CN114318358A - Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application - Google Patents
Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application Download PDFInfo
- Publication number
- CN114318358A CN114318358A CN202111327404.8A CN202111327404A CN114318358A CN 114318358 A CN114318358 A CN 114318358A CN 202111327404 A CN202111327404 A CN 202111327404A CN 114318358 A CN114318358 A CN 114318358A
- Authority
- CN
- China
- Prior art keywords
- nickel
- cobalt
- modulated
- mof
- based electrocatalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 74
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 38
- 239000010941 cobalt Substances 0.000 title claims abstract description 38
- 239000013246 bimetallic metal–organic framework Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 28
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000012621 metal-organic framework Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- 229910001453 nickel ion Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 32
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 14
- 239000004202 carbamide Substances 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract 1
- 239000013384 organic framework Substances 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 41
- 239000000243 solution Substances 0.000 description 38
- 239000006260 foam Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 12
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000007723 transport mechanism Effects 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- UIFOTCALDQIDTI-UHFFFAOYSA-N arsanylidynenickel Chemical compound [As]#[Ni] UIFOTCALDQIDTI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- -1 nickel hydroxide terephthalate hydrate Chemical compound 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical class [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Abstract
The invention relates to a modulated nickel/cobalt bimetallic organic framework (MOF) based electrocatalyst, a preparation method and application thereof. The catalyst comprises an electric conductive substrate and ferrocenecarboxylic acid modulated nickel/cobalt bimetallic MOF (NiCoMOF-Fc) material loaded on the surface of the electric conductive substrate, wherein the NiCoMOF-Fc material has catalytic activity. The catalyst is prepared by a simple one-step solvothermal method, and comprises the following specific steps: mixing N, N-Dimethylformamide (DMF) solution dissolved with terephthalic acid and ferrocenecarboxylic acid and DMF solution dissolved with nickel salt and cobalt salt in a reaction kettle with a conductive substrate, carrying out solvothermal reaction, taking out the conductive substrate after the reaction is finished, washing and drying to obtain the catalyst. The nickel/cobalt bimetallic MOF-based electrocatalyst prepared by the method has excellent Urea Oxidation Reaction (UOR) electrocatalytic activity, is simple in preparation process and easy for large-scale production, and has important practical application values in urea-assisted water decomposition, urea-containing wastewater treatment and direct urea fuel cells.
Description
Technical Field
The application relates to the technical field of electrocatalysis, in particular to a modulated nickel/cobalt bimetallic MOF-based electrocatalyst and a preparation method and application thereof.
Background
With the exacerbation of the traditional energy crisis and the increasing prominence of environmental problems, renewable energy and clean energy have attracted more and more attention. Among new energy sources, hydrogen energy is considered as one of the most potential clean energy sources in the 21 st century because it is carbon neutral and has a very high energy density. Electrocatalytic water splitting is an effective way of producing hydrogen, and the cathodic Hydrogen Evolution Reaction (HER) and the anodic Oxygen Evolution Reaction (OER) are their conventional half reactions. According to the thermodynamics of the reaction, the voltage required for water decomposition is as high as 1.23V using the half reaction described above. In fact, the voltage of the working cell is even higher due to the overpotential on both sides. This results in low energy conversion efficiency and high cost, which severely hampers the large-scale application of this technology.
Substitution of the OER by UOR is one solution to the above problem, since the theoretical cell voltage is only 0.37V for hydrogen production by electrolysis of urea solutions. In addition, the urea also has the advantages of rich source and high stability, and can be obtained through domestic wastewater. Therefore, the strategy can be used for preparing hydrogen at low cost and is an effective method for purifying sewage, and has high practical value. However, the six electron transfer process (CO (NH) of UOR2)2+6OH-→CO2+N2+5H2O+6e-) Limiting its kinetic reaction. Therefore, there is a great need for efficient UOR catalysts to address the problem of kinetic retardation.
In recent years, nickel-based catalysts have been made out of the research of UOR catalysts due to their advantages of low cost, good catalytic performance and the like. Currently, nickel alloys, nickel hydroxides, nickel-based Layered Double Hydroxides (LDHs) and phosphides all show good catalytic activity towards UOR. However, the simple, low cost and large scale preparation of highly catalytically active UOR catalysts remains a challenge.
