CN114774983A - Ultra-small Ru nanocluster loaded on MoO3-xDouble-function composite material of nanobelt and preparation method and application thereof - Google Patents
Ultra-small Ru nanocluster loaded on MoO3-xDouble-function composite material of nanobelt and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000002127 nanobelt Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910015675 MoO3−x Inorganic materials 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
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- 239000002074 nanoribbon Substances 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
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- 239000011609 ammonium molybdate Substances 0.000 claims description 10
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- 238000002156 mixing Methods 0.000 claims description 10
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
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- 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 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 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
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
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- 239000006185 dispersion Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 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
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- 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
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- 238000004458 analytical method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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 loaded on MoO3‑xA bifunctional composite material of a nanobelt, a preparation method and application thereof. The method uses MoO3The nano-belt is used as a carrier, ruthenium salt is used as a metal precursor, and the ultra-small Ru nanocluster loaded on MoO can be obtained by high-temperature reduction3‑xA bifunctional composite of nanoribbons. Compared with the traditional material of Ru clusters loaded on other substrates, the invention realizes the effect of the sub-nanometer ruthenium clusters on MoO3‑xThe homogeneous embedding in the physical phase, the homogeneous structural appearance of the composite material, and has realized the high dispersion. MoO3The negative charge regulation effectively avoids the agglomeration of Ru and Ostwald ripening in the reaction process. The invention has simple process, and simultaneously has the characteristics of large specific surface area, more active sites and the likeThe compound has excellent electrocatalytic activity in alkaline hydrazine oxidation reaction and alkaline electrolytic water device cathode and anode half reaction, and has wide application range.
Description
Technical Field
The invention belongs to the field of ruthenium-based electrocatalyst preparation technology and application thereof, and particularly relates to a method for loading ultra-small Ru nanoclusters on MoO3-xA bifunctional composite material of a nanobelt, a preparation method and application thereof.
Background
Along with increasingly serious environmental pollution and energy crisis brought by social and economic development, the development of green pollution-free clean energy has great significance. Hydrogen is considered to be the energy currency of the 21 st century and is widely considered as an effective way to solve the energy crisis. The commercial production of hydrogen continues to be the main source of fossil fuel cracking. However, the process flow has the defects of poor hydrogen purity, non-green environmental protection, non-sustainability 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, environmental friendliness, no pollution and the like, and accords with the current carbon neutralization and sustainable development concept. In addition, hydrazine and its compounds have also received widespread attention for soil and water pollution during green development. At present, the electrochemical oxidation treatment of hydrazine waste is an effective method which is green and environment-friendly, and the products are nitrogen and hydrogen. If the electrochemical hydrazine oxidation reaction is used as an anode and combined with the cathode half reaction of water electrolysis hydrogen evolution, 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 are mainly Pt and Pd-based materials with high intrinsic catalytic activity, however, the large-scale application of palladium and platinum is restricted by the defects of rare reserves, high price and the like in the nature. Therefore, how to develop a highly efficient and highly active hydrazine oxidation and hydrogen evolution catalyst is an effective strategy to solve the problem. By selecting a cheaper Ru-based catalyst and reducing the loading capacity of the Ru-based catalyst, the cluster with the sub-nanometer scale is prepared, is uniformly loaded on a stable substrate with a special morphology, and can expose more catalytic active sites, so that the catalytic performance and efficiency are improved. The size of the Ru-based nano material is controlled to be in a sub-nanometer level, so that the Ru-based nano material can show the most excellent catalytic activity and price advantage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an ultra-small Ru nanocluster loaded on MoO3-xThe target product is prepared by combining hydrothermal reaction and high-temperature reduction technology, and the target product shows excellent electrocatalytic hydrogen production activity in alkaline hydrazine oxidation reaction and alkaline water electrolysis device cathode-anode half reaction so as to meet the requirements of application and development of related fields.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
ultra-small Ru nanocluster loaded on MoO3-xThe preparation method of the bifunctional composite material of the nanobelt comprises the following steps of:
(1) dissolving a molybdenum salt precursor and a morphology control agent in deionized water, mixing uniformly by ultrasonic waves, injecting strong inorganic acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle and the reaction kettle in an oven for hydrothermal reaction at 180-220 ℃ for 3-5 hours, and after the reaction is finished, centrifugally washing for several times to obtain MoO3A nanoribbon;
(2) the prepared MoO3Dispersing the nanobelts and ruthenium metal salt in water, dipping for 2-6 hours while performing ultrasonic treatment, performing freeze drying treatment, and reducing for 2-3 hours in a tubular furnace at 350-550 ℃ in an argon-protected hydrogen atmosphere to obtain the ultra-small Ru nanocluster loaded on MoO3-xA bifunctional composite of nanoribbons.
