CN114618551A - Supported nano alloy catalyst and universal preparation method - Google Patents
Supported nano alloy catalyst and universal preparation method Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 42
- 239000000956 alloy Substances 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 34
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 238000005341 cation exchange Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 27
- 239000004005 microsphere Substances 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 4
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910015373 AuCo Inorganic materials 0.000 claims description 2
- 229910002711 AuNi Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021118 PdCo Inorganic materials 0.000 claims description 2
- 229910002669 PdNi Inorganic materials 0.000 claims description 2
- 229910002837 PtCo Inorganic materials 0.000 claims description 2
- 229910002836 PtFe Inorganic materials 0.000 claims description 2
- 229910002844 PtNi Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000005275 alloying Methods 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 229960003638 dopamine Drugs 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 229910000531 Co alloy Inorganic materials 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 229910000640 Fe alloy Inorganic materials 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 3
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 2
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 2
- KVDBPOWBLLYZRG-UHFFFAOYSA-J tetrachloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)(Cl)Cl KVDBPOWBLLYZRG-UHFFFAOYSA-J 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- FHKNFXAIEAYRKQ-UHFFFAOYSA-N [Cu].[Ir] Chemical compound [Cu].[Ir] FHKNFXAIEAYRKQ-UHFFFAOYSA-N 0.000 description 1
- XCEAGAJKBRACAD-UHFFFAOYSA-N [Cu].[Ru] Chemical compound [Cu].[Ru] XCEAGAJKBRACAD-UHFFFAOYSA-N 0.000 description 1
- PIOYDHPEUPDGHD-UHFFFAOYSA-N [Fe].[Ir] Chemical compound [Fe].[Ir] PIOYDHPEUPDGHD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- ITXSHZFXAHDNMK-UHFFFAOYSA-N iron ruthenium Chemical compound [Fe].[Ru] ITXSHZFXAHDNMK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
Abstract
The invention relates to a load type nanometer alloy catalyst and a preparation method thereof, firstly, silicon dioxide nanometer particles are used as a template, and metal ions are introduced through cation exchange to form a precursor containing stable metal (hydrogen) oxide; and (3) coating a layer of polymer on the surface of the precursor while soaking noble metal ions, carrying out high-temperature treatment in inert gas to realize metal alloying, and etching the template to obtain the hollow carbon nitrogen carrier-loaded alloy nano-frame catalyst. The prepared catalyst takes carbon nitrogen with a hollow structure as a carrier, and small-size nano-frame alloy is uniformly loaded on the surface of the catalyst. The invention adopts a double-layer space limited pyrolysis strategy, a surfactant is not needed in the alloy preparation process, and the synthesized nano-framework alloy has small size and uniform distribution, thereby not only overcoming the problem that the surfactant residue shields active sites, but also solving the problem of high-temperature agglomeration of nano-particles. The method has universality and is suitable for synthesis of various nano-framework alloy catalysts. The catalyst has excellent performance and can be used in the field of electrocatalysis.
Description
Technical Field
The invention belongs to the technical field of preparation of nano-alloy catalysts, relates to a supported nano-alloy catalyst and a universal preparation method, and particularly relates to a method for preparing a hollow carbon nitrogen microsphere supported noble metal-non-noble metal nano-alloy composite material by a double-layer space confinement strategy.
Background
Noble metal alloying is one of the important methods for solving the problems of scarcity and high price of noble metals, and has attracted extensive attention of researchers. The other transition metal is introduced into the crystal lattice of the noble metal to adjust the electron and the crystal lattice structure, so that the use amount of the noble metal is reduced, the cost is reduced, and the electrocatalytic activity can be improved. It is reported that the introduction of inexpensive 3d transition metals (e.g., Fe, Co, Ni, Cu, Ln, Zn, etc.) into the lattice of the Pt catalyst can weaken the adsorption of oxygen species, thereby improving electrocatalytic performance.
The hollow structure is beneficial to increasing the load sites of active species, so that the contact area with reactants is increased, and meanwhile, the regulation and control of the alloy structure are also beneficial to improving the utilization rate of the active sites. In addition, the introduction of nitrogen element is also beneficial to the stabilization of the active center.
