阅读说明：本技术 一种纳米粒状氧化铈物复合钌铂钯氧化物的制备方法 (Preparation method of nano-granular cerium oxide composite ruthenium platinum palladium oxide ) 是由 段德良 樊微微 王全 郝天辉 曾丽娟 吴晨曦 于 2019-11-27 设计创作，主要内容包括：本发明涉及一种纳米微粒状氧化铈物复合钌铂钯氧化物的制备方法,制备方法包括以下步骤：1)配置铈盐、钌盐、铂盐和钯盐的混合溶液,在搅拌条件下,加入沉淀剂溶液,反应结束后得到反应混合物；2)将步骤(1)得到的反应混合物加入反应釜内,将反应釜密封,在一定温度下反应,然后放置冷却至室温,反应物经过滤、洗涤、干燥后得到纳米微粒状氧化铈物复合钌铂钯氧化物。本发明的材料及方法具有工艺简单易行、实验流程短、条件温和的优点；其制备方法：在稀土金属铈的氧化物中负载少量的RuO<Sub>2</Sub>和Pt和Pd,结合水热合成技术产生特征结构的精细组合,得到的纳米微粒状氧化铈物复合钌铂钯氧化物成为超级电容器用理想的电极材料,非常适合大批量生产。(The invention relates to a preparation method of a nano-particle cerium oxide composite ruthenium platinum palladium oxide, which comprises the following steps: 1) preparing a mixed solution of cerium salt, ruthenium salt, platinum salt and palladium salt, adding a precipitator solution under the condition of stirring, and obtaining a reaction mixture after the reaction is finished; 2) and (2) adding the reaction mixture obtained in the step (1) into a reaction kettle, sealing the reaction kettle, reacting at a certain temperature, standing and cooling to room temperature, and filtering, washing and drying reactants to obtain the nano-particle cerium oxide composite ruthenium platinum palladium oxide. The material and the method have the advantages of simple and feasible process, short experimental flow and mild conditions; the preparation method comprises the following steps: in the rare earth metal ceriumIn which a small amount of RuO is supported 2 And Pt and Pd, and the fine combination of the characteristic structures is generated by combining the hydrothermal synthesis technology, so that the obtained nano-particulate cerium oxide composite ruthenium platinum palladium oxide becomes an ideal electrode material for the super capacitor, and is very suitable for mass production.)

1. A preparation method of a nanometer particulate cerium oxide composite ruthenium platinum palladium oxide is characterized by comprising the following steps: 1) preparing a mixed solution of cerium salt, ruthenium salt, platinum salt and palladium salt, adding a precipitator solution under the condition of stirring, and obtaining a reaction mixture after the reaction is finished; 2) and (2) adding the reaction mixture obtained in the step (1) into a reaction kettle, sealing the reaction kettle, reacting at a certain temperature, standing and cooling to room temperature, and filtering, washing and drying reactants to obtain the nano-particle cerium oxide composite ruthenium platinum palladium oxide.

2. The method according to claim 1, wherein the step 1 comprises: when the precipitant solution is added under stirring, the solution is added dropwise.

3. The method according to claim 1 or 2, wherein the step 1 comprises: and (3) adding the precipitant solution while stirring, dropwise adding sodium citrate with the mass percent concentration of 10%, wherein the color of the dropwise added solution is changed, and finally the solution is turbid.

4. The preparation method according to claim 1, wherein the solvent of the mixed solution is a mixture obtained by mixing one or more of water, ethanol, methanol and acetone in any proportion;

the cerium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of cerium according to any proportion; the ruthenium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of ruthenium according to any proportion; the platinum salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of platinum according to any proportion; the palladium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of palladium according to any proportion;

the precipitant in the precipitant solution is KOH, NaOH or Na₂CO₃、NH₃·H₂And one or more of O is mixed according to any proportion to obtain a mixture.

5. The production method according to claim 4, wherein the concentrations of the cerium salt, the ruthenium salt, the platinum salt and the palladium salt in the mixed solution are each 0.0001 to 1.00 mol/L; the mass percentage concentration of the precipitant solution is 1-25%; the molar ratio of the cerium ions, the ruthenium ions, the platinum ions and the palladium ions in the mixed solution is 1: 0.001-0.2: 0.0001-0.05.

