CN115557469B - Amorphous noble metal oxide material and preparation method and application thereof - Google Patents

Amorphous noble metal oxide material and preparation method and application thereof Download PDF

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CN115557469B
CN115557469B CN202211136620.9A CN202211136620A CN115557469B CN 115557469 B CN115557469 B CN 115557469B CN 202211136620 A CN202211136620 A CN 202211136620A CN 115557469 B CN115557469 B CN 115557469B
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魏呵呵
龚学庆
李辉
刘慧慧
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East China University of Science and Technology
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Abstract

The invention relates to an amorphous noble metal oxide material and a preparation method and application thereof. Compared with the prior art, the method has the characteristics of simple synthesis method, high yield, excellent product performance, strong stability, small pollution hazard and the like, and has the potential of realizing large-scale production.

Description

Amorphous noble metal oxide material and preparation method and application thereof
Technical Field
The invention relates to the technical fields of material science and engineering technology and chemistry, in particular to an amorphous noble metal oxide material and a preparation method and application thereof.
Background
Metal oxides are common states of presence of metals. Metallic materials, which are important inorganic substances, are over two thirds of the element species of the periodic table, and possess rich and attractive physicochemical properties. Besides common iron, copper, zinc, aluminum and other indispensable high-abundance metal elements and noble metals in life, the rare material with more complex structure is widely used in the fields of catalysis, electronics, optical imaging, information storage, sensing, medicine and the like, and has irreplaceable functions and technological application potential. Research shows that the metal oxide has unique physical and chemical properties, is closely related to a series of physical parameters such as size, shape, oxidation degree and structure, and the like, and the accurate control of the related parameters is important in the preparation process of corresponding high-performance special metal oxide materials. In particular, amorphous nanomaterials are complex in structure, but possess high catalytic selectivity, activity and stability due to unique disordered structures and internal defects, and have attracted wide attention in electrochemical applications such as lithium ion batteries, sensors and water oxidation.
How to increase the effective utilization rate of noble metal atoms as active sites in a very wide variety of catalytic reaction processes, thereby increasing the activity and reducing the cost of large-scale application is always a core problem in the fields of material science and catalysis. Compared with the traditional noble metal-based catalyst, the amorphous noble metal catalyst not only can remarkably improve the effective utilization rate of metal serving as a catalytic reaction active site according to defects and complex surface structures so as to realize higher quality activity, but also has better catalytic selectivity and stability. Therefore, the high-performance noble metal amorphous material with the nano structure is prepared in a large scale, and the high catalytic activity, the high quality activity and the high stability and the green and safe production cycle way are obtained, so that the low-cost and high-efficiency green catalyst is realized and is put into large-scale use, and the method has important scientific significance and economic value.
Considering that the structure of the metal amorphous material is easy to be damaged under the pyrolysis, the preparation method represented by the way of regulating and controlling the precursor and calcining at the present stage has higher metal loading, but lower relative metal mass activity, low yield and low utilization rate. How to prepare amorphous noble metal oxide catalysts with high-quality activity on a large scale on the premise of ensuring the performance is still a problem to be solved in the related field.
Disclosure of Invention
The invention aims to provide an amorphous noble metal oxide material, and a preparation method and application thereof.
The aim of the invention can be achieved by the following technical scheme: a process for preparing the amorphous noble metal oxide material includes such steps as mixing the precursor solution of metal organic salt with reducer to obtain redox reaction solution, fully mixing, dispersing, and solvothermal reaction.
Further preferably, the mixing and dispersing process is performed in an environment at normal temperature and normal pressure.
Preferably, in the metal organic salt precursor solution, the metal is one or more of Ag, ru, pd, ir, pt, mo, co, ce, cu, fe, mn, and the solvent is one or more of water, methanol, ethanol, acetic acid, ethylene glycol, isopropanol, glycerol, acetone, chloroform, diethyl ether, tetrahydrofuran, dimethylformamide and formaldehyde. The organic ligand groups related to the metal organic salt precursor have key influence factors on the structure and defect regulation of the amorphous state.
