CN117512646A - Heterojunction nano-ring electrocatalyst and preparation method and application thereof - Google Patents
Heterojunction nano-ring electrocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN117512646A CN117512646A CN202311505925.7A CN202311505925A CN117512646A CN 117512646 A CN117512646 A CN 117512646A CN 202311505925 A CN202311505925 A CN 202311505925A CN 117512646 A CN117512646 A CN 117512646A
- Authority
- CN
- China
- Prior art keywords
- electrocatalyst
- ring
- heterojunction nano
- porous graphene
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 63
- 239000002063 nanoring Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000004767 nitrides Chemical class 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- -1 VIB group transition metal Chemical class 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims description 32
- 239000006185 dispersion Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 11
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 11
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- 150000003057 platinum Chemical class 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000013094 zinc-based metal-organic framework Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000012621 metal-organic framework Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000001132 ultrasonic dispersion Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- 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
- C25B11/057—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
Abstract
The invention discloses a heterojunction nano-ring electrocatalyst, a preparation method and application thereof, wherein the heterojunction nano-ring electrocatalyst is a porous graphene net loaded with platinum-based intermetallic compound-nitride, the metal is VB group and/or VIB group transition metal, the mass fraction of the platinum-based intermetallic compound is 10-20%, and the mass fraction of the nitride is 5-10%. According to the preparation method, a metal-organic framework derived carbon template strategy is adopted, the Pt-based intermetallic compound-nitride heterojunction with the nano cyclic structure is firmly anchored on the porous graphene net, and the preparation method is simple in preparation process, low in raw material, convenient in source, environment-friendly and high in repeatability. The heterojunction nano-ring electrocatalyst provided by the invention can show excellent hydrogen evolution catalytic activity and durability under high current density, and is beneficial to large-scale commercial application.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a heterojunction nano-ring electrocatalyst and a preparation method and application thereof.
Background
Under the conditions of green energy transformation requirement and serious environmental pollution, development of green, efficient and sustainable clean energy is urgently needed to obtainReplacing traditional fossil fuel systems. Wherein the hydrogen energy (H) 2 ) As an environmentally friendly energy carrier with high energy density, attention has been paid to a large number of researchers. Among the various hydrogen production approaches, electrolytic water hydrogen production is considered as a sustainable hydrogen production approach with great prospect due to the advantages of simple operation, no emission of harmful greenhouse gases in the hydrogen production process, and flexible coupling with renewable energy sources (such as wind energy or solar energy). Electrocatalytic water splitting involves cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER). Among them, platinum (Pt) is currently known to perform best for HER reactions, but it still presents challenges of high cost, slow kinetics and poor stability, which significantly limits its large-scale commercial application. In view of this, the development of inexpensive, high catalytic activity and long durability HER catalysts by reducing Pt usage and incorporating inexpensive transition metals is now the focus of research in the academy and industry.
Pt-based intermetallic compounds consisting of noble metals Pt and transition metals (M) are very promising HER electrocatalytic alloy materials (adv. Mater.2023,35,2302067). Thanks to the strong d-orbital interaction and ordered stoichiometry, the intermetallic compound not only shows the optimization of the electronic structure and the improvement of the catalytic efficiency, but also realizes the stability of enthalpy, and the stability of the catalyst is greatly improved. However, the intermetallic compounds alone are susceptible to agglomeration due to strong cohesive energy, and the active sites are not fully utilized, and the catalytic activity is still required for further release.
Meanwhile, transition Metal Nitrides (TMNs) are ideal candidates for pure water or seawater decomposition due to their high conductivity and strong corrosion resistance. However, since TMN adsorbs hydrogen atom at the active site, gibbs free energy (. DELTA.G H* ) Less than optimal, most of the TMN-based electrocatalysts reported previously have poorer HER catalytic performance than Pt (ChemCatChem, 2020,12,2962-296). However, due to the high conductivity and strong corrosion resistance of these TMNs, they can be composited with Pt-based intermetallics to achieve an overall improvement in catalytic activity and durability, but the rational construction of metal nitrides and Pt-based intermetallics remains a major challenge.