As an emerging multifunctional material, Metal Organic Frameworks (MOFs) have attracted a great deal of attention in the field of catalysis due to their large surface area, high porosity, abundance of metal active sites, and adjustable physical and chemical properties. However, the poor electrical conductivity and low active site availability inherent to MOFs results in low catalytic activity and is not generally directly available for UOR electrocatalysis. Further oxidation, phosphating or sulfidation of MOFs as precursors has been shown to be an effective strategy for the synthesis of efficient UOR electrocatalysts. However, this requires high temperature calcination or intervention of toxic chemicals. Recently, it has been found that defect tailoring and bimetallic/trimetallic coupling effects can also greatly improve the electrocatalytic activity of MOF-based catalysts. It would be desirable to prepare MOF-based UOR electrocatalysts of high catalytic activity in a simple and one-step manner by defect engineering and metal node engineering.
Disclosure of Invention
The invention aims to provide a prepared nickel/cobalt bimetallic MOF-based catalyst, which solves the problems of poor conductivity and low catalytic activity of MOF, has a simple preparation method, and can directly use the product in UOR high-efficiency electrocatalysis.
To achieve the above object, a first aspect of the present invention provides a modulated nickel/cobalt bimetallic MOF-based catalyst having good electrical conductivity and excellent catalytic activity.
In a second aspect of the invention, there is provided a simple method of preparing the above-described modulated nickel/cobalt bimetallic MOF-based catalyst.
A third aspect of the invention provides the use of the above-described modulated nickel/cobalt bimetallic MOF-based catalyst in UOR electrocatalysis.
In a first aspect the present invention provides a modulated nickel/cobalt bimetallic MOF based catalyst comprising: the conductive substrate and NiCoMOF-Fc material loaded on the surface of the conductive substrate. The NiCoMOF-Fc material consists of six elements of carbon, hydrogen, oxygen, iron, cobalt and nickel, wherein the content of the carbon element is 30-50 wt.%, the content of the hydrogen element is 1-10 wt.%, the content of the oxygen element is 20-40 wt.%, the content of the iron element is 1-10 wt.%, the content of the cobalt element is 10-30 wt.%, and the content of the nickel element is 10-30 wt.%.
According to one embodiment of the invention, the electrically conductive substrate is nickel foam. The specification of the nickel foam is not particularly limited in the present invention, and commercially available nickel foam known to those skilled in the art may be used.
According to one embodiment of the invention, the NiCoMOF-Fc material has a nanowire bundle morphology formed by mutually stacking nanowires, and the diameter of each nanowire is 80-100 nm.
According to one embodiment of the invention, ferrocenecarboxylic acid in the NiCoMOF-Fc material is introduced as a non-bridging ligand, so that terephthalic acid as a bridging ligand in the catalyst is partially substituted, a connector of a Ni active site is lost, and a defect is generated in the NiCoMOF-Fc material, so that the coordination environment of the Ni active site is changed, the oxidation state of the Ni active site is raised, and the catalytic activity of the NiCoMOF-Fc is improved. In addition, the introduction of ferrocenecarboxylic acid changes the electron transfer mode in the MOF material, and improves the conductivity of NiCoMOF-Fc through a charge hopping transport mechanism.
According to one embodiment of the invention, the NiCoMOF-Fc material comprises Co2+The introduction of (2) makes some electrons transfer from Ni to Co through the oxygen of the ligand, thereby optimizing the electronic structure of the Ni active site, improving the oxidation state of the Ni active site and further improving the catalytic activity of the Ni active site.
According to one embodiment of the invention, the synergistic effect of ferrocenecarboxylic acid modulation and Co doping in the NiCoMOF-Fc material can improve the catalytic activity of the catalyst.
A second aspect of the invention provides a process for the preparation of a modulated nickel/cobalt bimetallic MOF based catalyst comprising the steps of:
s1: terephthalic acid and ferrocenecarboxylic acid were dissolved in DMF, and sodium hydroxide solution was added thereto.
S2: the nickel and cobalt salts were dissolved in DMF.
S3: and (3) mixing the DMF solutions obtained in the steps S1 and S2 in a reaction kettle with a conductive substrate, carrying out solvothermal reaction, taking out the conductive substrate after the reaction is finished, washing and drying to obtain the prepared nickel/cobalt bimetallic MOF-based catalyst.
According to an embodiment of the present invention, the preparation method further includes a step of pretreating the nickel foam before step S1.
According to one embodiment of the invention, the pre-treatment comprises washing and drying of the nickel foam.
According to one embodiment of the invention, the cleaning comprises the step of putting the foamed nickel into a 3M hydrochloric acid solution, deionized water and absolute ethyl alcohol in sequence for ultrasonic treatment, and the drying refers to the step of vacuum drying of the cleaned foamed nickel.