The metal salt organic ligand group mainly selected by the invention is an acetyl acetonate group, and is characterized by having abundant C=O and C-O bonds and being capable of being combined with metal ions in a specific valence state, such as Ir 4+ The metal is reduced, fine crystal is nucleated, organic ligand is coated and grown and cured in the reaction process, so that the unique amorphous metal oxide structure is formed.
Further preferably, the preparation method of the metal organic salt precursor solution comprises the steps of dissolving levulinones organic salt in a solvent, adding an aqueous solution of chloroiridium acid, and mixing to obtain the metal organic salt precursor solution.
Still more preferably, the solvent is a mixed solution of water and glycol which are formed by a certain proportion, and the glycol has the effects of both the solvent and the reducing agent.
Preferably, the molar concentration of the metal in the metal organic salt precursor solution is 0.001-1.0mol/L.
Preferably, the reducing agent is a weak reducing agent, and the nucleation growth of crystals is controlled.
Further preferably, the reducing agent comprises formic acid, ethanol, acetic acid, ethylene glycol, isopropanol, glycerol, ascorbic acid, glucose, CO (NH) 2 ) 2 、Na 2 SO 3 、K 2 SO 3 Or H 2 C 2 O 4 One or more of the following. The metal organic salt precursor is controlled to be reduced, nucleated and aggregated and coated in a high-temperature and high-pressure environment of hydrothermal reaction by the chemical reagent with weak reducibility, and finally the nano-scale dispersed amorphous noble metal oxide material is formed.
Preferably, in the redox reaction solution, the solvent is a mixture of water and one of ethanol, acetic acid, ethylene glycol, isopropanol, glycerol, acetone, chloroform, diethyl ether, tetrahydrofuran, dimethylformamide or formaldehyde.
Preferably, the mixing and dispersing process adopts ultrasonic and magnetic stirring.
Preferably, the solvothermal reaction temperature is 80-300 ℃ and the reaction time is 0-72h.
Further preferably, the solvothermal reaction temperature is 80-300 ℃ and the reaction time is 1-72h.
Still more preferably, the solvothermal reaction temperature is 80-300 ℃ and the reaction time is 1-48h.
Preferably, the product generated by the solvothermal reaction is further subjected to purification and acid washing for 0-12 hours, so that a material with better activity and stability can be obtained.
Further preferably, the dried product is subjected to ultrasonic dispersion cleaning for a plurality of times by using an acid solution with the concentration of 1 mol per liter, and is kept stand for 1 to 12 hours, and the product is subjected to centrifugal cleaning and drying again, so that the high-purity nano-level dispersed amorphous noble metal oxide composite material can be obtained.
An amorphous noble metal oxide material is prepared by the preparation method.
Preferably, the amorphous noble metal oxide material is dispersed in the nanometer scale.
Further preferably, the prepared nano-scale dispersed amorphous noble metal oxide material is subjected to centrifugal or vacuum filtration and cleaning at normal temperature and normal pressure, and then is dried to obtain the corresponding high-performance material.
Further preferably, the nano-sized dispersed amorphous noble metal oxide material comprises a single metal, multi-metal nanocluster or ultra-fine metal oxide or other structure.
The amorphous noble metal oxide material is used in hydrogen evolution, oxygen evolution and full hydrolysis.
