CN107519899B - Cobalt selenide cocatalyst, and preparation method and application thereof - Google Patents
Cobalt selenide cocatalyst, and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 title claims description 20
- 238000006722 reduction reaction Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003504 photosensitizing agent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012327 Ruthenium complex Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910003424 Na2SeO3 Inorganic materials 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011781 sodium selenite Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 230000009466 transformation Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 229910001428 transition metal ion Inorganic materials 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 description 20
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 14
- 229910017052 cobalt Inorganic materials 0.000 description 14
- 239000010941 cobalt Substances 0.000 description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 14
- 229910052711 selenium Inorganic materials 0.000 description 14
- 229940091258 selenium supplement Drugs 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- YAZJAPBTUDGMKO-UHFFFAOYSA-L potassium selenate Chemical compound [K+].[K+].[O-][Se]([O-])(=O)=O YAZJAPBTUDGMKO-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229960001881 sodium selenate Drugs 0.000 description 2
- 239000011655 sodium selenate Substances 0.000 description 2
- 235000018716 sodium selenate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/23—
-
- B01J35/30—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention provides a cocatalyst Co0.85Se and a preparation method and application thereof, belonging to the field of photocatalysis. The cocatalyst is a nano-layered material synthesized by a solvothermal method, and the material combines the advantages of the transmission performance of transition metal ions to electrons, the large specific surface area, the high active exposure ratio and the like of a two-dimensional material, and can efficiently promote photocatalytic CO2Performance of the reduction reaction. The preparation method is simple and easy to implement, the reaction system has mild conditions, and CO is realized by utilizing solar energy2Has wide application prospect in the aspects of fixation, transformation and the like.
Description
Technical Field
The invention belongs to the technical field of novel material preparation and photocatalytic carbon dioxide reduction, and particularly relates to a cobalt selenide cocatalyst, and a preparation method and application thereof.
Background
With the increasing severity of environmental problems such as energy crisis and greenhouse effect, the sustainable development of the human society faces a great challenge, and how to effectively utilize solar energy to fix and convert carbon dioxide has attracted wide attention of all countries in the world.
By means of photocatalysis2Conversion to more valuable chemicals, e.g. CO, CH4、CH3OH, HCHO, HCOOH and the like, not only can realize the reaction to CO2The fixation of the compound can relieve the greenhouse effect to a certain extent and can also provide important chemical raw materials for human beings. Thus, the CO is treated by the photocatalysis technology2Is a very attractive and challenging issue. But at present photocatalytically CO2The reduction reaction efficiency is low, the practical application of the catalyst is greatly restricted, and the introduction of the cocatalyst is considered to be one of improving the photocatalytic CO2Effective means of reduction efficiency, so that the successful development and design of a novel efficient cocatalyst is to realize CO by utilizing solar energy2One of the key technologies for immobilization and transformation.
Disclosure of Invention
The invention aims to provide a cocatalyst Co0.85Se and its preparation method and application, the preparation method is simple and easy, the used equipment is cheap and simple, the synthesis condition is mildAnd, suitable for the industrialized development, help to popularize; application to visible light catalysis of CO2Reducing to promote CO efficiently2Performance of photocatalytic reduction reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cobalt selenide cocatalyst is characterized by comprising the following specific steps:
dissolving a cobalt source compound in a solvent to obtain a cobalt source solution, and dissolving a selenium source compound in the solvent to obtain a selenium source solution;
and (II) dropwise adding a selenium source solution into the cobalt source solution while stirring, continuously stirring for 30-180 minutes after dropwise adding, transferring into a high-pressure reaction kettle, keeping the temperature at 90-240 ℃ for 12-24 hours, centrifugally washing the obtained precipitate with water and ethanol until the total ion concentration is less than 10ppm, drying at 40-120 ℃ for 6-24 hours, and grinding to obtain cobalt selenide cocatalyst powder.
The cobalt source compound in the step (I) is one of cobalt chloride, cobalt acetate, cobalt nitrate and cobalt sulfate.
The selenium source compound in the step (I) adopts one of sodium selenate and potassium selenate.
The solvent in the step (one) adopts one or two of deionized water and diethylenetriamine.
The concentration of the cobalt source solution is 0.1-1 mol/L, and the concentration of the selenium source solution is 0.1-1 mol/L; the molar ratio of the selenium source to the cobalt source in the cobalt source solution and the selenium source solution is 1-3: 1.
The cobalt selenide cocatalyst prepared by the preparation method has the chemical formula of Co0.85Se。
The cobalt selenide cocatalyst prepared by the preparation method can catalyze CO in visible light2Application in a reduction system.
