CN114807968A - Preparation method of metaphosphate-loaded ruthenium phosphide catalytic material and application of metaphosphate-loaded ruthenium phosphide catalytic material in electrocatalytic total decomposition water - Google Patents
Preparation method of metaphosphate-loaded ruthenium phosphide catalytic material and application of metaphosphate-loaded ruthenium phosphide catalytic material in electrocatalytic total decomposition water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 46
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 33
- 125000005341 metaphosphate group Chemical group 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 title description 3
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- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims abstract description 16
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
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- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
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- 238000009210 therapy by ultrasound Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
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- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/056—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of textile or non-woven fabric
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
Abstract
The invention relates to a preparation method of a metaphosphate-loaded ruthenium phosphide catalytic material and application of the metaphosphate-loaded ruthenium phosphide catalytic material in electrocatalytic total-hydrolysis water, which comprises the following steps: A. washing the carbon cloth; B. taking Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O, 2-methylimidazole solution, and uniformly stirring to obtain a solution a; C. immersing the carbon cloth washed in the step A into the solution a obtained in the step B, and obtaining a precursor CoNi-ZIF/CC after the impregnation is finished; D. dissolving ruthenium trichloride hydrate into deionized water to obtain a solution d, immersing CoNi-ZIF/CC obtained in the step C into the solution d, and drying at constant temperature after the immersion is finished to obtain RuCoNi-ZIF/CC; E. separately adding NaH 2 PO 2 ·H 2 O, placing the RuCoNi-ZIF/CC obtained in the step D at the upstream and downstream of the flow direction of inert protective gas, heating the inert gas to 400-550 ℃ at the speed of 2-5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain a solid prefabricated object; F. and E, alternately washing the solid prefabricated object obtained in the step E with ethanol and deionized water, and drying at constant temperature to obtain RuP/CoNiP 4 O 12 a/CC nanocomposite.
Description
Technical Field
The invention relates to the field of catalytic materials, in particular to a preparation method of a metaphosphate-loaded ruthenium phosphide catalytic material and application of the metaphosphate-loaded ruthenium phosphide catalytic material in electrocatalytic total decomposition water.
Background
At present, the energy consumption structure is still the dominant position of fossil energy such as coal, petroleum, natural gas and the like. However, with the rapid development of economy and the increasing progress of industrialization, the limited fossil energy reserves have failed to meet the increasing energy consumption needs. In addition, the excessive use of traditional fossil fuels leads to the increase of the discharge amount of carbon dioxide, nitrogen oxides, dust and other environmental pollutants year by year, and the problem of environmental pollution is increased. In view of the ever-increasing environmental problems and the ever-increasing energy demand, attention has turned to eco-friendly renewable energy sources.
Among the various renewable energy sources, hydrogen energy is considered to be one of the most potential renewable energy sources to replace fossil energy due to its advantages of high combustion heat value, clean combustion products, no pollution and the like. Wherein, the hydrogen production by electrolyzing water is an advanced hydrogen production technology which does not discharge greenhouse gases and can produce high-purity hydrogen on a large scale. The hydrogen production by water electrolysis can be carried out under the environment of normal temperature and normal pressure, and the reaction condition is very mild. Therefore, in order to improve the efficiency of hydrogen production by water electrolysis, it is imperative to find a highly efficient and stable catalytic material.
At present, the catalytic material commonly used for Oxygen Evolution Reaction (OER) is a transition metal-supported metaphosphate catalytic material, and metaphosphates have high phosphorus content and rigid structure and are excellent in the OER catalytic process. However, the Hydrogen Evolution Reaction (HER) performance of the catalytic material loaded with the transition metal metaphosphate is poor, and the main content of the current research still focuses on the development of the OER performance of the transition metal metaphosphate, and the HER performance of the OER is less researched.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a metaphosphate-loaded ruthenium phosphide catalytic material, which mainly comprises the following stepsThe impregnation method and the low-temperature calcination method combine the ruthenium phosphide and the cobalt nickel metaphosphate, and the prepared total hydrolysis catalytic material RuP/CoNiP is prepared by utilizing the interface synergistic effect of the ruthenium phosphide and the cobalt nickel metaphosphate 4 O 12 the/CC shows excellent performance in both HER and OER catalytic processes.
In order to solve the technical problem, the invention provides a preparation method of a metaphosphate-loaded ruthenium phosphide catalytic material, which is characterized by comprising the following steps of:
A. washing the carbon cloth;
B. taking Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 Uniformly stirring an O and 2-methylimidazole solution to obtain a solution a;
C. immersing the carbon cloth washed in the step A into the solution a obtained in the step B, and obtaining a precursor CoNi-ZIF/CC after the impregnation is finished;
D. dissolving ruthenium trichloride hydrate into deionized water to obtain a solution d, immersing CoNi-ZIF/CC obtained in the step C into the solution d, and drying at constant temperature after the immersion is finished to obtain RuCoNi-ZIF/CC;
E. separately adding NaH 2 PO 2 ·H 2 O, placing the RuCoNi-ZIF/CC obtained in the step D at the upstream and downstream of the flow direction of inert protective gas, heating the inert gas to 400-550 ℃ at the speed of 2-5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain a solid prefabricated object;
F. and E, alternately washing the solid prefabricated object obtained in the step E with ethanol and deionized water, and drying at constant temperature to obtain RuP/CoNiP 4 O 12 a/CC nanocomposite.