In addition, compounding a metal-based material with a carbon-based material is generally considered to be an effective solution to the problem of easy agglomeration of the metal-based catalyst. Not only can effectively promote the dispersion of the metal-based material and the exposure of the active site of the metal-based material, but also can greatly improve the corrosion resistance of the catalyst in the strong acid/alkaline electrolyte and enhance the catalytic stability due to the introduction of the carbon material (adv. Mater.2023,35,2303). The carbon-based carriers which have been developed so far include porous carbon, graphene, carbon nanotubes, etc., but the carbonaceous material/metal-based composite catalyst which has been developed so far also has problems of relatively poor proton transport ability, such as slow transfer of reaction intermediates and gas product H 2 Is insufficient in its escape ability. When such materials are used as catalysts, they tend to have less desirable hydrogen evolution catalytic activity when applied under conditions that meet the high current densities required for industrial water electrolysis to produce hydrogen. Therefore, further large-scale industrial application of the material is always hindered.
Disclosure of Invention
In order to solve the technical problems, the invention provides the heterojunction nano-ring electrocatalyst, and the preparation method and application thereof, wherein the heterojunction nano-ring electrocatalyst is a porous graphene net loaded with platinum-based intermetallic compound-nitride, and the preparation method has the advantages of simple process, cheap raw materials, convenient sources, environmental friendliness and high repeatability, and the obtained electrocatalyst has excellent hydrogen evolution catalytic activity under high current density, thereby being beneficial to larger-scale commercial application.
The invention is realized by the following technical scheme:
the first aspect of the invention provides a heterojunction nano-ring electrocatalyst which is a porous graphene net loaded with platinum-based intermetallic compound-nitride, wherein the metal is VB group and/or VIB group transition metal, the mass fraction of the platinum-based intermetallic compound is 10-20%, and the mass fraction of the nitride is 5-10%.
According to the invention, the nitrogen-doped porous graphene net is used as a substrate, so that the stacking of the Pt-based intermetallic compound-nitride heterojunction can be effectively inhibited due to the high specific surface area and the doping of nitrogen element, and the uniform dispersion of the Pt-based intermetallic compound-nitride heterojunction is promoted. Meanwhile, the strong coupling effect between the carbon matrix and the nano ring can be realized by the double-solvent adsorption and carbothermic reduction method, so that the Pt-based intermetallic compound-nitride heterojunction is firmly anchored. And the porous nature of the graphene net can promote proton transmission of the catalyst in the working process, so that the catalytic activity of the catalyst can be greatly improved. On the other hand, due to the special nano-ring structure of the Pt-based intermetallic compound-nitride heterojunction, active sites can be effectively exposed and excellent stability of structural properties can be exhibited during operation. Meanwhile, the existence of the metal nitride in the heterostructure can further improve the conductivity and corrosion resistance of the catalyst, and the electronic structure of the Pt-based intermetallic compound is modulated, so that the HER reaction energy barrier is further reduced. These outstanding advantages make the catalyst exhibit excellent performance for electrocatalytic hydrogen evolution reactions.
Further, the transition metal is one or more of W, mo and V.
The second aspect of the invention provides a preparation method of the heterojunction nano-ring electrocatalyst according to the first aspect, comprising the following steps:
s1: mixing a zinc-based metal organic frame material with a stripping agent, heating in an inert gas environment, and pickling to remove zinc impurities to obtain a nitrogen-doped porous graphene net;
s2: dispersing the nitrogen-doped porous graphene net in an organic solvent to obtain a dispersion liquid, adding a platinum salt solution and a transition metal salt solution into the dispersion liquid, drying, and then performing heating treatment in an inert gas environment to obtain the heterojunction nano-ring electrocatalyst.
According to the preparation method, a metal-organic framework derived carbon template strategy is adopted, and the Pt-based intermetallic compound-nitride heterojunction with the nano cyclic structure is firmly anchored on the ultrathin porous graphene net. The Pt-based metal organic framework material is derived into a nitrogen-doped porous graphene net by adopting a fused salt assisted thermal stripping method, then the material is taken as a substrate, metal salt containing Pt and transition metal is adsorbed on the nitrogen-doped porous graphene net by adopting a double-solvent adsorption method, and the porous graphene net loaded Pt-based intermetallic compound-nitride heterojunction nano-ring electrocatalyst is prepared by high-temperature thermal reduction.
The preparation method provided by the invention has the advantages of simple process, cheap raw materials, convenient sources, environmental friendliness and high repeatability, and a large number of porous graphene network supported platinum-based intermetallic compound-nitride heterojunction nano-rings are prepared and generated. The method can be extended to the synthesis of a multi-element Pt-based intermetallic compound and multi-element metal nitride heterojunction supported by a porous graphene network; or a porous graphene network with adjustable thickness and porosity supported by the porous graphene network, and a complex of a multi-element Pt-based intermetallic compound and a multi-element metal nitride heterojunction, which shows quite universality and expansibility.