However, a surfactant is inevitably used in the synthesis process of the small-sized alloy catalyst, and there is a problem that a residue remains on the surface of the alloy after removal, burying active sites, and seriously lowering the utilization rate of platinum. Meanwhile, the problem of high-temperature agglomeration of the nano particles is also urgently solved. Therefore, the synthesis of small-sized, uniformly distributed alloy catalysts without the use of surfactants is a great challenge at present.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a supported nano alloy catalyst and a universal preparation method. Aiming at the prior technical situation that in the process of preparing a noble metal nano alloy catalyst at present, during high-temperature reduction or pyrolysis, metal is easy to agglomerate due to the high surface free energy of the noble metal, and the size of alloy nano particles is inevitably controlled by a surfactant in the synthesis process, a universal method for preparing a noble metal @ non-noble metal nano frame alloy/hollow carbon nitrogen carrier composite material by a double-layer space limited domain strategy is provided. The invention also aims to provide application of the nano alloy catalyst.
Technical scheme
A supported nano alloy catalyst is characterized in that: the hollow carbon nitrogen microsphere is used as a carrier, the alloy of noble metal and other metals is used as an active component, and the alloy is loaded on the carrier to form the alloy nano-frame catalyst loaded by the hollow carbon nitrogen carrier.
The universal preparation method of the supported nano alloy catalyst is characterized by comprising the following steps:
step 1: ultrasonically dispersing the silicon dioxide microspheres and metal salt into deionized water, wherein the concentration of the silicon dioxide microspheres is 0.04 g/mL; after cation exchange reaction for 12-16h at 80 ℃, centrifuging, separating and drying to obtain the silicon dioxide microspheres containing metal ions;
the silicon dioxide microspheres containing metal ions are put into the air atmosphere and heated to 350 ℃ and 400 ℃ at a speed of 10 ℃/min and then the temperature is kept for 2h to obtain the silicon dioxide/metal (hydrogen) oxide precursor
Step 2: dispersing the precursor in a mixed solution of deionized water and ethanol, performing ultrasonic dispersion uniformly, simultaneously adding a mixed solution containing a noble metal source, performing immersion reaction for 4-8h at room temperature, adding a mixed solution of water and ethanol containing dopamine hydrochloride, adding a mixed solution containing ammonia water after 3h, and continuously stirring for reaction for 12-16h at room temperature;
after the reaction is finished, transferring the product to a tubular furnace in the nitrogen atmosphere after centrifugation, water and ethanol washing, separation and drying, heating to 600-900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, finally placing the calcined product into an ammonium bifluoride aqueous solution, reacting at 80 ℃ for 2-6h, and removing the template to obtain the hollow carbon nitrogen microsphere load alloy nano-frame material.
The metal salt is one of chloride, nitrate, sulfate and acetylacetone salt of Cr, Mn, Ni, Co, Fe, Cu, Zn, Al, Ag, Cd, In, Sn, Ce, Sm, Eu or Gd.
The noble metal source is one of acid, chloroaminoate, chloride and acetate of Ru, Pd, Ir, Pt or Au.
V in the mixed solution of the deionized water and the ethanolWater (W)﹕VEthanol＝1﹕1。
The concentration range of the metal salt is 2.47mol/L-1.03 mol/L.
The concentration range of the noble metal source is 1.93-3.86 mmol/L.
The concentration range of the dopamine hydrochloride is 0.1-0.15 mol/L.
The concentration of the ammonium bifluoride is 1.25 mol/L.
The alloy nano-framework comprises PtCu, PtNi, PtCo, PtFe, PdNi, PdCo, RuFe, RuCu, AuCo, AuNi, IrFe or IrCu.
Advantageous effects
The invention provides a supported nano alloy catalyst and a universal preparation method, firstly, silicon dioxide nano particles are used as a template, metal ions are introduced through cation exchange, and then a precursor containing stable metal (hydrogen) oxide is formed through roasting; the precursor is further impregnated with noble metal ions, a layer of polymer is coated on the surface of the precursor, then the precursor is treated at high temperature in inert gas to realize metal alloying, and finally the template is etched to obtain the alloy nano-frame catalyst loaded by the hollow carbon nitrogen carrier. The prepared catalyst takes carbon nitrogen with a hollow structure as a carrier, and small-size nano-frame alloy is uniformly loaded on the surface of the catalyst. Compared with the prior art, the invention adopts a double-layer space limited pyrolysis strategy, the preparation process of the alloy does not need a surfactant, and the synthesized nano-framework alloy has small size and uniform distribution, thereby not only overcoming the problem that the surfactant remains to shield active sites, but also solving the problem of high-temperature agglomeration of nano-particles. In addition, the method has universality, is suitable for synthesis of various nano-framework alloy catalysts, has the advantages of simple process, controllable preparation, large-scale synthesis and the like, and can be used in the field of electrocatalysis.