In visible light to catalyze CO2In the reduction system, the system is a batch type photocatalytic CO2 reduction reaction system under normal pressure, and bipyridyl ruthenium complex [ Ru (bpy)3]Cl2•6H2O as visible light photosensitizer and triethanolamine as photosensitizerThe electron sacrificial agent uses acetonitrile or a mixed solution of acetonitrile and water as a solvent.
Said Co0.85The dosage of Se is 1-15% of the mass of the photosensitizer.
The photocatalytic CO2The reaction temperature of the reduction system is 10-60 ℃, and the reaction time is 15-180 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention applies cobalt selenide as a cocatalyst to the field of photocatalysis for the first time, and can effectively improve photocatalytic CO2The efficiency of the reduction reaction;
(2) the preparation method of the cocatalyst cobalt selenide is simple and easy, does not need complex and expensive equipment, has mild synthesis conditions, and is beneficial to large-scale popularization;
(3) the reaction system of the invention is simple and easy to operate, the dosage of the auxiliary agent is less, the environment-friendly pollution is less, the resource is saved, the reaction condition is mild, and the invention is beneficial to CO2Popularization and application in the fixing technology.
Drawings
FIG. 1 shows Co in example 1 of the present invention0.85An X-ray diffraction pattern of Se;
FIG. 2 shows Co in example 1 of the present invention0.85Scanning electron micrograph of Se;
FIG. 3 shows Co in example 1 of the present invention0.85Photocatalytic CO with Se as CO-catalyst2Reduction activity diagram.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a cobalt selenide cocatalyst, which comprises the following specific scheme:
dissolving a cobalt source compound in a solvent to obtain a cobalt source solution, and dissolving a selenium source compound in the solvent to obtain a selenium source solution;
and (II) dropwise adding a selenium source solution into the cobalt source solution while stirring, continuously stirring for 30-180 minutes after dropwise adding, transferring into a high-pressure reaction kettle, keeping the temperature at 90-240 ℃ for 12-24 hours, centrifugally washing the obtained precipitate with water and ethanol until the total ion concentration is less than 10ppm, drying at 40-120 ℃ for 6-24 hours, and grinding to obtain cobalt selenide cocatalyst powder.
The cobalt source compound in the step (I) is one of cobalt chloride, cobalt acetate, cobalt nitrate and cobalt sulfate.
The selenium source compound in the step (I) adopts one of sodium selenate and potassium selenate.
The solvent in the step (one) adopts one or two of deionized water and diethylenetriamine.
The concentration of the cobalt source solution is 0.1-1 mol/L, and the concentration of the selenium source solution is 0.1-1 mol/L; the molar ratio of the selenium source to the cobalt source in the cobalt source solution and the selenium source solution is 1-3: 1.
Cobalt selenide catalyst promoter, the chemical formula of the cobalt selenide catalyst promoter is Co0.85Se。
Application of cobalt selenide cocatalyst in visible light catalysis of CO2Application in a reduction system.
In visible light to catalyze CO2In a reduction system, the system is intermittent photocatalytic CO under normal pressure2Reduction reaction system with bipyridine ruthenium complex [ Ru (bpy) ]3]Cl2•6H2O is used as a visible light photosensitizer, triethanolamine is used as an electron sacrificial agent, and acetonitrile or a mixed solution of the acetonitrile and water is used as a solvent.
Said Co0.85The dosage of Se is 1-15% of the mass of the photosensitizer.
The photocatalytic CO2The reaction temperature of the reduction system is 10-60 ℃, and the reaction time is 15-180 min.
Example 1
0.249 g of Co (Ac) was weighed out2·H2O and 0.173 g Na2SeO3Dissolved in 40 mL of Diethylenetriamine (DETA) and deionized water (H)2O) mixed solution(VH2O:VDETAIn =2:1), adding Na2SeO3The solution was slowly dropped into Co (Ac)2·H2Stirring for 30 min, transferring to a high-pressure reaction kettle of 100 mL, performing hydrothermal treatment at 180 ℃ for 16 h, cooling to room temperature, performing centrifugal washing, and performing vacuum drying at 80 ℃ for 12 h to obtain Co0.85Se；
FIG. 1 is an X-ray diffraction chart of the material prepared in this example, and it can be seen from FIG. 1 that the sample prepared is Co in hexagonal phase0.85Se（JCPDS:52-1008）。
FIG. 2 is a schematic representation of Co preparation in example 10.85And (3) scanning electron microscope images of the Se samples, wherein the samples can be seen from the images in FIG. 2 to be in a nanometer layered shape.