By the above technical scheme, firstly, Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O and 2-methylimidazole react, and the reaction equation is Co (NO) 3 ) 2 ·6H 2 O+Ni(NO 3 ) 2 ·6H 2 O+C 4 H 6 N 2 → CoNi-ZIF, the carbon cloth is immersed in the solution a, and the generated CoNi-ZIF is attached to the carbon cloth.
Then CoNi-ZIImmersing F/CC in ruthenium trichloride solution, Ru 3+ Enters a ZIF system through ion exchange, and has a reaction formula of Ru 3+ +CoNi-ZIF→RuCoNi-ZIF。
Finally, taking sodium hypophosphite as a phosphorus source, wherein the sodium hypophosphite reacts as follows: 2H 2 PO 2 - →PH 3 ↑+HPO 4 2- ；HPO 4 2- →PO 3 - +OH - 。H 2 PO 2 - At a temperature above 150 ℃ by disproportionation to pH 3 And HPO 4 2- HPO when the phosphorylation temperature is increased to 300-450 DEG C 4 2- Will be further converted into PO 3 - And OH - A metaphosphoric acid phase is formed and a soft carbon matrix is formed. The sodium hypophosphite is placed at the upstream, so that the Ar atmosphere is favorable for carrying the components decomposed by the phosphorus source to flow to the downstream RuCoNi-ZIF/CC, and the reaction is smoothly carried out. At this time, PO 3 - The cobalt nickel metaphosphate is generated by the reaction with CoNi-ZIF, and RuP is generated by Ru ions loaded on the cobalt nickel metaphosphate in the atmosphere of phosphine, and the reaction equation is as follows: PO (PO) 3 - +PH 3 ↑+RuCoNi-ZIF→RuP/CoNiP 4 O 12 。
Further, the method for preparing a metaphosphate-supported ruthenium phosphide catalytic material according to claim 1, wherein: and D, the concentration of the ruthenium trichloride hydrate in the solution D in the step D is 0.1-15 mmol/L.
Further, in the step D, the CoNi-ZIF/CC soaking time is 0.5-1.5h, and the drying temperature is 40-80 ℃.
Further, the preparation process of the solution a in the step B is as follows: taking Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 Uniformly dispersing O in deionized water to obtain a solution b, and uniformly dispersing 2-methylimidazole in deionized water to obtain a solution c; and pouring the solution c into the solution b, and uniformly stirring to obtain a solution a.
Further, Co (NO) in solution b 3 ) 2 ·6H 2 The concentration of O is 50-X mmol/L, and Ni (NO) in the solution b 3 ) 2 ·6H 2 The concentration of O is X mmol/L, wherein X is more than or equal to 0 and less than or equal to 25; the concentration of the 2-methylimidazole in the solution c is 0.3-0.5 mmol/L.
Further, the carbon cloth is washed by ultrasonic in acetone and ethanol in sequence, and then washed by ultrasonic in deionized water after being repeatedly washed for 3-5 times by a large amount of deionized water; then in concentrated HNO 3 And (4) carrying out medium ultrasonic washing for 4h, and repeatedly carrying out ultrasonic washing for 3-5 times by using deionized water until the pH value is neutral to obtain the cleaned carbon cloth.
Further, the inert protective gas is argon or argon-hydrogen mixed gas, wherein the argon content in the argon-hydrogen mixed gas is 98%, and the hydrogen content in the argon-hydrogen mixed gas is 2%.
Further, in step E, NaH 2 PO 2 ·H 2 The mass of O is 1-2 g.
Further, the RuP/CoNiP 4 O 12 the/CC nano composite material is a dual-function electrode material of cobalt-nickel metaphosphate micron sheets loaded on ruthenium phosphide spherical particles, wherein the cobalt-nickel metaphosphate micron sheets loaded on the ruthenium phosphide spherical particles are in a nano array on carbon fibers, the particle size of the spherical particles is 3-5nm, and the particle size of the micron sheets is 2-3 mu m.
The invention also provides application of the metaphosphate-loaded ruthenium phosphide catalytic material in electrocatalytic total hydrolysis.
The noble metal phosphide has remarkable performance in the aspect of HER catalysis, wherein the price of the ruthenium phosphide is about 1/10 of Pt as a cheap noble metal, so the ruthenium phosphide has a very high application prospect. The carbon cloth loaded ruthenium phosphide has better corrosion resistance and electrocatalysis performance in the electrolyte. However, ruthenium phosphide is very limited in OER catalysis.
