CN116603538B - A heterogeneous nano-flower electrocatalyst and preparation method thereof - Google Patents
A heterogeneous nano-flower electrocatalyst and preparation method thereof Download PDFInfo
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- 239000002057 nanoflower Substances 0.000 title claims abstract description 57
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 38
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000002135 nanosheet Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 15
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical group [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 15
- 239000012692 Fe precursor Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000012696 Pd precursors Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000009423 ventilation Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- 239000000047 product Substances 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 5
- 239000002060 nanoflake Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000575 Ir alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 and in particular Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- OCLXJTCGWSSVOE-UHFFFAOYSA-N ethanol etoh Chemical compound CCO.CCO OCLXJTCGWSSVOE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B22F1/0551—Flake form nanoparticles
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
本发明公开了一种异质纳米花电催化剂及其制备方法，该电催化剂由超薄钯基合金纳米片与四氧化三铁纳米片交叉组装构建而成的异质纳米花，异质纳米花包含钯基合金与四氧化三铁两种物相，钯基合金纳米片与四氧化三铁纳米片相互交叉形成清晰的界面，其制备方法简易可行，过程可控；该异质纳米花电催化剂具有丰富的界面位点，可显著增强电催化性能，是一种新型的合金/氧化物耦合材料体系，对于电催化活性及耐久性的提升具有重要意义。
The invention discloses a heterogeneous nanoflower electrocatalyst and a preparation method thereof. The electrocatalyst is a heterogeneous nanoflower constructed by cross-assembly of ultrathin palladium-based alloy nanosheets and ferroferric oxide nanosheets. The heterogeneous nanoflower contains two physical phases, palladium-based alloy and ferroferric oxide. The palladium-based alloy nanosheets and ferroferric oxide nanosheets cross each other to form a clear interface. The preparation method is simple and feasible, and the process is controllable. The heterogeneous nanoflower electrocatalyst has abundant interface sites, can significantly enhance the electrocatalytic performance, is a new alloy/oxide coupling material system, and is of great significance for improving the electrocatalytic activity and durability.
Description
Technical Field
The invention belongs to the technical field of nano material electrocatalysis, and particularly relates to a heterogeneous nano flower electrocatalyst and a preparation method thereof.
Background
The electric power generated by clean energy is utilized to convert water, carbon dioxide, nitrogen and the like into hydrogen, methanol, ammonia and other fuels to be stored, and then chemical energy is released and applied again through electrochemical devices such as metal-air batteries, electrolytic water, fuel cells and other technologies, so that the method is a key measure for solving the current climate and energy crisis problems. The above-described energy conversion techniques all involve an electrocatalytic process occurring at the electrode-electrolyte interface that can accelerate the rate of charge transfer reactions, thereby achieving efficient conversion of energy. Among them, the electrocatalyst is the "heart" of the electrocatalytic reaction, so the development of high-performance, low-cost electrocatalysts is critical for the next generation energy conversion technology.
Palladium is in the same group as platinum in the periodic table and exhibits very similar physicochemical properties as platinum, and thus becomes one of the best candidate electrocatalysts for replacing platinum. In addition, palladium is more abundant in earth reserves, and the historical price is only 1/2-1/3 of that of platinum. Therefore, reducing the cost of palladium-based electrocatalysts while maximizing catalytic activity and durability is a critical scientific problem to be solved in the field of electrocatalysis. Morphology regulation is an effective strategy for enhancing the catalytic performance of electrocatalysts, and in particular, electrocatalysts with larger electrochemically active areas are designed. In the electrocatalyst with various morphologies, the ultra-thin two-dimensional structure with atomic-level thickness and the three-dimensional nanoflower constructed by ultra-thin nanosheets can expose surface atoms to the maximum extent, can provide higher catalytic activity, and is beneficial to maximizing the utilization rate of noble metals and reducing the cost of the catalyst. The advantages of such electrocatalysts composed of ultra-thin two-dimensional structures are mainly derived from the low coordination peaks or slightly varying edge sites caused by the reduced thickness, and quantum size effects and/or strain effects caused by the reduced thickness of the nanoplatelets, contributing to enhanced electrocatalytic performance.
By utilizing the synergy between the multiple components, the interfacial engineering in the electrocatalyst can optimize the electrocatalytic activity, durability, selectivity, etc. by balancing the adsorption and/or desorption of intermediates and regulating the transport of electrons and protons. The interface of the alloy and the metal compound can be constructed to provide an accessible interface for electron transmission, and has great promotion significance for enhancing the electrocatalytic reaction performance of oxygen reduction, alcohol oxidation and the like. Combining the palladium-based alloy ultrathin nanosheets with the interface structure, constructing the ultrathin metal/oxide heterogeneous nanoflower may provide new opportunities for further enhancing electrocatalytic performance, however, no controllable preparation of the structure has been achieved so far.