According to an embodiment of the present invention, in step S1, the concentration of terephthalic acid in the DMF solution is 0.05M to 0.10M, the concentration of ferrocenecarboxylic acid is 0.007M to 0.017M, and the pH of the DMF solution after the sodium hydroxide solution is added is 12 to 14.
According to a preferred embodiment of the present invention, in step S1, the concentration of terephthalic acid in the DMF solution is 0.075M; the concentration of ferrocenecarboxylic acid is 0.01M; the pH of the DMF solution after the addition of the sodium hydroxide solution was 13.
According to an embodiment of the present invention, in step S2, the concentration of nickel salt in the DMF solution is 0.013M to 0.075M, and the concentration of cobalt salt in the DMF solution is 0.013M to 0.075M.
According to one embodiment of the present invention, the nickel salt functions to provide a nickel source and the cobalt salt functions to provide a cobalt source in step S2.
According to an embodiment of the present invention, in step S2, the nickel salt is nickel nitrate hexahydrate, and the cobalt salt is cobalt nitrate hexahydrate. Other nickel salts (e.g., nickel chloride hexahydrate, nickel acetate tetrahydrate, and the like) and cobalt salts (e.g., cobalt chloride hexahydrate, cobalt acetate tetrahydrate, and the like) may also be used in the preparation of the NiCoMOF-Fc material.
According to a preferred embodiment of the present invention, in step S2, the concentration of nickel nitrate hexahydrate is 0.019M and the concentration of cobalt nitrate hexahydrate is 0.056M.
According to one embodiment of the present invention, in step S3, the solvent is subjected to a thermal reaction at 100 ℃ for 14 h.
In a third aspect of the invention there is provided the use of a modulated nickel/cobalt bimetallic MOF based catalyst in UOR electrocatalysis.
According to one embodiment of the invention, the prepared nickel/cobalt bimetallic MOF-based catalyst can be used in the technical field of new energy sources such as urea-assisted hydrogen production and the like.
The invention has the advantages that:
(1) the modulated nickel/cobalt bimetallic MOF-based catalyst provided by the invention improves the conductivity of the material, optimizes the electronic structure of the Ni active site, improves the oxidation state of the Ni active site and greatly enhances the electrocatalytic activity due to the synergistic effect of the modulation of ferrocenecarboxylic acid and the doping of cobalt.
(2) The preparation process of the modulated nickel/cobalt bimetallic MOF-based catalyst provided by the invention is simple, high-temperature calcination and subsequent chemical reaction are not needed, and the large-scale production is easy.
(3) The prepared nickel/cobalt bimetallic MOF-based catalyst has low initial potential and high current density in the application of UOR electrocatalysis, and the current density is 140mA cm under the potential of 1.299V vs-2At a potential of 1.5V vs. RHE, the current density was 782 mA cm-2The turnover frequency (TOF) was 0.679s-1Furthermore, the catalyst was at 20mA cm-2The voltage of the battery is only increased by 5.9 percent when the battery is tested for 10 hours continuously, and the battery shows excellent UOR electrocatalytic activity and stability.
Drawings
FIG. 1 is a scanning electron micrograph of the product obtained in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of a product obtained in comparative example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of the product obtained in comparative example 2 of the present invention.
FIG. 4 is an X-ray diffraction pattern of the products obtained in example 1 of the present invention and comparative examples 1 and 2.
FIG. 5 shows the radiation photoelectron spectrum of Ni 2p X of the product of example 1 and comparative examples 1 and 2.
FIG. 6 is a Co 2p X ray photoelectron spectrum of the products of example 1 of the present invention and comparative example 3.
FIG. 7 is a four-probe sheet resistance plot of the products obtained in comparative example 1 and comparative example 2 of the present invention.
FIG. 8 is a linear sweep voltammogram of the product obtained in example 1, comparative examples 1 and 2 of the present invention and foamed nickel in a 1M KOH solution containing 0.33M urea.
FIG. 9 is a graph showing the impedance of the product obtained in example 1 of the present invention, comparative examples 1 and 2, and foamed nickel in a 1M KOH solution containing 0.33M urea.
FIG. 10 shows the turnover number at a voltage of 1.5V of the products obtained in example 1 of the present invention and comparative examples 1 and 2.
FIG. 11 is a graph showing the results of stability tests on the product obtained in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to examples, comparative examples and the accompanying drawings, but the present invention is not limited to the following examples and comparative examples.
Example 1
The embodiment prepares a modulated nickel/cobalt bimetallic MOF-based catalyst, and the specific preparation method comprises the following steps:
a piece of nickel foam (1 cm. times.3 cm) was ultrasonically cleaned with 3M hydrochloric acid, deionized water, and absolute ethanol in this order, and then subjected to drying treatment in vacuum.