Therefore, in the technical scheme of the invention, ruthenium phosphide and cobalt nickel metaphosphate are combined by an impregnation method and a low-temperature calcination method, and the obtained RuP/CoNiP is prepared by utilizing the interface synergistic action of the ruthenium phosphide and the cobalt nickel metaphosphate 4 O 12 the/CC nanocomposite shows excellent performance in both HER catalysis and OER catalysis. The technical scheme of the invention has simple steps, strong operability and easy repetition.
RuP/CoNiP prepared by the invention 4 O 12 the/CC nano composite material has excellent electrochemical full-hydrolytic performance and the current density reaches 10mA/cm 2 The potential required by HER is only-28 mV, which is better than that of Pt/C, namely-35 mV; the overpotential of OER is only 227mV, which is superior to that of pure CoNiP 4 O 12 PerCC (234mV) and commercial RuO 2 (345mV)。
RuP/CoNiP 4 O 12 the/CC nanocomposite acts as both cathode and anode, RuP/CoNiP 4 O 12 /CC||RuP/CoNiP 4 O 12 The current density can reach 10mA/cm only by 1.56V/CC 2 Is superior to commercial RuO 2 and/CC | | Pt filament (1.65V).
The method is based on that highly dispersed ruthenium phosphide nano-particles and cobalt nickel metaphosphate micron sheets are loaded on carbon cloth, the coordination environment of Ru in RuP is adjusted, so that the ruthenium phosphide nano-particles not only have Ru-P components, but also are bonded with a metaphosphate substrate, Ru-O is increased, the electronic structure of the material is improved, the number of active sites is increased, meanwhile, the contact between the material and electrolyte is increased by utilizing the structural characteristics of a cobalt nickel metaphosphate nano-array, the rapid release of generated gas is facilitated, and the electrocatalytic activity and stability of the material are synergistically improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is an SEM image of a cleaned carbon cloth of example one after washing.
FIG. 2 is an SEM image of CoNi-ZIF/CC in the first example.
FIG. 3 is an SEM image of RuCoNi-ZIF/CC in the first example.
FIG. 4 shows RuP/CoNiP in the first embodiment 4 O 12 SEM image of/CC.
FIG. 5 RuCl at a concentration of 5mmol/L 3 Impregnation (a, b) and RuCl at a concentration of 10mmol/L 3 SEM images of impregnated CoNi-ZIF.
FIG. 6 is a CoNiP of comparative example I 4 O 12 /CC, RuP/CoNiP in example one 4 O 12 XRD diffractogram of/CC, RuP/CC in comparative example, and standard card contrast.
FIG. 7 shows RuP/CoNiP of the first embodiment 4 O 12 High Resolution Transmission Electron Microscopy (HRTEM) for/CC.
FIG. 8 shows RuP/CoNiP in the first embodiment 4 O 12 PerCC, RuP/CC in comparative example II, RuO 2 And X-ray absorption spectrum (XAS) of Ru (a) X-ray near-edge absorption fine structure spectrum (XANES); (b) extended X-ray absorption fine structure spectrum (EXAFS).
FIG. 9 shows RuP/CoNiP in the first embodiment 4 O 12 /CC, RuP/CC in comparative example II, CoNiP in comparative example I 4 O 12 HER polarization curves for/CC and Pt/C.
FIG. 10 shows RuP/CoNiP in the first embodiment 4 O 12 /CC, RuP/CC in comparative example II, CoNiP in comparative example I 4 O 12 /CC and RuO 2 OER polarization curve of/CC.
FIG. 11 shows RuP/CoNiP in the first embodiment 4 O 12 LSV polarization curve of/CC full water splitting performance test.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The experimental procedures in the following examples are conventional unless otherwise specified. Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean value or the mean value ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a preparation method of a metaphosphate-loaded ruthenium phosphide catalytic material, which is characterized by comprising the following steps of:
A. washing the carbon cloth;
B. taking Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 Uniformly stirring an O and 2-methylimidazole solution to obtain a solution a;
C. immersing the carbon cloth washed in the step A into the solution a obtained in the step B, and obtaining a precursor CoNi-ZIF/CC after the impregnation is finished;
D. dissolving ruthenium trichloride hydrate into deionized water to obtain a solution d, immersing CoNi-ZIF/CC obtained in the step C into the solution d, and drying at constant temperature after the immersion is finished to obtain RuCoNi-ZIF/CC;
E. separately adding NaH 2 PO 2 ·H 2 O, placing the RuCoNi-ZIF/CC obtained in the step D at the upstream and downstream of the flow direction of inert protective gas, heating the inert gas to 400-550 ℃ at the speed of 2-5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain a solid prefabricated object;
F. and E, alternately washing the solid prefabricated object obtained in the step E with ethanol and deionized water, and drying at constant temperature to obtain RuP/CoNiP 4 O 12 a/CC nanocomposite.