Further, in step S1, the preparation method of the zinc-based organic framework material includes: mixing the aqueous solution of zinc nitrate hexahydrate and dimethyl imidazole, stirring for reaction, separating precipitate and drying to obtain the zinc-based metal organic framework material.
Further, the mole ratio of the zinc nitrate hexahydrate to the dimethyl imidazole is 1 (8-10).
Further, in the step S1, the adding amount of the zinc-based metal organic framework material is 200-500 mg.
In step S1, the stripping agent is potassium chloride and lithium chloride, and the mass ratio of the potassium chloride to the lithium chloride is (4-10): 1.
Further, in step S1, the amount of the stripping agent added is 3 to 5g.
In step S1, the acid washing is performed with dilute acid, where the dilute acid is dilute hydrochloric acid or dilute sulfuric acid, and the concentration is 0.5-2M.
Further, in step S1, the temperature of the heating treatment is 900-1000 ℃ and the time is 2-4 h.
Further, in the step S2, the concentration of the nitrogen doped porous graphene net in the dispersion liquid is 5-15 mg/mL.
Further, in step S2, the concentration of the platinum salt solution is 0.2 to 0.3M, and the concentration of the transition metal salt is set with reference to the concentration of the platinum salt according to the different element types of the platinum-based intermetallic compound.
Further, in step S2, the platinum salt is preferably H 2 PtCl 6 The transition metal salt is preferably an anhydrous chloride salt.
Further, in the step S2, the temperature of the heating treatment is 900-1000 ℃ and the time is 2-4 h.
Specifically, the preparation method of the heterojunction nano-ring electrocatalyst comprises the following steps:
s1: mixing the aqueous solution of zinc nitrate hexahydrate and dimethyl imidazole, stirring and reacting for 30-40 min, standing for 4-5 h, separating and precipitating, and drying to obtain the zinc-based metal organic frame material; fully mixing and grinding a zinc-based metal organic frame material and a stripping agent, putting the mixture into a tube furnace with inert atmosphere for heating treatment, soaking the mixture into deionized water for many times, washing the mixture with acid to remove salt and zinc impurities, washing the mixture with deionized water again, and drying the washed mixture to obtain a nitrogen-doped porous graphene net;
s2: dispersing the nitrogen-doped porous graphene net in an organic solvent to obtain a dispersion liquid, adding DMF solution for dissolving platinum salt and transition metal salt into the dispersion liquid, sucking supernatant, drying bottom sediment, and then placing the dried bottom sediment into a tube furnace in inert atmosphere for heating treatment to obtain the heterojunction nano-ring electrocatalyst.
The third aspect of the invention provides a three-electrode electrolytic cell comprising a working electrode, a counter electrode, a reference electrode and an electrolyte, wherein the heterojunction nano-ring electrocatalyst according to the first aspect is deposited on the working electrode.
Further, the method for depositing the heterojunction nano-ring electrocatalyst on the working electrode comprises the following steps: dispersing the heterojunction nano-ring electrocatalyst in ethanol containing perfluorinated sulfonic acid group polymer (Nafion) to obtain a dispersion liquid, and dripping the dispersion liquid on the working electrode until the loading mass reaches 0.8-1 mg cm -2 。
Further, the working electrode is a glassy carbon electrode, the counter electrode is a carbon rod, and the reference electrode is an Hg/HgO electrode.
Further, the electrolyte is a hydrogen saturated KOH solution.
According to a fourth aspect of the invention, there is provided the use of the heterojunction nano-ring electrocatalyst according to the first aspect or the three-electrode cell according to the third aspect in the electrolysis of water.
The electrocatalyst obtained by the invention has excellent hydrogen evolution catalytic activity and durability under high current density, and is beneficial to large-scale commercial application.
The invention has the beneficial effects that:
1. the invention provides a heterojunction nano-ring electrocatalyst with far-beyond-commercial Pt/C electrocatalyst catalytic activity for electrolytic water hydrogen evolution reaction. The nitrogen doped graphene net derived from the metal organic framework material has high conductivity, high specific surface area and rich micro-mesoporous pores, effectively improves electron transfer capability, enhances mass transfer capability, fully exposes active sites, promotes transfer of reaction intermediates and generated gas products in hydrogen evolution reaction, has higher reaction kinetics, and can be used as a carbon substrate to firmly anchor Pt-based intermetallic compound-nitride heterojunction nano-rings. More importantly, the catalyst has high catalytic activity, long-time corrosion resistance and high stability due to the construction of the heterostructure of the Pt-based intermetallic compound and the metal nitride, and the Pt-based intermetallic compound-nitride heterojunction nano ring structure can effectively prevent structural damage and activity attenuation of the catalyst in the reaction process while effectively improving the utilization rate of active sites.