The obtained Co0.85Se material as cocatalyst for photocatalytic reduction of CO2The reaction is carried out in a self-made normal-pressure batch reaction device, a 300W xenon lamp is used as a light source (a 420 nm optical filter is added), the temperature of a reaction system is controlled at 20 ℃ by circulating condensed water, and 0.1 mg Co is weighed0.85Se cocatalyst and 8 mg bipyridine ruthenium complex ([ Ru (bpy))3]Cl2·6H2O) photosensitizer, then adding 3 mL of water, 2 mL of acetonitrile and 1 mL of triethanolamine, and uniformly stirring. Vacuumizing the system by a mechanical pump, and then filling high-purity CO2And (5) carrying out adsorption equilibrium on the gas for 30 min, and then turning on the lamp for reaction. The gas phase product generated by the reaction is detected and analyzed by gas chromatography.
FIG. 3 is a sample prepared in example 1 for photocatalytic reduction of CO2Photocatalytic CO in system2Activity diagram of reduction, under the system, the main reduction products are CO and H2After 2 hours of light exposure, CO and H2The yield reaches 36.0 mu mol and 9.4 mu mol respectively.
Table 1 shows Co in example 1 of the present invention0.85Photocatalytic CO with Se as CO-catalyst2And (5) carrying out reduction reaction blank control experiment results.
| Reaction conditions | CO/μmol | H2/μmol | CO+H2/μmol |
| Normal reaction | 36.0 | 9.4 | 45.4 |
| Without illumination | -- | -- | -- |
| Nothing [ Ru (bpy)3]Cl2·6H2O | -- | -- | -- |
| Co-free0.85Se | 1.6 | 1.8 | 3.4 |
| N2Substitute for CO2 | -- | 1.2 | 1.2 |
As can be seen from Table 1, the reaction system is visible light driven CO2Reducing agentSystem, cocatalyst Co0.85The introduction of Se greatly improves CO2Efficiency of the reduction reaction.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (3)
1. The application of cobalt selenide catalyst promoter is characterized in that: visible light photocatalysis CO of cobalt selenide cocatalyst by taking bipyridyl ruthenium complex as photosensitizer2The application in a reduction system; in visible light to catalyze CO2In the reduction system, the system is a batch type photocatalytic CO2 reduction reaction system under normal pressure, and bipyridyl ruthenium complex [ Ru (bpy)3]Cl2•6H2O is used as a visible light photosensitizer, triethanolamine is used as an electronic sacrificial agent, and acetonitrile or a mixed solution of the acetonitrile and water is used as a solvent;
the preparation method of the cobalt selenide cocatalyst comprises the following specific steps:
0.249 g of Co (Ac) was weighed out2·H2O and 0.173 g Na2SeO3Dissolved in 40 mL of diethylenetriamine DETA and deionized water H2In a mixed solution of O, VH2O:VDETA=2:1, adding Na2SeO3The solution was slowly dropped into Co (Ac)2·H2Stirring for 30 min, transferring to a high-pressure reaction kettle of 100 mL, performing hydrothermal treatment at 180 ℃ for 16 h, cooling to room temperature, performing centrifugal washing, and performing vacuum drying at 80 ℃ for 12 h to obtain Co0.85Se, cobalt selenide promoter.
2. Use of a cobalt selenide promoter according to claim 1, wherein: said Co0.85The dosage of Se is 1-15% of the mass of the photosensitizer.
3. Use of a cobalt selenide promoter according to claim 1 or 2, wherein: the photocatalytic CO2The reaction temperature of the reduction system is 10-60 ℃, and the reaction time is 15-180 min.
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| CN107999093A (en) * | 2017-12-29 | 2018-05-08 | 郑州大学 | A kind of cobalt doped two dimension tungsten selenide elctro-catalyst and preparation method thereof |
| CN109400898B (en) * | 2018-10-25 | 2021-05-18 | 陕西科技大学 | Manganese coordination polymer and preparation method and application thereof |
| CN109569659B (en) * | 2019-01-07 | 2021-04-27 | 福州大学 | Photocatalytic auxiliary agent for reducing carbon dioxide and preparation method thereof |
| CN111905771B (en) * | 2020-08-12 | 2022-11-11 | 西安理工大学 | Preparation method of catalyst for modifying cuprous oxide with different crystal faces by selenium |
| CN113145138B (en) * | 2021-03-11 | 2022-12-13 | 福州大学 | Thermal response type composite photocatalyst and preparation method and application thereof |
| CN113593918B (en) * | 2021-07-27 | 2022-09-30 | 陕西君普新航科技有限公司 | Self-assembly preparation method of lamellar cobalt selenide nanosheet array electrode |
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