CN102861576A - Pd/ZnO/C composite nano catalyst and preparation method thereof - Google Patents
Pd/ZnO/C composite nano catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Pd/ZnO/C composite nano catalyst and a preparation method thereof. The Pd/ZnO/C composite nano catalyst is the nano catalyst formed by compounding Pd, ZnO and C in a mass ratio of the Pd to the ZnO to the C being0.5:1:1, wherein the C is active carbon which can be sieved by a sieve being 200 meshes. The preparation method comprises the steps of firstly, preparing ZnO nano particles; and sufficiently agitating the active carbon which can be sieved by the sieve being 200 meshes and the ZnO nano particles in an ethylene glycol water solution and uniformly mixing to obtain a mixed solution, and loading nano Pd particles on the mixed solution by using a liquid-phase reduction method to obtain the Pd/ZnO/C composite nano catalyst. The Pd/ZnO/C composite nano catalyst has a strong anti-poisoning capability and has a good catalytic oxidization performance to ethanol in an alkaline solution.
Description
Technical field
The invention belongs to the nano-catalyst material preparing technical field, be specifically related to a kind of ethanol to be had high catalytic activity Pd/ZnO/C composite nano-catalyst and preparation method thereof
Background technology
More and more to the research of fuel cell at present, this mainly is because some micromolecular compounds are extensive such as Material Sources such as methyl alcohol, ethanol, can be used in and directly do fuel in the fuel cell.But methyl alcohol has certain volatility and toxicity, can produce harm to the person, and ethanol has high-energy-density, can be used for some electronic equipments and electric automobile, and is more concerned about the research of Direct Ethanol Fuel Cell
[1-5]Pt is a kind of metal many to the oxidation of ethanol research and comparison, but the complete oxidation of ethanol is the reaction of 12 electronics, and the sluggish on simple metal Pt and it are acetic acid to the end product major part of oxidation of ethanol, are not CO
2 [6-7], in the oxidizing process of ethanol, can generate the intermediate product of some class CO, can cause the Pt catalyst poisoning, catalytic activity can obviously descend.
Studies show that the adding oxide can improve the oxidability to ethanol in catalyst, resist CO and poison.Pang
[8]Prepared SnO with sol-gel process
2-CNTs/Pt catalyst, this catalyst has very high catalytic activity, SnO to ethanol in acid solution
2Introducing so that the long-time cycle performance of catalyst is better.Zhang
[9]Deng having synthesized the have nucleocapsid structure Pt/CNT@SnO of (thick about 2nm)
2Catalyst is 1.57 times of Pt/C to the oxidation current of ethanol in acid solution.B.RuizCamacho
[10]Research is found adding oxide S nO
2, TiO
2, ZnO prepares Pt/SnO
2/ C, Pt/TiO
2/ C and Pt/ZnO/C have reasonable electrocatalysis characteristic with respect to Pt/C, but the catalytic stability of Pt/ZnO/C is bad.And the costliness of Pt itself, reserves are limited, have in actual applications certain limitation.Comparatively speaking the price of Pd is relatively cheap, and reserves are abundant, replace Pt with Pd, can reduce the cost of alcohols fuel cell anode catalyst. and Pd/C has better catalytic activity with respect to Pt/C to ethanol in alkaline solution, stable and anti-CO poisoning capability
[11]
Catalytic activity in view of ZnO, the present invention has prepared a kind of new catalyst Pd/ZnO/C that ethanol is had better catalytic activity and stability in alkaline solution, it is complicated that traditional laboratory prepares the required equipment of Pt/ZnO/C catalyst, and productive rate is low, the present invention elder generation synthesizing zinc oxide, raw material are cheap, simple to operate, and productive rate is higher, carried metal Pd particle diameter is less and be evenly distributed again, compare with the Pd/C catalyst, catalytic activity is significantly improved.Because at present Direct Ethanol Fuel Cell research is limited, and the not equal reason of each experimental system, there is no similar report of the present invention.
List of references
[1] Song SQ, Zhou WJ, Zhou ZH, Jiang LH, Sun GQ, Xin Q, et al.Direct ethanol PEM fuel cells:the case of platinum based anodes[J]. Int J Hydrogen Energy 2005;30:995-1001
[2] Lamy C, Rousseau S, Belgsir EM, Coutanceau C, Leger JM.Recent progress in the direct ethanol fuel cell: develo pment of new platinum -tin electrocatalysts[J]. Electrochim Acta 2004; 49:3901-3018
[3] Rousseau S, Coutanceau C, Lamy C. Direct ethanol fuel cell (DEFC): electrical performances and react ion products distribution under operating conditions with different platinum-based anodes[J]. J Power Sources 2006;158:18-24
[4]Antolini E. Catalysts for direct ethanol fuel cells[J]. J. Power Sources 2007; 170: 1-12
[5]E. Antolini,F. Colmati,E.R. Gonzalez.Ethanol oxidation on carbon supported (PtSn) alloy/SnO
2 and (PtSnPd) alloy/SnO
2 catalysts with a fixed Pt/SnO
2 atomic ratio:Effect of the alloy phase characteristics[J].Journal of Power Sources 193 (2009) 555-561
[6]H. Wang, Z. Jusys, R.J. Behm. Ethanol Electro oxidation on a Carbon-Supported Pt Catalyst: Reaction Kinetics and Product Yields[J]. J. Phys. Chem. B., 2004, 108, 19413-19424
[7]G.A. Camara, T. Iwasita, Parallel pathways of ethanol oxidation: The effect of ethanol concentration[J]. Journal of Electroanalytical Chemistry.2005,578,315-321
[8]H.L. Pang, J.P. Lu, J.H. Chen, C.T. Huang, B. Liu, X.H. Zhang.Preparation of SnO2-CNTs supported Pt catalysts and their electrocatalytic properties for ethanol oxidation [J].Electrochimica Acta 54 (2009) 2610-2615
[9]Xinwei Zhang,Hong Zhu,Zhijun Guo, et al.Design and preparation of CNT@SnO2 core-shell composites with thin shell and its application for ethanol oxidation[J].International Journal of Hydrogen Energy 35 (2010) 8841-8847
[10]B.RuizCamachoa, C. Moraisa,et al. Enhancing oxygen reduction reaction activity and stability of platinum via oxide-carbon composites[J]. Catalysis Today,2012,1-8
[11]Liang Ma, Deryn Chu, Rongrong Chen. Comparison of ethanol electro-oxidation on Pt/C and Pd/C catalysts in alkaline media[J]. International Journal of Hydrogen Energy,37(2012)11185-11194
Summary of the invention
Technical problems such as one of purpose of the present invention is lower in order to solve above-mentioned catalyst activity, less stable and a kind of high catalytic activity that has is provided, the Pd/ZnO/C composite nano-catalyst of stable and anti-poisoning capability.
Two of purpose of the present invention provides the preparation method of above-mentioned a kind of Pd/ZnO/C composite nano-catalyst.
Know-why of the present invention
Consider 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, ZnO has good electro-chemical activity, and hydrothermal stability is a kind of eelctro-catalyst and catalyst carrier of function admirable.ZnO is incorporated into the Pd catalyst system of Catalytic oxidation of ethanol, is prepared into the Pd/ZnO/C composite nano-catalyst, result of study shows that this catalyst has very high catalytic activity to the oxidation of ethanol reaction.
Technical scheme of the present invention
A kind of Pd/ZnO/C composite nano-catalyst, wherein Pd, ZnO, C calculate in mass ratio, and namely Pd:ZnO:C is the nanocatalyst that the ratio of 0.5:1:1 is composited;
Wherein said C was the active carbon of 200 mesh sieves, and the active carbon of described mistake 200 mesh sieves is preferably Vulcan XC-72 activated carbon powder.
The preparation method of above-mentioned a kind of Pd/ZnO/C composite nano-catalyst specifically comprises the steps:
(1), ZnO nano particle preparation
With ZnSO
4Solution, NaOH solution and carbonic hydroammonium react under stirring condition and generate tiny basic zinc carbonate particle, again with the basic zinc carbonate particle after drying under 80 ℃ of conditions, under 400 ℃ of conditions, calcine, obtain white particle, be the ZnO particle;
(2), then be 1:1 according to mass ratio, the ZnO nano particle of the active carbon of crossing 200 mesh sieves and step (1) gained is stirred in glycol water fully mix, obtain mixed solution;
Described glycol water, namely ethylene glycol and deionized water are calculated by volume, i.e. ethylene glycol: deionized water is the solution that the ratio of 1:3 forms;
Described pretreated Vulcan XC-72 activated carbon powder, namely controlling temperature is 90 ℃, with the HNO of active carbon Vulcan XC-72 at 5mol/L
3Middle strong stirring backflow 5h is cooled to and filters after the room temperature and washing, the control temperature in 130 ℃ of vacuum drying, grinding, cross 200 mesh sieves, namely get pretreated Vulcan XC-72 activated carbon powder;
(3), with liquid phase reduction loaded with nano Pd particle;
Dropwise add PdCl in the mixed liquor that step (2) obtains
2The aqueous solution, after stirring, add and contain the trisodium citrate of two crystallizations water as stabilizing agent, the mol ratio of control metal Pd and trisodium citrate is 1:5, and ultrasonic concussion mixes, and uses the pH value to 11 of alkaline solution NaOH regulator solution again, then add sodium borohydride as reducing agent, continue isothermal reaction 3h, then be cooled to room temperature, filter and wash to the filter cake without Cl
-, the control temperature is 90 ℃ of lower vacuum drying, namely obtains black powder shape Pd/ZnO/C composite nano-catalyst, wherein the load capacity of metal Pd is wt.20%;
The PdCl that adds in the above-mentioned mixed liquor
2The amount of the aqueous solution, trisodium citrate and sodium borohydride is pressed Zn:PdCl contained in the mixed liquor
2Contained metal Pd in the aqueous solution: trisodium citrate: the mol ratio of sodium borohydride is 2.6:1:5:6.
A kind of Pd/ZnO/C composite nano-catalyst of above-mentioned gained has very high catalytic activity to the oxidation reaction of ethanol.
Beneficial effect of the present invention
A kind of Pd/ZnO/C composite nano-catalyst of the present invention, owing to contain ZnO, thus having improved the anti-poisoning capability of Pd/ZnO/C composite nano-catalyst, Pd/ZnO/C composite nano-catalyst stability is better.
Further, a kind of Pd/ZnO/C composite nano-catalyst of the present invention has fine catalytic oxidation performance to ethanol in alkaline solution.
In sum, a kind of Pd/ZnO/C composite nano-catalyst of the present invention distributes at particle diameter, and to the catalytic performance of ethanol, and there is better effect stable aspect.
Description of drawings
The TEM figure of Fig. 1, Pd/ZnO/C composite nano-catalyst;
The XRD figure of Fig. 2, Pd/ZnO/C composite nano-catalyst;
Fig. 3, Pd/ZnO/C composite nano-catalyst are at 1molL
-1Stripping Voltammetry curve in the KOH solution;
Fig. 4, Pd/C catalyst and Pd/ZnO/C composite nano-catalyst are respectively at 1mol/LCH
3CH
2Cyclic voltammetry curve in OH and the 1mol/L KOH solution;
Fig. 5, Pd/C catalyst and Pd/ZnO/C composite nano-catalyst are at 1M KOH+1M C
2H
5Time current curve among the OH.
The specific embodiment
Also by reference to the accompanying drawings the present invention is further set forth below by specific embodiment, but do not limit the present invention.
X-ray powder diffraction instrument is German Bruker D8-ADVANCE type, and radiation source is CuK
(
=0.15418nm), and 0.0167 ° of step-length, per step stops 1s, and sweep limits is 20-90 °;
The Shanghai occasion China CHI660A of instrument company electrochemical workstation;
The reagent that the present invention is used or the specification of raw material and manufacturer's information are as follows:
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 (Solution on Chemical Reagents in Shanghai Co., Ltd analyzes pure);
Ammonium hydrogencarbonate (Shanghai fine horse favour chemical industry Co., Ltd analyzes pure);
Zinc vitriol (Nanjing Chemistry Reagent Co., Ltd. analyzes pure);
Nafion solution (5 (wt) %, U.S. DuPont company).
Embodiment 1
A kind of preparation method of Pd/ZnO/C composite nano-catalyst, concrete steps are as follows:
(1), the preparation of ZnO nano particle
Get 1.0mol/LZnSO
4Solution 50ml, dripping concentration under the rapid stirring is the NaOH solution 10ml of 0.5mol/L, dropwising rear adding 6g carbonic hydroammonium continues to stir, this moment the raw material emulsion state that is translucent, generated tiny basic zinc carbonate particle, it is under 80 ℃ of conditions after the drying that the zinc carbonate particle is put into baking oven control temperature, calcines 1h under 400 ℃ of conditions, obtain white particle, be the ZnO nano particle;
(2), the preparation of composite catalyst
Be 1:1 according to mass ratio, the common 40mg of the ZnO nano particle that passes through pretreated Vulcan XC-72 activated carbon powder and step (1) gained is joined 120ml to be calculated by volume by ethylene glycol and deionized water, be ethylene glycol: deionized water is in the glycol water of 1:3 composition, the control temperature is 60 ℃, utilize the magnetic stirring apparatus strong stirring fully to mix, obtain mixed liquor;
Described pretreated Vulcan XC-72 activated carbon powder is about to Vulcan XC-72 activated carbon powder at the HNO of 5mol/L
3, the control temperature is 90 ℃, strong stirring 5h is cooled to and filters after the room temperature and washing; Control again temperature at 130 ℃ of vacuum drying 6h, then grind and mistake 200 mesh sieves, obtain pretreated Vulcan XC-72 activated carbon powder;
(3), with liquid phase reduction loaded with nano Pd particle
The PdCl that dropwise adds 2mmol/L in the mixed liquor that step (2) obtains
2Solution 46.99mL, after stirring 1h, add the trisodium citrate that contains two crystallizations water of 138.18mg as stabilizing agent, the mol ratio of namely controlling metal Pd and trisodium citrate is 1:5, ultrasonic concussion 30min, mix, with the pH value to 11 of alkaline solution NaOH regulator solution, then add the sodium borohydride of 21.33mg as reducing agent again, continue reaction 3h, then be cooled to room temperature, filter and wash to the filter cake without Cl
-, the control temperature is 90 ℃ of lower vacuum drying 12h, namely obtains black powder shape Pd/ZnO/C composite nano-catalyst, the load capacity of metal Pd is wt.20%.
Utilize transmission electron microscope that the Pd/ZnO/C composite nano-catalyst of above-mentioned gained is scanned, the TEM picture of gained as shown in Figure 1, as can be seen from Figure 1 Pd is dispersed in the catalyst, and the catalyst of doing has good dispersiveness, and the Pd particle size is about 2-4nm.
Utilize x-ray powder diffraction instrument that the Pd/ZnO/C composite nano-catalyst of above-mentioned gained is carried out XRD scanning, used x-ray powder diffraction instrument is German Bruker D8-ADVANCE type, and radiation source is CuK
(
=0.15418nm), 0.0167 ° of step-length, per step stops 1s, sweep limits is 20-90 °, obtain the XRD figure of Pd/ZnO/C composite nano-catalyst as shown in Figure 2, and with the XRD figure of Fig. 2 gained and the standard card (JCPDS of Pd, No. 65-6174) characteristic diffraction peak of Pd appears at 40.11 ° (111), ° 46.65 (200), ° 68.11 (220), ° 82.03 (311), 86.60 ° of (222) positions contrast the standard card (JCPDS of ZnO simultaneously, No. 65-3358), the ZnO diffraction maximum appears at 82.09 ° (112), and 86.54 ° (201) show that thus this preparation method has successfully prepared the composite nano-catalyst that contains Pd and ZnO.
The Pd/ZnO/C composite nano-catalyst of above-mentioned gained is prepared catalysis electrode, and concrete steps are as follows:
Take by weighing the Pd/ZnO/C composite nano-catalyst of a certain amount of above-mentioned preparation, calculate in mass ratio, be the Pd/ZnO/C composite nano-catalyst: deionized water: ethanol: 5% Nafion solution is that the ratio of 1:160:32:22 is with Pd/ZnO/C composite nano-catalyst and deionized water, ethanol and 5%Nafion solution are mixed, ultrasonic concussion 30min, obtain the watery Pd/ZnO/C composite nano-catalyst of black ink mixed solution, measure the Pd/ZnO/C composite nano-catalyst mixed solution of 4 μ l with pipettor, be overlying on the glass-carbon electrode surface, naturally after drying, electrode fabrication is finished, and namely obtains covering the catalysis electrode that the Pd/ZnO/C composite nano-catalyst is arranged.
Described glass carbon (GC) electrode (d=3mm) uses front with 0.3
The Al of m
2O
3Powder is milled to minute surface at chamois leather, uses respectively deionized water and absolute ethyl alcohol supersound washing again.
The catalytic property of the Pd/ZnO/C composite nano-catalyst of above-mentioned gained characterizes
With the catalysis electrode with Pd/ZnO/C composite nano-catalyst for preparing as working electrode, take saturated calomel electrode (SCE) as reference electrode, the metal platinum electrode is that auxiliary electrode forms three electrode test systems, carries out cyclic voltammetry and the test of time current curve at CHI660A.
At first measure the Pd/ZnO/C composite nano-catalyst at 1molL
-1Stripping Voltammetry curve in the KOH solution as can be seen from Figure 3 the adsorption peak of hydrogen occurred, has shown that the Pd/ZnO/C composite nano-catalyst has certain specific activity surface area at-0.5V as shown in Figure 3.
Further the Pd/C catalyst of mensuration the same terms preparation and Pd/ZnO/C composite nano-catalyst are respectively at 1mol/LCH
3CH
2Cyclic voltammetry curve in OH and the 1mol/L KOH solution as shown in Figure 4, from Fig. 4, can find out, the catalytic performance of Pd/ZnO/C composite nano-catalyst is higher than the Pd/C catalyst far away, the Pd/ZnO/C composite nano-catalyst is in just inswept journey, under very low current potential, be about-0.6V(vs.SCE), ethanol just begins to occur catalytic oxidation, when-0.2 V, reach maximum, the about 85mA/cm of its peak current density
2And the peak current density of Pd/C catalyst only is 28.8mA/cm at this moment
2, add ZnO, make its current density increase by 2.95 times.During reverse scan, because the Pd in the Pd/ZnO/C composite nano-catalyst changes active Pd atom again into, again absorption ethanol is thereon carried out catalytic oxidation, its oxidation peak reaches maximum at-0.40 V, and catalytic current reaches 60mA/cm
2, as can be seen from Figure 4, the catalytic activity of Pd/C catalyst is starkly lower than the Pd/ZnO/C composite nano-catalyst.
Further measure Pd/C catalyst and Pd/ZnO/C composite nano-catalyst at 1M KOH+1M C
2H
5The time current curve as shown in Figure 5 among the OH, as can be seen from Figure 5 along with the prolongation in reaction time, Pd/C catalyst and Pd/ZnO/C composite nano-catalyst all have decline to the oxidation of ethanol peak current density, but the speed that the Pd/C catalyst descends is faster, electric current tends towards stability behind the state, and the size of the current density of Pd/ZnO/C composite nano-catalyst is 0.96 mA/cm
2, the current density size of Pd/C catalyst is 0.73 mA/cm
2Prolong in time, the intermediate product of oxidation of ethanol can make catalyst poisoning, activity decreased, but the attenuation amplitude of Pd/ZnO/C composite nano-catalyst is little, illustrate to add the anti-poisoning capability that ZnO has improved the Pd/ZnO/C composite nano-catalyst, Pd/ZnO/C composite nano-catalyst stability is better.
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. a Pd/ZnO/C composite nano-catalyst is characterized in that wherein Pd, ZnO, C calculate in mass ratio, and namely Pd:ZnO:C is the nanocatalyst that the ratio of 0.5:1:1 is composited;
Wherein said C was the active carbon of 200 mesh sieves.