2. The preparation method provided by the invention has the advantages of simple process, cheap raw materials, convenient sources, environmental friendliness and high repeatability. The method can be extended to the synthesis of a multi-element Pt-based intermetallic compound and multi-element metal nitride heterojunction supported by a porous graphene network; or a porous graphene network with adjustable thickness and porosity supported by the porous graphene network, and a complex of a multi-element Pt-based intermetallic compound and a multi-element metal nitride heterojunction, which shows quite universality and expansibility.
3. The heterojunction nano-ring electrocatalyst obtained by the invention has excellent hydrogen evolution catalytic activity and durability under high current density, and is beneficial to larger-scale commerceAnd (5) chemical application. In a KOH electrolyte of 1M, the overpotential of the catalyst when hydrogen evolution reaction is carried out is eta respectively 10mA·cm-2 =28 mV and η 500mA·cm-2 =370 mV, and can hold 10ma·cm -2 And the large current density of (2) reaches 26h without degradation.
Drawings
FIG. 1 shows Pt as example 1 of the present invention 2 X-ray powder diffraction pattern of W-WN@PGM electrocatalyst.
FIG. 2 shows Pt as example 1 of the present invention 2 Transmission electron microscopy of W-wn@pgm electrocatalyst.
FIG. 3 is a Pt of comparative example 1 of the present invention 3 Transmission electron microscopy of sn@pgm electrocatalyst.
FIG. 4 shows Pt as example 1 of the present invention 2 W-WN@PGM, pt of comparative example 1 3 HER linear sweep voltammogram for sn@pgm and 20wt% pt/C electrocatalyst.
FIG. 5 shows Pt as example 1 of the present invention 2 HER current density versus time plot for W-wn@pgm electrocatalyst.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used, unless otherwise specified, are commercially available.
Example 1
Heterojunction nano-ring electrocatalystPt-loaded 2 W intermetallic-nitride porous graphene network (Pt 2 W-WN@PGM), the Pt 2 The mass fraction of W is 10%, the mass fraction of WN is 5%, and the preparation method comprises the following steps:
s1: 0.89g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and 1.64g of dimethyl imidazole are respectively dissolved in 40mL of deionized water, then the solutions are mixed, stirred and reacted for 30min, then the mixture is stood for 4h, white precipitate is separated and dried, and the zinc-based metal organic frame material is obtained; fully mixing 300mg of zinc-based metal organic frame material with 8g of KCl and 1g of LiCl, grinding, putting into a tube furnace in nitrogen atmosphere, heating at 900 ℃ for 4 hours, soaking for many times with deionized water to remove salt, washing residual zinc impurities with 1M dilute hydrochloric acid, washing with deionized water again, and drying to obtain a nitrogen-doped porous graphene net;
s2: dispersing 40mg of nitrogen-doped porous graphene net in 4mL of n-ethanol, performing ultrasonic dispersion uniformly to obtain a dispersion liquid, and dissolving 0.265. 0.265M H in 0.2mL of the dispersion liquid 2 PtCl 6 ·(H 2 O) 6 And 0.2M WCl 6 Adding DMF solution of (B) into the dispersion, continuing ultrasonic dispersion for 1 hr, sucking supernatant, drying the bottom precipitate, and heating at 1000deg.C in a tube furnace in nitrogen atmosphere for 2 hr to obtain the heterojunction nano-ring electrocatalyst (Pt 2 W-WN@PGM)。
Fig. 1 is a heterojunction nano-ring electrocatalyst (Pt 2 W-WN@PGM), from which Pt can be seen 2 The derivative peak of W-WN@PGM is mainly attributed to Pt 2 W and WN simultaneously show a broad peak ascribed to carbon at about 26 degrees, which proves that the porous graphene net carries Pt 2 Successful synthesis of W intermetallic-tungsten nitride heterojunction nanoring complexes.
Fig. 2 is a heterojunction nano-ring electrocatalyst (Pt 2 W-WN@PGM), as can be seen from the TEM images of FIGS. 2 (a) - (c), pt 2 The W-WN@PGM material presents a structure that a two-dimensional ultrathin graphene net uniformly loads a nano ring, and the diameter of the nano ring is 50-100 nm; the high-power transmission electron microscope (HRTEM) of FIG. 2d clearly shows lattices at 0.19nm and 0.23nmStripes, which correspond to the (101) plane of WN and Pt, respectively 2 The (101) crystal face of W proves Pt 2 And forming a heterostructure of W and WN.