The improvement is that the molybdenum salt precursor in the step (1) is ammonium molybdate, and the concentration is 20-50 mg mL-1。
The improvement is that 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.
In a further improvement, the chromium inorganic salt is chromium chloride, chromium sulfate or chromium nitrate.
The improvement is that the strong inorganic acid in the 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 MoO3The mass ratio of the nanobelts is 1: 4-10.
The improvement is that the mass concentration of the ruthenium metal salt in the step (2) is 3-6 mg mL-1。
The improvement is that 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 nanocluster prepared by any one of the methods is loaded on MoO3-xA bifunctional composite of nanoribbons.
Any of the above ultra-small Ru nanoclusters is loaded on MoO3-xThe bifunctional composite material of the nanobelt is applied to a catalyst for an alkaline hydrazine oxidation reaction or an alkaline water electrolysis hydrogen production reaction.
Has the advantages that:
compared with the prior art, the ultra-small Ru nanocluster loaded on MoO3-xThe bifunctional composite material of the nanobelt 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 supported MoO is prepared by a two-step method of impregnation and high-temperature reduction3-xThe raw materials of the bifunctional composite material of the nanobelt are non (low) toxic reagents, and the bifunctional composite material is easy to purchase, low in reaction risk, green and environment-friendly in product and easy for large-scale preparation.
2. The ultra-small Ru nanocluster prepared by the method is loaded on MoO3-xThe bifunctional composite material of the nanobelt has the advantages of uniform size, large specific surface area, many active sites, stable structure and the like, shows excellent electrocatalytic activity in alkaline hydrazine oxidation reaction and alkaline electrolytic water device cathode-anode half reaction, and has very wide energy application prospect.
Drawings
FIG. 1 shows that the ultra-small Ru nanoclusters prepared in example 2 of the invention are supported on MoO3-xScanning of bifunctional composite materials for nanoribbonsElectron Microscope (SEM) and High Resolution Transmission Electron Microscope (HRTEM) photographs, wherein (a) is an SEM photograph, (b) is a TEM photograph, (c) is an HRTEM photograph, and (d) is a lattice fringe pattern under HRTEM;
FIG. 2 shows that the ultra-small Ru nanoclusters prepared in example 2 of the invention are supported on MoO3-xAn X-ray diffraction (XRD) pattern of the nanobelt bifunctional composite;
FIG. 3 shows that the ultra-small Ru nanoclusters prepared in example 2 of the invention are supported on MoO3-xAn X-ray photoelectron (XPS) spectrum of the nanobelt bifunctional composite;
FIG. 4 shows that the ultra-small Ru nanoclusters prepared in example 2 of the present invention are supported on MoO3-xThe hydrazine electrocatalytic oxidation performance of the nanobelt bifunctional composite material;
FIG. 5 shows that the ultra-small Ru nanoclusters prepared in example 2 of the present invention are supported on MoO3-xElectrocatalytic hydrogen evolution performance of the bifunctional composite material of the nanobelt;
FIG. 6 shows that the ultra-small Ru nanoclusters prepared in example 2 of the present invention are supported on MoO3-xA water electrolysis device diagram of the bifunctional composite material of the nanobelt;
FIG. 7 shows that the ultra-small Ru nanoclusters prepared in example 2 of the present invention are supported on MoO3-xThe water electrolysis performance of the bifunctional composite material of the nanobelt.
