CN114774983B - Ultra-small Ru nanocluster supported on MoO 3-x Double-function composite material of nano belt and preparation method and application thereof - Google Patents
Ultra-small Ru nanocluster supported on MoO 3-x Double-function composite material of nano belt and preparation method and application thereof Download PDFInfo
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- 239000002127 nanobelt Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002074 nanoribbon Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical group [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 150000002751 molybdenum Chemical class 0.000 claims description 6
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 5
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 4
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000001016 Ostwald ripening Methods 0.000 abstract 1
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000003303 ruthenium Chemical class 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000010287 polarization Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004744 fabric Substances 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- 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
Ultra-small Ru nanocluster supported on MoO 3‑x A dual-function composite material of nano-belt and its preparing process and application are disclosed. The method uses MoO 3 The nano belt is used as a carrier, ruthenium salt is used as a metal precursor, and the ultra-small Ru nano cluster is obtained by high-temperature reduction and is loaded on MoO 3‑x A dual-function composite of nanoribbons. Compared with the traditional Ru cluster loaded on other substrates, the invention realizes that the sub-nanoscale Ru cluster is formed on MoO 3‑x The composite material has uniform structure and morphology and realizes high dispersion. MoO (MoO) 3 The agglomeration of Ru and the Ostwald ripening in the reaction process are effectively avoided by the negative charge regulation and control. The invention has the characteristics of simple process, large specific surface area, multiple active sites and the like, and has excellent electrocatalytic activity in alkaline hydrazine oxidation reaction and cathode-anode half reaction of an alkaline water electrolysis device, and wide application range.
Description
Technical Field
The invention belongs to the field of ruthenium-based electrocatalyst preparation technology and application thereof, and in particular relates to a method for loading ultra-small Ru nanoclusters on MoO 3-x A dual-function composite material of nano-belt and its preparing process and application are disclosed.
Background
Along with the increasingly serious environmental pollution and energy crisis brought by the development of social economy, the development of green pollution-free clean energy has great significance. Hydrogen is considered as 21 st century energy currency and is widely recognized as an effective way to address energy crisis. Commercial production of hydrogen still takes the cracking of fossil fuels as a major source. However, the process flow has the defects of poor hydrogen purity, non-environmental protection, unsustainable and the like. The hydrogen prepared by electrolyzing water is used as a high-efficiency hydrogen production technology, has the characteristics of high hydrogen purity, green and pollution-free property and the like, and accords with the current ideas of carbon neutralization and sustainable development. In addition, in the green development process, hydrazine and its compounds have also received a great deal of attention for pollution of soil and water quality. The current electrochemical oxidation treatment of hydrazine waste is an effective method which is environment-friendly, and the products are nitrogen and hydrogen. If the electrochemical hydrazine oxidation reaction is taken as an anode and combined with the cathode half reaction of hydrogen evolution of electrolyzed water, the high-efficiency preparation of hydrogen, excellent stability and comprehensive utilization of hydrazine can be realized.
At present, commercial hydrogen evolution catalysts and hydrazine oxidation catalysts still take Pt and Pd-based materials with high intrinsic catalytic activity as main materials, however, the disadvantages of rare reserves of palladium and platinum in the nature, high price and the like limit the large-scale application of the catalysts. Therefore, how to develop a highly efficient and highly active hydrazine oxidation and hydrogen evolution catalyst is an effective strategy to solve this problem. By selecting a cheaper Ru-based catalyst and reducing the load, clusters with sub-nanometer scale are prepared to be uniformly loaded on a substrate which is stable and has special morphology, and more catalytic active sites can be exposed, so that the improvement of catalytic performance and efficiency is realized. The Ru-based nanomaterial is controlled to be sub-nanometer in size, which will make it exhibit the most excellent catalytic activity and price advantage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for loading ultra-small Ru nanoclusters on MoO 3-x The target product is prepared by combining a hydrothermal reaction and a high-temperature reduction technology, and the target product shows excellent electrocatalytic hydrogen production activity in alkaline hydrazine oxidation reaction and cathode-anode half reaction of an alkaline water electrolysis device so as to meet the requirements of application and development in related fields.