Terephthalic acid (0.075M) and ferrocene carboxylic acid (0.01M) were dissolved in 5mL of DMF. Then, 1mL of 0.2M NaOH solution was added. Thereafter, the above solution was slowly mixed with 5mL of a DMF solution in which nickel nitrate hexahydrate (0.019M) and cobalt nitrate hexahydrate (0.056M) were dissolved in a 30mL autoclave containing nickel foam (1 cm. times.3 cm) inside. Finally, the autoclave was heated at 100 ℃ for 14 hours. The nickel foam was removed, washed twice with each of DMF and ethanol, and dried under vacuum. NiCoMOF-Fc material on foam nickelIn an amount of about 1.4mg cm-2。
The electron micrograph of the prepared modulated nickel/cobalt bimetallic MOF-based catalyst is shown in figure 1. The prepared NiCoMOF-Fc can be seen to be stacked on a foamed nickel substrate and present a nano-wire bundle morphology.
Example 2
The preparation method of the modulated nickel/cobalt bimetallic MOF-based catalyst with different mixture ratio from that of the example 1 comprises the following steps:
terephthalic acid (0.075M) and ferrocene carboxylic acid (0.01M) were dissolved in 5mL of DMF. Then, 1mL of 0.2M NaOH solution was added. Thereafter, the above solution was slowly mixed with 5mL of a DMF solution containing nickel nitrate hexahydrate (0.013M) and cobalt nitrate hexahydrate (0.063M) in a 30mL autoclave containing nickel foam (1 cm. times.3 cm) therein. Finally, the autoclave was heated at 100 ℃ for 14 hours. The nickel foam was removed, washed twice with each of DMF and ethanol, and dried under vacuum. The NiCoMOF-Fc material loading on the foam nickel was about 1.4mg cm-2。
Example 3
The preparation method of the modulated nickel/cobalt bimetallic MOF-based catalyst with different mixture ratio from that of the example 1 comprises the following steps:
terephthalic acid (0.075M) and ferrocene carboxylic acid (0.01M) were dissolved in 5mL of DMF. Then, 1mL of 0.2M NaOH solution was added. Thereafter, the above solution was slowly mixed with 5mL of a DMF solution containing nickel nitrate hexahydrate (0.063M) and cobalt nitrate hexahydrate (0.013M) in a 30mL autoclave containing nickel foam (1 cm. times.3 cm) therein. Finally, the autoclave was heated at 100 ℃ for 14 hours. The nickel foam was removed, washed twice with each of DMF and ethanol, and dried under vacuum. The NiCoMOF-Fc material loading on the foam nickel was about 1.4mg cm-2。
Comparative example 1
The nickel-based MOF (NiMOF) catalyst without introduced cobalt ions and ferrocenecarboxylic acid is prepared by the specific preparation method comprising the following steps of:
terephthalic acid (0.075M) was dissolved in 5mL of DMF. Then, 1mL of 0.2M NaOH solution was added. After thatThe above solution was slowly mixed with 5mL of DMF solution containing nickel nitrate hexahydrate (0.075M) in a 30mL autoclave containing nickel foam (1 cm. times.3 cm) therein. Finally, the autoclave was heated at 100 ℃ for 14 hours. The nickel foam was removed, washed twice with DMF and ethanol each, and dried under vacuum. The loading of NiMOF on the nickel foam was about 2.2mg cm-2。
An electron microscope image of the prepared NiMOF catalyst is shown in figure 2, and compared with figure 1, the NiMOF catalyst is completely different in morphology, is represented as a nano array composed of nano sheets, and is uniformly distributed on a foamed nickel substrate, and the thickness of the nano sheets is about 50 nm.
Comparative example 2
The embodiment prepares a ferrocenecarboxylic acid modulated nickel-based MOF (NiMOF-Fc) catalyst without introducing cobalt ions, and the specific preparation method comprises the following steps:
terephthalic acid (0.075M) and ferrocene carboxylic acid (0.01M) were dissolved in 5mL of DMF. Then, 1mL of 0.2M NaOH solution was added. Thereafter, the above solution was slowly mixed with 5mL of a DMF solution containing nickel nitrate hexahydrate (0.075M) in a 30mL autoclave containing nickel foam (1 cm. times.3 cm) therein. Finally, the autoclave was heated at 100 ℃ for 14 hours. The nickel foam was removed, washed twice with each of DMF and ethanol, and dried under vacuum. The load of NiMOF-Fc on the foamed nickel is about 1.4mg cm-2。
An electron microscope image of the NiMOF-Fc catalyst is shown in the attached drawing 3, compared with the attached drawing 1 and the attached drawing 2, the NiMOF-Fc material is similar to the NiMOF in morphology and is a nano sheet, but the thickness of the nano sheet is about 30nm, and the layering between the sheets is not clear enough.