Detailed Description
The technical solutions of the present invention are further described in detail by the following specific examples, but it should be noted that the following examples are only used for describing the content of the present invention and should not 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, ultrasonically mixing uniformly, injecting 5mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle and the reaction kettle in an oven for hydrothermal reaction at 200 ℃ for 3 hours, and after the reaction is finished, centrifuging and washing for several times to obtain MoO3A nanoribbon;
(2) 0.02g of MoO3Dispersing the nanobelt and 2.7mg ruthenium chloride in 10mL of water, immersing for 2 hours while carrying out ultrasonic treatment, and freeze-dryingTreating, placing in a tube furnace, reducing for 3 hours at 350 ℃ in hydrogen atmosphere (the volume fraction of hydrogen is 5%) protected by argon, and obtaining the ultra-small Ru nanocluster loaded on MoO3-xBifunctional composite of nanoribbons.
Example 2
(1) Dissolving 0.6g of ammonium molybdate and chromium chloride in 25mL of deionized water, ultrasonically mixing uniformly, injecting 5mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven for hydrothermal reaction at 200 ℃ for 4 hours, and after the reaction is finished, centrifugally washing for several times to obtain MoO3A nanoribbon;
(2) 0.03g of MoO3Dispersing the nanobelts and 3.0mg of ruthenium chloride in 10mL of water, soaking for 3 hours while carrying out ultrasonic treatment, then carrying out freeze drying treatment, placing the mixture in a tube furnace, and reducing the mixture for 2 hours at 450 ℃ in an argon-protected hydrogen atmosphere (the volume fraction of hydrogen is 10%) to obtain the ultra-small Ru nanoclusters loaded on MoO3-xBifunctional composite of nanoribbons.
Example 3
(1) Dissolving 1.0g of ammonium molybdate and chromium nitrate in 50mL of deionized water, ultrasonically mixing uniformly, injecting 10mL of concentrated hydrochloric acid, stirring uniformly, transferring to a reaction kettle, placing the reaction kettle in an oven for hydrothermal reaction at 180 ℃ for 4 hours, and after the reaction is finished, centrifugally washing for several times to obtain MoO3A nanoribbon;
(2) 0.2g of MoO3Dispersing the nanobelts and 27 mg of ruthenium chloride in 100mL of water, soaking for 3 hours while performing ultrasonic treatment, performing freeze drying treatment, and reducing the mixture in a tubular furnace at 400 ℃ for 2 hours in an argon-protected hydrogen atmosphere (the volume fraction of hydrogen is 5%) to obtain ultra-small Ru nanoclusters loaded on MoO3-xA bifunctional composite of nanoribbons.
Example 4
(1) Dissolving 1.0g of ammonium molybdate and chromium sulfate in 55mL of deionized water, ultrasonically mixing uniformly, injecting 12mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle and the reaction kettle in an oven for hydrothermal reaction at 200 ℃ for 3 hours, and after the reaction is finished, centrifuging and washing for several times to obtain MoO3A nanoribbon;
(2) 0.2g of MoO3Dispersing the nanobelts and 20mg of ruthenium nitrate in 100mL of water, soaking for 6 hours while carrying out ultrasonic treatment, then carrying out freeze drying treatment, placing the mixture in a tube furnace, and reducing the mixture for 2 hours at 500 ℃ in an argon-protected hydrogen atmosphere (the volume fraction of hydrogen is 5%) to obtain the ultra-small Ru nanoclusters loaded on MoO3-xA bifunctional composite of nanoribbons.
Example 5
(1) Dissolving 1.0g of ammonium molybdate and chromium chloride salt in 55mL of deionized water, ultrasonically mixing uniformly, injecting 12mL of concentrated hydrochloric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle and the reaction kettle in an oven for hydrothermal reaction at 200 ℃ for 5 hours, and after the reaction is finished, centrifugally washing for several times to obtain MoO3A nanoribbon;
(2) 0.2g of MoO3Dispersing the nanobelts and 32mg of ruthenium acetylacetonate in 130mL of water, soaking for 5 hours while performing ultrasonic treatment, performing freeze drying treatment, and reducing for 2 hours at 550 ℃ in a tubular furnace in an argon-protected hydrogen atmosphere (the volume fraction of hydrogen is 5%) to obtain the ultra-small Ru nanocluster loaded on MoO3-xBifunctional composite of nanoribbons.
