CN118108954A - Cu-based coordination polymer and preparation method and application thereof - Google Patents
Cu-based coordination polymer and preparation method and application thereof Download PDFInfo
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- CN118108954A CN118108954A CN202410205810.4A CN202410205810A CN118108954A CN 118108954 A CN118108954 A CN 118108954A CN 202410205810 A CN202410205810 A CN 202410205810A CN 118108954 A CN118108954 A CN 118108954A
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 33
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- 150000001879 copper Chemical class 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 claims description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 2
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229940108925 copper gluconate Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- -1 nitrogen-containing heterocyclic compounds Chemical class 0.000 claims description 2
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000001955 polymer synthesis method Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention relates to a Cu-based coordination polymer, and a preparation method and application thereof. The method utilizes an in-situ wet chemical method to prepare the Cu-based coordination polymer, and comprises the following specific steps: firstly, copper salt and coordination monomer with the molar ratio of 1:1 are respectively added into ethanol. The two were thoroughly mixed and stirred at 60 ℃ for 24 hours, the precipitate was suction filtered, and washed with ethanol and water alternately several times, and dried at 60 ℃ for 12 hours to obtain a Cu-based coordination polymer. The polymer material can be used as an efficient electrocatalyst to catalyze urea synthesis under mild conditions, and the Cu-based coordination polymer synthesis method has the characteristics of mild conditions, less energy consumption, simple process, low cost and the like, and is suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a Cu-based coordination polymer, a preparation method and application thereof, in particular to a preparation method of an electrocatalytic material of the Cu-based coordination polymer and application thereof in preparing urea by co-reduction of electrocatalytic carbon dioxide and nitrogen-containing waste liquid.
Background
The urea can be used for nitrogenous fertilizer, supports a great part of crop yield increase, and ensures the grain supply of human beings. In industrial production urea is synthesized by the Bosch-Meiser process, wherein carbon dioxide and liquid ammonia are converted to urea under severe high pressure conditions (150-250 bar) and high temperatures (150-200 ℃). In addition, industrial ammonia production (the Haber-Bosch process) is highly energy intensive, consuming large amounts of fossil fuels and side-by-side with large amounts of carbon dioxide. Thus, current urea synthesis schemes are far from meeting the demands of sustainable development in society. In contrast, the electrosynthesis can directly synthesize the high-value urea product by using renewable energy sources under the condition of normal temperature and normal pressure, is a more sustainable process, and is an important link in a plurality of steps for realizing deep decarburization in the chemical manufacturing industry.
Substances containing active nitrogen-oxygen bonds, such as Nitric Oxide (NO) and nitrate/nitrite (NO 3 -/NO2 -) ions, are more active nitrogen sources than nitrogen (N 2). Of these, NO 3 - is a nitrogen-containing reactant with good intrinsic instability, and can be obtained from industrial wastewater. In addition, the lower dissociation energy of the nitrogen-oxygen bond (204 kJ mol -1) favors the coupling of NO 3 - reduction with CO 2 reduction to complete urea electrosynthesis. Thus, the conversion of NO 3 - to urea is a suitable model reaction for studying electrochemical C-N bond formation, as well as potential synthetic schemes for urea. Although various catalysts have been reported to efficiently CO-reduce CO 2 and NO 3 - to urea, the catalytic activity, selectivity of the current catalysts are still insufficient to meet the industrial needs due to the complex 16 electron and double coupling reduction limitations. Therefore, the Faraday efficiency and the current density of urea conversion are improved by designing the catalytic material which is efficient and can be prepared on a large scale, and the method is important for sustainable development.
Disclosure of Invention
The invention aims to provide a preparation method of a Cu-based coordination polymer. The preparation method is simple wet chemical method and can prepare Cu-based coordination polymer in large scale.
Still another object of the present invention is: a Cu-based coordination polymer product and application are provided.