Example 2
Heterojunction nano-ring electrocatalyst, which is Pt-loaded 3 Porous graphene network of Mo intermetallic-nitride (Pt 3 Mo-MoN@PGM), said Pt 3 The mass fraction of Mo is 10%, the mass fraction of MoN is 5%, and the preparation method comprises the following steps:
s1: 0.89g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and 1.64g of dimethyl imidazole are respectively dissolved in 40mL of deionized water, then the solutions are mixed, stirred and reacted for 30min, then the mixture is stood for 4h, white precipitate is separated and dried, and the zinc-based metal organic frame material is obtained; fully mixing 300mg of zinc-based metal organic frame material with 8g of KCl and 1g of LiCl, grinding, putting into a tube furnace in nitrogen atmosphere, heating at 900 ℃ for 4 hours, soaking for many times with deionized water to remove salt, washing residual zinc impurities with 1M dilute hydrochloric acid, washing with deionized water again, and drying to obtain a nitrogen-doped porous graphene net;
s2: dispersing 40mg of nitrogen-doped porous graphene net in 4mL of n-ethanol, performing ultrasonic dispersion uniformly to obtain a dispersion liquid, and dissolving 0.265. 0.265M H in 0.2mL of the dispersion liquid 2 PtCl 6 ·(H 2 O) 6 And 0.15M MoCl 5 Adding DMF solution of (B) into the dispersion, continuing ultrasonic dispersion for 1 hr, sucking supernatant, drying the bottom precipitate, and heating at 1000deg.C in a tube furnace in nitrogen atmosphere for 2 hr to obtain the heterojunction nano-ring electrocatalyst (Pt 3 Mo-MoN@PGM)。
Example 3
Heterojunction nano-ring electrocatalyst, which is Pt-loaded 3 V intermetallic-nitride porous graphene network (Pt 3 V-VN@PGM), the Pt 3 The mass fraction of V is 10%, the mass fraction of VN is 5%, and the preparation method comprises the following steps:
s1: 0.89g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and 1.64g of dimethyl imidazole are respectively dissolved in 40mL of deionized water, then the solutions are mixed, stirred and reacted for 30min, then the mixture is stood for 4h, white precipitate is separated and dried, and the zinc-based metal organic frame material is obtained; fully mixing 300mg of zinc-based metal organic frame material with 8g of KCl and 1g of LiCl, grinding, putting into a tube furnace in nitrogen atmosphere, heating at 900 ℃ for 4 hours, soaking for many times with deionized water to remove salt, washing residual zinc impurities with 1M dilute hydrochloric acid, washing with deionized water again, and drying to obtain a nitrogen-doped porous graphene net;
s2: dispersing 40mg of nitrogen-doped porous graphene net in 4mL of n-ethanol, performing ultrasonic dispersion uniformly to obtain a dispersion liquid, and dissolving 0.265. 0.265M H in 0.2mL of the dispersion liquid 2 PtCl 6 ·(H 2 O) 6 And 0.15M VCl 6 Adding DMF solution of (B) into the dispersion, continuing ultrasonic dispersion for 1 hr, sucking supernatant, drying the bottom precipitate, and heating at 1000deg.C in a tube furnace in nitrogen atmosphere for 2 hr to obtain the heterojunction nano-ring electrocatalyst (Pt 3 V-VN@PGM)。
Example 4
Heterojunction nano-ring electrocatalyst, which is Pt-loaded 2 W 0.5 Mo 0.5 Intermetallic-nitride porous graphene network (Pt 2 W 0.5 Mo 0.5 -W 0.5 Mo 0.5 N@PGM), the Pt 2 W 0.5 Mo 0.5 Is 10% by mass, W 0.5 Mo 0.5 The mass fraction of N is 5%, and the preparation method comprises the following steps:
s1: 0.89g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and 1.64g of dimethyl imidazole are respectively dissolved in 40mL of deionized water, then the solutions are mixed, stirred and reacted for 30min, then the mixture is stood for 4h, white precipitate is separated and dried, and the zinc-based metal organic frame material is obtained; mixing 300mg zinc-based metal organic frame material with 8g KCl and 1g LiCl, grinding, heating at 900deg.C in a tube furnace under nitrogen atmosphere for 4 hr, soaking with deionized water for several times to remove salt, washing with 1M diluted hydrochloric acid to remove residual zinc impurities, and washing with deionized water againDrying to obtain a nitrogen-doped porous graphene net;