In some embodiments, the concentration of ruthenium trichloride hydrate in solution D in step D is from 0.1 to 15 mmol/L.
In some embodiments, in step D, the CoNi-ZIF/CC impregnation time is 0.5-1.5h and the drying temperature is 40-80 ℃.
Preferably, in the step D, the CoNi-ZIF/CC soaking time is 1h, and the drying temperature is 60 ℃.
In some embodiments, the preparation of solution a in step B is as follows: taking Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 Uniformly dispersing O in deionized water to obtain a solution b, and uniformly dispersing 2-methylimidazole in deionized water to obtain a solution c; and pouring the solution c into the solution b, and uniformly stirring to obtain a solution a.
In some embodiments, Co (NO) in solution b 3 ) 2 ·6H 2 The concentration of O is 50-X mmol/L, and Ni (NO) in the solution b 3 ) 2 ·6H 2 The concentration of O is X mmol/L, wherein X is more than or equal to 0 and less than or equal to 25; the concentration of the 2-methylimidazole in the solution c is 0.3-0.5 mmol/L.
Preferably, Co (NO) in solution b 3 ) 2 ·6H 2 The concentration of O is 40mmol/L, and Ni (NO) in the solution b 3 ) 2 ·6H 2 The concentration of O is 10mmol/L, wherein X is equal to 10; the concentration of 2-methylimidazole in solution c was 0.4 mmol/L.
In some embodiments, the stirring time of solution b and solution c is 2 min.
Through the technical scheme, the 2-methylimidazole plays a role of ligand in the reaction system, and the 2-methylimidazole can be coordinated with the metal site (and Co 2+ Complexation) to form a supramolecular microporous network structure material.
In some embodiments, the carbon cloth is washed by ultrasonic washing in acetone and ethanol in sequence, and then ultrasonic washing in deionized water after repeatedly rinsing with a large amount of deionized water for 3-5 times; then in concentrated HNO 3 And (4) carrying out medium ultrasonic washing for 4h, and repeatedly carrying out ultrasonic washing for 3-5 times by using deionized water until the pH value is neutral to obtain the cleaned carbon cloth.
Preferably, the carbon cloth is washed in acetone and ethanol for 30min respectively.
Preferably, the carbon cloth is ultrasonically washed in deionized water for 30 min.
Preferably, the carbon cloth is in concentrated HNO 3 And (5) carrying out medium ultrasonic washing for 4 h.
Preferably, the pH of the carbon cloth in deionized water is adjusted to neutral.
Preferably, the solution for adjusting the pH is ammonia water.
Preferably, the washed carbon cloth is immersed in deionized water, and the deionized water is periodically replaced.
By the technical scheme, the acetone and the ethanol are used for removing organic impurities attached to the surface of the carbon cloth; deionized water is used for further cleaning acetone and ethanol remained on the surface of the carbon cloth so as to avoid generating impurities and harmful gas by the reaction with subsequent concentrated nitric acid; the concentrated nitric acid is used for carrying out surface modification on the carbon cloth so as to make the carbon cloth more hydrophilic; the deionized water is used again to wash the residual concentrated nitric acid on the surface of the carbon cloth so that the carbon cloth is neutral.
In some embodiments, in step C, the carbon cloth is impregnated for 3 to 12 hours.
Preferably, in step C, the carbon cloth is impregnated for 4 hours.
In some embodiments, the drying temperature of step C is 40-80 ℃.
Preferably, the drying temperature of the step C is 60 DEG C
In some embodiments, the impregnated CoNi-ZIF/CC is subjected to a cleaning and drying treatment.
In some embodiments, the RuCoNi-ZIF/CC impregnated in step D requires a cleaning process.
In some embodiments, the inert shielding gas is argon or argon-hydrogen mixture gas, wherein the argon is 98% and the hydrogen is 2% in the argon-hydrogen mixture gas.
Preferably, the inert shielding gas is argon.
In some embodiments, in step F, the drying temperature is from 40 to 80 c,
preferably, in step F, the drying temperature is 60 ℃.
In some embodiments, in step E, NaH 2 PO 2 ·H 2 The mass of O is 1-2 g.
Preferably, in step E, NaH 2 PO 2 ·H 2 The mass of O was 2 g.
In some embodiments, the RuP/CoNiP 4 O 12 the/CC nano composite material is a dual-function electrode material of cobalt-nickel metaphosphate micron sheets loaded on ruthenium phosphide spherical particles, wherein the cobalt-nickel metaphosphate micron sheets loaded on the ruthenium phosphide spherical particles are in a nano array on carbon fibers, the particle size of the spherical particles is 3-5nm, and the particle size of the micron sheets is 2-3 mu m.