Comparative example 3
In the embodiment, a ferrocenecarboxylic acid modulated cobalt-based MOF (CoMOF-Fc) catalyst is prepared, and the specific preparation method comprises the following steps:
terephthalic acid (0.075M) was dissolved in 5mL of DMF. Then, 1mL of 0.2M NaOH solution was added. Thereafter, the above solution was slowly mixed with 5mL of a DMF solution containing cobalt nitrate hexahydrate (0.075M) in a 30mL autoclave containing nickel foam (1 cm. times.3 cm) therein. Finally, the autoclave was heated at 100 ℃ for 14 hours. The nickel foam was removed, washed twice with DMF and ethanol each, and dried under vacuum.
FIG. 4 is an X-ray diffraction pattern of the products obtained in example 1 of the present invention and comparative examples 1 and 2. The diffraction peaks of comparative example 1 matched well with those of nickel hydroxide terephthalate hydrate (PDF #35-1677), and the peaks were sharp, indicating that comparative example 1 had an ideal crystal structure. The diffraction peak of comparative example 2 was substantially the same as that of comparative example 1 except that a new peak appeared at 17.48 °, which is a characteristic peak of ferrocenyl moieties. The X-ray diffraction pattern of example 1 is significantly different from them. The map is compared with the reported anhydrous Ni2(OH)2(C8H4O4) And Co2(OH)2(C8H4O4) And (4) complete matching. The lattice type of example 1 has been transformed from the original triclinic system of comparative example 1 to a monoclinic system by spectroscopic analysis. This result also explains why comparative example 1, comparative example 2 and example 1 are significantly different in appearance.
FIG. 5 shows the radiation photoelectron spectrum of Ni 2p X of the product of the present invention in example 1 and comparative examples 1 and 2. Comparative example 2 compared to comparative example 1, Ni 2p3/2The binding energy of (3) is increased by 0.29 eV. The result shows that the introduction of ferrocenecarboxylic acid causes the deletion of a connector in NiMOF, and further causes the change of the coordination environment of an active metal center. Ni 2p in example 13/2Moving further to higher binding energies. This is probably because some electrons are transferred from Ni to Co through the oxygen of the ligand, thereby optimizing the electronic structure of the Ni active site and contributing to the improvement of its catalytic activity.
FIG. 6 is a Co 2p X ray photoelectron spectrum of the products of example 1 of the present invention and comparative example 3. Co 2p in example 1 compared to comparative example 33/2The binding energy of (a) is reduced by 0.26 eV. This further demonstrates the presence of electron transfer from Ni to Co. Thus, ferrocenecarboxylic acid and Co2+The coordination environment can be changed, the electronic structure of the Ni active site is optimized, and the Ni element has a higher oxidation state. This is to improve nickel-based MOF catalysisThe catalytic properties of the catalyst play a critical role.
FIG. 7 is a four-probe sheet resistance plot of the products obtained in comparative example 1 and comparative example 2 of the present invention. It can be seen from the figure that the resistance of comparative example 2 is significantly lower than that of comparative example 1. This is because the introduction of Fc can improve the conductivity of MOFs through a charge transition transport mechanism.
Application example
Using the products prepared in the above example 1 and comparative examples 1 and 2 and foamed nickel as working electrodes, platinum sheet electrodes as counter electrodes, and Hg/HgO electrodes as reference electrodes, linear sweep voltammetry and voltage-time response tests were performed under a three-electrode system to evaluate their UOR electrocatalytic activity and stability, and the electrolyte solution was a 1M KOH solution containing 0.33M urea.
FIG. 8 shows the linear sweep voltammograms of the product obtained in example 1, comparative example 2 and foamed nickel in a 1M KOH solution containing 0.33M urea. As can be seen from the graph, example 1 has the lowest initial potential and the largest current density among them. At a current density of 140mA cm-1In this case, the potential (1.299V) of example 1 was significantly lower than that of comparative example 1(1.418V) and comparative example 2 (1.398V). In contrast to them, the current density of foamed nickel is essentially negligible. This shows that the above catalyst materials are all catalytically active towards UOR, whereas example 1 is the most catalytically active. The reason is that modulation of ferrocenecarboxylic acid causes NiMOF to lack part of connectors, changes the coordination environment of Ni active sites, improves the oxidation state of the Ni active sites, and improves the catalytic activity of the NiMOF. The introduction of Co transfers the electrons of the Ni active sites to Co, further improves the oxidation state of the Ni active sites, and further improves the catalytic activity of the NiMOF material. The modulation of ferrocenecarboxylic acid and the doping of Co have synergistic effect, which together make example 1 have the highest catalytic activity.