s2: dispersing 40mg of nitrogen-doped porous graphene net in 4mL of n-ethanol, performing ultrasonic dispersion uniformly to obtain a dispersion liquid, and dissolving 0.265. 0.265M H in 0.2mL of the dispersion liquid 2 PtCl 6 ·(H 2 O) 6 、0.1M WCl 6 And 0.1M MoCl 6 Adding DMF solution of (B) into the dispersion, continuing ultrasonic dispersion for 1 hr, sucking supernatant, drying the bottom precipitate, and heating at 1000deg.C in a tube furnace in nitrogen atmosphere for 2 hr to obtain the heterojunction nano-ring electrocatalyst (Pt 2 W 0.5 Mo 0.5 -W 0.5 Mo 0.5 N@PGM)。
Example 5
Heterojunction nano-ring electrocatalyst, which is supported Pt 2 W 1/3 Mo 1/3 V 1/3 Intermetallic-nitride porous graphene network (Pt 2 W 1/3 Mo 1/3 V 1/3 -W 1/3 Mo 1/3 V 1/3 N@PGM), the Pt 2 W 1/ 3 Mo 1/3 V 1/3 Is 10% by mass, W 1/3 Mo 1/3 V 1/3 The mass fraction of N is 5%, and the preparation method comprises the following steps:
s1: 0.89g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and 1.64g of dimethyl imidazole are respectively dissolved in 40mL of deionized water, then the solutions are mixed, stirred and reacted for 30min, then the mixture is stood for 4h, white precipitate is separated and dried, and the zinc-based metal organic frame material is obtained; fully mixing 300mg of zinc-based metal organic frame material with 8g of KCl and 1g of LiCl, grinding, putting into a tube furnace in nitrogen atmosphere, heating at 900 ℃ for 4 hours, soaking for many times with deionized water to remove salt, washing residual zinc impurities with 1M dilute hydrochloric acid, washing with deionized water again, and drying to obtain a nitrogen-doped porous graphene net;
s2: dispersing 40mg of nitrogen-doped porous graphene net in 4mL of n-ethanol, performing ultrasonic dispersion uniformly to obtain a dispersion liquid, and dissolving 0.265. 0.265M H in 0.2mL of the dispersion liquid 2 PtCl 6 ·(H 2 O) 6 、0.065M WCl 6 MoCl 0.065M 6 And 0.065M VCl 3 Adding DMF solution of (B) into the dispersion, continuing ultrasonic dispersion for 1 hr, sucking supernatant, drying the bottom precipitate, and heating at 1000deg.C in a tube furnace in nitrogen atmosphere for 2 hr to obtain the heterojunction nano-ring electrocatalyst (Pt 2 W 1/3 Mo 1/ 3 V 1/3 -W 1/3 Mo 1/3 V 1/3 N@PGM)。
Comparative example 1
Porous graphene network loaded Pt 3 Sn intermetallic electrocatalyst (Pt 3 Sn@pgm), the preparation method comprises the following steps:
s1: 0.89g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and 1.64g of dimethyl imidazole are respectively dissolved in 40mL of deionized water, then the solutions are mixed, stirred and reacted for 30min, then the mixture is stood for 4h, white precipitate is separated and dried, and the zinc-based metal organic frame material is obtained; fully mixing 300mg of zinc-based metal organic frame material with 8g of KCl and 1g of LiCl, grinding, putting into a tube furnace in nitrogen atmosphere, heating at 900 ℃ for 4 hours, soaking for many times with deionized water to remove salt, washing residual zinc impurities with 1M dilute hydrochloric acid, washing with deionized water again, and drying to obtain a nitrogen-doped porous graphene net;
s2: dispersing 40mg of nitrogen-doped porous graphene net in 4mL of n-ethanol, performing ultrasonic dispersion uniformly to obtain a dispersion liquid, and dissolving 0.265. 0.265M H in 0.2mL of the dispersion liquid 2 PtCl 6 ·(H 2 O) 6 And 0.1M SnCl 2 ·2H 2 Adding DMF solution of O into the dispersion liquid, continuing ultrasonic dispersion for 1 hour, sucking the supernatant, drying the bottom precipitate, and then placing into a tube furnace in nitrogen atmosphere for heating treatment at 1000 ℃ for 2 hours to obtain porous graphene network loaded Pt 3 Sn intermetallic electrocatalyst (Pt 3 Sn@PGM)。
FIG. 3 is a porous graphene network loaded Pt 3 Sn intermetallic electrocatalyst (Pt 3 Sn@PGM), from which it can be seen that Pt 3 The Sn@PGM material presents a structure that a two-dimensional graphene net uniformly loads nano particles, and the diameter of the nano particles is 100Around nm, the nanoring structure is not formed.