Solution synthesis is a conventional method for mass production of metal materials, and can effectively control the growth process of crystals. The traditional method controls the generation of related crystals by controlling the concentration of the solution and changing the temperature, so that the reliability is low, and the yield of the product and the utilization rate of the metal cannot be greatly improved. Considering that the solvent and the reducing agent are taken as important components for influencing the chemical reaction kinetics and the reaction, the proper solvent and the reducing agent can be used for obviously controlling the growth mechanism of crystals and inhibiting the agglomeration of the metal nano particles, thereby improving the dispersion degree of the metal nano particles in the carrier, and further exposing more active sites to obtain the nano-scale dispersed metal atom composite material with high quality activity and specific activity. In addition, the precursor is selected from corresponding organic metal salt, the nucleation of crystals is controlled in a solvothermal controllable high-pressure high-temperature reaction environment, and organic functional groups are doped into the product, so that the amorphous oxide metal material with characteristics can be generated. Therefore, the invention provides and realizes a method for optimizing the composition of the solvent and the reducing agent, and the method and the process for preparing the amorphous noble metal oxide high-performance functional material with large-scale nanoscale dispersion are realized by controlling the precursor preparation flow and the solvothermal reaction condition and selecting a special organic metal salt precursor.
The reaction system constructed by the invention is a liquid-phase solvothermal oxidation-reduction reaction system, and chemical reduction and thermal reduction are carried out by ensuring that the carrier and the precursor are uniformly dispersed in a solvent.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a synthesis method of a high-quality active high-performance nano-level dispersed amorphous noble metal oxide material, which has simple process and easy operation, effectively adsorbs and stabilizes metal clusters obtained by various processes such as chemical reduction, thermal reduction and the like on the surfaces of various carriers, controls the growth of crystals and ligands thereof, and is suitable for the preparation process of the amorphous noble metal oxide material with various metal and transition metal nano structures such as Ag, ru, pd, ir, pt, mo, co, ce, cu, fe, mn and the like;
2. the method is different from the traditional high-temperature calcination and impregnation methods, and the nano material synthesized by controlling the types and concentration ratio of the precursor can effectively regulate and control the metal dispersion degree and the load capacity, has the advantages of low metal load capacity, high efficiency, strong applicability and the like, and has remarkable advantages in the large-scale commercial development process;
3. the method selects the correct metal organic salt precursor and utilizes the ultrasonic dispersion and magnetic stirring methods to lead the precursor to be fully and uniformly dispersed in the solvent, thus being a key factor for regulating and controlling the final shape and distribution of the material;
4. the method reduces the metal organic salt precursor into the metal amorphous state through the reaction of the weak reducing agent at high temperature, and compared with the traditional impregnation method and pyrolysis method for preparing the noble metal crystal loading material, the method has the characteristics of uniform loading, adjustable defect structure, high metal activity and the like.
Drawings
FIG. 1 is a transmission electron microscope image of an iridium molybdenum oxide amorphous material prepared by the method of the present invention;
FIG. 2 is a scanning transmission electron microscope image of an iridium molybdenum oxide amorphous material prepared by the method of the present invention;
FIG. 3 is a graph of the performance of an oxygen evolution reaction of an iridium molybdenum oxide amorphous material;
FIG. 4 is a scanning transmission electron microscope image of iridium molybdenum oxide amorphous material supported on nanocarbon spheres;
FIG. 5 is an X-ray diffraction pattern of a series of noble metal oxide amorphous materials;
fig. 6 is a graph of stability testing of iridium molybdenum oxide amorphous material in a long-term oxygen evolution reaction.
FIG. 7 is a graph comparing the performance of a bi-electrode acidic environment perhydrolysis system, iridium molybdenum oxide amorphous material with a commercial catalyst.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The following examples are given by way of illustration of detailed embodiments and specific procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
And (3) preparing the nano iridium molybdenum oxide amorphous composite material.
First, a certain amount of acetylacetone is addedMolybdenum was used in a volume ratio of about 4:1 in water/glycol mixed solution to obtain a molybdenum acetylacetonate dispersion B. Subsequently, the chloroiridium acid solution was added to and mixed with the dispersion B to prepare an iridium concentration (about 2mM L -1 ) And molybdenum acetylacetonate (about 3mg ml) -1 ) The water/glycol mixed solution of (2) is used as the reaction solution of the system, and the glycol in the solution is used as Ir in chloroiridium acid at the same time 4+ A reducing agent for the metal precursor. Next, the reaction solution was placed in an ultrasonic cleaner, and dispersed at a full power of 300W for at least 30 minutes. After the ultrasonic dispersion is completed, adding a magneton into the reaction solution to continue magnetic stirring and dispersion, wherein the rotation speed is kept above 900rpm, and the stirring time is not less than 12 hours. And then immediately placing the PPL lining with the uniformly dispersed reaction liquid into a Teflon hydrothermal reaction kettle, performing solvent heat sealing reaction for 6-48 hours at 160 ℃, and then completing material recovery and cleaning by utilizing centrifugal separation and naturally drying at room temperature. And (3) carrying out ultrasonic dispersion cleaning on the dried product for a plurality of times by using hydrochloric acid with the concentration of one mole, standing for 1-6h, and carrying out centrifugal cleaning and drying on the product again to obtain the high-purity nano-level dispersed iridium-molybdenum oxide amorphous composite material.
The transmission and scanning transmission electron microscope pictures of the nano iridium molybdenum oxide amorphous composite material prepared by the embodiment are shown in figures 1-2, and it can be seen from the figures that the amorphous material is in a whole block in the high-angle annular dark field image, and no obvious particle distribution exists. Under a high-definition transmission electron microscope, the size of the iridium molybdenum oxide amorphous composite material is about 50-100 nanometers, the iridium molybdenum oxide amorphous composite material is dispersed in a nanometer level, crystal face morphology and lattice fringes are not observed under the high-power transmission electron microscope, and a lattice is not generated in Fourier analysis.
The nano iridium molybdenum oxide amorphous composite material prepared by the embodiment is used for hydrogen evolution, oxygen evolution and full hydrolysis reaction. The test method is that the nano iridium molybdenum oxide amorphous composite material and nano carbon are fully mixed on a glassy carbon electrode with the diameter of 5 mm, the ink is completely dried to prepare a working electrode, and then the relationship between voltage and current density is tested through a three-electrode system (using silver/silver chloride as a reference electrode and a carbon rod as a counter electrode), as shown in fig. 3, 4 and 6, the composite material of the embodiment has excellent oxygen evolution catalysis performance, and the overpotential only needs 361 millivolts under the current density reaching 100 milliampere per square centimeter. Meanwhile, the catalyst has excellent stability of acid oxygen evolution reaction. Under a scanning transmission microscope, the nano iridium molybdenum oxide amorphous composite material can be fully dispersed, and becomes fine nanoclusters to be loaded in 40-60 nano carbon spheres.
Example 2
And (3) preparing the nano iridium cerium oxide amorphous composite material.
Firstly, a certain amount of cerium acetylacetonate is weighed, and the cerium acetylacetonate is dissolved by using an aqueous solution A of a water/glycol mixed solution with a volume ratio of about 4:1, so as to obtain a cerium acetylacetonate dispersion liquid B. During this period, chloroiridic acid was added to and mixed with the dispersion liquid B to prepare a water/glycol mixed solution of iridium concentration and cerium acetylacetonate as a reaction solution. Then, the reaction solution was placed in an ultrasonic cleaner, and dispersed for 30 minutes at a full power of 300W. After the ultrasonic dispersion is completed, adding a magneton into the reaction solution to continue magnetic stirring and dispersion, wherein the rotation speed is kept above 900rpm, and the stirring time is not less than 12 hours. And then immediately placing the PPL lining with the uniformly dispersed reaction liquid into a Teflon hydrothermal reaction kettle, performing solvent heat sealing reaction for 6-48 hours at 160 ℃, fully completing material recovery and cleaning by utilizing centrifugal separation, and naturally drying at room temperature. Thus obtaining the nano-dispersed iridium cerium oxide amorphous composite material.
Example 3
And (3) preparing the nanoscale iridium iron oxide amorphous composite material.
Firstly, a certain amount of ferric acetylacetonate is weighed, and the ferric acetylacetonate is dissolved by using an aqueous solution A of a water/glycol mixed solution with a volume ratio of about 4:1, so as to obtain a ferric acetylacetonate dispersion liquid B. During this period, chloroiridic acid was added to and mixed with the dispersion liquid B to prepare a water/glycol mixed solution of iridium concentration and iron acetylacetonate as a reaction solution. Then, the reaction solution was placed in an ultrasonic cleaner, and dispersed for 30 minutes at a full power of 300W. After the ultrasonic dispersion is completed, adding a magneton into the reaction solution to continue magnetic stirring and dispersion, wherein the rotation speed is kept above 900rpm, and the stirring time is not less than 12 hours. And then immediately placing the PPL lining with the uniformly dispersed reaction liquid into a Teflon hydrothermal reaction kettle, performing solvent heat sealing reaction for 6-48 hours at 160-200 ℃, fully completing material recovery and cleaning by utilizing centrifugal separation, and naturally drying at room temperature. Thus obtaining the nano-dispersed iridium-iron oxide amorphous composite material.
Example 4
And (3) preparing the nano iridium cobalt oxide amorphous composite material.
Firstly, a certain amount of cobalt acetylacetonate is weighed, and the cobalt acetylacetonate is dissolved by using an aqueous solution A of a water/glycol mixed solution with a volume ratio of about 4:1, so as to obtain a cobalt acetylacetonate dispersion liquid B. During this period, chloroiridic acid was added to and mixed with the dispersion liquid B to prepare a water/glycol mixed solution of iridium concentration and cobalt acetylacetonate as a reaction solution. Then, the reaction solution was placed in an ultrasonic cleaner, and dispersed for 30 minutes at a full power of 300W. After the ultrasonic dispersion is completed, adding a magneton into the reaction solution to continue magnetic stirring and dispersion, wherein the rotation speed is kept above 900rpm, and the stirring time is not less than 12 hours. And then immediately placing the PPL lining with the uniformly dispersed reaction liquid into a Teflon hydrothermal reaction kettle, performing solvent heat sealing reaction for 6-48 hours at 160-200 ℃, fully completing material recovery and cleaning by utilizing centrifugal separation, and naturally drying at room temperature. Thus obtaining the nano-dispersed iridium cobalt oxide amorphous composite material.
Example 5
And (3) preparing the nanoscale iridium-carbon composite material.
Firstly, a certain amount of XC72R carbon carrier (hollow carbon sphere, diameter 40-60 nm) is weighed, and aqueous solution A of water/glycol mixed solution with volume ratio of about 4:1 is added, during which time, the aqueous solution of chloroiridic acid is added into the mixture to obtain reaction solution B. Then, the reaction solution was placed in an ultrasonic cleaner, and dispersed for 30 minutes at a full power of 300W. After the ultrasonic dispersion is completed, adding magnetons into the reaction solution to continue magnetic stirring and dispersing, wherein the rotating speed is kept above 900rpm, and the stirring time is not less than 12 hours, so as to prepare the iridium ion and water/glycol mixed reaction solution with uniformly dispersed carbon carriers. And then, immediately placing the uniformly dispersed reaction solution into a PPL lining, then placing into a Teflon hydrothermal reaction kettle, performing solvent heat sealing reaction for 6-48 hours at 160-200 ℃, fully completing material recovery and cleaning by utilizing centrifugal separation, and naturally drying at room temperature. Thus obtaining the nano-dispersed iridium-carbon composite material.
As shown in the figure 5, the peak shape of the iridium-carbon composite material dispersed in the nanometer level is seriously widened in the X-ray diffraction spectrum, which indicates that the crystallinity of the material is very weak, and the iridium-carbon composite material is a structure similar to an amorphous state. The diffraction peak of the (111) crystal face of iridium element is close to the diffraction peak of the diffraction broad peak, which proves the existence of iridium element. Compared with the samples prepared by other examples, the nanometer iridium molybdenum, iridium iron and iridium cobalt oxide X-ray diffraction spectrograms have extremely serious broadening, do not form peaks, and can judge the unique amorphous structure by combining a transmission electron microscope image and a scanning transmission electron microscope image.
The invention has the characteristics of simple synthesis method, high yield, excellent product performance, strong stability, little pollution hazard and the like, and has excellent catalytic performance and stability when being used as a catalytic material for producing hydrogen by hydrolysis of a proton exchange membrane electrolytic cell as shown in an illustration, thereby having the potential of realizing large-scale production.
Comparative example 1
Comparison of full hydrolysis Performance of commercial platinum carbon catalyst and Iridium oxide catalyst
The acidic proton exchange membrane electrolyzed water system has the characteristics of small volume, high energy density, mature membrane separation and stability technology and the like. However, many transition metals and their oxides having excellent ability to promote water splitting cannot exist stably due to the strong acid environment. At the cathode end, the oxygen evolution reaction requires higher overpotential to drive the reaction to proceed because of slow catalytic reaction dynamics, which restricts the electrolysis of water by the acidic proton exchange membrane. The nano noble metal amorphous oxide composite material prepared by the invention has excellent hydrogen evolution and oxygen evolution reaction promotion performance and excellent stability. Compared with the most excellent commercial catalyst at present, namely the anode is a platinum carbon catalyst, and the cathode is an iridium oxide catalyst, the catalytic performance is obviously improved. As shown in fig. 7, only 1.55 volts is needed to drive the reaction to occur at a current density of 10 milliamps per square centimeter.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (8)

1. The preparation method of the amorphous noble metal oxide material is characterized in that a metal organic salt precursor solution is uniformly mixed, a reducing agent is added to obtain an oxidation-reduction reaction solution, and after mixing and dispersing, the amorphous noble metal oxide material is obtained through solvothermal reaction;
the preparation method of the metal organic salt precursor solution comprises the steps of dissolving levulinones organic salt in a solvent, adding an aqueous solution of chloroiridium acid, and mixing to obtain the metal organic salt precursor solution; the organic acetylacetonate salt is molybdenum acetylacetonate, cerium acetylacetonate, iron acetylacetonate or cobalt acetylacetonate;
the prepared amorphous noble metal oxide material is used for hydrogen evolution, oxygen evolution and full hydrolysis reaction.
2. The method for preparing an amorphous noble metal oxide material according to claim 1, wherein the molar concentration of the metal in the metal organic salt precursor solution is 0.001 to 1.0mol/L.
3. The method for preparing amorphous noble metal oxide material according to claim 1, wherein the reducing agent comprises formic acid, ethanol, acetic acid, ethylene glycol, isopropanol, glycerol, ascorbic acid, glucose, CO (NH) 2 ) 2 、Na 2 SO 3 、 K 2 SO 3 Or H 2 C 2 O 4 One or more of the following.
4. The method for preparing amorphous noble metal oxide material according to claim 1, wherein the solvent in the redox reaction solution is a mixture of water and one of ethanol, acetic acid, ethylene glycol, isopropanol, glycerol, acetone, chloroform, diethyl ether, tetrahydrofuran, dimethylformamide or formaldehyde.
5. The method for preparing amorphous noble metal oxide material according to claim 1, wherein the mixing and dispersing process adopts ultrasonic and magnetic stirring.
6. The method for preparing amorphous noble metal oxide material according to claim 1, wherein the solvothermal reaction temperature is 80-300 ℃ and the reaction time is 1-72h.
7. An amorphous noble metal oxide material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 6.
8. The amorphous noble metal oxide material of claim 7, wherein the amorphous noble metal oxide material is nano-scale dispersed.
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CN116618041A (en) * 2023-04-06 2023-08-22 广东工业大学 Method for preparing ultra-low-load single-atom noble metal catalyst by weak reduction method and application

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