In summary, in the technical scheme of the invention, ruthenium phosphide and cobalt nickel metaphosphate are combined by an impregnation method and a low-temperature calcination method, and RuP/CoNiP is prepared by utilizing the interface synergistic effect of the ruthenium phosphide and the cobalt nickel metaphosphate 4 O 12 the/CC nanocomposite shows excellent performance in both HER catalysis and OER catalysis. The technical scheme of the invention has simple steps, strong operability and easy repetition.
Example one
A. And (3) ultrasonically washing the carbon cloth in acetone and ethanol in sequence, and washing for 30min respectively. Then repeatedly washing with a large amount of deionized water for 3-5 times, and performing ultrasonic treatment for 30min for the last time. Then in concentrated HNO 3 And (3) carrying out medium ultrasonic washing for 4h, repeatedly washing for 3-5 times by using deionized water, carrying out ultrasonic washing for 30min each time until the pH value is neutral, and adding a drop of ammonia water to adjust the pH value if necessary to obtain the treated carbon cloth. FIG. 1 is an SEM image of a clean carbon cloth after washing in example one.
B. 0.4546g of Co (NO) 3 ) 2 ·6H 2 O and 0.1163g Ni (NO) 3 ) 2 ·6H 2 Dispersing O into 40mL of deionized water, and uniformly stirring by magnetic force to obtain a light purple red transparent solution b; 1.3136g of 2-methylimidazole were dispersed in 40mL of deionized water and dissolved by stirring to obtain a uniform, colorless transparent solution c. Adding solution c into solution b under continuous magnetic stirring, stirring for 2min to obtain purple opaque solution a, and magnetically sucking with magnetAnd (5) performing secondary treatment.
C. The carbon cloth (1X 2 cm) washed in the step A is put into a container 2 ) And D, immersing the carbon cloth into the solution a obtained in the step B at room temperature for 4 hours, pouring out redundant liquid, taking out the carbon cloth, washing the carbon cloth for multiple times by using deionized water, and drying the carbon cloth at a constant temperature of 60 ℃ to obtain a precursor CoNi-ZIF/CC. FIG. 2 is an SEM image of CoNi-ZIF/CC in the first example.
D. And C, weighing 0.0053g of ruthenium trichloride hydrate, dissolving in 5mL of deionized water to obtain a solution d, wherein the concentration of the ruthenium trichloride solution is 5mmol/L, immersing the CoNi-ZIF/CC dried in the step C into the solution d, taking out after immersion for 1h, washing with deionized water, then placing in a drying oven, and drying at a constant temperature of 60 ℃ to obtain RuCoNi-ZIF/CC. FIG. 3 is an SEM image of RuCoNi-ZIF/CC in the first example.
E. D, putting the RuCoNi-ZIF/CC obtained in the step D into a porcelain boat, putting the porcelain boat at the downstream of the tube furnace, and filling the other porcelain boat with 2g NaH 2 PO 2 ·H 2 And placing the ceramic boat of O at the upstream of the tube furnace, heating to 500 ℃ at the speed of 2 ℃/min under the argon atmosphere, preserving the heat for 2h, and naturally cooling to room temperature to obtain the solid prefabricated object.
F. Alternately washing the solid prefabricated material with ethanol and deionized water for 3-5 times, and drying at constant temperature of 60 ℃ to obtain RuP/CoNiP 4 O 12 the/CC-5 nanometer composite material. FIG. 4 shows RuP/CoNiP in the first embodiment 4 O 12 SEM image of/CC.
Example two differs from example one in that the concentration of ruthenium trichloride hydrate was 0.5mmol/L, yielding RuP/CoNiP 4 O 12 the/CC-0.5 nano composite material.
Example three differs from example one in that the concentration of ruthenium trichloride hydrate was 2.5mmol/L, yielding RuP/CoNiP 4 O 12 the/CC-2.5 nanometer composite material.
Example four differs from example one in that the concentration of ruthenium trichloride hydrate was 4mmol/L, yielding RuP/CoNiP 4 O 12 the/CC-4 nano composite material.
Example five differs from example one in that the concentration of ruthenium trichloride hydrate was 6mmol/L, yielding RuP/CoNiP 4 O 12 a/CC-6 nanocomposite material.
Example six differs from example one in that the concentration of ruthenium trichloride hydrate was 8mmol/L, yielding RuP/CoNiP 4 O 12 the/CC-8 nanometer composite material.
Example seven differs from example one in that the concentration of ruthenium trichloride hydrate was 10mmol/L, yielding RuP/CoNiP 4 O 12 the/CC-10 nanometer composite material.
Comparative example 1
A. And (3) ultrasonically washing the carbon cloth in acetone and ethanol in sequence, and washing for 30min respectively. Then repeatedly washing with a large amount of deionized water for 3-5 times, and performing ultrasonic treatment for 30min for the last time. Then in concentrated HNO 3 And (3) carrying out medium ultrasonic washing for 4h, repeatedly washing for 3-5 times by using deionized water, carrying out ultrasonic washing for 30min each time until the pH value is neutral, and adding a drop of ammonia water to adjust the pH value if necessary to obtain the treated carbon cloth.