Test example 1
For Pt of example 1 2 W-WN@PGM electrocatalyst, pt of comparative example 1 3 The Sn@PGM electrocatalyst and commercial 20wt% Pt/C electrocatalyst were tested for electrocatalytic HER performance by:
an Hg/HgO electrode is used as a reference electrode, a carbon rod is used as a counter electrode, and an electrocatalyst is deposited on the glassy carbon electrode to be used as a working electrode. Linear sweep voltammetric testing was performed in a 1M KOH solution with electrolyte saturated with hydrogen at a sweep rate of 5 millivolts per second.
Wherein, the specific steps of the electro-catalyst deposited on the glassy carbon electrode are as follows: dispersing 5mg of electrocatalyst in a mixed solution of 970 mu L of ethanol and 30 mu L of Nafion, carrying out ultrasonic treatment until the mixture is uniformly dispersed, and dripping the slurry on a glassy carbon electrode until the loading mass reaches 0.85 mg.cm -2 。
The test results are shown in FIG. 4, FIG. 4 shows Pt according to example 1 of the present invention 2 W-WN@PGM, pt of comparative example 1 3 HER linear sweep voltammogram of Sn@PGM and 20wt% Pt/C electrocatalyst, from which it can be seen that Pt 2 W-WN@PGM electrocatalyst reaches 10 mA.cm -2 Only a 28mV overpotential is required for the current density of (c); to 500mA cm -2 Only 370mV overpotential is needed for the large current density of (2), which is far superior to Pt 3 HER performance of sn@pgm materials and commercial 20wt% pt/C catalyst.
Test example 2
For Pt of example 1 2 The W-WN@PGM electrocatalyst is subjected to an electrocatalytic HER performance test, and the test method comprises the following steps: pt (Pt) 2 W-WN@PGM electrocatalyst loading of 10mA.cm -2 HER current density in 1M KOH electrolyte.
The test results are shown in FIG. 5, FIG. 5 shows Pt according to example 1 of the present invention 2 HER current density versus time plot for W-WN@PGM electrocatalyst, from which Pt can be seen 2 The W-WN@PGM electrocatalyst is kept at 10 mA.cm -2 The current density of the catalyst reaches 26h without degradation, and the excellent hydrogen evolution catalytic stability and durability are reflected.
When the electrocatalysts prepared in examples 2 to 5 were used in the electrochemical hydrogen evolution reaction, the results were comparable to those obtained in example 1.
According to the invention, the porous graphene net is used for loading the Pt-based intermetallic compound-nitride heterojunction nano-ring, so that not only is the electron and proton transmission capacity enhanced, but also the uniform dispersion of the Pt-based intermetallic compound-nitride heterojunction nano-ring is promoted, and the exposure of active sites is promoted. In addition, the Pt-based intermetallic compound-nitride heterojunction nano-ring structure can not only realize full utilization of active sites, but also realize great improvement of intrinsic catalytic activity and durability. Thus, the electrocatalyst exhibits excellent electrocatalytic activity and durability in hydrogen evolution reactions at large currents.
It is to be understood that the above examples of the present invention are provided by way of illustration only and are not intended to limit the scope of the invention. It will be appreciated by persons skilled in the art that other variations or modifications may be made in the various forms based on the description above. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The heterojunction nano-ring electrocatalyst is characterized by being a porous graphene net loaded with platinum-based intermetallic compound-nitride, wherein the metal is VB group and/or VIB group transition metal, the mass fraction of the platinum-based intermetallic compound is 10-20%, and the mass fraction of the nitride is 5-10%.
2. The heterojunction nano-ring electrocatalyst according to claim 1, wherein said transition metal is one or more of W, mo, V.
3. A method for preparing the heterojunction nano-ring electrocatalyst according to claim 1, comprising the steps of:
s1: mixing a zinc-based metal organic frame material with a stripping agent, heating in an inert gas environment, and pickling to remove zinc impurities to obtain a nitrogen-doped porous graphene net;
s2: dispersing the nitrogen-doped porous graphene net in an organic solvent to obtain a dispersion liquid, adding a platinum salt solution and a transition metal salt solution into the dispersion liquid, drying, and then performing heating treatment in an inert gas environment to obtain the heterojunction nano-ring electrocatalyst.