Disclosure of Invention
Therefore, the invention aims to provide a heterogeneous nanoflower electrocatalyst and a preparation method thereof, wherein the electrocatalyst is a heterogeneous nanoflower formed by the cross assembly of an ultrathin palladium-based alloy nanosheet and a ferroferric oxide nanosheet, the heterogeneous nanoflower comprises two phases of palladium-based alloy and ferroferric oxide, the palladium-based alloy nanosheet and the ferroferric oxide nanosheet are mutually crossed to form a clear interface, and the preparation method is simple and feasible and has a controllable process.
In one aspect, the invention provides a heterogeneous nano flower electrocatalyst, which is formed by cross-assembling a palladium-based alloy nano sheet and a ferroferric oxide nano sheet, wherein the thicknesses of the palladium-based alloy nano sheet and the ferroferric oxide nano sheet are 1.3-1.7 nm, the diameter of the heterogeneous nano flower is 90-150 nm, the palladium-based alloy is a PdM alloy, and the metal M comprises but is not limited to copper, iridium, manganese, chromium, platinum or ruthenium.
As one preferable mode of the invention, the mol percentage of each metal element in the heterogeneous nanoflowers is 30% -50% of palladium, 10% -35% of metal M and 10% -35% of iron.
The preparation method comprises the following steps of S1, continuously ventilating to form an inert atmosphere to protect a reaction environment, then taking a certain amount of palladium precursor salt, adding the palladium precursor salt into a certain amount of oleylamine, magnetically stirring and dissolving at room temperature to form a uniform solution, S2, maintaining the reaction environment in the step S1, heating the uniform solution formed in the step S1 to 95-115 ℃, then adding a certain amount of iron precursor salt, continuously preserving heat for 30-60 minutes, S3, adding a certain amount of metal M precursor salt into a certain amount of oleylamine, ultrasonically stirring and dissolving to form a uniform solution, S4, maintaining the reaction environment in the step S1, adding a certain amount of the uniform solution formed in the step S3 into the uniform solution in the step S2, heating to 150-210 ℃, continuously reacting for 10-60 minutes, stopping heating and cooling to room temperature, S5, stopping adding a certain amount of ethanol into the solution after the reaction in the step S4, centrifuging, separating the ethanol, and washing the ethanol-ethanol mixed solution, and obtaining the heterogeneous nano flower electrocatalyst.
The preparation method provided by the invention is essentially based on a wet chemical-sequential reduction/oxidation method, and promotes sequential reduction and oxidation of metals through a gradient heating mode. The method comprises the steps of dissolving palladium precursor salt in oleylamine, heating, adding iron precursor salt to enable palladium to be reduced preferentially, adding metal M precursor salt, heating, alloying with palladium to form palladium-based alloy nano-sheets, oxidizing iron element to form ferroferric oxide nano-sheets, and washing with cyclohexane/ethanol to obtain heterogeneous nanoflower formed by self-assembly of palladium-based alloy and ferroferric oxide nano-sheets.
It will be appreciated by those skilled in the art that, based on the chemical reaction mechanism between the above components, the "certain amount" in the above steps is just enough to meet the requirement of the reaction, and the amount of the heterogeneous nanoflower electrocatalyst in the final product is more and less, so that those skilled in the art can flexibly grasp the amount of the heterogeneous nanoflower electrocatalyst in the final product as required.
Furthermore, it will be appreciated by those skilled in the art that the "amount" referred to in the above steps, based on the chemical reaction mechanism between the above components, may affect the mole percent of each metal element in the final product heterogeneous nanoflower electrocatalyst for different amounts of the different components.
In a preferred embodiment of the present invention, in the step S1, the palladium precursor salt is palladium acetylacetonate, in the step S2, the iron precursor salt is iron hexacarbonyl, and in the step S3, the metal M precursor salt includes but is not limited to acetylacetonate, chloride, formate or acetate.
Further, in the step S1, a certain amount of palladium precursor salt is 0.04-0.10 mmol of palladium acetylacetonate, a certain amount of oleylamine is 5-15 mL of oleylamine, in the step S2, a certain amount of iron precursor salt is 10-40 mu L of iron hexacarbonyl, in the step S3, the concentration of the uniform solution formed in the step S3 is 0.02-0.05 mol/L, in the step S4, a certain amount of the uniform solution formed in the step S3 is 1-3 mL of uniform solution, and in the step S5, a certain amount of ethanol is 10-30 mL of ethanol.