In order to solve the problems in the prior art, the invention adopts the following technical scheme:
ultra-small Ru nanocluster supported on MoO 3-x The preparation method of the dual-function composite material of the nano belt comprises the following steps:
(1) Dissolving a molybdenum salt precursor and a morphology regulator in deionized water, uniformly mixing by ultrasonic, injecting strong inorganic acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven for hydrothermal reaction at 180-220 ℃ for 3-5 hours, and centrifuging and washing for several times after the reaction is finished to obtain MoO 3 A nanobelt;
(2) The prepared MoO 3 Dispersing the nanobelt and ruthenium metal salt in water, immersing for 2-6 hours while ultrasonic treatment, freeze-drying, placing in a tubular furnace, and reducing for 2-3 hours at 350-550 ℃ in a hydrogen atmosphere protected by argon gas to obtain ultra-small Ru nanoclusters loaded on MoO 3-x A dual-function composite of nanoribbons.
As an improvement, the molybdenum salt precursor in the step (1) is ammonium molybdate with the concentration of 20-50 mg mL -1 。
As an improvement, the morphology regulator in the step (1) is chromium inorganic salt, and the mass ratio of the morphology regulator to the molybdenum salt precursor is 1:10-20.
Further improved is that the inorganic salt of chromium is chromium chloride, chromium sulfate or chromium nitrate.
As an improvement, the strong mineral acid in step (1) is concentrated nitric acid or concentrated hydrochloric acid.
The improvement is that the ruthenium metal salt in the step (2) is ruthenium chloride, ruthenium nitrate, ruthenium acetylacetonate or ruthenium acetate, and the ruthenium metal salt is mixed with MoO 3 The mass ratio of the nano-belts is 1:4-10.
As an improvement, the mass concentration of the ruthenium metal salt in the step (2) is 3-6 mg mL -1 。
As an improvement, the reducing atmosphere in the step (2) is a mixed gas of argon and hydrogen, and the volume fraction of the hydrogen is 5-20%.
The ultra-small Ru nanoclusters prepared by any one of the methods are supported on MoO 3-x A dual-function composite of nanoribbons.
Any of the above ultra-small Ru nanoclusters are supported on MoO 3-x The double-function composite material of the nano belt is applied to catalysts for alkaline hydrazine oxidation reaction or alkaline water electrolysis hydrogen production reaction.
The beneficial effects are that:
compared with the prior art, the ultra-small Ru nanocluster is loaded on MoO 3-x The dual-function composite material of the nano belt and the preparation method and the application thereof have the following advantages:
1. the method has simple process operation and easy synthesis, and the ultra-small Ru nanocluster loaded on MoO is prepared by a two-step method of dipping and high-temperature reduction 3-x The dual-function composite material of the nano belt adopts raw materials which are all (low) toxic reagents, is easy to purchase, has low reaction danger, is environment-friendly and is easy to prepare in a large scale.
2. The ultra-small Ru nanocluster prepared by the method is loaded on MoO 3-x The dual-function composite material of the nano belt has the advantages of uniform size, large specific surface area, more active sites, stable structure and the like, shows excellent electrocatalytic activity in alkaline hydrazine oxidation reaction and cathode-anode half reaction of an alkaline water electrolysis device, and has very wide energy application prospect.
Drawings
FIG. 1 shows the ultra-small Ru nanoclusters prepared according to example 2 of the present invention supported on MoO 3-x Scanning Electron Microscope (SEM) and High Resolution Transmission Electron Microscope (HRTEM) photographs of the dual-function composite material of the nanobelt, wherein (a) is an SEM photograph, (b) is a TEM photograph, (c) is an HRTEM photograph, and (d) is a lattice fringe pattern under the HRTEM;
FIG. 2 shows the ultra-small Ru nanoclusters prepared according to example 2 of the present invention supported on MoO 3-x X-ray diffraction (XRD) patterns of the dual-function composite of nanoribbons;
FIG. 3 shows the ultra-small Ru nanoclusters prepared according to example 2 of the present invention supported on MoO 3-x X-ray photoelectron (XPS) spectra of the dual-function composite of nanoribbons;
FIG. 4 is a schematic illustration of the present inventionThe ultra-small Ru nanoclusters prepared in example 2 were supported on MoO 3-x The hydrazine electrocatalytic oxidation performance of the nano-belt double-function composite material;
FIG. 5 shows the ultra-small Ru nanoclusters prepared according to example 2 of the present invention supported on MoO 3-x Electrocatalytic hydrogen evolution performance of the dual-function composite material of the nanobelt;
FIG. 6 shows the ultra-small Ru nanoclusters prepared according to example 2 of the present invention supported on MoO 3-x A water electrolysis device diagram of the dual-function composite material of the nano belt;
FIG. 7 shows the ultra-small Ru nanoclusters prepared according to example 2 of the present invention supported on MoO 3-x Electrolytic water properties of the dual-function composite of nanoribbons.