FIG. 9 is a graph showing the impedance of the product obtained in example 1 of the present invention, comparative examples 1 and 2, and foamed nickel in a 1M KOH solution containing 0.33M urea. The graph was used to evaluate the charge transfer resistance (R) of the catalyst/electrolyte interfacect). As shown in the figure, RctFrom nickel foam, comparative example 1, comparativeExample 2 gradually decreases to example 1. This illustrates that example 1 has the fastest charge transfer process, which provides a kinetic explanation for its excellent catalytic activity.
FIG. 10 shows TOF values of the products obtained in example 1 of the present invention and comparative examples 1 and 2 at a voltage of 1.5V. It was used to evaluate the intrinsic activity of the catalyst. TOF value of example 1 was highest (0.679 s)-1) Is obviously higher than that of comparative example 2(0.229 s)-1) And comparative example 1(0.091 s)-1). This indicates that the improvement in catalytic performance of example 1 is due to the increase in the intrinsic activity of the active center.
FIG. 11 is a graph of voltage vs. time for a 1M KOH solution containing 0.33M urea for the product obtained in example 1 of the invention. As shown, the catalyst was at 20mA cm-2Was tested for 10 hours and the voltage was found to rise only 5.9%, indicating that example 1 catalyzed UOR in a 1M KOH solution containing 0.33M urea had good durability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A modulated nickel/cobalt bimetallic MOF-based electrocatalyst comprises an electrically conductive substrate and NiCoMOF-Fc material loaded on the surface of the electrically conductive substrate.
2. The modulated nickel/cobalt bimetallic MOF-based electrocatalyst according to claim 1, characterized in that the electrically conductive substrate is foamed nickel.
3. The modulated nickel/cobalt bimetallic MOF-based electrocatalyst according to claim 1, wherein ferrocenecarboxylic acid in the NiCoMOF-Fc material is used as a non-bridged ligand to partially substitute for bridged ligand terephthalic acid, and is coordinated with nickel ions and cobalt ions as metal nodes, the NiCoMOF-Fc material is composed of six elements of carbon, hydrogen, oxygen, iron, cobalt and nickel, the content of carbon element is 30 wt.% to 50 wt.%, the content of hydrogen element is 1 wt.% to 10 wt.%, the content of oxygen element is 20 wt.% to 40 wt.%, the content of iron element is 1 wt.% to 10 wt.%, the content of cobalt element is 10 wt.% to 30 wt.%, the content of nickel element is 10 wt.% to 30 wt.%, the NiCoMOF-Fc material exhibits a nano-bundle morphology of nanowires stacked on each other, and the diameter of the nanowires is 80nm to 100 nm.
4. A method of making the modulated nickel/cobalt bimetallic MOF based electrocatalyst according to claims 1-3 comprising the steps of:
s1: terephthalic acid and ferrocenecarboxylic acid were dissolved in DMF, which was added with 0.2M aqueous sodium hydroxide solution;
s2: dissolving nickel salt and cobalt salt in DMF;
s3: and (3) mixing the DMF solutions obtained in the steps S1 and S2 in a reaction kettle with a conductive substrate, carrying out solvothermal reaction, taking out the conductive substrate after the reaction is finished, and washing and drying to obtain the modulated nickel/cobalt bimetallic MOF-based electrocatalyst.
5. The preparation method of the modulated nickel/cobalt bimetallic MOF-based electrocatalyst according to claim 4, characterized in that in step S1, the concentration of terephthalic acid in the DMF solution is 0.05M to 0.10M, the concentration of ferrocenecarboxylic acid is 0.007M to 0.017M, and the pH value of the DMF solution after the sodium hydroxide solution is added is 12 to 14.
6. The method of preparing a bimetallic nickel/cobalt MOF-based electrocatalyst according to claim 4, wherein in step S2, the concentration of nickel salt is 0.013M to 0.075M and the concentration of cobalt salt is 0.013M to 0.075M in the DMF solution.
7. The method for preparing the modulated nickel/cobalt bimetallic MOF-based electrocatalyst according to claim 4, characterized in that in step S3, the solvothermal reaction is carried out at 80-120 ℃ for 10-16 h.