The specific technical scheme for realizing the aim of the invention is as follows: copper salt and coordination monomer are used as raw materials, and a Cu-based coordination polymer is prepared in situ by a wet chemical method, and the method comprises the following steps:
step 1: preparation of copper salt solution:
dissolving copper salt in absolute ethanol, and stirring for 15min to obtain 100mM solution;
step 2: preparation of Cu-based coordination polymer material:
Adding coordination monomer into absolute ethanol with the concentration of 100mM, adding into the copper salt solution, and stirring for 24 hours at 60 ℃; the precipitate was filtered and washed alternately with ethanol and water several times and dried at 60℃for 12h to give a coordination polymer. .
Further, in the preparation method of the Cu-based coordination polymer, the copper salt solution in the step 1 can be any copper salt solution such as copper sulfate, copper acetate, copper gluconate and the like.
Further, in the preparation method of the Cu-based coordination polymer, the coordination monomer in the step 2 can be sulfur-containing and nitrogen-containing heterocyclic compounds such as 2-mercaptopyrimidine, 2-hydroxypyrimidine, benzothiazole-2-thione, 2-mercapto-4, 6-dihydroxypyrimidine, 4, 5-dihydrothiazole-2-mercaptan and the like, and the molar ratio of copper to the coordination monomer is regulated and controlled according to a certain proportion.
The Cu-based coordination polymer is prepared according to the preparation method.
The invention also provides an application of the Cu-based coordination polymer catalytic material in co-reduction of electrocatalytic carbon dioxide and nitrogen-containing waste liquid.
It is also an object of the present invention to provide the use of a Cu-based coordination polymer catalytic material prepared according to the method provided by the present invention for co-reduction of electrocatalytic carbon dioxide and nitrogen containing waste streams, in particular for electrocatalytic urea production.
The preparation method of the Cu-based coordination polymer catalyst provided by the invention has the advantages that:
The Cu-based coordination polymer material prepared by the method takes copper chloride dihydrate, 2-mercaptopyrimidine and the like as raw materials, and is environment-friendly, clean, wide in raw materials and excellent in price.
The wet chemical method is adopted, the operation is convenient, and the preparation can be carried out on a large scale, thereby being convenient for realizing industrial production.
The prepared Cu-based coordination polymer has the characteristics of higher electrocatalytic activity, strong structural stability and the like.
Drawings
FIG. 1 is an XRD pattern of a Cu-2-mercaptopyrimidine polymer material prepared in example 1;
FIG. 2 is a graph of the electrocatalytic properties of the Cu-2-mercaptopyrimidine polymer material prepared in example 1;
FIG. 3 is a high resolution mass spectrum of a product prepared by electrocatalytic carbon dioxide and nitrate co-reduction of a Cu-2-mercaptopyrimidine polymer material prepared in the example.
Detailed Description
The technical scheme of the present invention will be described in further detail with reference to the accompanying drawings and specific examples, but the present invention is not limited to the following examples.
Example 1
0.17G of copper chloride dihydrate was added to 10mL of absolute ethanol and stirred until completely dissolved, designated A. 0.112g of 2-mercaptopyrimidine was added to 10mL of absolute ethanol, and the mixture was stirred and dispersed, designated B. And (3) adding the A into the B in the stirring process, transferring to an oil bath pot after the dripping is finished, and stirring for 24 hours at 60 ℃. After the reaction was completed, the mixture was cooled to room temperature, vacuum filtered, and washed with ethanol and water alternately. Oven-drying at 60deg.C for 12 hr to obtain brown yellow solid.
FIG. 1 is an XRD pattern of the Cu-2-mercaptopyrimidine polymer catalyst obtained in example 1, and it is understood from FIG. 1 that the diffraction peaks of the Cu-2-mercaptopyrimidine polymer are different from those of the standard phases of conventional Cu powder, cuO and CuS, thereby proving that the coordination polymer was successfully prepared.
Example 2
0.17G of copper chloride dihydrate was added to 10mL of absolute ethanol and stirred until completely dissolved, designated A. 0.144g of 2-mercapto-4, 6-dihydroxypyrimidine was added to 10mL of absolute ethanol, and the mixture was stirred and dispersed, designated B. And (3) adding the A into the B in the stirring process, transferring to an oil bath pot after the dripping is finished, and stirring for 24 hours at 60 ℃. After the reaction was completed, the mixture was cooled to room temperature, vacuum filtered, and washed with ethanol and water alternately. Oven drying at 60deg.C for 12 hr to obtain pale yellow solid.