Detailed Description
The following detailed description of the present invention is given by way of specific examples, which are given for illustrative purposes only and are not to be construed as limiting the scope of the present invention.
Example 1
(1) Dissolving 0.5g of ammonium molybdate and chromium chloride in 25mL of deionized water, uniformly mixing by ultrasonic, injecting 5mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven, carrying out hydrothermal reaction at 200 ℃ for 3 hours, and centrifugally washing for several times after the reaction is finished to obtain MoO 3 A nanobelt;
(2) 0.02g MoO 3 Dispersing the nano-belt and 2.7mg of ruthenium chloride in 10mL of water, immersing for 2 hours while ultrasonic treatment, freeze-drying, placing in a tube furnace, and reducing for 3 hours at 350 ℃ in a hydrogen atmosphere (the volume fraction of hydrogen is 5%) protected by argon, thus obtaining the ultra-small Ru nano-cluster loaded on MoO 3-x A dual-function composite of nanoribbons.
Example 2
(1) Dissolving 0.6g of ammonium molybdate and chromium chloride in 25mL of deionized water, uniformly mixing by ultrasonic, injecting 5mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven, carrying out hydrothermal reaction at 200 ℃ for 4 hours, and centrifugally washing for several times after the reaction is finished to obtain MoO 3 A nanobelt;
(2) 0.03g MoO 3 Dispersing the nano-belt and 3.0mg ruthenium chloride in 10mL of water, immersing for 3 hours while ultrasonic treatment, freeze-drying, placing in a tube furnace, and reducing for 2 hours at 450 ℃ in a hydrogen atmosphere (the volume fraction of hydrogen is 10%) protected by argon, thus obtaining the ultra-small Ru nano-cluster loaded on MoO 3-x A dual-function composite of nanoribbons.
Example 3
(1) Dissolving 1.0g of ammonium molybdate and chromium nitrate in 50mL of deionized water, uniformly mixing by ultrasonic, injecting 10mL of concentrated hydrochloric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven for hydrothermal reaction at 180 ℃ for 4 hours, and centrifugally washing for several times after the reaction is finished to obtain MoO 3 A nanobelt;
(2) 0.2g MoO 3 Dispersing the nano-belt and 27 mg ruthenium chloride in 100mL of water, immersing for 3 hours while ultrasonic treatment, freeze-drying, placing in a tube furnace, and reducing for 2 hours in a hydrogen atmosphere (the volume fraction of hydrogen is 5%) protected by argon at 400 ℃ to obtain the ultra-small Ru nano-cluster loaded on MoO 3-x A dual-function composite of nanoribbons.
Example 4
(1) Dissolving 1.0g of ammonium molybdate and chromium sulfate in 55mL of deionized water, uniformly mixing by ultrasonic, injecting 12mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven, carrying out hydrothermal reaction at 200 ℃ for 3 hours, and centrifugally washing for several times after the reaction is finished to obtain MoO 3 A nanobelt;
(2) 0.2g MoO 3 Dispersing the nanobelt and 20mg of ruthenium nitrate in 100mL of water, immersing for 6 hours while ultrasonic treatment, freeze-drying, placing in a tubular furnace, and reducing for 2 hours in a hydrogen atmosphere (the volume fraction of hydrogen is 5%) protected by argon at 500 ℃ to obtain ultra-small Ru nanoclusters loaded on MoO 3-x A dual-function composite of nanoribbons.
Example 5
(1) 1.0g of ammonium molybdate and chromium chloride salt are dissolved in 55mL of deionized water, and are mixed evenly by ultrasonic, and after 12mL of concentrated hydrochloric acid is injected again, the mixture is stirred evenly continuously and transferred to a reaction kettle, and the reaction kettle is placed in an oven together with the reaction kettleCarrying out hydrothermal reaction at 200 ℃ for 5 hours, and centrifugally washing for several times after the reaction is finished to obtain MoO 3 A nanobelt;
(2) 0.2g MoO 3 Dispersing the nanobelt and 32mg of ruthenium acetylacetonate in 130mL of water, immersing for 5 hours while ultrasonic treatment, freeze-drying, placing in a tubular furnace, and reducing for 2 hours in a hydrogen atmosphere (the volume fraction of hydrogen is 5%) protected by argon at 550 ℃ to obtain ultra-small Ru nanoclusters loaded on MoO 3-x A dual-function composite of nanoribbons.