Example 6
(1) Dissolving 1.0g of ammonium molybdate and chromium chloride in 55mL of deionized water, ultrasonically mixing uniformly, 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 after the reaction is finished, centrifugally washing for several times to obtain MoO3A nanoribbon;
(2) 0.2g of MoO3Dispersing the nanobelts and 28mg of ruthenium acetate in 100mL of water, soaking for 5 hours while performing ultrasonic treatment, performing freeze drying treatment, and reducing the mixture in a tubular furnace at 450 ℃ for 2 hours in an argon-protected hydrogen atmosphere (the volume fraction of hydrogen is 5%) to obtain ultra-small Ru nanoclusters loaded on MoO3-xA bifunctional composite of nanoribbons.
Example 7
(1) Dissolving 1.0g of ammonium molybdate and chromium nitrate in 55mL of deionized water, ultrasonically mixing uniformly, injecting 7mL of concentrated nitric acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle and the reaction kettle in an oven for hydrothermal reaction at 200 ℃ for 3 hours, and after the reaction is finished, centrifugally washing for several timesObtain MoO3A nanoribbon;
(2) 0.2g of MoO3Dispersing the nanobelts and 22mg of ruthenium chloride in 100mL of water, soaking for 6 hours while performing ultrasonic treatment, performing freeze drying treatment, and reducing the mixture in a tubular furnace at 400 ℃ for 2 hours in an argon-protected hydrogen atmosphere (the volume fraction of hydrogen is 5%) to obtain ultra-small Ru nanoclusters loaded on MoO3-xA bifunctional composite of nanoribbons.
Example 8
(1) Dissolving 1.5g of ammonium molybdate and chromic nitrate in 75mL of deionized water, ultrasonically mixing uniformly, injecting 15mL of concentrated hydrochloric acid, continuously stirring uniformly, transferring to a reaction kettle, putting the reaction kettle and the reaction kettle in an oven for hydrothermal reaction at 200 ℃ for 3 hours, and after the reaction is finished, centrifugally washing for several times to obtain MoO3A nanoribbon;
(2) 0.3g of MoO3Dispersing the nanobelts and 45mg of ruthenium chloride in 150mL of water, soaking for 6 hours while performing ultrasonic treatment, performing freeze drying treatment, and reducing for 3 hours at 450 ℃ in a tubular furnace in an argon-protected hydrogen atmosphere (the volume fraction of hydrogen is 20%) to obtain the ultra-small Ru nanocluster loaded on MoO3-xA bifunctional 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 test
MoO-loaded ultra-small Ru nanoclusters prepared in example 2 by HRTEM and SEM3-xThe bifunctional composite of nanoribbons was physically characterized. It can be seen from FIG. 1 (a) that the ultra-small Ru nanoclusters prepared according to the method of the present invention are supported on MoO3-xBifunctional composite material of nanobelt (marked as Ru/MoO)3-x) Is a relatively uniform nanobelt, the band-shaped structure can provide a larger specific surface area and more active sites. The morphology and structure of the samples were further characterized by (HRTEM), 0Lattice spacings of 23nm and 0.33nm with (100) and MoO of Ru, respectively3-xIs matched with the (012) crystal plane. FIG. 2 shows MoO3And Ru/MoO3-xXRD pattern of (1), MoO prepared according to method example 23Diffraction peak and monoclinic MoO of3Corresponds to the standard card (JCPDS # 05-508). In Ru/MoO3-xThe diffraction peak of Ru corresponds to that of hexagonal Ru (JCPDS # 88-1734), indicating that the Ru clusters are in hexagonal form and no MoO is observed3-xDiffraction peaks of the oxides, indicating that they are present in amorphous form. Reducing the crystallinity of the components to an amorphous state can minimize the effect of lattice strain on nearby components, which can advantageously increase the reaction rate. XPS for analysis of Ru/MoO3-xChemical composition and elemental state. XPS survey spectrum showing Ru/MoO3-xIn the presence of Ru, Mo and O (figure 3). According to Ru/MoO3-xMo 3 ofdXPS results show that Mo is6+And Mo5+Are all present in Ru/MoO3-x。Ru-MoO3-xO1 of (A)sThe spectra demonstrate the presence of oxygen defects. Ru-MoO3-xRu 3 of (2)pThe spectra demonstrate that Ru nanoclusters exist at zero valence.