8. Use of the modulated nickel/cobalt bimetallic MOF-based electrocatalyst according to any one of claims 1 to 3 or the modulated nickel/cobalt bimetallic MOF-based electrocatalyst obtained by the preparation method according to any one of claims 4 to 7 in UOR electrocatalysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111327404.8A CN114318358A (en) | 2021-11-10 | 2021-11-10 | Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111327404.8A CN114318358A (en) | 2021-11-10 | 2021-11-10 | Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114318358A true CN114318358A (en) | 2022-04-12 |
Family
ID=81044630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111327404.8A Pending CN114318358A (en) | 2021-11-10 | 2021-11-10 | Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114318358A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115029729A (en) * | 2022-07-11 | 2022-09-09 | 江南大学 | Chromium oxide/metal oxide composite material and preparation method and application thereof |
| CN115522213A (en) * | 2022-08-30 | 2022-12-27 | 天津大学 | Sulfur-phosphorus co-doped self-supporting NiFe-MOFs derivative material and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130273461A1 (en) * | 2012-04-11 | 2013-10-17 | Uchicago Argonne, Llc | Synthesis of electrocatalysts using metal-organic framework materials |
| US20150180045A1 (en) * | 2010-09-27 | 2015-06-25 | Uchicago Argonne, Llc | Non-platinum group metal electrocatalysts using metal organic framework materials and method of preparation |
| US20170326536A1 (en) * | 2016-05-13 | 2017-11-16 | King Fahd University Of Petroleum And Minerals | Metal organic frameworks as catalysts and hydrocarbon oxidation methods thereof |
| CN109208030A (en) * | 2018-11-16 | 2019-01-15 | 北京师范大学 | A kind of Metal Hydroxide-Metal organic frame composite material and preparation method |
| WO2019100497A1 (en) * | 2017-11-23 | 2019-05-31 | 中科合成油技术有限公司 | Porous carbon-supported fischer-tropsch synthesis catalyst, preparation method therefor, and use thereof |
| CN111883367A (en) * | 2020-06-11 | 2020-11-03 | 安徽师范大学 | Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof |
| CN111921560A (en) * | 2020-08-18 | 2020-11-13 | 浙江大学 | Lattice-distorted ultrathin metal organic framework nanosheet catalyst, and preparation method and application thereof |
| WO2020262451A1 (en) * | 2019-06-25 | 2020-12-30 | 学校法人立教学院 | Metal-organic framework having terephthalic acid based ligand |
| CN112886024A (en) * | 2021-03-05 | 2021-06-01 | 福州大学 | Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst |
| CN112899723A (en) * | 2021-02-01 | 2021-06-04 | 厦门大学 | Metal organic framework derived iron-nickel metal sulfide catalyst, preparation and application thereof |
| WO2021212923A1 (en) * | 2020-04-20 | 2021-10-28 | 苏州大学 | P-n heterojunction composite material supported on surface of nickel foam, preparation method therefor and use thereof |
-
2021
- 2021-11-10 CN CN202111327404.8A patent/CN114318358A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150180045A1 (en) * | 2010-09-27 | 2015-06-25 | Uchicago Argonne, Llc | Non-platinum group metal electrocatalysts using metal organic framework materials and method of preparation |
| US20130273461A1 (en) * | 2012-04-11 | 2013-10-17 | Uchicago Argonne, Llc | Synthesis of electrocatalysts using metal-organic framework materials |
| US20170326536A1 (en) * | 2016-05-13 | 2017-11-16 | King Fahd University Of Petroleum And Minerals | Metal organic frameworks as catalysts and hydrocarbon oxidation methods thereof |
| WO2019100497A1 (en) * | 2017-11-23 | 2019-05-31 | 中科合成油技术有限公司 | Porous carbon-supported fischer-tropsch synthesis catalyst, preparation method therefor, and use thereof |
| CN109208030A (en) * | 2018-11-16 | 2019-01-15 | 北京师范大学 | A kind of Metal Hydroxide-Metal organic frame composite material and preparation method |
| WO2020262451A1 (en) * | 2019-06-25 | 2020-12-30 | 学校法人立教学院 | Metal-organic framework having terephthalic acid based ligand |
| WO2021212923A1 (en) * | 2020-04-20 | 2021-10-28 | 苏州大学 | P-n heterojunction composite material supported on surface of nickel foam, preparation method therefor and use thereof |
| CN111883367A (en) * | 2020-06-11 | 2020-11-03 | 安徽师范大学 | Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof |
| CN111921560A (en) * | 2020-08-18 | 2020-11-13 | 浙江大学 | Lattice-distorted ultrathin metal organic framework nanosheet catalyst, and preparation method and application thereof |
