preparing BHMF by performing HMF electrocatalytic hydrogenation on the PMA/Cu catalyst prepared in the embodiment 1 of the present invention is shown in FIG. 11. The testing method comprises the following steps: using Metrohm Vionic electrochemical workstation, selecting H-type electrolytic cell, testing in a three-electrode system with Ag/AgCl as reference electrode, platinum mesh as counter electrode and PMA/Cu as working electrode, wherein catholyte is 0.25M PBS solution of HMF, configuring 250ml or 500ml catholyte in a single circulation mode, pumping electrolyte in a storage bottle into the electrolytic cell through peristaltic pump, and pumping the reacted electrolyte out of the electrolytic cell, so that the electrolyte in the electrolytic cell is always kept at 20ml. The electrochemical hydrogenation stability test of HMF was performed by applying a voltage of-0.3V to the cathode catalyst relative to a standard hydrogen electrode, setting the coulomb number of the reaction to 101% of the theoretical coulomb number required to assume full conversion of HMF, wherein the total volume of the cathode electrolyte in the first 3 cycles was 250ml and the total volume of the electrolyte in the second two cycles was 500ml. Electrolysis was suspended for 2 minutes every 58 minutes, and the peristaltic pump liquid circulation was maintained during the suspension of electrolysis so that the HMF concentration in the reaction cell tended to coincide with the concentration in the storage bottle. After the electrolyte of the single storage bottle reaches 101% of theoretical coulomb number, the fresh catholyte is replaced.
The result shows that the PMA/Cu catalyst prepared by the invention can maintain good stability within the time range of 80 hours.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A catalyst for electrochemical hydrogenation, comprising: the Cu nanowire and the modifier loaded on the Cu nanowire are Keggin type heteropolyacid and/or heteropolyacid salt.
2. The catalyst for electrochemical hydrogenation according to claim 1, wherein said Keggin-type heteropolyacid is at least one of phosphomolybdic acid, silicotungstic acid, phosphotungstic acid;
and/or the Keggin type heteropolyacid salt is at least one of sodium phosphomolybdate and ammonium phosphotungstate;
And/or the mass ratio of the modifier to the Cu nanowire is 0.1-10%, preferably 0.5-2%;
And/or the length of the Cu nanowire is 0.5-12 mu m, and the width is 50-200 nm.
3. A method for preparing a catalyst for electrochemical hydrogenation, which is characterized by comprising the following steps:
S1, dissolving a modifier in an alcohol solvent to form a modifier solution, wherein the modifier is Keggin type heteropolyacid and/or heteropolyacid salt;
S2, placing the CuO nanowire and/or the Cu (OH) 2 nanowire in the modifier solution, soaking for the first time, taking out, drying, and calcining under the condition of existence of protective gas or air to obtain a precursor; or alternatively
Placing Cu nanowires in the modifier solution, soaking for a first time, taking out, drying, and calcining under the condition of existence of protective gas or air to obtain a catalyst;
And S3, performing electrochemical reduction by taking the precursor as a cathode, taking out the reduced cathode, cleaning, and drying to obtain the catalyst.
4. The method for producing a catalyst for electrochemical hydrogenation according to claim 3, wherein the concentration of said modifier solution is 0.3mmol/L to 2mmol/L;
and/or the Keggin type heteropolyacid is at least one of phosphomolybdic acid, silicotungstic acid and phosphotungstic acid;
and/or the Keggin type heteropolyacid salt is at least one of sodium phosphomolybdate and ammonium phosphotungstate;
And/or the alcohol solvent is at least one of methanol, ethanol and isopropanol.
5. The method for preparing a catalyst for electrochemical hydrogenation according to claim 3, wherein said first time is 20min to 4h, preferably 30min to 1h;
and/or, the drying temperature in the step S2 is 25-80 ℃;
and/or the calcining temperature is 200-350 ℃, the heating speed is 1-5 ℃/min, and the time is 1-5 h;
and/or the shielding gas is at least one of nitrogen and argon.
6. The method for producing a catalyst for electrochemical hydrogenation according to claim 3, wherein in step S3, the reduction potential is-0.2V to-0.7V and the reduction time is 20min to 1h;
And/or, in step S3, ag/AgCl is used as a reference electrode, the platinum electrode is a counter electrode, and the cathode and the anolyte are 0.5M PBS solution with ph=7.
7. Use of the catalyst for electrochemical hydrogenation according to claim 1 or 2 or the catalyst for electrochemical hydrogenation produced by the production process according to any one of claims 3 to 6 for the catalytic electro-hydrogenation of 5-hydroxymethylfurfural to produce 2, 5-furandimethanol.
8. A process for preparing 2, 5-furandimethanol, comprising the steps of:
A catalyst is adopted as a cathode, the cathode is placed in a catholyte solution in which 5-hydroxymethylfurfural is dissolved, and negative voltage is applied to perform electrochemical hydrogenation reaction;
The catalyst is the catalyst for electrochemical hydrogenation according to claim 1 or 2 or the catalyst for electrochemical hydrogenation produced by the production method according to any one of claims 3 to 6.
9. The process for preparing 2, 5-furandimethanol of claim 8, wherein said cathode has an electrode area of 1cm 2;
And/or the negative voltage is-0.15V to-0.4V;
And/or, the coulomb number of the electrochemical hydrogenation reaction is 101% of the theoretical coulomb number required for assuming complete conversion of 5-hydroxymethylfurfural.
10. The process for preparing 2, 5-furandimethanol of claim 8, wherein the molar concentration of 5-hydroxymethylfurfural in said catholyte is 100mM to 1000mM;
And/or, the catholyte further comprises 0.5M PBS having ph=7;
and/or adopting Ag/AgCl as a reference electrode and platinum as a counter electrode;
and/or the anolyte is a 0.5M H 2SO4 solution.
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