Example 6
(1) Dissolving 1.0g of ammonium molybdate and chromium chloride in 55mL of deionized water, uniformly mixing by ultrasonic, injecting 8mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven for hydrothermal reaction at 180 ℃ for 3 hours, and centrifugally washing for several times after the reaction is finished to obtain MoO 3 A nanobelt;
(2) 0.2g MoO 3 Dispersing the nano-belt and 28mg of ruthenium acetate in 100mL of water, immersing for 5 hours while carrying out ultrasonic treatment, then carrying out freeze drying treatment, and placing the mixture in a tubular furnace for reduction for 2 hours at 450 ℃ in a hydrogen atmosphere (the volume fraction of hydrogen is 5%) protected by argon, thus obtaining the ultra-small Ru nano-cluster loaded on MoO 3-x A dual-function composite of nanoribbons.
Example 7
(1) Dissolving 1.0g of ammonium molybdate and chromium nitrate in 55mL of deionized water, uniformly mixing by ultrasonic, injecting 7mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven, carrying out hydrothermal reaction at 200 ℃ for 3 hours, and centrifugally washing for several times after the reaction is finished to obtain MoO 3 A nanobelt;
(2) 0.2g MoO 3 Dispersing the nano-belt and 22mg of ruthenium chloride in 100mL of water, immersing for 6 hours while ultrasonic treatment, freeze-drying, placing in a tube furnace, and reducing for 2 hours at 400 ℃ in a hydrogen atmosphere (the volume fraction of hydrogen is 5%) protected by argon to obtain ultra-small Ru nanoclusters loaded on MoO 3-x A dual-function composite of nanoribbons.
Example 8
(1) 1.5g of ammonium molybdate and chromium nitrate are dissolved in 75mL of deionized water and evenly mixed by ultrasonicAfter 15mL of concentrated hydrochloric acid is injected again, stirring is continued to be uniform, the mixture is transferred to a reaction kettle, the reaction kettle and the mixture are placed in an oven to carry out hydrothermal reaction for 3 hours at 200 ℃, and after the reaction is finished, the mixture is centrifugally washed for a plurality of times to obtain MoO 3 A nanobelt;
(2) 0.3g MoO 3 Dispersing the nano-belt and 45mg of ruthenium chloride in 150mL of water, immersing for 6 hours while ultrasonic treatment, freeze-drying, placing in a tube furnace, and reducing for 3 hours at 450 ℃ in a hydrogen atmosphere (the volume fraction of hydrogen is 20%) protected by argon to obtain ultra-small Ru nanoclusters loaded on MoO 3-x A dual-function composite of nanoribbons.
Example 9
Referring to example 2, ruthenium chloride was replaced with ruthenium nitrate.
Example 10
Referring to example 2, ruthenium chloride was replaced with ruthenium acetylacetonate.
Example 11
Referring to example 2, ruthenium chloride was replaced with ruthenium acetate.