Preferably, in the step S2, the heating rate is 2 to 10 ℃ per minute, and/or in the step S4, the heating rate is 2 to 5 ℃ per minute.
Preferably, in the step S1, the inert atmosphere is nitrogen and/or argon.
Preferably, in the step S2, the adding of the certain amount of the iron precursor salt is specifically that the microsyringe is used for injecting the certain amount of the iron precursor salt.
Preferably, in the step S5, the rotational speed of the centrifugal separation is 3000-8000 rpm/min for 3-6 minutes, the volume ratio of cyclohexane/ethanol is 1/1-9/1, and the number of times of washing is 1-4.
Compared with the prior art, the invention has the following advantages:
(1) The heterogeneous nanoflower electrocatalyst prepared by the invention is a palladium-based alloy/ferroferric oxide heterogeneous nanoflower electrocatalyst formed by self-assembling two-dimensional ultrathin nanoflakes with stable structure, wherein the heterogeneous nanoflower is formed by cross self-assembling palladium-based alloy nanoflakes and ferroferric oxide nanoflakes, the thickness of the nanoflakes is nano and/or sub-nano, and the alloy and oxide nanoflakes are mutually combined to form a clear interface;
(2) The heterogeneous nano flower electrocatalyst prepared by the invention has strong interface coupling interaction of alloy and metal oxide, so that the electronic structure of metal can be regulated and controlled, and not only can the electrocatalytic activity be improved, but also the durability can be improved;
(3) The heterogeneous nano-flower electrocatalyst prepared by the method has rich interface sites, can obviously enhance the electrocatalytic performance, is a novel alloy/oxide coupling material system, and has important significance for improving the electrocatalytic activity and durability;
(4) The preparation method provided by the invention is simple in process, and the size, thickness, components and the like of the product can be regulated and controlled by controlling the concentration, reaction temperature, reaction time and the like of the metal precursor salt.
Drawings
The foregoing and/or additional aspects and advantages of the present application will become apparent and may be better understood from the following description of embodiments, taken in conjunction with the accompanying drawings. In the drawings, the same reference numerals refer to the same or similar parts or elements throughout the several views unless otherwise specified. The figures are not necessarily drawn to scale. It is to be understood that these drawings depict only some embodiments in accordance with the application and are therefore not to be considered limiting of its scope, for the application will be described with additional understanding. Wherein:
FIG. 1 is an X-ray diffraction pattern of a palladium copper/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared by the invention;
FIG. 2 is a low-power transmission electron microscope image of a palladium manganese/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared by the invention;
FIG. 3 is a high-power transmission electron microscope image of the palladium manganese/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared by the invention;
FIG. 4 is a transmission electron microscope image of a palladium platinum/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared according to the invention;
FIG. 5 is an elemental surface distribution diagram of a palladium iridium/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments. It should be understood that the particular embodiments described herein are illustrative only and should not be taken as limiting the invention.
Firstly, the invention provides a heterogeneous nano flower electrocatalyst which is formed by cross-assembling a palladium-based alloy nano sheet and a ferroferric oxide nano sheet, wherein the thicknesses of the palladium-based alloy nano sheet and the ferroferric oxide nano sheet are 1.3-1.7 nm, the diameter of the heterogeneous nano flower is 90-150 nm, the palladium-based alloy is a PdM alloy, and the metal M comprises but is not limited to copper, iridium, manganese, chromium, platinum or ruthenium.
As one preferable mode of the invention, the mol percentage of each metal element in the heterogeneous nanoflowers is 30% -50% of palladium, 10% -35% of metal M and 10% -35% of iron.
On the other hand, the invention further provides a preparation method for preparing the heterogeneous nanoflower electrocatalyst, which comprises the following steps of S1, continuously ventilating to form an inert atmosphere to protect a reaction environment, then taking a certain amount of palladium precursor salt, adding the palladium precursor salt into the certain amount of oleylamine, magnetically stirring and dissolving at room temperature to form a uniform solution, S2, maintaining the reaction environment in the step S1, heating the uniform solution formed in the step S1 to 95-115 ℃, then adding a certain amount of iron precursor salt, continuously preserving heat for 30-60 minutes, S3, taking a certain amount of metal M precursor salt, adding the certain amount of oleylamine, ultrasonically stirring and dissolving to form a uniform solution, S4, maintaining the reaction environment in the step S1, adding a certain amount of the uniform solution formed in the step S3 into the uniform solution in the step S2, continuously reacting for 10-60 minutes after heating to 150-210 ℃, then stopping heating and cooling to room temperature, S5, stopping ventilating, adding a certain amount of ethanol into the solution after the reaction in the step S4, centrifuging, separating cyclohexane and washing the ethanol/ethanol mixed solution, and obtaining the heterogeneous nanoflower electrocatalyst.