B. Mixing 40mM Co (NO) 3 ) 2 ·6H 2 O and 10mM Ni (NO) 3 ) 2 ·6H 2 Dispersing O into 40mL of deionized water, and uniformly stirring by magnetic force to obtain a light purple red transparent solution b; dispersing 0.4M 2-methylimidazole into 40mL of deionized water, and stirring for dissolving to obtain a uniform, colorless and transparent solution c. And (3) under the action of continuous magnetic stirring, pouring the solution c into the solution b, stirring for 2min to obtain a purple opaque solution a, and then sucking out magnetons by using a magnet.
C. The carbon cloth (1X 2 cm) washed in the step A is put into a container 2 ) And D, immersing the carbon cloth into the solution a obtained in the step B at room temperature for 4 hours, pouring out redundant liquid, taking out the carbon cloth, washing the carbon cloth for multiple times by using deionized water, and drying the carbon cloth at a constant temperature of 60 ℃ to obtain a precursor CoNi-ZIF/CC.
D. C, placing the CoNi-ZIF/CC obtained in the step C into a porcelain boat, placing the porcelain boat at the downstream of the tube furnace, and filling the other porcelain boat with 2g of NaH 2 PO 2 ·H 2 And placing the ceramic boat of O at the upstream of the tube furnace, heating to 500 ℃ at the speed of 2 ℃/min under the argon atmosphere, preserving the heat for 2h, and naturally cooling to room temperature to obtain the solid prefabricated object.
E. Alternately washing the solid prefabricated object with ethanol and deionized water for 3-5Then drying at constant temperature of 60 ℃ to obtain CoNiP 4 O 12 a/CC nanocomposite.
Comparative example 2
A. And (3) ultrasonically washing the carbon cloth in acetone and ethanol in sequence, and washing for 30min respectively. Then repeatedly washing with a large amount of deionized water for 3-5 times, and finally performing ultrasonic treatment for 30 min. Then in concentrated HNO 3 And (3) carrying out medium ultrasonic washing for 4h, repeatedly washing for 3-5 times by using deionized water, carrying out ultrasonic washing for 30min each time until the pH value is neutral, and adding a drop of ammonia water to adjust the pH value if necessary to obtain the treated carbon cloth.
B. Weighing 5mM ruthenium trichloride hydrate, dissolving the ruthenium trichloride hydrate in 5mL of deionized water, immersing the carbon cloth washed in the step A into the ruthenium trichloride solution, taking out the carbon cloth after the carbon cloth is immersed for 1h, washing the carbon cloth with the deionized water, then placing the carbon cloth into an oven, and drying the carbon cloth at the constant temperature of 60 ℃ to obtain RuCl 3 /CC。
C. The RuCl obtained in the step B 3 the/CC was placed in a porcelain boat, which was placed downstream of the tube furnace, and the other was charged with 2g NaH 2 PO 2 ·H 2 And placing the porcelain boat of O at the upstream of the tube furnace, heating to 500 ℃ at the speed of 2 ℃/min under the argon atmosphere, preserving heat for 1h, and naturally cooling to room temperature to obtain the solid prefabricated object.
D. And alternately washing the solid prefabricated object with ethanol and deionized water for 3-5 times, and drying at the constant temperature of 60 ℃ to obtain the RuP/CC nano composite material.
The nanocomposite prepared in the first to seventh examples and the first to second comparative examples was subjected to performance tests, and the results of the performance tests were as follows:
FIG. 6 is a CoNiP of comparative example I 4 O 12 /CC, RuP/CoNiP in example one 4 O 12 XRD diffractogram of/CC, RuP/CC in comparative example, and standard card contrast.
FIG. 7 shows RuP/CoNiP of the first embodiment 4 O 12 High Resolution Transmission Electron Microscopy (HRTEM) for/CC. As shown in FIG. 7, RuP/CoNiP prepared by the present invention was confirmed 4 O 12 In the/CC, Ru is present in RuP form, and RuP particles are observed to be uniformly loaded on CoNiP 4 O 12 On a substrate.
FIG. 8 shows RuP/CoNiP in the first embodiment 4 O 12 PerCC, RuP/CC in comparative example II, RuO 2 And X-ray absorption spectrum (XAS) of Ru (a) X-ray near-edge absorption fine structure spectrum (XANES); (b) extended X-ray absorption fine structure spectrum (EXAFS). As shown in fig. 8, the near-edge absorption fine structure spectra of both the ruthenium phosphide and the ruthenium phosphide/metaphosphate samples were observed to be very similar in line shape and peak position, demonstrating the presence of ruthenium phosphide. Analysis from the expanded edge showed RuP/CoNiP 4 O 12 Both Ru-O and Ru-P components proved RuP of the surface and carrier CoNiP 4 O 12 Strong interaction is generated between the two, and the coordination environment of Ru is changed, which is also an important source of good catalytic performance of the Ru.
FIG. 9 shows RuP/CoNiP in the first embodiment 4 O 12 /CC, RuP/CC in comparative example II, CoNiP in comparative example I 4 O 12 HER polarization curves for/CC and Pt/C. As shown in FIG. 9, the current density was 10mA/cm 2 RuP/CoNiP 4 O 12 28mV for/CC, 35mV for Pt/C, 58mV for RuP/CC, RuO 2 A CC of 149mV, CoNiP 4 O 12 the/CC was 245 mV. The performance of the composite material is far better than that of pure RuP/CC and CoNiP 4 O 12 /CC due to RuP and CoNiP 4 O 12 Interaction occurs on the interface, the catalytic activity is improved, and the doping of Ru greatly improves the HER performance of the cobalt nickel metaphosphate catalyst.
FIG. 10 shows RuP/CoNiP of the first embodiment 4 O 12 /CC, RuP/CC in comparative example II, CoNiP in comparative example I 4 O 12 /CC and RuO 2 OER polarization curve of/CC. As shown in FIG. 10, at 10mA/cm 2 RuP/CoNiP at current density relative to pure RuP/CC 4 O 12 The performance (227mV) of the/CC is greatly improved, which is probably similar to that of Ru and carrier CoNiP in RuP 4 O 12 The binding of O in (1) is concerned. Commercial RuO with overpotential ratio loaded on CC 2 There is also a significant reduction.
FIG. 11 shows RuP/CoNiP in the first embodiment 4 O 12 LSV polarization curve of/CC full water splitting performance test. RuP/CoNiP as shown in FIG. 11 4 O 12 /CC||RuP/CoNiP 4 O 12 the/CC can reach 10mA/cm only by 1.56V 2 Current density of (2) is superior to that of commercial RuO 2 The result is also superior to most published full hydrolysis catalyst researches on/CC | | Pt filament (1.65V).
In conclusion, the invention loads the high-dispersion ruthenium phosphide nano-particles and the cobalt nickel metaphosphate micron sheet on the carbon cloth, adjusts the coordination environment of Ru in RuP, ensures that the ruthenium phosphide nano-particles not only have Ru-P components, but also generate bonding with a metaphosphate substrate, increases Ru-O, improves the electronic structure of the material, increases the number of active sites, simultaneously utilizes the structural characteristics of the cobalt nickel metaphosphate self nano-array to increase the contact between the material and the electrolyte, is favorable for the rapid release of generated gas, and synergistically improves the electrocatalytic activity and stability of the material.
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being included in the description of the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of metaphosphate-loaded ruthenium phosphide catalytic material is characterized by comprising the following steps:
A. washing the carbon cloth;
B. taking Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O, 2-methylimidazole solution is evenly stirred to obtain solution a；
C. Immersing the carbon cloth washed in the step A into the solution a obtained in the step B, and obtaining a precursor CoNi-ZIF/CC after the impregnation is finished;
D. dissolving ruthenium trichloride hydrate into deionized water to obtain a solution d, immersing CoNi-ZIF/CC obtained in the step C into the solution d, and drying at constant temperature after the immersion is finished to obtain RuCoNi-ZIF/CC;
E. separately reacting NaH 2 PO 2 ·H 2 O, placing the RuCoNi-ZIF/CC obtained in the step D at the upstream and downstream of the flow direction of inert protective gas, heating the inert gas to 400-550 ℃ at the speed of 2-5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain a solid prefabricated object;
F. and E, alternately washing the solid prefabricated object obtained in the step E with ethanol and deionized water, and drying at constant temperature to obtain RuP/CoNiP 4 O 12 a/CC nanocomposite.
2. The method for preparing a metaphosphate-supported ruthenium phosphide catalytic material according to claim 1, wherein: and D, the concentration of the ruthenium trichloride hydrate in the solution D in the step D is 0.1-15 mmol/L.
3. The method for preparing a metaphosphate-supported ruthenium phosphide catalytic material according to claim 1, wherein: in the step D, the CoNi-ZIF/CC dipping time is 0.5-1.5h, and the drying temperature is 40-80 ℃.
4. The method for preparing metaphosphate-supported ruthenium phosphide catalytic material according to claim 1, wherein: the preparation process of the solution a in the step B is as follows: taking Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 Uniformly dispersing O in deionized water to obtain a solution b, and uniformly dispersing 2-methylimidazole in deionized water to obtain a solution c; and pouring the solution c into the solution b, and uniformly stirring to obtain a solution a.
5. A metaphosphate load according to claim 4The preparation method of the ruthenium phosphide catalytic material is characterized by comprising the following steps: co (NO) in solution b 3 ) 2 ·6H 2 The concentration of O is 50-X mmol/L, and Ni (NO) in the solution b 3 ) 2 ·6H 2 The concentration of O is X mmol/L, wherein X is more than or equal to 0 and less than or equal to 25; the concentration of the 2-methylimidazole in the solution c is 0.3-0.5 mmol/L.