| CN112899723A (en) * | 2021-02-01 | 2021-06-04 | 厦门大学 | Metal organic framework derived iron-nickel metal sulfide catalyst, preparation and application thereof |
| CN112886024A (en) * | 2021-03-05 | 2021-06-01 | 福州大学 | Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst |
Non-Patent Citations (1)
| Title |
|---|
| "Mono-coordinated metallocene ligands endow metal-organic frameworks with highly efficient oxygen evolution and urea electrolysis", CHEMICAL ENGINEERING JOURNAL, vol. 430, 30 September 2021 (2021-09-30), pages 1 - 10 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115029729A (en) * | 2022-07-11 | 2022-09-09 | 江南大学 | Chromium oxide/metal oxide composite material and preparation method and application thereof |
| CN115029729B (en) * | 2022-07-11 | 2023-08-08 | 江南大学 | Chromium oxide/metal oxide composite material and preparation method and application thereof |
| CN115522213A (en) * | 2022-08-30 | 2022-12-27 | 天津大学 | Sulfur-phosphorus co-doped self-supporting NiFe-MOFs derivative material and application thereof |
| CN115522213B (en) * | 2022-08-30 | 2023-07-07 | 天津大学 | Sulfur-phosphorus co-doped self-supporting NiFe-MOFs derivative material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6749983B2 (en) | Method for producing bismuth nanosheet and use thereof | |
| CN113828300B (en) | Preparation method of metal doped bismuth layered oxide and electrocatalytic reduction of CO 2 Application in (a) | |
| CN110639534B (en) | Oxygen evolution electrocatalytic material and preparation method and application thereof | |
| CN114318358A (en) | Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application | |
| CN110743603A (en) | Cobalt-iron bimetallic nitride composite electrocatalyst and preparation method and application thereof | |
| Li et al. | NiCo-BDC nanosheets coated with amorphous Ni-S thin film for high-efficiency oxygen evolution reaction and urea oxidation reaction | |
| CN110560117A (en) | Bimetallic cobalt ruthenium-nitrogen phosphorus doped porous carbon electrocatalyst and preparation method and application thereof | |
| CN111129515B (en) | Heterostructure self-supporting electrode material and preparation method and application thereof | |
| CN110404564B (en) | Double-function full-electrolysis water-electricity catalyst and preparation method and application thereof | |
| CN113957456A (en) | Nickel-based alkaline electrolytic water catalyst with co-doped combination heterostructure and preparation method thereof | |
| CN112899723B (en) | Metal organic framework derived iron-nickel metal sulfide catalyst, preparation and application thereof | |
| CN113122876A (en) | Preparation method and application of molybdenum-doped ferronickel Prussian blue analogue @ carbon felt | |
| Chen et al. | Lignin‐assisted alloying engineering of CoNiRu trimetallic nano‐catalyst for effective overall water splitting | |
| CN105214733B (en) | Titanium dioxide covalently loads efficient oxygen reduction electro-catalyst of copper complex and preparation method thereof | |
| CN114685806B (en) | Acid-modified ultrathin metal organic framework nanosheet catalyst and preparation method and application thereof | |
| CN115110113B (en) | Rod-shaped Co 2 C-MoN composite material and preparation method and application thereof | |
| CN116581306B (en) | Plant fiber derived transition metal porous nitrogen-doped carbon catalyst and preparation method and application thereof | |
| CN115652357B (en) | Sulfur-doped yttrium ruthenate, preparation method thereof and oxygen evolution reaction electrode | |
| CN115094475B (en) | Electrode material with high-performance oxygen evolution catalytic activity and preparation method thereof | |
| Yu et al. | NiFe-Based Semi-MOF Embedded by Sulfide Particles Reconstructed a Three-Layer Sandwich Structure for Alkaline Overall Water Splitting | |
| CN116180138A (en) | Method for preparing high-efficiency self-supporting oxygen evolution electrocatalyst by cation exchange method | |
| CN116926957A (en) | Preparation method and application of dysprosium-doped nickel-metal organic frame composite material | |
| Song et al. | Steering the electronic communication between Al/Ru bimetallic clusters in metal–organic framework composites for accelerating hydrogen evolution kinetics | |
| CN116876032A (en) | Method for synthesizing organic acid ligand hybrid nickel cobalt hydroxide catalyst by one-step hydrothermal method and application | |
| CN116613330A (en) | Alkaline system direct methanol fuel cell anode catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |