CN102806079A - Preparation method of Pd/SnO2/C composite nanometer catalyst - Google Patents

Preparation method of Pd/SnO2/C composite nanometer catalyst Download PDF

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CN102806079A
CN102806079A CN2012102894029A CN201210289402A CN102806079A CN 102806079 A CN102806079 A CN 102806079A CN 2012102894029 A CN2012102894029 A CN 2012102894029A CN 201210289402 A CN201210289402 A CN 201210289402A CN 102806079 A CN102806079 A CN 102806079A
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CN102806079B (en
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李巧霞
毛宏敏
刘明爽
徐群杰
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Shanghai University of Electric Power
University of Shanghai for Science and Technology
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Abstract

The invention relates to a preparation method of a Pd/SnO2/C composite nanometer catalyst. According to the preparation method, SnO2 nanometer particles are prepared by a hydrothermal method, Vulcan XC-72 active carbon powder and the SnO2 nanometer particles are fully and uniformly mixed in mixed solution of glycol and deionized water, a liquid phase reduction method is used for loading nanometer Pd particles, finally, the suction filtration and the drying are carried out, and the Pd/SnO2/C composite nanometer catalyst is obtained. Compared with the prior art, the preparation has the advantages that SnO2 is introduced into a Pd catalyst system catalyzed and oxidized by ethanol, the Pd/SnO2/C composite nanometer catalyst is prepared, and the catalyst has high catalytic activity on ethanol oxidation reaction.

Description

A kind of Pd/SnO 2The preparation method of/C composite nano-catalyst
Technical field
The invention belongs to the nano-catalyst material preparing technical field, especially relate to a kind of Pd/SnO 2The preparation method of/C composite nano-catalyst.
Background technology
Directly the alcohols battery (fuel cell FC) is a kind of emerging electrochmical power source, it with the chemical energy of fuel be converted into electric energy, do not receive the restriction of Carnot cycle, energy conversion efficiency is high; Product has been got rid of NOx, SO basically XDeng the influence of polluter, has environmental friendliness; Specific power is high; Characteristics such as specific energy height.Yet in realizing the commercialization process, also there are a lot of technology, economic headache.
At present Pt is catalyst based better to alcohols catalytic oxidation effect, but is fuel for adopting methyl alcohol, and the intermediate product of methanol oxidation can be strong is adsorbed on the Pt surface; Cause catalyst poisoning; Catalytic performance fails very soon, and Pt costs an arm and a leg, and reserves are limited.Pd is considered to one of important substitution material.Pd content in the earth's crust is abundanter, and relative price is cheap, and under alkali condition, ethanol is had better catalytic activity.
Be further to improve the catalytic activity of catalyst, reduce catalyst consumption, can improve fuel cell performance from two aspects: the one, prepare the catalyst of highly active polymolecularity, two are to use the porous carrier of high specific area.Present research is illustrated in and adds different metal or oxide on the Pd catalyst basis, is prepared into Pd base binary or multicomponent catalyst and can significantly improves the catalytic activity to ethanol.T.Maiyalagan has introduced second kind of metal Ni, has prepared the Pd-Ni/C catalyst, and with respect to Pd/C, when oxidation ethanol, the initial oxidation current potential is negative to move 200mv, and peak current density is four times of Pd/C.R.Mmalewane has prepared Pd-Sn/C and two kinds of catalyst of Pd-Ru-Sn/C; The binary metal catalyst that wherein only contains metal Sn has better catalytic activity of pair ethanol and anti-CO poisoning capability in alkaline solution; And catalytic activity is significantly improved than Pd/C after adding Sn; In the XRD figure sheet of Pd-Sn/C, there are Pd and SnO 2The crystal peak.C.Mahendiran adds oxide NiO/MgO in the Pd catalyst, the Pd/ of preparation (NiO/MgOC) catalyst, and it has active and stable preferably in alkaline solution to oxidation of ethanol.In fuel-cell catalyst, add SnO 2, have clear improvement for improving catalytic activity and the anti-CO poisoning capability of catalyst.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of Pd/SnO that the oxidation of ethanol reaction is had very high catalytic activity to be provided 2The preparation method of/C composite nano-catalyst.
The object of the invention can be realized through following technical scheme:
A kind of Pd/SnO 2The preparation method of/C composite nano-catalyst may further comprise the steps:
(1) Hydrothermal Preparation SnO 2Nano particle;
A, Macrogol 2000 (PEG2000) is dissolved in the absolute ethyl alcohol, adds SnCl again after the dissolving fully 22H 2O forms mixed solution, 50 ℃ of temperature controls reaction 2h under the magnetic agitation, ageing 12h at room temperature then;
B, in autoclave, carry out high-temperature high-voltage reaction, filtering drying obtains pale yellow powder and is SnO 2Nano particle;
(2) with Vulcan XC-72 activated carbon powder and SnO 2The nano particle mass ratio is that mixing in 1: 1 is placed in the mixed solvent of ethylene glycol and deionized water composition Vulcan XC-72 activated carbon powder and SnO 2The addition of nano particle is the 40mg/120ml mixed solvent, and the control temperature is 60 ℃, utilizes powerful stirring of magnetic stirring apparatus fully to mix;
(3) with liquid phase reduction loaded with nano Pd particle:
The PdCl that in the mixed liquor that step (2) obtains, dropwise adds 2mmol/L 2Solution stirred after one hour, and the trisodium citrate that adding contains two crystallizations water is as stabilizing agent; The mol ratio of control metal Pd and trisodium citrate is 1: 5, and ultrasonic concussion 30min mixes; With the pH value to 11 of alkaline solution NaOH regulator solution, add reducing agent then again, continue isothermal reaction 3h; Be cooled to room temperature then, filtering to wash to filter cake does not have Cl-, and vacuum drying 12h promptly obtains the Pd/SnO of black 2/ C catalyst.
In the mixed solution described in the step (1), the concentration of Macrogol 2000 is 0.004-0.005g/ml, SnCl 2Concentration be 0.04-0.05g/ml.
Vulcan XC-72 activated carbon powder described in the step (2) through preliminary treatment, may further comprise the steps before mixing: the control temperature is 90 ℃, with the HNO of active carbon Vulcan XC-72 at 5mol/L 3In the powerful 5h that stirs, filter and washing after being cooled to room temperature; Control temperature again at 130 ℃ of vacuum drying 6h, grinding the active carbon after handling also, 200 mesh sieve branches obtain even-grained Vulcan XC-72 activated carbon powder.
The volume ratio of ethylene glycol described in the step (2) and deionized water is 1: 3.
Reducing agent described in the step (3) is a sodium borohydride.
Pd/SnO described in the step (3) 2The load capacity of nanometer Pd particle is 20wt% in the/C catalyst.
Compared with prior art, the present invention considers that in alkaline environment Pd has the activity higher than Pt to the catalytic oxidation of ethanol, in acid, alkaline media, good stability is arranged all, is a kind of eelctro-catalyst and catalyst carrier of function admirable, SnO 2Good electro-chemical activity is arranged, and hydrothermal stability is SnO 2Be incorporated into the Pd catalyst system of alcohol catalysis oxidation, be prepared into Pd/SnO 2/ C composite nano-catalyst, this catalyst has very high catalytic activity to the oxidation of ethanol reaction.
Description of drawings
Fig. 1 is Pd/SnO 2/ C composite nano-catalyst and/SnO 2TEM figure.
Fig. 2 is Pd/SnO 2/ C composite nano-catalyst and SnO 2XRD figure.
Fig. 3 is Pd/SnO 2The stripping volt-ampere curve of/C composite nano-catalyst in 1molL-1KOH solution.Analysing of hydrogen occurred and attached the peak, shown that catalyst has the certain activity specific area.
Fig. 4 is Pd/C catalyst and Pd/SnO 2/ C composite nano-catalyst is respectively at 0.1mol/LCH 3CH 2Cyclic voltammetry curve in OH and the 0.1mol/L KOH solution.
Fig. 5 is Pd/C catalyst and Pd/SnO 2/ C composite nano-catalyst is at 1M KOH+1M C 2H 5Time current curve among the OH.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
X-ray powder diffraction instrument is German Bruker D8-ADVANCE type, and radiation source is that (per step stops 1s to CuK α for λ=0.15418nm), 0.0167 ° of step-length, and sweep limits is 20～90 °; The Shanghai occasion China CHI660C of instrument company electrochemical workstation; Palladium bichloride (PdCl 2, Shanghai fine chemistry industry Materials Research Laboratories is analyzed pure); Vulcan XC-72 (U.S. Cabot company, 98%); Ethanol (Chinasun Specialty Products Co., Ltd analyzes pure); Ethylene glycol (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure); NaOH (chemical reagent Co., Ltd in Shanghai analyzes pure); Nafion solution (5 (wt) %, U.S. DuPont company).
Embodiment 1
The preparation of 1 composite catalyst:
Hydrothermal Preparation SnO 2Nano particle is 1: 1 according to mass ratio then, pretreated VulcanXC-72 activated carbon powder of process and SnO 2Nano particle fully mixes in ethylene glycol and deionized water (volume ratio is 1: 3) solution, and magnetic stirring apparatus is powerful to be stirred.With liquid phase reduction loaded with nano Pd particle, load capacity is wt.20%, in the reduction process, needs to add certain amount of stabilizer, and trisodium citrate drips excessive borane reducing agent sodium hydride, and after reaction a period of time, through filtering, oven dry obtains Pd/SnO 2/ C composite nano-catalyst.This catalyst has very high catalytic activity to the oxidation reaction of ethanol.
Fig. 1 is Pd/SnO 2/ C composite nano-catalyst and/SnO 2TEM figure, utilize transmission electron microscope to Pd/SnO 2/ C nanocatalyst scans, and the TEM picture of gained is as shown in Figure 1, from Fig. 1, can clearly find out finely dispersed Pd nano particle, and particle diameter is about 3-5nm.Fig. 2 is Pd/SnO 2/ C composite nano-catalyst and SnO 2XRD figure, from SnO 2XRD figure, with SnO 2Standard card (JCPDS No.41-1445) relatively, can find out SnO 2Characteristic diffraction peak 2 θ=26.6 ° (110), 33.9 ° (101), 51.8 ° (211), 64.7 ° (112); Contrast Pd/SnO 2The XRD figure of/C composite nano-catalyst, but the diffraction maximum of SnO2 has skew offset amplitude to a certain degree little.In the XRD figure of composite catalyst, (JCPDS, No.46-1043) relatively, 40.1 °, 46.7 °, 82.0 ° of the diffraction maximums of Pd are respectively 111,200,311 crystal faces of Pd with the accurate card of the change of Pd.
The preparation of 2 catalysis electrodes:
Take by weighing the catalyst of a certain amount of above-mentioned preparation, measure deionized water, ethanol, 5%Nafion solution by a certain percentage, catalyst and mixed solution is mixed; Ultrasonic concussion 30min; Obtain the watery catalyst of black ink, measure a certain amount of ink, be overlying on the glass-carbon electrode surface with pipette; Naturally after drying, electrode completes.Working electrode is glass carbon (GC) electrode (d=3mm), uses preceding Al with 0.3 μ m 2O 3Powder is milled to minute surface on chamois leather, spend the supersound washing of ionic hydration absolute ethyl alcohol more respectively.
3 catalytic properties characterize:
As working electrode, is reference electrode with SCE with the electrode for preparing, and the Pt electrode carries out cyclic voltammetric test and the test of time current curve for electrode is formed three electrode test systems on CHI660C.
Fig. 3 is Pd/SnO 2/ C composite nano-catalyst is at 1molL -1Stripping volt-ampere curve in the KOH solution analysing of hydrogen occurred and has attached the peak, shows that catalyst has the certain activity specific area.Fig. 4 is Pd/C catalyst and Pd/SnO 2/ C composite nano-catalyst is respectively at 0.1mol/LCH 3CH 2Cyclic voltammetry curve in OH and the 0.1mol/LKOH solution.On scheming, can find out Pd/SnO 2The catalytic performance of/C composite nano-catalyst is higher than Pd/C catalyst, Pd/SnO far away 2/ C composite nano-catalyst under very low current potential, is about-0.4V (vs.SCE) in just inswept journey, ethanol just begins to take place catalytic oxidation, when-0.25V, reaches maximum, the about 60mA/cm of its peak current density 2During reverse scan, because of catalyst P d changes active Pd atom again into, again above that ethanol of absorption is carried out catalytic oxidation, its oxidation peak reaches maximum at-0.42V, and catalytic current reaches 58mA/cm 2Fig. 5 is Pd/C catalyst and Pd/SnO 2/ C composite nano-catalyst is at 1M KOH+1M C 2H 5Time current curve among the OH.Prolong in time, current attenuation, but attenuation amplitude is little, explains that the anti-CO poisoning capability of composite catalyst is relatively good, contrasts two groups of data and can find out Pd/SnO 2It is littler than Pd/C that the current density of/C composite nano-catalyst reduces amplitude, and this explanation adds SnO 2Better anti-CO poisoning capability is arranged.
Embodiment 2
A kind of Pd/SnO 2The preparation method of/C composite nano-catalyst may further comprise the steps:
(1) Hydrothermal Preparation SnO 2Nano particle:
A, Macrogol 2000 (PEG2000) is dissolved in the absolute ethyl alcohol, adds SnCl again after the dissolving fully 22H 2O forms mixed solution, and the concentration of Macrogol 2000 is 0.004g/ml in the mixed solution, SnCl 2Concentration be 0.04g/ml, 50 ℃ of temperature controls reaction 2h under the magnetic agitation, ageing 12h at room temperature then;
B, in autoclave, carry out high-temperature high-voltage reaction, filtering drying obtains pale yellow powder and is SnO 2Nano particle;
(2) with Vulcan XC-72 activated carbon powder and SnO 2The nano particle mass ratio is that mixing in 1: 1 is placed in the mixed solvent of ethylene glycol and deionized water (volume ratio is 1: 3) composition Vulcan XC-72 activated carbon powder and SnO 2The addition of nano particle is the 40mg/120ml mixed solvent, and the control temperature is 60 ℃, utilizes powerful stirring of magnetic stirring apparatus fully to mix;
(3) with liquid phase reduction loaded with nano Pd particle:
The PdCl that in the mixed liquor that step (2) obtains, dropwise adds 2mmol/L 2Solution stirred after one hour, and the trisodium citrate that adding contains two crystallizations water is as stabilizing agent; The mol ratio of control metal Pd and trisodium citrate is 1: 5, and ultrasonic concussion 30min mixes; With the pH value to 11 of alkaline solution NaOH regulator solution, add the borane reducing agent sodium hydride then again, continue isothermal reaction 3h; Be cooled to room temperature then, filtering to wash to filter cake does not have Cl -, vacuum drying 12h promptly obtains the Pd/SnO of black 2/ C catalyst, the load capacity of nanometer Pd particle are 20wt%.
Wherein, Vulcan XC-72 activated carbon powder through preliminary treatment, may further comprise the steps before mixing: the control temperature is 90 ℃, with the HNO of active carbon Vulcan XC-72 at 5mol/L 3In the powerful 5h that stirs, filter and washing after being cooled to room temperature; Control temperature again at 130 ℃ of vacuum drying 6h, grinding the active carbon after handling also, 200 mesh sieve branches obtain even-grained Vulcan XC-72 activated carbon powder.
Embodiment 3
A kind of Pd/SnO 2The preparation method of/C composite nano-catalyst may further comprise the steps:
(1) Hydrothermal Preparation SnO 2Nano particle:
A, Macrogol 2000 (PEG2000) is dissolved in the absolute ethyl alcohol, adds SnCl again after the dissolving fully 22H 2O forms mixed solution, and the concentration of Macrogol 2000 is 0.005g/ml in the mixed solution, SnCl 2Concentration be 0.05g/ml, 50 ℃ of temperature controls reaction 2h under the magnetic agitation, ageing 12h at room temperature then;
B, in autoclave, carry out high-temperature high-voltage reaction, filtering drying obtains pale yellow powder and is SnO 2Nano particle;
(2) with Vulcan XC-72 activated carbon powder and SnO 2The nano particle mass ratio is that mixing in 1: 1 is placed in the mixed solvent of ethylene glycol and deionized water (volume ratio is 1: 3) composition Vulcan XC-72 activated carbon powder and SnO 2The addition of nano particle is the 40mg/120ml mixed solvent, and the control temperature is 60 ℃, utilizes powerful stirring of magnetic stirring apparatus fully to mix;
(3) with liquid phase reduction loaded with nano Pd particle:
The PdCl that in the mixed liquor that step (2) obtains, dropwise adds 2mmol/L 2Solution stirred after one hour, and the trisodium citrate that adding contains two crystallizations water is as stabilizing agent; The mol ratio of control metal Pd and trisodium citrate is 1: 5, and ultrasonic concussion 30min mixes; With the pH value to 11 of alkaline solution NaOH regulator solution, add the borane reducing agent sodium hydride then again, continue isothermal reaction 3h; Be cooled to room temperature then, filtering to wash to filter cake does not have Cl -, vacuum drying 12h promptly obtains the Pd/SnO of black 2/ C catalyst, the load capacity of nanometer Pd particle are 20wt%.
Wherein, Vulcan XC-72 activated carbon powder through preliminary treatment, may further comprise the steps before mixing: the control temperature is 90 ℃, with the HNO of active carbon Vulcan XC-72 at 5mol/L 3In the powerful 5h that stirs, filter and washing after being cooled to room temperature; Control temperature again at 130 ℃ of vacuum drying 6h, grinding the active carbon after handling also, 200 mesh sieve branches obtain even-grained Vulcan XC-72 activated carbon powder.
Embodiment 4
A kind of Pd/SnO 2The preparation method of/C composite nano-catalyst may further comprise the steps:
(1) Hydrothermal Preparation SnO 2Nano particle:
1. take by weighing 0.23g Macrogol 2000 (PEG2000) and be dissolved in the 50ml absolute ethyl alcohol, add 3.2gSnCl again after the dissolving fully 22H 2O forms mixed solution, 50 ℃ of reactions of magnetic agitation temperature control 2h, the 12h of room temperature ageing afterwards;
2. in autoclave, carry out high-temperature high-voltage reaction, filtering drying obtains pale yellow powder and is SnO 2Nano particle.
(2) with Vulcan XC-72 activated carbon powder and SnO 2Nano particle fully mixes in the mixed solution of ethylene glycol and deionized water, and magnetic stirring apparatus is powerful to be stirred;
(3) with liquid phase reduction loaded with nano Pd particle:
1. be active carbon and stannic oxide particle 40mg after taking by weighing processing at 1: 1 according to mass ratio, join in the 120ml water-ethylene glycol solution, (volume ratio of water and ethylene glycol is 1: 3), temperature control evenly stirs for 60 ℃, obtains mixed solution 1;
2. the PdCl that in mixed liquor 1, dropwise adds 2mmol/L 2Solution 46.99ml stirred after one hour, and the trisodium citrate 138.18mg that adding contains two crystallizations water is as stabilizing agent; (mol ratio that is metal Pd and trisodium citrate is 1: 5); Ultrasonic concussion 30min mixes, afterwards with the pH value to 11 of alkaline solution NaOH regulator solution; Add borane reducing agent sodium hydride 21.3mg then, continue isothermal reaction 3h, obtain mixed solution 2;
3. with mixed solution 2 cool to room temperature, filtering to wash to filter cake does not have Cl -, vacuum drying 12h afterwards; Obtain the Pd-SnO of black 2/ C catalyst, the load capacity of nanometer Pd particle are 20wt%.
(4) after nanometer Pd particulate load is accomplished,, promptly obtain Pd/SnO through suction filtration, oven dry 2/ C composite nano-catalyst.
Wherein, Vulcan XC-72 activated carbon powder before mixing through preliminary treatment: weighing 1g active carbon VulcanXC-72 is at 90 °, (100ml) HNO of 5mol/L 3The powerful 5h that stirs in the solution; Cooling is a room temperature, filters washing; 130 ° of vacuum drying 6h obtain even-grained activated carbon granule with active carbon grinding and 200 mesh sieve branches after handling afterwards.

Claims (6)

1. Pd/SnO 2The preparation method of/C composite nano-catalyst is characterized in that, this method may further comprise the steps:
(1) Hydrothermal Preparation SnO 2Nano particle:
A, Macrogol 2000 (PEG2000) is dissolved in the absolute ethyl alcohol, adds SnCl again after the dissolving fully 22H 2O forms mixed solution, 50 ℃ of temperature controls reaction 2h under the magnetic agitation, ageing 12h at room temperature then;
B, in autoclave, carry out high-temperature high-voltage reaction, filtering drying obtains pale yellow powder and is SnO 2Nano particle;
(2) with Vulcan XC-72 activated carbon powder and SnO 2The nano particle mass ratio is that mixing in 1: 1 is placed in the mixed solvent of ethylene glycol and deionized water composition Vulcan XC-72 activated carbon powder and SnO 2The addition of nano particle is the 40mg/120ml mixed solvent, and the control temperature is 60 ℃, utilizes powerful stirring of magnetic stirring apparatus fully to mix;
(3) with liquid phase reduction loaded with nano Pd particle:
The PdCl that in the mixed liquor that step (2) obtains, dropwise adds 2mmol/L 2Solution stirred after one hour, and the trisodium citrate that adding contains two crystallizations water is as stabilizing agent; The mol ratio of control metal Pd and trisodium citrate is 1: 5, and ultrasonic concussion 30min mixes; With the pH value to 11 of alkaline solution NaOH regulator solution, add reducing agent then again, continue isothermal reaction 3h; Be cooled to room temperature then, filtering to wash to filter cake does not have Cl-, and vacuum drying 12h promptly obtains the Pd/SnO of black 2/ C catalyst.
2. a kind of Pd/SnO according to claim 1 2The preparation method of/C composite nano-catalyst is characterized in that, in the mixed solution described in the step (1), the concentration of Macrogol 2000 is 0.004-0.005g/ml, SnCl 2Concentration be 0.04-0.05g/ml.
3. a kind of Pd/SnO according to claim 1 2The preparation method of/C composite nano-catalyst is characterized in that, the Vulcan XC-72 activated carbon powder described in the step (2) through preliminary treatment, may further comprise the steps before mixing: the control temperature is 90 ℃, with the HNO of active carbon Vulcan XC-72 at 5mol/L 3In the powerful 5h that stirs, filter and washing after being cooled to room temperature; Control temperature again at 130 ℃ of vacuum drying 6h, grinding the active carbon after handling also, 200 mesh sieve branches obtain even-grained Vulcan XC-72 activated carbon powder.
4. a kind of Pd/SnO according to claim 1 2The preparation method of/C composite nano-catalyst is characterized in that, the volume ratio of ethylene glycol described in the step (2) and deionized water is 1: 3.
5. a kind of Pd/SnO according to claim 1 2The preparation method of/C composite nano-catalyst is characterized in that, the reducing agent described in the step (3) is a sodium borohydride.
6. a kind of Pd/SnO according to claim 1 2The preparation method of/C composite nano-catalyst is characterized in that, the Pd/SnO described in the step (3) 2The load capacity of nanometer Pd particle is 20wt% in the/C catalyst.
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CN105606656A (en) * 2015-11-06 2016-05-25 上海戴维蓝普传感技术有限公司 Anti-silicon poisoning anti-sulfur-poisoning hot wire methane sensor
CN106981672A (en) * 2017-05-12 2017-07-25 湖北大学 A kind of fuel battery anode catalysis material and its preparation method and application
CN108311145A (en) * 2017-01-17 2018-07-24 中国科学院上海高等研究院 The preparation of palladium on carbon tin nanometer alloy catalyst and its application in carbon dioxide electro-catalysis reduction
CN109110803A (en) * 2018-08-03 2019-01-01 中国工程物理研究院化工材料研究所 More chemical state PdOxModify SnO2Nano composite air-sensitive material and preparation method thereof
CN110137486A (en) * 2019-05-21 2019-08-16 南京工业大学 A kind of preparation method of the transition metal oxide nano-material synthesized from top to bottom

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105606656A (en) * 2015-11-06 2016-05-25 上海戴维蓝普传感技术有限公司 Anti-silicon poisoning anti-sulfur-poisoning hot wire methane sensor
CN105606656B (en) * 2015-11-06 2020-04-21 上海戴维蓝普传感技术有限公司 Hot wire type methane sensor with silicon resistance and sulfur poisoning resistance
CN108311145A (en) * 2017-01-17 2018-07-24 中国科学院上海高等研究院 The preparation of palladium on carbon tin nanometer alloy catalyst and its application in carbon dioxide electro-catalysis reduction
CN106981672A (en) * 2017-05-12 2017-07-25 湖北大学 A kind of fuel battery anode catalysis material and its preparation method and application
CN106981672B (en) * 2017-05-12 2019-07-16 湖北大学 A kind of fuel battery anode catalysis material and its preparation method and application
CN109110803A (en) * 2018-08-03 2019-01-01 中国工程物理研究院化工材料研究所 More chemical state PdOxModify SnO2Nano composite air-sensitive material and preparation method thereof
CN110137486A (en) * 2019-05-21 2019-08-16 南京工业大学 A kind of preparation method of the transition metal oxide nano-material synthesized from top to bottom

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