Example 3
0.17G of copper chloride dihydrate was added to 10mL of absolute ethanol and stirred until completely dissolved, designated A. 0.119g of 4, 5-dihydrothiazole-2-thiol is added to 10mL of absolute ethanol, and the mixture is stirred and dispersed, designated B. And (3) adding the A into the B in the stirring process, transferring to an oil bath pot after the dripping is finished, and stirring for 24 hours at 60 ℃. After the reaction was completed, the mixture was cooled to room temperature, vacuum filtered, and washed with ethanol and water alternately. And drying at 60 ℃ for 12 hours to obtain light green solid.
Example 4
The corresponding electrochemical test experiments were all completed on a Shanghai Chenhua electrochemical workstation (CHI 660E). The electrolytic tests were carried out in an H-type cell using a three electrode system comprising a working electrode (Cu-based coordination polymer electrode), a platinum mesh as counter electrode and Ag/AgCl as reference electrode. In the electrolysis process, a cathode/anode chamber is separated by a Nafion-117 proton exchange membrane, and electrolyte of the cathode chamber and the anode chamber is 0.1M KNO 3+0.5M K2SO4 mixed electrolyte. Before each electrolysis, CO 2 is introduced into the electrolyte and kept for 30 minutes to obtain the corresponding saturated electrolyte. In the potentiostatic mode, each potential was electrolyzed for 1h, respectively, and gas and liquid products were collected.
The components of the gaseous and liquid products were detected and analyzed by gas chromatography (Agilent 8890), ultraviolet spectrophotometry (UV-1900 i) and nuclear magnetic resonance spectroscopy (1H NMR,Bruker Ascend 500MHz). As shown in FIG. 2, the Faraday efficiency of the Cu-2-mercaptopyrimidine polymer electrode was 80.2% at-0.59V vs. RHE electrolysis potential with a bias current density of 2.43mA cm -2.
In addition to the determination of product formation by uv and nuclear magnetism, we performed high resolution mass spectrometry tests on the liquid product by extraction, as shown in fig. 3, in which a 60.032 urea peak was detected, further confirming urea formation.
Applicant states that specific embodiments of the present invention have been described in detail above, but they are merely examples, and the present invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (6)
1. A preparation method of a Cu-based coordination polymer is characterized in that the preparation method can realize large-scale preparation of uniform Cu-based coordination polymer electrocatalytic materials by a simple wet chemical method.
2. The method for preparing a Cu-based coordination polymer as recited in claim 1, comprising the specific steps of:
step 1: preparation of copper salt solution:
dissolving copper salt in absolute ethanol, and stirring for 15min to obtain 100mM solution;
step 2: preparation of Cu-based coordination polymer material:
adding coordination monomer into absolute ethanol with the concentration of 100mM, adding into the copper salt solution, and stirring for 24 hours at 60 ℃; filtering the precipitate, alternately washing the precipitate with ethanol and water for several times, and drying the precipitate at 60 ℃ for 12 hours to obtain the Cu-based coordination polymer.
3. The method for preparing a Cu-based coordination polymer as recited in claim 2, wherein the copper salt solution in step 2 is any one of copper salt solutions of copper sulfate, copper acetate and copper gluconate.
4. The method for preparing a Cu-based coordination polymer as recited in claim 2, wherein the coordination monomer in step 2 may be any one of sulfur-containing and nitrogen-containing heterocyclic compounds such as 2-mercaptopyrimidine, 2-hydroxypyrimidine, benzothiazole-2-thione, 2-mercapto-4, 6-dihydroxypyrimidine, 4, 5-dihydrothiazole-2-thiol, and the molar ratio of copper to the coordination monomer is regulated in a certain ratio.
5. The Cu-based coordination polymer prepared by the preparation method according to any one of claims 1 to 4.
6. The use of the Cu-based coordination polymer material of claim 5 in the co-reduction of electrocatalytic carbon dioxide and nitrogen containing waste streams to produce urea.
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| CN202410205810.4A CN118108954A (en) | 2024-02-26 | 2024-02-26 | Cu-based coordination polymer and preparation method and application thereof |
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