Performance testing
Supported ultra-small Ru nanoclusters prepared in example 2 on MoO using HRTEM and SEM 3-x The dual-function composite of nanoribbons is physically characterized. From FIG. 1 (a), it can be seen that the ultra-small Ru nanoclusters prepared according to the method of the present invention are supported on MoO 3-x Double-functional composite material of nano-belt (recorded as Ru/MoO) 3-x ) Is a relatively uniform nanoribbon, and the ribbon structure can provide a larger specific surface area and more active sites. The morphology and structure of the samples were further characterized by (HRTEM), with lattice spacings of 0.23nm and 0.33nm corresponding to Ru (100) and MoO, respectively 3-x Is matched with the (012) crystal plane. FIG. 2 is MoO 3 And Ru/MoO 3-x Is prepared according to the XRD pattern of MoO prepared in example 2 of the method 3 Diffraction peaks and monoclinic MoO of (2) 3 Corresponds to the standard card (JCPLDS# 05-508). In Ru/MoO 3-x In XRD of (C), the diffraction peak of Ru corresponds to hexagonal Ru (JCPDS#88-1734), indicating that Ru clusters exist in hexagonal form, and no MoO is observed 3-x Diffraction peaks of the oxide indicate that the form of the oxide is amorphous.Reducing the crystallinity of a component to an amorphous state can minimize the effect of lattice strain on nearby components, which is beneficial for increasing the reaction rate. XPS for analysis of Ru/MoO 3-x Chemical composition and elemental state of (a). XPS full spectrum shows Ru/MoO 3-x The existence of Ru, mo and O elements (figure 3). According to Ru/MoO 3-x Mo 3 of (2)dXPS results revealed that Mo 6+ And Mo (Mo) 5+ Are all present in Ru/MoO 3-x 。Ru-MoO 3-x O1 of (2)sThe spectrum demonstrates the presence of oxygen defects. Ru-MoO 3-x Ru 3 of (F)pThe spectrum demonstrates that Ru nanoclusters exist at zero valence.
By loading the ultra-small Ru nanoclusters of example 2 on MoO 3-x The dual-function composite material of the nano belt and a commercial Pt/C catalyst (purchased from Shanghai national medicine group Co., ltd.) are used for detecting the oxidation performance of the hydrazine, and the detection method comprises the following steps: the test is carried out by adopting a CHI660E electrochemical workstation, a standard three-electrode battery is used for the test, the prepared catalyst modified carbon cloth (1 cm multiplied by 1 cm) is used as a working electrode, a high-purity graphite rod and Hg/HgO (1.0M potassium hydroxide filler) are respectively used as a counter electrode and a reference electrode, and the test solution is 1M KOH+0.5M N 2 H 4 . Polarization curves were obtained using a potential window of-1.1 to-0.3V. Measured at a rate of 5.0mV s −1 All Linear Sweep Voltammetry (LSV) polarization curves were converted to RHE and IR corrected according to the formula of E (RHE) =e (Hg/HgO) +0.095+0.059ph, with hydrazine oxidation performance polarization curve test results shown in fig. 4, ru/MoO 3-x Has lower hydrazine oxidation overpotential and more excellent reaction kinetics than commercial Pt/C. As shown in Table 1, the catalytic activity of the catalyst has obvious advantages compared with other catalysts which have been reported at present.
TABLE 1 comparative case of hydrazine Oxidation Properties of different materials
By loading the ultra-small Ru nanoclusters of example 2 on MoO 3-x Nanoribbon bifunctional composites and commercial Pt/C catalysts (purchased fromShanghai national medicine group Co., ltd.) to detect hydrogen evolution performance, the method used for the detection is specifically as follows: the test is carried out by adopting a CHI660E electrochemical workstation, a standard three-electrode battery is used for the test, the prepared catalyst modified carbon cloth (1 cm multiplied by 1 cm) is used as a working electrode, a high-purity graphite rod and Hg/HgO (1.0M potassium hydroxide filler) are respectively used as a counter electrode and a reference electrode, and the test solution is 1M KOH. Polarization curves were obtained using a potential window of-1.4 to-0.8V. Measured at a rate of 5.0mV s −1 All Linear Sweep Voltammetry (LSV) polarization curves were converted to RHE and IR corrected according to the formula of E (RHE) =e (Hg/HgO) +0.095+0.059ph, performance polarization curve test results for hydrogen evolution are shown in fig. 5, ru/MoO 3-x At 10mA cm -2 The overpotential at this point has a better advantage over commercial Pt/C catalysts.
By loading the ultra-small Ru nanoclusters of example 2 on MoO 3-x The dual-functional composite material of the nano belt and commercial Pt/C (purchased from Shanghai national medicine group Co., ltd.) are used for detecting the performance of the electrolytic water assisted by hydrazine, and the detection method comprises the following steps: the H-type bipolar battery was filled with 1.0M potassium hydroxide+0.5M hydrazine and 1.0M potassium hydroxide, respectively. In which a catalyst-modified carbon cloth (1 cm. Times.1 cm) was used as a cathode and an anode, and the apparatus used was as shown in FIG. 6, it can be seen from the figure that both the cathode and the anode have a large amount of bubble generation, indicating excellent hydrogen evolution and hydrazine oxidation properties. FIG. 7 is a graph of hydrazine assisted electrolyzed water performance, as determined by the full water electrolysis polarization curve test, in the apparatus, 10mA cm -2 Ru/MoO at 3-x The water splitting voltage of (2) was only 13mV, which is significantly better than 154mV required for commercial Pt/C. The performance was also significantly superior to most catalysts reported so far (as shown in table 2).
TABLE 2 comparison of electrolyzed water properties of different materials
In conclusion, the method is simple to operate and easy to synthesize, and the obtained ultra-small Ru nanocluster is loaded on MoO 3-x Nanoribbon ofThe dual-function composite material has the advantages of uniform morphology, easy large-scale preparation, large specific surface area, more active sites, high adsorption selectivity, stable structure, excellent hydrogen production performance by water electrolysis and the like, and has very wide commercial production application potential.
In the foregoing, the protection scope of the present invention is not limited to the preferred embodiments of the present invention, and any simple changes or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention disclosed in the present invention fall within the protection scope of the present invention.
Claims (5)
1. Ultra-small Ru nanocluster supported on MoO 3-x The preparation method of the dual-function composite material of the nano belt is characterized by comprising the following steps:
(1) Dissolving a molybdenum salt precursor and a morphology regulator in deionized water, uniformly mixing by ultrasonic, injecting strong inorganic acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven for hydrothermal reaction at 180-200 ℃ for 3-5 hours, and centrifuging and washing for several times after the reaction is finished to obtain MoO 3 The nano belt, wherein the molybdenum salt precursor is ammonium molybdate, and the concentration is 20-50 mg.mL -1 The morphology regulator is chromium inorganic salt, and the mass ratio of the morphology regulator to the molybdenum salt precursor is 1:10-20;
(2) The prepared MoO 3 Dispersing the nanobelt and ruthenium metal salt in water, immersing for 5-6 hours while ultrasonic treatment, freeze-drying, placing in a tubular furnace, and reducing for 2-3 hours at 350-550 ℃ in a hydrogen atmosphere protected by argon gas to obtain ultra-small Ru nanoclusters loaded on MoO 3-x The dual-function composite material of the nanobelt comprises mixed gas of argon and hydrogen, wherein the volume fraction of the hydrogen is 5-20%, ruthenium metal salt is ruthenium chloride, ruthenium nitrate, ruthenium acetylacetonate or ruthenium acetate, and the ruthenium metal salt and MoO are mixed together 3 The mass ratio of the nanobelts is 1:4-10, and the mass concentration of the ruthenium metal salt is 3-6mg.mL -1 。
2. An ultra-small Ru nanocluster according to claim 1Cluster loading on MoO 3-x The preparation method of the dual-function composite material of the nano belt is characterized by comprising the following steps: the inorganic chromium salt is chromium chloride, chromium sulfate or chromium nitrate.
3. An ultra-small Ru nanocluster according to claim 1 supported on MoO 3-x The preparation method of the dual-function composite material of the nano belt is characterized by comprising the following steps: the strong mineral acid in the step (1) is concentrated nitric acid or concentrated hydrochloric acid.
4. Supported MoO of ultra-small Ru nanoclusters prepared based on the method of any of claims 1-3 3-x A dual-function composite of nanoribbons.
5. Supported ultra-small Ru nanoclusters prepared based on any one of the preparation methods of claims 1-3 on MoO 3-x The double-function composite material of the nano belt is applied to catalysts for alkaline hydrazine oxidation reaction or alkaline water electrolysis hydrogen production reaction.
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| CN111569953A (en) * | 2020-05-01 | 2020-08-25 | 赵玉平 | High-load Ru-MnOXPreparation method of graphene denitration catalyst |
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| CN111569953A (en) * | 2020-05-01 | 2020-08-25 | 赵玉平 | High-load Ru-MnOXPreparation method of graphene denitration catalyst |
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| Dual Active Centers Bridged by Oxygen Vacancies of Ruthenium Single-Atom Hybrids Supported on Molybdenum Oxide for Photocatalytic Ammonia Synthesis;Haibo Yin等;《Angew. Chem. Int. Ed.》;第61卷;第e202114242-1—e202114242-11页及支持信息 * |
| Hydrothermal Synthesis and Gas Sensing of Monoclinic MoO3 Nanosheets;Teodóra Nagyné-Kovács等;《Nanomaterials》;第10卷;第891-1—891-12页 * |
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