Further, in the step S1, the palladium precursor salt is palladium acetylacetonate, in the step S2, the iron precursor salt is iron hexacarbonyl, and in the step S3, the metal M precursor salt includes but is not limited to acetylacetonate, chloride, formate or acetate.
Further, in the step S1, a certain amount of palladium precursor salt is 0.04-0.10 mmol of palladium acetylacetonate, a certain amount of oleylamine is 5-15 mL of oleylamine, in the step S2, a certain amount of iron precursor salt is 10-40 mu L of iron hexacarbonyl, in the step S3, the concentration of the uniform solution generated in the step S3 is 0.02-0.05 mol/L, in the step S4, a certain amount of the uniform solution generated in the step S3 is 1-3 mL of the uniform solution, and in the step S5, a certain amount of ethanol is 10-30 mL of ethanol
In this example, the experimental equipment used in the preparation method described above includes a four-necked flask, a splash-proof ball, a heating jacket, a program temperature controller, a microsyringe, and the like.
Example 1
(1) Continuously introducing nitrogen to form an inert atmosphere to protect a reaction environment, weighing 0.06mmol of palladium acetylacetonate and 10mL of oleylamine, placing in a four-neck flask, and magnetically stirring at room temperature until the palladium acetylacetonate and the 10mL of oleylamine are dissolved;
(2) Heating the uniform solution obtained in the step (1) to 105 ℃ at a heating rate of 5 ℃ per minute, injecting 20 mu L of iron hexacarbonyl by using a microsyringe, and continuously preserving heat for 30 minutes;
(3) Copper chloride is dissolved in oleylamine by ultrasonic action to obtain a uniform solution with the concentration of 0.02 mol/L;
(4) 3mL of the uniform solution obtained in the step (3) is injected into the reaction system of the step (2), the temperature is raised to 160 ℃ at the temperature rising rate of 5 ℃ per minute, the heat preservation is continued for 30 minutes, and the heating sleeve is removed, so that the reaction system is cooled to the room temperature;
(5) Stopping ventilation, adding 20mL of ethanol into the product obtained in the step (4), centrifuging for 4min at a rotation speed of 5000rpm/min, and washing the collected product with a cyclohexane/ethanol mixed solution with a volume ratio of 3/1 for 4 times to obtain the palladium copper/ferroferric oxide heterogeneous nanoflower electrocatalyst.
The composition of the palladium-copper/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared in the embodiment is disclosed in fig. 1, which shows that the heterogeneous nanoflower comprises two phase structures of face-centered cubic palladium-copper alloy and spinel structure ferroferric oxide, thereby forming a heterogeneous nanoflower structure.
Example two
(1) Continuously introducing nitrogen to form an inert atmosphere to protect a reaction environment, weighing 0.06mmol of palladium acetylacetonate and 10mL of oleylamine, placing in a four-neck flask, and magnetically stirring at room temperature until the palladium acetylacetonate and the 10mL of oleylamine are dissolved;
(2) Heating the uniform solution obtained in the step (1) to 105 ℃ at a heating rate of 5 ℃ per minute, injecting 20 mu L of iron hexacarbonyl by using a microsyringe, and continuously preserving heat for 30 minutes;
(3) Dissolving manganese acetylacetonate into oleylamine by ultrasonic action to obtain a uniform solution with the concentration of 0.03 mol/L;
(4) 2mL of the uniform solution obtained in the step (3) is injected into the reaction system of the step (2), the temperature is raised to 160 ℃ at the temperature rising rate of 5 ℃ per minute, the heat preservation is continued for 30 minutes, and the heating sleeve is removed, so that the reaction system is cooled to the room temperature;
(5) Stopping ventilation, adding 10mL of ethanol into the product obtained in the step (4), centrifuging for 5min at the rotating speed of 4000rpm/min, and washing the collected product with a cyclohexane/ethanol mixed solution with the volume ratio of 2/1 for 3 times to obtain the palladium-manganese/ferroferric oxide heterogeneous nanoflower electrocatalyst.
Wherein, the figure 2-3 reveals the appearance characteristics of the palladium manganese/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared by the embodiment, and the figure shows that the prepared product presents uniform nanoflower appearance, the average diameter is 120nm, and the average thickness of the nanosheets is 1.4nm.