6. The method for preparing a metaphosphate-supported ruthenium phosphide catalytic material according to claim 1, wherein:
the carbon cloth is washed in acetone and ethanol in sequence by ultrasonic waves, and then is washed in deionized water by ultrasonic waves after being repeatedly washed for 3 to 5 times by a large amount of deionized water; then in concentrated HNO 3 And (4) carrying out medium ultrasonic washing for 4h, and repeatedly carrying out ultrasonic washing for 3-5 times by using deionized water until the pH value is neutral to obtain the cleaned carbon cloth.
7. The method for preparing a metaphosphate-supported ruthenium phosphide catalytic material according to claim 1, wherein: the inert protective gas is argon or argon-hydrogen mixed gas, wherein the argon content in the argon-hydrogen mixed gas is 98%, and the hydrogen content in the argon-hydrogen mixed gas is 2%.
8. The method for preparing a metaphosphate-supported ruthenium phosphide catalytic material according to claim 1, wherein: in step E, NaH 2 PO 2 ·H 2 The mass of O is 1-2 g.
9. The method for preparing a metaphosphate-supported ruthenium phosphide catalytic material according to claim 1, wherein: the RuP/CoNiP 4 O 12 the/CC nano composite material is a dual-function electrode material of cobalt-nickel metaphosphate micron sheets loaded on ruthenium phosphide spherical particles, wherein the cobalt-nickel metaphosphate micron sheets loaded on the ruthenium phosphide spherical particles are in a nano array on carbon fibers, the particle size of the spherical particles is 3-5nm, and the particle size of the micron sheets is 2-3 mu m.
10. Use of a metaphosphate supported ruthenium phosphide catalytic material as defined in claims 1-9 in electrocatalytic total hydrolysis water.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001010550A1 (en) * | 1999-08-05 | 2001-02-15 | Sumitomo Chemical Company, Limited | Supported ruthenium oxide catalyst, process for preparing supported ruthenium catalyst and process for producing chlorine |
| CN110124704A (en) * | 2019-06-19 | 2019-08-16 | 哈尔滨工业大学 | A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate |
| CN110479328A (en) * | 2019-08-16 | 2019-11-22 | 安徽师范大学 | A kind of Fe doping hydroxyl phosphorous acid cobalt nano-chip arrays structural material and its preparation method and application |
| CN112877715A (en) * | 2021-02-10 | 2021-06-01 | 济宁学院 | Preparation method and application of porous carbon supported ruthenium phosphide catalyst |
| US20210189574A1 (en) * | 2018-04-12 | 2021-06-24 | University Of Houston System | High Performance Bifunctional Porous Non-Noble Metal Phosphide Catalyst for Overall Water Splitting |
-
2022
- 2022-05-13 CN CN202210520304.5A patent/CN114807968B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001010550A1 (en) * | 1999-08-05 | 2001-02-15 | Sumitomo Chemical Company, Limited | Supported ruthenium oxide catalyst, process for preparing supported ruthenium catalyst and process for producing chlorine |
| US20210189574A1 (en) * | 2018-04-12 | 2021-06-24 | University Of Houston System | High Performance Bifunctional Porous Non-Noble Metal Phosphide Catalyst for Overall Water Splitting |
| CN110124704A (en) * | 2019-06-19 | 2019-08-16 | 哈尔滨工业大学 | A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate |
| CN110479328A (en) * | 2019-08-16 | 2019-11-22 | 安徽师范大学 | A kind of Fe doping hydroxyl phosphorous acid cobalt nano-chip arrays structural material and its preparation method and application |
| CN112877715A (en) * | 2021-02-10 | 2021-06-01 | 济宁学院 | Preparation method and application of porous carbon supported ruthenium phosphide catalyst |
Non-Patent Citations (3)
| Title |
|---|
| JIANYING ZHAO ET AL.: "Strong phosphide-metaphosphate interaction in RuP/CoNiP 4 O 12 for enhanced electrocatalytic water splitting", 《APPLIED CATALYSIS B: ENVIRONMENTAL 》, vol. 328, pages 122447 * |
| QINGBO CHANG ET AL.: "Controllable Synthesis of Ruthenium Phosphides (RuP and RuP 2 ) for pH-Universal Hydrogen Evolution Reaction", 《ACS SUSTAINABLE CHEM. ENG. 》, vol. 6, pages 6388, XP055745050, DOI: 10.1021/acssuschemeng.8b00187 * |
| YUZHI LI ET AL.: "Metal–Organic Frameworks Derived Interconnected Bimetallic Metaphosphate Nanoarrays for Efficient Electrocatalytic Oxygen Evolution", 《ADV.FUNCT.MATER》, pages 1 - 9 * |
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