6. The method according to claim 5, wherein the step 1 comprises: adding precipitant solution and sodium citrate under stirring, and controlling reaction time at 10-40 min.

7. The method as set forth in claim 1, wherein the step 2 comprises: the reaction temperature in the reaction kettle is 80-220 ℃; keeping the temperature and reacting for 4-18 h.

8. The method as set forth in claim 7, wherein the step 2 includes: the reaction temperature in the reaction kettle is preferably 160-200 ℃; keeping the temperature and reacting for 4-8 h.

9. The method as set forth in claim 1, wherein the step 2 comprises: the drying temperature in the drying is 40-180 ℃; the drying time is 2-24 h. The preferred drying conditions are: at 60-80 deg.C; drying for 3-6 h.

10. Use of the nano-particulate ceria-ruthenium platinum palladium oxide obtained by the method for producing a nano-particulate ceria-ruthenium platinum palladium oxide according to any one of claims 1 to 9, as a catalytic oxidation electrode material or a supercapacitor electrode material.

Technical Field

The invention relates to a preparation method and application of a composite ruthenium platinum palladium oxide of a nano-particulate cerium oxide, belonging to the technical field of inorganic material preparation.

Background

The development of nano science opens up a new field for the research of new materials, the regulation and synthesis of the micro-nano material with a special structure have important significance in basic scientific research and practical application, and particularly, a complex nano structure with a special shape and structure, which is obtained by self-assembly of low-dimensional nano units, can obtain better physical or chemical properties.

The controllability of grain size and grain size distribution can be achieved by controlling the synthesis conditions (such as reactant concentration, temperature, crystallization time, etc.). Dongcing et al (hydrothermal crystallization method for preparing CeO)₂Nanocrystalline, rare metal materials and engineering, 2002,31(4):312.) hydrothermal method to obtain CeO with average particle size of about 8nm₂And (4) nanocrystals. Shouchu et al (ammonium bicarbonate precipitation method for preparing cerium dioxide ultrafine powder, mining and metallurgy engineering, 2003,23(1):41.) uses (N H)₄)HCO₃The CeO with the average grain diameter less than 20nm is prepared by a precipitation method₂. CeO2 material prepared by decomposition of ammonium carbonate (prepared by two-step precipitation method and having high temperature resistance and excellent reducing performance, reported in inorganic chemistry, 2O12,28(5):1001)₂The material is aged for 3h at 900 ℃, and the specific surface area of the material is still 27 m/g. Geo et al (Graphene-based therapeutics, chemical bulletin 1998,61(12):51.) prepared CeO by microemulsion method using oil-in-water microemulsion system as reaction medium₂Ultrafine particles. Xuhong et al (carbon nanotube macro-filmsfor energystorage, Shenzhen university proceedings, science and technology edition, 2002, l9(2):13.) CeO with particle size less than 100nm is prepared by room temperature wet solid phase reaction method (room temperature solid phase reaction method)₂(ii) a G uillou et al (AReview of electrode materials for electric cell)Using an inert gas condensation method to prepare CeO with uniform particle size of 3.0-3.5 nm₂(ii) a R.D. Purohit et al (A new particulate reduced graphene oxide material/polyanilino oxide superconductor electrolyte material, Mater Res Bull,2001,36(15):2711.) have been synthesized by combustion method to obtain superfine CeO with average particle size of 10nm and good sintering property₂。CeO₂The structural and structural properties of (a) and the stability of its material require further and more intensive research. The main problems are as follows: the material has unstable tissue and structural characteristics, small holes and large holes respectively have sintering, collapse and other phenomena under the high-temperature condition, and the specific surface, the pore volume, the pore size distribution, the oxygen storage performance and other aspects of the material are seriously influenced due to the serious agglomeration of acting force among particle groups, so the stability of the material is also influenced.

Different raw material ratios have an influence on the composition and electrochemical properties of the product. The organic template is removed to obtain inorganic material with specific morphology and structure, and the method may be dissolution or calcination. The commonly used organic template agents include polysaccharides, microemulsions formed by surfactants (such as CTAB), block copolymers (such as P123), polypeptides, LB membranes, and the like. The hydrothermal method is that a mixed salt solution containing divalent and trivalent metal ions and a precipitator are quickly mixed to form nuclei, the obtained slurry is quickly transferred into a hydrothermal kettle and reacts for a period of time under the hydrothermal condition, and therefore the crystallinity of the hydrotalcite can be improved. And after the hydrothermal kettle is naturally cooled, taking out the mixed slurry in the hydrothermal kettle, repeatedly washing and filtering, and finally drying the filter cake to obtain the target product. The aging temperature and pressure in the process are two important factors that affect crystallinity.

Ruthenium dioxide (RuO)₂) The specific capacitance of the metal oxide is firstly studied as an electrode material and can reach 1170F g^-1. Oxidation-reduction capacitance characteristics and RuO of Iridium dioxide₂Similarly, although good conductivity, high specific capacity, high energy density and high power density (J.Power Sources,1996,62(2):155-The main reason for this is that they are toxic and expensive. There is a continuing effort to find alternative inexpensive alternative oxides.

However, the specific capacity of these materials is not comparable to that of ruthenium dioxide. Ruthenium dioxide (RuO)₂) Various problems are faced in the selection of alternative materials as electrode materials, amorphous RuO₂The particles are loose, proton diffusion is facilitated, the capacitance characteristic is good, and the utilization rate of the material is increased; crystalline RuO₂Large specific surface area and long charge-discharge life. In 1992, Raiis thermally decomposes and oxidizes RuCl dissolved in water or ethanol at 300-800 DEG C₃·xH₂Precursor solution of O to obtain specific surface area of about 120m²/g, specific capacity can reach 380F/g ultra-fine micro-crystalline RuO₂And (3) a membrane. Jow et al (J.ElectrochemSoc,1995,142: L6-L8) prepared amorphous hydrated ruthenium oxide with specific capacity up to 768F/g and good charge-discharge performance at low temperature of 150 ℃ by the most common sol-gel method. The use of a large amount of ruthenium dioxide with high content has the disadvantages of high price, complex preparation process and the like.

The invention fully considers economic factors on the premise of not sacrificing power density, can carry out reasonable and effective large-scale production, and finally designs and develops an electrode material with high energy density, which is a technical problem to be solved urgently.

Disclosure of Invention

Based on the understanding of the defects of the problems, the invention finds a practical material with excellent performance by combining rare earth metal and noble metal, and replaces expensive noble metal RuO by a preparation process method₂It becomes possible. The material and the method have the advantages of simple and feasible process, short experimental flow and mild conditions; the preparation method comprises the following steps: loading small amount of RuO in rare earth metal cerium oxide₂And Pt and Pd, and the fine combination of the characteristic structures is generated by combining the hydrothermal synthesis technology, so that the obtained nano-particulate cerium oxide composite ruthenium platinum palladium oxide becomes an ideal electrode material for the super capacitor, and is very suitable for mass production.

The invention is realized by adopting the following technical scheme.

The invention discloses a preparation method of a nanometer particulate cerium oxide composite ruthenium platinum palladium oxide, which comprises the following steps: 1) preparing a mixed solution of cerium salt, ruthenium salt and platinum salt, adding a precipitator solution under the condition of stirring, and obtaining a reaction mixture after the reaction is finished; 2) and (2) adding the reaction mixture obtained in the step (1) into a reaction kettle, sealing the reaction kettle, reacting at a certain temperature, standing and cooling to room temperature, and filtering, washing and drying reactants to obtain the nano-particle cerium oxide composite ruthenium platinum palladium oxide.

Further, step 1 of the present invention includes: when the precipitant solution is added under stirring, the solution is added dropwise.

Further, step 1 of the present invention includes: and (3) adding the precipitant solution while stirring, dropwise adding sodium citrate with the mass percent concentration of 10%, wherein the color of the dropwise added solution is changed, and finally the solution is turbid.

Further, the solvent of the mixed solution is a mixture obtained by mixing one or more of water, ethanol, methanol and acetone according to any proportion;

the cerium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of cerium according to any proportion; the ruthenium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of ruthenium according to any proportion; the platinum salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of platinum according to any proportion; the palladium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of palladium according to any proportion;

the precipitant in the precipitant solution is KOH, NaOH or Na₂CO₃、NH₃·H₂And one or more of O is mixed according to any proportion to obtain a mixture.

Further, the concentrations of cerium salt, ruthenium salt, platinum salt and palladium salt in the mixed solution are all 0.0001-1.00 mol/L; the mass percentage concentration of the precipitant solution is 1-25%; the molar ratio of the cerium ions, the ruthenium ions, the platinum ions and the palladium ions in the mixed solution is 1: 0.001-0.2: 0.0001-0.05.

Further, step 1 of the present invention includes: adding precipitant solution and sodium citrate under stirring, and controlling reaction time at 10-40 min.

Further, step 2 of the present invention includes: the reaction temperature in the reaction kettle is 80-220 ℃; keeping the temperature and reacting for 4-18 h.

Further, step 2 of the present invention includes: the reaction temperature in the reaction kettle is preferably 160-200 ℃; keeping the temperature and reacting for 4-8 h.

Further, step 2 of the present invention includes: the drying temperature in the drying is 40-180 ℃; the drying time is 2-24 h. The preferred drying conditions are: at 60-80 deg.C; drying for 3-6 h.

The application of the nano granular cerium oxide composite ruthenium platinum palladium oxide prepared by the preparation method of the nano granular cerium oxide composite ruthenium platinum palladium oxide is used as a catalytic oxidation electrode material or a super capacitor electrode material.

The invention has the beneficial effects that (1) the nanometer particle cerium oxide compound ruthenium platinum palladium oxide prepared by the method has the characteristics of nanometer structure and high electron transfer rate and storage capacity, and is suitable for being used as a catalytic material and an energy storage material; is suitable for reasonable, effective and efficient large-scale preparation; the prepared material has specific capacity of 680F/g, and can be used as an electrode material with excellent performance and a super capacitor electrode material;

(2) according to the method, the effective regulation and control of the nano granular morphology can be realized by regulating the temperature, the gradual rise of the temperature is beneficial to the forming of the complete granular nano granular structure, the ruthenium, the platinum and the palladium are uniformly embedded into the cerium oxide, the forming rate of the nano granular structure is influenced by the over-high temperature, the structure becomes finer and is not beneficial to forming;

(3) the method can regulate and synthesize various rare earth metal composite noble metal micro/nano materials with a multistage structure by a simple hydrothermal synthesis method without adding any template agent and surfactant.

The invention is further explained below with reference to the drawings and the detailed description.

Drawings

FIG. 1 is an infrared spectrum of a composite material obtained in example 1 of the present invention.

FIG. 2 is a scanning electron micrograph of the composite material obtained in example 1 of the present invention.

FIG. 3 is an X-ray diffraction chart of the composite material obtained in example 1 of the present invention.

FIG. 4 is an electrocatalytic oxidation diagram of the composite material obtained in example 3 of the present invention.

FIG. 5 is a graph of the electrocatalytic oxidation of anisodamine of the composite material obtained in example 3 of the present invention.

Detailed Description

The following will explain in detail the nanoparticulate ceria-ruthenium platinum-palladium composite oxide material prepared in example 1 by way of example.

The invention discloses a preparation method of a nanometer particulate cerium oxide composite ruthenium platinum palladium oxide, which comprises the following steps: 1) preparing a mixed solution of cerium salt, ruthenium salt, platinum salt and palladium salt, adding a precipitator solution under the condition of stirring, and obtaining a reaction mixture after the reaction is finished; 2) and (2) adding the reaction mixture obtained in the step (1) into a reaction kettle, sealing the reaction kettle, reacting at a certain temperature, standing and cooling to room temperature, and filtering, washing and drying reactants to obtain the nano-particle cerium oxide composite ruthenium platinum palladium oxide.