MoO loading by ultra-small Ru nanoclusters of example 23-xThe hydrazine oxidation performance detection is carried out on the bifunctional composite material of the nanobelt and a commercial Pt/C catalyst (purchased from Shanghai national medicine group Co., Ltd.), and the detection method specifically comprises the following steps: a standard three-electrode cell was used for the test using the CHI660E electrochemical workstation, prepared with the catalyst modified carbon cloth (1 cm. times.1 cm) as the working electrode, the high purity graphite rod and the Hg/HgO (1.0M KOH packing) as the counter and reference electrodes, respectively, and the test solution 1M KOH +0.5M N2H4. Polarization curves were obtained using a potential window of-1.1 to-0.3V. Measurement at a rate of 5.0mV s−1Was performed at a sweep rate of (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, the performance polarization curve test results for hydrazine oxidation are shown in FIG. 4, Ru/MoO3-xHas lower hydrazine oxidation overpotential and more excellent reaction kinetics than the commercial Pt/C. As shown in table 1, which catalyzesThe activity has obvious advantages compared with other catalysts reported at present.
TABLE 1 comparison of hydrazine oxidation performance of different materials
MoO loading by ultra-small Ru nanoclusters of example 23-xThe hydrogen evolution performance detection of the double-function composite material of the nanobelt and a commercial Pt/C catalyst (purchased from Shanghai national drug group Co., Ltd.) is carried out by the following specific steps: a standard three-electrode cell was used for the test using the electrochemical workstation CHI660E, the prepared catalyst modified carbon cloth (1cm x 1cm) was the working electrode, the high purity graphite rod and Hg/HgO (1.0M potassium hydroxide filler) were the counter and reference electrodes, respectively, and the test solution was 1M KOH. Polarization curves were obtained using a potential window of-1.4 to-0.8V. Measurement at a rate of 5.0mV s−1Is performed at a scanning rate of (2), all Linear Sweep Voltammetry (LSV) polarization curves are converted to RHE according to the formula of E (RHE) = E (Hg/HgO) +0.095+0.059pH and IR-corrected, and the performance polarization curve test result of hydrogen evolution is shown in FIG. 5, wherein Ru/MoO3-xAt 10mA cm-2The overpotential has a better advantage compared to the commercial Pt/C catalyst.
MoO loading by ultra-small Ru nanoclusters of example 23-xThe hydrazine-assisted electrolytic water performance detection is carried out on the bifunctional composite material of the nanobelt and commercial Pt/C (purchased from Shanghai national drug group, Co., Ltd.), and the detection method specifically 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 catalyst-modified carbon cloths (1cm × 1cm) were used as the cathode and the anode, and the apparatus used was as shown in fig. 6, from which it can be seen that a large number of bubbles were generated at both the cathode and the anode, indicating that they had excellent hydrogen evolution and hydrazine oxidation properties. FIG. 7 is a hydrazine assisted electrolyzed water performance graph as determined by a full electrolyzed water polarization curve test in which 10mA cm is placed in the apparatus-2Is Ru/MoO3-xThe water splitting voltage of the catalyst is only 13mV, which is obviously better than 154mV needed by commercial Pt/C. Phase of performance thereofAlso has significant advantages over most of the catalysts reported so far (as shown in table 2).
TABLE 2 comparison of the Water Electrolysis Performance 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 MoO3-xThe bifunctional composite material of the nanobelt has uniform appearance, is easy to prepare on a large scale, simultaneously has the advantages of large specific surface area, more active sites, high adsorption selectivity, stable structure, excellent hydrogen production performance by electrolyzing water and the like, and has very wide commercial production and application potential.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications 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 are within the scope of the present invention.
Claims (10)
1. Ultra-small Ru nanocluster loaded on MoO3-xThe preparation method of the bifunctional composite material of the nanobelt is characterized by comprising the following steps of:
(1) dissolving a molybdenum salt precursor and a morphology control agent in deionized water, mixing uniformly by ultrasonic waves, injecting strong inorganic acid, continuously stirring uniformly, transferring to a reaction kettle, placing the reaction kettle and the reaction kettle in an oven for hydrothermal reaction at 180-220 ℃ for 3-5 hours, and after the reaction is finished, centrifugally washing for several times to obtain MoO3A nanoribbon;
(2) the prepared MoO3Dispersing the nanobelts and ruthenium metal salt in water, dipping for 2-6 hours while carrying out ultrasonic treatment, then carrying out freeze drying treatment, placing the mixture in a tube furnace, and reducing for 2-3 hours at 350-550 ℃ in hydrogen atmosphere protected by argon to obtain ultra-small Ru nanocluster loaded on MoO3-xBifunctional composite of nanoribbons.
2. According toThe ultra-small Ru nanocluster of claim 1 supported on MoO3-xThe preparation method of the bifunctional composite material of the nanobelt is characterized by comprising the following steps of: the molybdenum salt precursor in the step (1) is ammonium molybdate, and the concentration is 20-50 mg mL-1。
3. The ultra-small Ru nanocluster of claim 1 supported on MoO3-xThe preparation method of the bifunctional composite material of the nanobelt is characterized by comprising the following steps of: 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.
4. The ultra-small Ru nanocluster according to claim 3 supported on MoO3-xThe preparation method of the bifunctional composite material of the nanobelt is characterized by comprising the following steps of: the chromium inorganic salt is chromium chloride, chromium sulfate or chromium nitrate.
5. The ultra-small Ru nanocluster according to claim 1 supported on MoO3-xThe preparation method of the bifunctional composite material of the nanobelt is characterized by comprising the following steps of: the strong inorganic acid in the step (1) is concentrated nitric acid or concentrated hydrochloric acid.
6. The ultra-small Ru nanocluster of claim 1 supported on MoO3-xThe preparation method of the bifunctional composite material of the nanobelt is characterized by comprising the following steps of: the ruthenium metal salt in the step (2) is ruthenium chloride, ruthenium nitrate, ruthenium acetylacetonate or ruthenium acetate, and the ruthenium metal salt and MoO3The mass ratio of the nanobelts is 1: 4-10.
7. The ultra-small Ru nanocluster of claim 1 supported on MoO3-xThe preparation method of the bifunctional composite material of the nanobelt is characterized by comprising the following steps of: the mass concentration of the ruthenium metal salt in the step (2) is 3-6 mg mL-1。
8. The ultra-small Ru nanocluster of claim 1 supported on MoO3-xNano beltThe preparation method of the bifunctional composite material is characterized by comprising the following steps: 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%.
9. Ultra-small Ru nanoclusters prepared based on the method of any one of claims 1 to 8 and loaded on MoO3-xA bifunctional composite of nanoribbons.
10. Loading of ultra-small Ru nanoclusters based on any one of claims 1-9 onto MoO3-xThe bifunctional composite material of the nanobelt is applied to a catalyst for an alkaline hydrazine oxidation reaction or an alkaline water electrolysis hydrogen production reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108682873A (en) * | 2018-05-28 | 2018-10-19 | 南京晓庄学院 | A kind of Ru-MoO3-x/ rGO composite material and preparation methods and application |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| HAIBO YIN等: "Dual Active Centers Bridged by Oxygen Vacancies of Ruthenium Single-Atom Hybrids Supported on Molybdenum Oxide for Photocatalytic Ammonia Synthesis", 《ANGEW. CHEM. INT. ED.》, vol. 61, pages 202114242 - 1 * |
| TEODÓRA NAGYNÉ-KOVÁCS等: "Hydrothermal Synthesis and Gas Sensing of Monoclinic MoO3 Nanosheets", 《NANOMATERIALS》, vol. 10, pages 891 - 1 * |
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