4. The preparation method according to claim 3, wherein in step S1, the preparation method of the zinc-based metal organic framework material comprises the following steps: mixing the aqueous solution of zinc nitrate hexahydrate and dimethyl imidazole, stirring for reaction, separating precipitate and drying to obtain the zinc-based metal organic framework material.
5. The method according to claim 4, wherein the molar ratio of zinc nitrate hexahydrate to dimethyl imidazole is 1 (8-10).
6. The method according to claim 3, wherein in the step S1, the stripping agent is potassium chloride and lithium chloride, and the mass ratio of the potassium chloride to the lithium chloride is (4-10): 1.
7. The method according to claim 3, wherein in step S2, the concentration of the nitrogen-doped porous graphene network in the dispersion is 5 to 15mg/mL.
8. The method according to claim 3, wherein the concentration of the platinum salt solution in step S2 is 0.2 to 0.3M.
9. A three-electrode electrolytic cell comprising a working electrode, a counter electrode, a reference electrode, and an electrolyte, wherein the heterojunction nano-ring electrocatalyst according to claim 1 is deposited on the working electrode.
10. Use of the heterojunction nano-ring electrocatalyst of claim 1 or the three-electrode cell of claim 9 for the electrolysis of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311505925.7A CN117512646A (en) | 2023-11-13 | 2023-11-13 | Heterojunction nano-ring electrocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311505925.7A CN117512646A (en) | 2023-11-13 | 2023-11-13 | Heterojunction nano-ring electrocatalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117512646A true CN117512646A (en) | 2024-02-06 |
Family
ID=89754484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311505925.7A Pending CN117512646A (en) | 2023-11-13 | 2023-11-13 | Heterojunction nano-ring electrocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117512646A (en) |
-
2023
- 2023-11-13 CN CN202311505925.7A patent/CN117512646A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109841854B (en) | Nitrogen-doped carbon-supported monatomic oxygen reduction catalyst and preparation method thereof | |
| CN107267124B (en) | MOFs (metal-organic frameworks) nitrogen-containing graphitized carbon material containing Ni/Fe bimetal | |
| CN110743603B (en) | Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof | |
| CN104549242B (en) | Preparation method of nanometer palladium-graphene three-dimensional porous composite electrocatalyst | |
| CN111933960B (en) | PtCo @ N-GNS catalyst and preparation method and application thereof | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN113529103B (en) | Method for preparing high-load transition metal monoatomic catalyst | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN109686990B (en) | Preparation method and application of Ni-Zn/nitrogen-sulfur double-doped three-dimensional graphene electrode material | |
| CN113445072B (en) | Foamed nickel composite electrode and preparation method and application thereof | |
| CN111659423A (en) | Preparation method and application method of cobalt-tellurium diatomic site catalyst | |
| CN109772336A (en) | A kind of porous double-metal hydroxide catalyst and its preparation method and application for the oxidation of electro-catalysis alcohols selectivity | |
| CN110302799B (en) | Catalyst for electrochemically reducing carbon dioxide into carbon monoxide and preparation method thereof | |
| Afzali et al. | Design of PdxIr/g-C3N4 modified FTO to facilitate electricity generation and hydrogen evolution in alkaline media | |
| JP5158334B2 (en) | Method for producing electrode catalyst for fuel cell | |
| CN115896848A (en) | Nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst and preparation method and application thereof | |
| CN114164455B (en) | Method for improving electrocatalytic performance of noble metal-based material through electrochemical etching | |
| CN111330569A (en) | Electrochemical catalyst capable of realizing mass amplification and noble metal atomic-level dispersion and preparation method thereof | |
| CN109192996B (en) | Spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst and preparation method and application thereof | |
| CN114864967B (en) | Preparation method of carbon-based monoatomic catalyst | |
| Hu et al. | FeOOH nanospheres decorated bimetallic NiFe-MOF as efficient dual-functional catalyst towards superior electrocatalytic performance | |
| CN114774983A (en) | Ultra-small Ru nanocluster loaded on MoO3-xDouble-function composite material of nanobelt and preparation method and application thereof | |
| CN113774420B (en) | Self-supporting nickel-ytterbium oxide composite electrode and preparation method and application thereof | |
| CN117512646A (en) | Heterojunction nano-ring electrocatalyst and preparation method and application thereof | |
| CN108993536B (en) | Palladium-nickel-cobalt-sulfur composite nanotube array electrocatalyst growing on conductive substrate and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |