CN106784899A - A kind of three-dimensional Pd-P alloy nanoparticles network structure material and its preparation method and application - Google Patents
A kind of three-dimensional Pd-P alloy nanoparticles network structure material and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of three-dimensional Pd-P alloy nanoparticles network structure material and its preparation method and application, and Sodium Hypophosphite and chlorine palladium acid sodium are prepared by hydro-thermal reaction one-step method, and selection formaldehyde is reducing agent, and APEO is surfactant.The characteristics of three-dimensional Pd-P alloy nanoparticles network structure prepared by the present invention has small size nano particle, and can self-supporting can produce more preferable gas permeability, Stability Analysis of Structures has very excellent performance in terms of Electrocatalytic Process for Oxidation of Formic Acid.
Description
Technical field
The invention belongs to the preparation field of noble metal nanometer material, a kind of three-dimensional Pd-P alloy nanos are related in particular to
The preparation method of grain network structure material.
Background technology
With the increasingly exhausted of conventional fossil fuel and brought environmental problem is used increasingly by fossil fuel
Seriously, the development and utilization of new cleaning fuel has seemed extremely urgent.In the new cleaning fuel of all polymorphic types, to have
Machine small molecule (such as methyl alcohol, ethanol, formic acid) efficiently can directly turn chemical energy as the direct fuel cell of fuel because of it
The advantages such as electric energy, fuel source are extensive, suitable application area is wide and environment-friendly are turned to, the pole of researchers is at home and abroad caused
Big interest, it is significant the problems such as to solving the energy, environment as the big focus in current new energy research field.
In every technology of direct fuel cell, the research of elctro-catalyst is considered as the big key skill for influenceing its development and promoting
Art, the performance of elctro-catalyst greatly affects the utilization rate of fuel and effect of fuel cell.With high-specific surface area and height
The nanostructured of the porous network shape of stability, helps to solve the dispersiveness of nano particle and stability problem, can keep away again
That exempts from carrier uses brought problem, is conducive to obtaining the catalyst of high activity, therefore, in the urgent need to development performance is more preferable
Catalyst carrier or build without carrier catalyst system.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of low cost, low energy consumption, the system of process is simple
The methods and applications of standby three-dimensional Pd-P alloy nanoparticle network structure materials, aid in synthesis strategy, by water using soft template
Thermal response synthesizes three-dimensional Pd-P alloy nanoparticle network structure materials, and it has very excellent in terms of Electrocatalytic Process for Oxidation of Formic Acid
Performance.
Technical purpose of the invention is achieved by following technical proposals：
A kind of three-dimensional Pd-P alloy nanoparticles network structure material, is made up of element palladium and phosphorus, and element palladium and phosphorus rub
You are than being (7-10)：1, based on palladium, metallic element palladium is doped with nonmetalloid phosphorus forms palladium phosphorus alloy.
The mol ratio of element palladium and phosphorus is preferably (7.5-8)：1.
Piled up by diameter 5-8 nanometers of particle in the three-dimensional net structure of structural material of the present invention and formed, specific surface area is put down
Up to 150-200m2/g。
A kind of preparation method of three-dimensional Pd-P alloy nanoparticles network structure material, is carried out as steps described below：
To the sodium hypophosphite (NaH mixed with formaldehyde (HCHO) and APEO2PO2·H2O) and chlorine palladium acid sodium
(Na2PdCl4) the aqueous solution carry out ultrasonically treated or magnetic agitation so that each component uniform dissolution and dispersion in water phase,
And using NaOH adjust whole reaction system pH value be 8-10；Under being placed in 150-180 degrees Celsius again seal reaction 8-
Gained sediment and centrifuge washing are collected after 10 hours, that is, obtains Pd-P alloy nanoparticle network structure materials.
In the above-mentioned technical solutions, used as reducing agent, its addition is relative to sodium hypophosphite and the acid of chlorine palladium for formaldehyde (HCHO)
It is excessive for sodium so that the chlorine palladium acid sodium and sodium hypophosphite of addition can be completely reduced.
In the above-mentioned technical solutions, used as surfactant, molecular formula is C to APEO16H33(OCH2CH2)20- OH,
Molecular weight is 1122, and using its network-like pattern of surfactant properties stable nanoparticles, its consumption is 0.25-0.4 quality
Part, preferably 0.3-0.4 mass parts, every part of mass parts are 1g.
In the above-mentioned technical solutions, sodium hypophosphite (NaH2PO2·H2O) as the source of element phosphor, chlorine palladium acid sodium
(Na2PdCl4) used as the source of element palladium, the molar ratio of element phosphor and element palladium is (2-4)：1, preferably (2.5-
3.5)：1.In preparation process, the element phosphor and element palladium of reduction are doped, based on palladium, with nonmetalloid phosphorus pair
Metallic element palladium is doped and forms palladium phosphorus alloy, and the mol ratio of element palladium and phosphorus is (7-10) in final alloy：1.
In the above-mentioned technical solutions, collect the gained sediment and with second alcohol and water centrifuge washing 4-6 times, that is, obtain
Pd-P alloy nanoparticle network structure materials.
In the above-mentioned technical solutions, selection autoclave is reaction vessel, and with polytetrafluoroethylene (PTFE) as liner.
One step hydrothermal synthesis method of three-dimensional Pd-P alloy nanoparticles network structure of the invention has low cost, synthesis temperature
The advantages of consumption, the material structure that the low, safety coefficient of degree is high, reduce noble metal are stably, electrocatalysis characteristic is good, greatly improve and urge
The performance of agent and anti-poisoning capability.The material of the carbon load for synthesizing at present relatively, the three-dimensional Pd-P prepared by the present invention is closed
The characteristics of gold nano grain network structure has small size nano particle, and can self-supporting can produce more preferable gas permeability, tie
Structure stabilization, has very excellent performance in terms of Electrocatalytic Process for Oxidation of Formic Acid.
Brief description of the drawings
Fig. 1 is that the SEM of the three-dimensional Pd-P alloy nanoparticles network structure material prepared by the present invention is schemed.
Fig. 2 is the three-dimensional Pd-P alloy nanoparticles network structure material and Three Dimensional Pure Pd nanometers prepared by the present invention
The XRD comparison diagrams of grain network structure material, wherein 1 is three-dimensional Pd-P alloy nanoparticle network structure materials, 2 is Three Dimensional Pure Pd
Network of nanoparticles structural material.
Fig. 3 is that the TEM of the three-dimensional Pd-P alloy nanoparticles network structure material prepared by the present invention is schemed.
Fig. 4 is the three-dimensional Pd-P alloy nanoparticles network structure material and Three Dimensional Pure Pd nanometers prepared by the present invention
The cyclic voltammogram of grain network structure and business Pd/C (20%) materials in 0.5 mole of every liter of aqueous sulfuric acid.
Fig. 5 is the three-dimensional Pd-P alloy nanoparticles network structure material and Three Dimensional Pure Pd nanometers prepared by the present invention
Grain network structure and business Pd/C (20%) materials are in 0.5 mole of every liter of aqueous sulfuric acid and 0.5 mole of every liter of aqueous formic acid
In cyclic voltammogram.
Fig. 6 is the three-dimensional Pd-P alloy nanoparticles network structure material and Three Dimensional Pure Pd nanometers prepared by the present invention
Grain network structure and business Pd/C (20%) materials are in 0.5 mole of every liter of aqueous sulfuric acid and 0.5 mole of every liter of aqueous formic acid
In current-time curvel.
Fig. 7 is the three-dimensional Pd-P alloy nanoparticles network structure material and Three Dimensional Pure Pd nanometers prepared by the present invention
The carbon monoxide stripping curve figure of grain network structure and business Pd/C (20%) materials in 0.5 mole of every liter of aqueous sulfuric acid.
Specific embodiment
Institute of the invention is commercially available chemical reagent using raw material, and the present invention is carried out specifically with reference to specific practical work example
It is bright.
| Material/agent | Purity/specification | Manufacturer/supplier |
| Chlorine palladium acid sodium Na2PdCl4 | Analysis is pure | Tianjin recovery fine chemistry industry research institute |
| Sodium hypophosphite NaH2PO2·H2O | Analysis is pure | Tianjin recovery fine chemistry industry research institute |
| Formaldehyde HCHO | Analysis is pure | Tianjin recovery fine chemistry industry research institute |
| APEO Brij58 | Analysis is pure | Beijing lark prestige Science and Technology Ltd. |
| Formic acid HCOOH | Analysis is pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Sulfuric acid H2SO4 | Analysis is pure | The factory of Tianjin chemical reagent five |
| Pd/C catalyst | 20wt% | JohnsonMatthey (U.S.) |
| Carbon monoxide CO | It is high-purity | The side's high-tech gas of Tianjin six |
| Nitrogen N2 | It is high-purity | The side's high-tech gas of Tianjin six |
Embodiment 1
0.3g APEOs and 0.03g sodium hypophosphites (NaH are weighed respectively2PO2·H2O) in 20 milliliters of autoclaves
In, 8 milliliters of water are added, magnetic agitation dissolves to it.To addition 0.1 milliliter of formaldehyde and 0.04 mM in the mixed liquor that stirred
Chlorine palladium acid sodium (Na2PdCl4), pH to 10 is adjusted with 1 molar sodium hydroxide, at room temperature magnetic agitation 5 minutes, after stirring, by it
Sealing is placed in 8 hours in 150 DEG C of baking ovens.Reactor is taken out and naturally cools to room temperature, reacted product autoreaction kettle transfer
To centrifuge tube, product is centrifuged with water and supersound washing, repeated 4-6 times, be placed in 40 DEG C of vacuum drying chambers and dry 12
Hour, that is, obtain pure three-dimensional Pd-P alloy nanoparticles network structure material.
Embodiment 2
0.3g APEOs and 0.01g sodium hypophosphites (NaH are weighed respectively2PO2·H2O) in 20 milliliters of autoclaves
In, 8 milliliters of water are added, magnetic agitation dissolves to it.To addition 0.1 milliliter of formaldehyde and 0.04 mM in the mixed liquor that stirred
Chlorine palladium acid sodium (Na2PdCl4), pH to 9 is adjusted with 1 molar sodium hydroxide, at room temperature magnetic agitation 5 minutes, after stirring, by it
Sealing is placed in 8 hours in 150 DEG C of baking ovens.Reactor is taken out and naturally cools to room temperature, reacted product autoreaction kettle transfer
To centrifuge tube, product is centrifuged with water and supersound washing, repeated 4-6 times, be placed in 40 DEG C of vacuum drying chambers and dry 12
Hour, that is, obtain pure three-dimensional Pd-P alloy nanoparticles network structure material.
Embodiment 3
0.3g APEOs and 0.03g sodium hypophosphites (NaH are weighed respectively2PO2·H2O) in 20 milliliters of autoclaves
In, 8 milliliters of water are added, magnetic agitation dissolves to it.To addition 0.1 milliliter of formaldehyde and 0.08 mM in the mixed liquor that stirred
Chlorine palladium acid sodium (Na2PdCl4), pH to 10 is adjusted with 1 molar sodium hydroxide, at room temperature magnetic agitation 5 minutes, after stirring, by it
Sealing is placed in 8 hours in 150 DEG C of baking ovens.Reactor is taken out and naturally cools to room temperature, reacted product autoreaction kettle transfer
To centrifuge tube, product is centrifuged with water and supersound washing, repeated 4-6 times, be placed in 40 DEG C of vacuum drying chambers and dry 12
Hour, that is, obtain pure three-dimensional Pd-P alloy nanoparticles network structure material.
Embodiment 4
0.3g APEOs and 0.03g sodium hypophosphites (NaH are weighed respectively2PO2·H2O) in 20 milliliters of autoclaves
In, 8 milliliters of water are added, magnetic agitation dissolves to it.To addition 0.1 milliliter of formaldehyde and 0.04 mM in the mixed liquor that stirred
Chlorine palladium acid sodium (Na2PdCl4), pH to 10 is adjusted with 1 molar sodium hydroxide, at room temperature magnetic agitation 5 minutes, after stirring, by it
Sealing is placed in 10 hours in 150 DEG C of baking ovens.Reactor is taken out and naturally cools to room temperature, reacted product autoreaction kettle transfer
To centrifuge tube, product is centrifuged with water and supersound washing, repeated 4-6 times, be placed in 40 DEG C of vacuum drying chambers and dry 12
Hour, that is, obtain pure three-dimensional Pd-P alloy nanoparticles network structure material.
Comparative example
Using the proportioning and process conditions of embodiment 1, chlorine palladium acid sodium (Na is only used2PdCl4) as raw material, without secondary
Sodium phosphate (NaH2PO2·H2O), Three Dimensional Pure Pd network of nanoparticles structures are directly prepared.
Resulting phosphorous precious metal alloys material still mainly will be with irregular pattern and structure in current research
Nano particle load on carbon material carrier, and the use of carbon material carrier catalysis inevitably increases the thickness of diffusion layer
Degree, so as to increased resistance to mass tranfer, while the combination between catalyst and carrier loosely often leads to catalyst particles abscission, gathers
Collection, sintering etc., these problems are still a major challenge that such elctro-catalyst faces in preparation and application process.Therefore, urgently
Need to develop the catalyst system of the more preferable catalyst carrier of performance or structure without carrier.With high-specific surface area and high stable
Property porous network shape nanostructured, contribute to solve nano particle dispersiveness and stability problem, can avoid again carry
The catalyst for using brought problem, being conducive to obtaining high activity of body.The present invention aids in synthesis strategy using soft template, leads to
Cross hydro-thermal reaction and synthesized three-dimensional Pd-P alloy nanoparticles network structure material, have very in terms of Electrocatalytic Process for Oxidation of Formic Acid
Excellent performance, while being contrasted as property from commercialized Pd/C catalyst and comparative example.
The SEM of the three-dimensional Pd-P alloy nanoparticles network structure material that Fig. 1 is prepared by the present invention schemes.The scanning of sample
The measure of electron microscopic observation and composition is the Hitachi S-4800 types by HIT equipped with energy dispersive x-ray
What the field emission scanning electron microscope of spectrometer was carried out.As can be seen from the figure we are successfully prepared using the inventive method
Fluffy network-like structure, and the network structure on a large scale is made up of nanometer little particle.
Fig. 2 is by the three-dimensional Pd-P alloy nanoparticles network structure (curve 1) of present invention preparation and Three Dimensional Pure Pd nanometers
The XRD comparison diagrams of particle network structure (curve 2) material.The material phase analysis of sample are the D8- by German Brooker AXS companies
Focus type X-ray powder diffractions instrument (Cu k α) is carried out.Three Dimensional Pure Pd network of nanoparticles structure is prepared except that need not add
Enter outside sodium hypophosphite, remaining step is consistent with the method that three-dimensional Pd-P alloy nanoparticle network structures are prepared in the present invention.Three
Pd and the atomic molar ratio of P element are 7.5 in dimension Pd-P alloy nanoparticle network structures:1 (as shown in table 1 below).By right
Can be seen that the sample relative to pure Pd than both XRDs, the diffraction maximum position of three-dimensional Pd-P alloys all to high angle
Skew, illustrates that P atoms form Pd-P alloys in being successfully incorporated into Pd-P samples.
Power spectrum (the contained Elements Atom mole) analysis of the sample of table 1
| Element | Pd | P |
| Atom/% | 88.2 | 11.8 |
The TEM of the three-dimensional Pd-P alloy nanoparticles network structure material that Fig. 3 is prepared by the present invention schemes.The transmission of sample
The Flied emission transmission electron microscope that electron microscopic observation and high-resolution-ration transmission electric-lens are viewed as the JEM-2100F types of JEOL is surveyed
Examination.It will be apparent from this figure that the sample is porous network-like structure, aperture heterogeneity, and the network structure is by a diameter of
5-8 nanometers of little particle composition.
Three-dimensional Pd-P alloy nanoparticles network structure material (curve 2) and Three Dimensional Pure Pd that Fig. 4 is prepared by the present invention
Network of nanoparticles structure (curve 3) and business Pd/C (20%) material (curve 1) are in 0.5 mole of every liter of aqueous sulfuric acid
Cyclic voltammogram.The electro-chemical test carried out in the present invention is in the electrochemical workstation (CH produced by Shanghai Chen Hua company
Carried out on 660D), be Pt electrode to electrode using typical three-electrode system, reference electrode is saturated calomel electrode, made
Standby sample drop is coated in as working electrode on glass-carbon electrode (a diameter of 3mm), and the load capacity of sample is 4 micrograms, and sweeping speed is
50mV s-1.The cyclic voltammetry electrolyte is 0.5 mole of every liter of sulfuric acid, using preceding using N2Air-blowing 30 minutes is ensuring to remove
Remaining oxygen in the solution.Being calculated from the figure to obtain, three-dimensional Pd-P alloy nanoparticles network structure material (curve
2) electrochemical surface area with Three Dimensional Pure Pd network of nanoparticles structure (curve 3) and business Pd/C (20%) material is respectively
18.92,12.16and 16.01m2gPd -1, illustrate that three-dimensional Pd-P alloy nanoparticles network structure material has bigger electrification
Active area is learned, is conducive to lifting electrocatalysis characteristic.
Fig. 5 is the three-dimensional Pd-P alloy nanoparticles network structure material (curve 2) and Three Dimensional Pure prepared by the present invention
Pd network of nanoparticles structure (curve 3) and business Pd/C (20%) material (curve 1) in 0.5 mole of every liter of sulfuric acid solution and
Cyclic voltammogram in 0.5 mole of every liter of formic acid solution.The test electrolyte rubs for 0.5 mole of every liter of aqueous sulfuric acid and 0.5
Your every liter of mixed liquor of aqueous formic acid, using preceding using N2Air-blowing 30 minutes is ensuring to remove remaining oxygen in the solution.From
As can be seen that three-dimensional Pd-P alloy nanoparticles network structure material has peak current density (3.22mA higher in the figure
cm-2), it is Three Dimensional Pure Pd network of nanoparticles structure (2.32mA cm-2) and business Pd/C (0.89mA cm-2) 1.39 times and
3.62 times.In sum, the three-dimensional Pd-P alloy nanoparticles network structure material for being prepared by the present invention has more preferable first
Sour electro-oxidizing-catalyzing activity.
Fig. 6 is the three-dimensional Pd-P alloy nanoparticles network structure material (curve 2) and Three Dimensional Pure prepared by the present invention
Pd network of nanoparticles structure (curve 3) and business Pd/C (20%) material (curve 1) in 0.5 mole of every liter of aqueous sulfuric acid and
Current versus time curve in 0.5 mole of every liter of aqueous formic acid.The test electrolyte be 0.5 mole of every liter of aqueous sulfuric acid and
0.5 mole of mixed liquor of every liter of aqueous formic acid, using preceding using N2Air-blowing 30 minutes is ensuring to remove remaining oxygen in the solution
Gas.It will be apparent from this figure that three-dimensional Pd-P alloy nanoparticles network structure material has slower current attenuation speed, and
When test proceeds to 5000 seconds, three-dimensional Pd-P alloy nanoparticles network structure material is than Three Dimensional Pure Pd network of nanoparticles structures
And business Pd/C (20%) material has current density higher.In sum, the three-dimensional Pd-P alloys for being prepared by the present invention
Network of nanoparticles structural material has more preferable electro-catalysis stability.
Fig. 7 is the three-dimensional Pd-P alloy nanoparticles network structure material (curve 2) and Three Dimensional Pure prepared by the present invention
Pd network of nanoparticles structure (curve 3) and business Pd/C (20%) material (curve 1) are in 0.5 mole of every liter of aqueous sulfuric acid
Carbon monoxide stripping curve figure.The test electrolyte is 0.5 mole of every liter of aqueous sulfuric acid, uses preceding use carbon monoxide (CO)
Gas air-blowing reaches saturation in 30 minutes with CO gases in ensuring solution.It will be apparent from this figure that three-dimensional Pd-P alloy nanos
Grain network structure material is with lower CO oxidations spike potential (0.69V), and Three Dimensional Pure Pd network of nanoparticles structure and business
Pd/C (20%) material then needs CO higher to aoxidize spike potential, respectively 0.73V and 0.74V.In sum, by the present invention
The three-dimensional Pd-P alloy nanoparticles network structure material of preparation has more preferable CO tolerance catalysts ability, is conducive to lifting electro-catalysis
Activity and stability.
The formula and technique recorded using present invention are adjusted the three-dimensional Pd-P alloy nanoparticles network of preparation
, there is difference in element proportioning in structural material, and microscopic appearance is consistent, and carries out above-mentioned electrochemical property test, shows
With the basic same property of above-mentioned test result.It can thus be appreciated that three-dimensional Pd-P alloy nanoparticles network structure material of the invention exists
Application in electro-catalysis field.
Exemplary description is done to the present invention above, it should explanation, do not departed from the situation of core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. a kind of three-dimensional Pd-P alloy nanoparticles network structure material, it is characterised in that be made up of element palladium and phosphorus, element palladium
It is (7-10) with the mol ratio of phosphorus：1, based on palladium, metallic element palladium is doped with nonmetalloid phosphorus forms palladium
Phosphorus alloy.
2. a kind of three-dimensional Pd-P alloy nanoparticles network structure material according to claim 1, it is characterised in that three-dimensional
Pd-P alloy nanoparticles network structure material is piled up by diameter 5-8 nanometers of particle and formed, and specific surface area average reachable 150-
200m2/g。
3. a kind of three-dimensional Pd-P alloy nanoparticles network structure material according to claims 1 or 2, its feature exists
In the mol ratio of element palladium and phosphorus is preferably (7.5-8)：1.
4. a kind of preparation method of three-dimensional Pd-P alloy nanoparticles network structure material, it is characterised in that as steps described below
Carry out：The aqueous solution to the sodium hypophosphite mixed with formaldehyde and APEO and chlorine palladium acid sodium carries out ultrasonically treated or magnetic force and stirs
Mix, so that each component uniform dissolution and dispersion in water phase, and be using the pH value that NaOH adjusts whole reaction system
8—10；Gained sediment and centrifuge washing are collected after reaction being sealed under being placed in 150-180 degrees Celsius again 8-10 hours, is obtained final product
To Pd-P alloy nanoparticle network structure materials, wherein sodium hypophosphite as element phosphor source, chlorine palladium acid sodium is used as element
The molar ratio of the source of palladium, element phosphor and element palladium is (2-4)：1.
5. the preparation method of a kind of three-dimensional Pd-P alloy nanoparticles network structure material according to claim 4, it is special
Levy and be, used as reducing agent, its addition is excessive for sodium hypophosphite and chlorine palladium acid sodium to formaldehyde so that addition
Chlorine palladium acid sodium and sodium hypophosphite can be completely reduced.
6. the preparation method of a kind of three-dimensional Pd-P alloy nanoparticles network structure material according to claim 4, it is special
Levy and be, used as surfactant, molecular formula is C to APEO16H33(OCH2CH2)20- OH, molecular weight is 1122, using it
The network-like pattern of surfactant properties stable nanoparticles, its consumption is 0.25-0.4 mass parts, preferably 0.3-0.4 quality
Part, every part of mass parts are 1g.
7. the preparation method of a kind of three-dimensional Pd-P alloy nanoparticles network structure material according to claim 4, it is special
Levy and be, the molar ratio of element phosphor and element palladium is (2.5-3.5)：1.
8. the preparation method of a kind of three-dimensional Pd-P alloy nanoparticles network structure material according to claim 4, it is special
Levy and be, selection autoclave is reaction vessel, and with polytetrafluoroethylene (PTFE) as liner.
9. a kind of three-dimensional Pd-P alloy nanoparticles network structure material as described in claim 1 or 2 is in electro-catalysis field
In application.
10. a kind of three-dimensional Pd-P alloy nanoparticles network structure material as described in claim 1 or 2 is in electro-catalysis formic acid
Application in oxidation.
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| CN109741796A (en) * | 2019-01-07 | 2019-05-10 | 厦门大学 | A kind of Parallel Particle Swarm Optimization alloy nano particle structural optimization method and system |
| CN111939927A (en) * | 2020-08-14 | 2020-11-17 | 西安建筑科技大学 | Copper-based catalyst with nanowire network structure and preparation method and application thereof |
| CN113697871A (en) * | 2021-08-04 | 2021-11-26 | 中国科学院广州地球化学研究所 | Preparation of short columnar PdO based on hydrolysis reaction2Method for producing nanoparticle material |
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| CN109741796A (en) * | 2019-01-07 | 2019-05-10 | 厦门大学 | A kind of Parallel Particle Swarm Optimization alloy nano particle structural optimization method and system |
| CN109741796B (en) * | 2019-01-07 | 2020-06-30 | 厦门大学 | Parallel particle swarm alloy nanoparticle structure optimization method and system |
| CN111939927A (en) * | 2020-08-14 | 2020-11-17 | 西安建筑科技大学 | Copper-based catalyst with nanowire network structure and preparation method and application thereof |
| CN111939927B (en) * | 2020-08-14 | 2022-11-04 | 西安建筑科技大学 | Copper-based catalyst with nanowire network structure and preparation method and application thereof |
| CN113697871A (en) * | 2021-08-04 | 2021-11-26 | 中国科学院广州地球化学研究所 | Preparation of short columnar PdO based on hydrolysis reaction2Method for producing nanoparticle material |
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