Drawings
FIG. 1 is an SEM image of a hollow carbon-nitrogen-supported platinum-cobalt alloy nano-framework catalyst prepared in example 1
FIG. 2 is a TEM image of a hollow carbon-nitrogen-supported platinum-cobalt alloy nano-framework catalyst prepared in example 1
FIG. 3 is an SEM image of a hollow carbon nitrogen-supported platinum-nickel alloy nano-framework catalyst prepared in example 2
FIG. 4 is a TEM image of the hollow carbon nitrogen-supported platinum-nickel alloy nano-framework catalyst prepared in example 2
FIG. 5 is an SEM image of a hollow carbon nitrogen-supported platinum-iron alloy nano-framework catalyst prepared in example 3
FIG. 6 is a TEM image of the hollow carbon nitrogen-supported platinum-iron alloy nano-framework catalyst prepared in example 3
FIG. 7 is an SEM image of a hollow carbon nitrogen-supported platinum-copper alloy nano-framework catalyst prepared in example 4
FIG. 8 is a TEM image of the hollow carbon nitrogen-supported platinum-copper alloy nano-framework catalyst prepared in example 4
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the invention provides a preparation method of a universal nano alloy catalyst, which takes silicon dioxide microspheres as a template and an inner layer limited domain barrier, forms metal (hydrogen) oxide in the template through cation exchange and roasting, soaks noble metal ions by a wet chemical method, takes polydopamine as an outer layer limited domain barrier, realizes alloying through synchronous pyrolysis, and finally removes the template to obtain the hollow carbon nitrogen loaded alloy nano frame catalyst, wherein the preparation method mainly comprises the following steps:
example 1
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of cobalt nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring, reacting for 16h, centrifuging, separating, and drying in vacuum after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 0.0386mmol of chloroplatinic acid into the solution, wherein the volume ratio of 10mL is 1: 1 for 6 hours, then weighing 1.0mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol, wherein the volume ratio of 1: 1, stirring and reacting for 5h, and adding 8mL of ammonia waterIs 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon-nitrogen-loaded platinum-cobalt alloy nano-frame material.
Example 2
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of nickel nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring for 14h, centrifuging, separating, performing vacuum drying after the reaction is finished, and roasting the obtained product at 400 ℃ in an air atmosphere for 30min to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 0.0386mmol of chloroplatinic acid in 10mL of ethanol with the volume ratio of 1: 1 for 6 hours, then weighing 1.2mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol, wherein the volume ratio of 1: 1, stirring and reacting for 3 hours, and then adding 8mL of ammonia water containing 2mL of ammonia water in a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon nitrogen-loaded platinum-nickel alloy nano frame material.
Example 3
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of ferric nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring for 12h, centrifuging, separating, and performing vacuum drying after the reaction is finished, and roasting the obtained product at 400 ℃ in an air atmosphere for 30min to obtain a precursor.
And 2, step: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 0.0386mmol of chloroplatinic acid in 10mL of ethanol with the volume ratio of 1: 1 for 6 hours, then weighing 1.5mmol of dopamine, dissolving in 30mL of mixed solution of water and ethanol with the volume ratio of 1: 1, adding a water and ethanol mixed solution, stirring and reacting for 3 hours, and then adding a solution containing 2m8mL of L-ammonia water in a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon-nitrogen-loaded platinum-iron alloy nano-frame material.
Example 4
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of copper nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring, reacting for 14h, centrifuging, separating, and drying in vacuum after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 0.0386mmol of chloroplatinic acid in 10mL of ethanol with the volume ratio of 1: 1 for 6 hours, then weighing 1.2mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol, wherein the volume ratio of 1: 1, stirring and reacting for 6 hours, and then adding 8mL of ammonia water containing 2mL of ammonia water in a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon-nitrogen-loaded platinum-copper alloy nano frame material.
Example 5
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of cobalt nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring, reacting for 14h, centrifuging, separating, and drying in vacuum after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 0.0257mmol of tetraammine dichloride palladium into the solution, wherein the volume ratio of 10mL is 1: 1 for 6 hours, and then weighing 1.2mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol with a volume ratio of 1: 1, adding the mixed solution of water and ethanol into the solution, and stirring the solutionAfter 6h, 8mL of ammonia containing 2mL of water at a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon-nitrogen-loaded palladium-cobalt alloy nano-frame material.
Example 6
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of nickel nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring and reacting for 14h, centrifuging, separating, and performing vacuum drying after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 0.0257mmol of tetraamminepalladium chloride in 10mL of a volume ratio of 1: 1 for 6 hours, then weighing 1.2mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol, wherein the volume ratio of 1: 1, stirring and reacting for 6 hours, and then adding 8mL of ammonia water containing 2mL of ammonia water in a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon-nitrogen-loaded palladium-nickel alloy nano frame material.
Example 7
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of ferric nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring, reacting for 12h, centrifuging, separating, and drying in vacuum after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 0.0386mmol of ruthenium acetate in 10mL of a volume ratio of 1: 1 for 6 hours, and then weighing 1.5mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol with a volume ratio of 1: 1 water and ethanolThe solution was added thereto and stirred for reaction for 3 hours, after which 8mL of ammonia water containing 2mL of ammonia water at a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon nitrogen-loaded ruthenium-iron alloy nano frame material.
Example 8
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of copper nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring, reacting for 14h, centrifuging, separating, and drying in vacuum after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
And 2, step: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 0.0386mmol of ruthenium acetate in 10mL of a volume ratio of 1: 1 for 6 hours, then weighing 1.2mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol, wherein the volume ratio of 1: 1, stirring and reacting for 6 hours, and then adding 8mL of ammonia water containing 2mL of ammonia water in a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon nitrogen-loaded ruthenium-copper alloy nano frame material.
Example 9
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of cobalt nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring for 14h, centrifuging, separating, performing vacuum drying after the reaction is finished, and roasting the obtained product at 400 ℃ in an air atmosphere for 30min to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, and adding 0.0257mmol of chloroauric acid in 10mL of a volume ratio of 1: 1 for 6 hours, then weighing 1.2mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol, wherein the volume ratio of 1:1, stirring and reacting for 6 hours, and then adding 8mL of ammonia water containing 2mL of ammonia water in a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon-nitrogen-loaded gold-cobalt alloy nano frame material.
Example 10
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of nickel nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring and reacting for 14h, centrifuging, separating, and performing vacuum drying after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, and adding 0.0257mmol of chloroauric acid in 10mL of a volume ratio of 1: 1 for 6 hours, then weighing 1.2mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol, wherein the volume ratio of 1: 1, and adding a water and ethanol mixed solution into the solution, stirring the solution for reaction for 6 hours, and then adding 8mL of ammonia water containing 2mL of ammonia water and having a volume ratio of 1: 1, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon nitrogen-loaded gold-nickel alloy nano frame material.
Example 11
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of ferric nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring, reacting for 12h, centrifuging, separating, and drying in vacuum after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 10mL of iridium tetrachloride hydrate containing 0.0193mmol of iridium tetrachloride in a volume ratio of 1: 1 in a mixed solution of water and ethanol, the reaction mixture was stirred for 6 hours, and then 1.5mmol of the compound was weighedDopamine dissolved in 30mL of a volume ratio of 1: 1, stirring and reacting for 3 hours, and then adding 8mL of ammonia water containing 2mL of ammonia water in a volume ratio of 1: 1, continuously stirring the mixed solution at room temperature for reaction for 12 hours, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating the product to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And removing the template in the aqueous solution reaction 2h to obtain the hollow carbon-nitrogen-loaded iridium iron alloy nano frame material.
Example 12
Step 1: dispersing 500mg of silicon dioxide microspheres in 40mL of water, adding 1g of copper nitrate, performing ultrasonic dispersion for 20min, reacting at 80 ℃, stirring, reacting for 14h, centrifuging, separating, and drying in vacuum after the reaction is finished, and roasting the obtained product at 400 ℃ for 30min in an air atmosphere to obtain a precursor.
Step 2: dispersing the precursor into a solution containing 20mL of water and 20mL of ethanol, adding 10mL of iridium tetrachloride hydrate containing 0.0193mmol of iridium tetrachloride in a volume ratio of 1: 1 for 6 hours, then weighing 1.2mmol of dopamine, dissolving in 30mL of a mixed solution of water and ethanol, wherein the volume ratio of 1: 1, stirring and reacting for 6 hours, and then adding 8mL of ammonia water containing 2mL of ammonia water in a volume ratio of 1: 1, continuously stirring the mixed solution at room temperature for reaction for 12 hours, after the reaction is finished, putting the product into a tubular furnace in nitrogen atmosphere, heating the product to 900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and finally putting 0.05mol of NH into the calcined product4HF2And (5) removing the template in the aqueous solution reaction for 2h to obtain the hollow carbon-nitrogen-loaded iridium-copper alloy nano-frame material.
Claims (10)
1. A supported nano alloy catalyst is characterized in that: the hollow carbon nitrogen microsphere is used as a carrier, the alloy of noble metal and other metals is used as an active component, and the alloy is loaded on the carrier to form the alloy nano-frame catalyst loaded by the hollow carbon nitrogen carrier.
2. The universal preparation method of the supported nano alloy catalyst, which is disclosed by claim 1, is characterized by comprising the following steps of:
step 1: ultrasonically dispersing the silicon dioxide microspheres and metal salt into deionized water, wherein the concentration of the silicon dioxide microspheres is 0.04 g/mL; after cation exchange reaction for 12-16h at 80 ℃, centrifuging, separating and drying to obtain the silicon dioxide microspheres containing metal ions;
the silicon dioxide microspheres containing metal ions are put into the air atmosphere and heated to 350 ℃ and 400 ℃ at a speed of 10 ℃/min and then the temperature is kept for 2h to obtain the silicon dioxide/metal (hydrogen) oxide precursor
Step 2: dispersing the precursor in a mixed solution of deionized water and ethanol, performing ultrasonic dispersion uniformly, simultaneously adding a mixed solution containing a noble metal source, performing immersion reaction for 4-8h at room temperature, adding a mixed solution of water and ethanol containing dopamine hydrochloride, adding a mixed solution containing ammonia water after 3h, and continuously stirring for reaction for 12-16h at room temperature;
after the reaction is finished, transferring the product to a tubular furnace in the nitrogen atmosphere after centrifugation, water and ethanol washing, separation and drying, heating to 600-900 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, finally placing the calcined product into an ammonium bifluoride aqueous solution, reacting at 80 ℃ for 2-6h, and removing the template to obtain the hollow carbon nitrogen microsphere load alloy nano-frame material.
3. The method of claim 2, wherein: the metal salt is one of chloride, nitrate, sulfate and acetylacetone salt of Cr, Mn, Ni, Co, Fe, Cu, Zn, Al, Ag, Cd, In, Sn, Ce, Sm, Eu or Gd.
4. The method of claim 2, wherein: the noble metal source is one of acid, chloroaminoate, chloride and acetate of Ru, Pd, Ir, Pt or Au.
5. The method of claim 2, wherein: v in the mixed solution of the deionized water and the ethanolWater (W)﹕VEthanol＝1﹕1。
6. The method of claim 2, wherein: the concentration range of the metal salt is 2.47mol/L-1.03 mol/L.
7. The method of claim 2, wherein: the concentration range of the noble metal source is 1.93-3.86 mmol/L.
8. The method of claim 2, wherein: the concentration range of the dopamine hydrochloride is 0.1-0.15 mol/L.
9. The method of claim 2, wherein: the concentration of the ammonium bifluoride is 1.25 mol/L.
10. The method of claim 2, wherein: the alloy nano-framework comprises PtCu, PtNi, PtCo, PtFe, PdNi, PdCo, RuFe, RuCu, AuCo, AuNi, IrFe or IrCu.
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