Further, step 1 of the present invention includes: when the precipitant solution is added under stirring, the solution is added dropwise.

Further, step 1 of the present invention includes: and (3) adding the precipitant solution while stirring, dropwise adding sodium citrate with the mass percent concentration of 10%, wherein the color of the dropwise added solution is changed, and finally the solution is turbid.

Further, the solvent of the mixed solution is a mixture obtained by mixing one or more of water, ethanol, methanol and acetone according to any proportion;

the cerium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of cerium according to any proportion; the ruthenium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of ruthenium according to any proportion; the platinum salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of platinum according to any proportion; the palladium salt is a mixture obtained by mixing one or more of nitrate, sulfate, halide, phosphate and organic carboxylate of palladium according to any proportion;

the precipitant in the precipitant solution is KOH, NaOH or Na₂CO₃、NH₃·H₂And one or more of O is mixed according to any proportion to obtain a mixture.

Further, the concentrations of cerium salt, ruthenium salt, platinum salt and palladium salt in the mixed solution are all 0.0001-1.00 mol/L; the mass percentage concentration of the precipitant solution is 1-25%; the molar ratio of cerium ions to ruthenium ions to platinum ions in the mixed solution is 1: 0.001-0.2: 0.0001-0.05.

Further, step 1 of the present invention includes: adding precipitant solution and sodium citrate under stirring, and controlling reaction time at 10-40 min.

Further, step 2 of the present invention includes: the reaction temperature in the reaction kettle is 80-220 ℃; keeping the temperature and reacting for 4-18 h.

Further, step 2 of the present invention includes: the reaction temperature in the reaction kettle is preferably 160-200 ℃; keeping the temperature and reacting for 4-8 h.

Further, step 2 of the present invention includes: the drying temperature in the drying is 40-180 ℃; the drying time is 2-24 h. The preferred drying conditions are: drying at 60-80 deg.C for 3-8 hr.

The application of the nano granular cerium oxide composite ruthenium platinum palladium oxide prepared by the preparation method of the nano granular cerium oxide composite ruthenium platinum palladium oxide is used as a catalytic oxidation electrode material or a super capacitor electrode material.

Establishment of the materials of the invention:

the infrared spectrum of the nanometer particulate cerium oxide composite ruthenium platinum palladium oxide material prepared by the method is shown in figure 1, wherein 3419 cm, 1632 cm, 1399 cm and 1117cm are shown^-1Nearby sharp absorption peak and stretching vibration (v) without hydrogen bond_Ce-O) Correlation, 480, 432cm^-1The nearby absorption peak is related to the lattice vibration of Ce — O.

The scanning electron microscope result of the material is shown in figure 2: the shape of the nano-crystalline material is nearly transparent and is provided with a plurality of folds from the scanning electron microscope picture, the particles exist in a pile, and a plurality of Ce/Ru/Pt/Pd-O exist in the nano-crystalline material₂The composite cerium oxide and ruthenium, platinum and palladium were present in the form of particles, and the particle size of the material was found to be<On the order of 20nm, multiple particles can be packed together to form a composite multilevel structure. The material can be judged to be nano-particle cerium oxide composite ruthenium platinum palladium oxide by an energy spectrum chart and data thereof.

The X-ray diffraction pattern of the material is shown in figure 3: the diffraction peak position in the figure shows that the prepared composite material has CeO₂The structure shows stronger diffraction peaks at 29.02 degrees, 33.04 degrees, 47.54 degrees, 56.96 degrees and other places of 2 theta, and the intensities and positions of the characteristic diffraction peaks are related to CeO reported in the literature₂The relative intensities and positions of the characteristic diffraction peaks remain substantially unchanged.

The nano-particulate cerium oxide composite ruthenium platinum palladium oxide material is loaded on a glassy carbon electrode, and the electrocatalytic oxidation activity is obviously improved, as shown in figure 4. And electrocatalytic oxidation of the anisodamine which is difficult to oxidize is realized, as shown in figure 5.

The following are specific details of the preparation of the materials of the present invention to illustrate the process steps of the present invention.