Example III
(1) Continuously introducing nitrogen to form an inert atmosphere to protect a reaction environment, weighing 0.04mmol of palladium acetylacetonate and 8mL of oleylamine, placing into a four-neck flask, and magnetically stirring at room temperature until the palladium acetylacetonate and the 8mL of oleylamine are dissolved;
(2) Heating the uniform solution obtained in the step (1) to 110 ℃ at a heating rate of 10 ℃ per minute, injecting 15 mu L of iron hexacarbonyl by using a microsyringe, and continuously preserving heat for 30 minutes;
(3) Platinum acetylacetonate is dissolved in oleylamine by ultrasonic action to obtain a uniform solution with the concentration of 0.03 mol/L;
(4) 2mL of the uniform solution obtained in the step (3) is injected into the reaction system of the step (2), the temperature is raised to 160 ℃ at the temperature rising rate of 5 ℃ per minute, the heat preservation is continued for 30 minutes, and the heating sleeve is removed, so that the reaction system is cooled to the room temperature;
(5) Stopping ventilation, adding 10mL of ethanol into the product obtained in the step (4), centrifuging for 5min at a rotation speed of 6000rpm/min, and washing the collected product with a cyclohexane/ethanol mixed solution with a volume ratio of 2/1 for 4 times to obtain the palladium platinum/ferroferric oxide heterogeneous nanoflower electrocatalyst.
Wherein, figure 4 reveals the morphological characteristics of the palladium platinum/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared in this example, and the prepared product also shows uniform nanoflower morphology.
Example IV
(1) Continuously introducing argon to form an inert atmosphere to protect a reaction environment, weighing 0.08mmol of palladium acetylacetonate and 15mL of oleylamine, placing in a four-neck flask, and magnetically stirring at room temperature until the palladium acetylacetonate and the 15mL of oleylamine are dissolved;
(2) Heating the uniform solution obtained in the step (1) to 100 ℃ at a heating rate of 5 ℃ per minute, injecting 35 mu L of iron hexacarbonyl by using a microsyringe, and continuously preserving heat for 30 minutes;
(3) Dissolving iridium acetylacetonate into oleylamine by ultrasonic action to obtain a uniform solution with the concentration of 0.03 mol/L;
(4) 3mL of the uniform solution obtained in the step (3) is injected into the reaction system of the step (2), the temperature is raised to 210 ℃ at the temperature rising rate of 3 ℃ per minute, the heat preservation is continued for 30 minutes, and the heating sleeve is removed, so that the reaction system is cooled to the room temperature;
(5) Stopping ventilation, adding 30mL of ethanol into the product obtained in the step (4), centrifuging for 6min at a rotating speed of 3000rpm/min, and washing the collected product with a cyclohexane/ethanol mixed solution with a volume ratio of 3/1 for 3 times to obtain the palladium iridium/ferroferric oxide heterogeneous nanoflower electrocatalyst.
Wherein, fig. 5 shows the element distribution of the palladium iridium alloy/ferroferric oxide heterogeneous nanoflower electrocatalyst prepared in example 4, it can be seen that two metal elements of palladium and iridium and two elements of iron and oxygen are distributed in the heterogeneous nanoflower in a crossing manner, and a clear interface is formed.
Example five
(1) Continuously introducing nitrogen to form an inert atmosphere to protect a reaction environment, weighing 0.05mmol of palladium acetylacetonate and 10mL of oleylamine, placing into a four-neck flask, and magnetically stirring at room temperature until the palladium acetylacetonate and the 10mL of oleylamine are dissolved;
(2) Heating the uniform solution obtained in the step (1) to 100 ℃ at a heating rate of 3 ℃ per minute, injecting 30 mu L of iron hexacarbonyl by using a microsyringe, and continuously preserving heat for 45 minutes;
(3) Dissolving chromium formate in oleylamine by ultrasonic action to obtain a uniform solution with the concentration of 0.05 mmol/mL;
(4) Injecting 1mL of the uniform solution obtained in the step (3) into the reaction system of the step (2), heating to 200 ℃ at a heating rate of 3 ℃ per minute, continuously preserving heat for 20 minutes, removing the heating sleeve, and cooling the reaction system to room temperature;
(5) Stopping ventilation, adding 10mL of ethanol into the product obtained in the step (4), centrifuging for 5min at a rotation speed of 5000rpm/min, and washing the collected product with a cyclohexane/ethanol mixed solution with a volume ratio of 2/1 for 3 times to obtain the palladium-chromium/ferroferric oxide heterogeneous nanoflower electrocatalyst.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
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