2. a kind of Pd/ZnO/C composite nano-catalyst as claimed in claim 1, the active carbon that it is characterized in that described mistake 200 mesh sieves is pretreated Vulcan XC-72 activated carbon powder;
Described pretreated Vulcan XC-72 activated carbon powder, namely controlling temperature is 90 ℃, with the HNO of active carbon Vulcan XC-72 at 5mol/L
3Middle strong stirring backflow 5h is cooled to and filters after the room temperature and washing, the control temperature in 130 ℃ of vacuum drying, grinding, cross 200 mesh sieves, namely get pretreated Vulcan XC-72 activated carbon powder.
3. the preparation method of a kind of Pd/ZnO/C composite nano-catalyst as claimed in claim 1 or 2 is characterized in that specifically comprising the steps:
(1), ZnO nano particle preparation
With ZnSO
4Solution, NaOH solution and carbonic hydroammonium react under stirring condition and generate the zinc carbonate particle, again with the zinc carbonate particle after drying under 80 ℃ of conditions, under 400 ℃ of conditions, calcine, obtain white particle, be the ZnO particle;
(2), be 1:1 according to mass ratio, the ZnO nano particle of the active carbon of crossing 200 mesh sieves and step (1) gained stirred in glycol water fully mix, obtain mixed solution;
(3), with liquid phase reduction loaded with nano Pd particle;
Dropwise add PdCl in the mixed liquor that step (2) obtains
2The aqueous solution, after stirring, add and contain the trisodium citrate of two crystallizations water as stabilizing agent, the mol ratio of control metal Pd and trisodium citrate is 1:5, and ultrasonic concussion mixes, and uses the pH value to 11 of alkaline solution NaOH regulator solution again, then add sodium borohydride as reducing agent, continue isothermal reaction 3h, then be cooled to room temperature, filter and wash to the filter cake without Cl
-, the control temperature is 90 ℃ of lower vacuum drying, namely obtains the Pd/ZnO/C composite nano-catalyst of black;
The PdCl that adds in the above-mentioned mixed liquor
2The amount of the aqueous solution, trisodium citrate, sodium borohydride is pressed Zn:PdCl contained in the mixed liquor
2Contained metal Pd in the aqueous solution: trisodium citrate: the mol ratio of sodium borohydride is 2.6:1:5:6.
4. the preparation method of a kind of Pd/ZnO/C composite nano-catalyst as claimed in claim 3, it is characterized in that pretreated Vulcan XC-72 active carbon in the step (2), the ZnO nano particle of step (1) gained and the consumption of glycol water, press mass volume ratio and calculate, be i.e. pretreated Vulcan XC-72 active carbon: the ZnO nano particle of step (1) gained: glycol water is 1g:1g:6L.
5. the preparation method of a kind of Pd/ZnO/C composite nano-catalyst as claimed in claim 4, it is characterized in that the glycol water described in the step (2), be that ethylene glycol and deionized water are calculated by volume, i.e. ethylene glycol: deionized water is the glycol water that the ratio of 1:3 forms.
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Cited By (5)
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| CN104998642A (en) * | 2015-07-23 | 2015-10-28 | 上海电力学院 | Preparation method for alcohol fuel zincode catalyst Pd-MnO2/GNRs |
| CN108671628A (en) * | 2018-05-08 | 2018-10-19 | 重庆鑫泽环保设备有限公司 | Filter fiber in waste gas treatment equipment and preparation method thereof |
| CN115011109A (en) * | 2022-07-26 | 2022-09-06 | 王卡 | Antibacterial platinum photocatalyst negative ion activated carbon filter cotton and preparation method thereof |
| CN115893473A (en) * | 2022-11-09 | 2023-04-04 | 福州大学 | Alcohol gas-sensitive material based on ZnO and activated carbon composite, and preparation method and application thereof |
| CN116058385A (en) * | 2022-11-18 | 2023-05-05 | 辽宁大学 | Palladium zinc oxide nano enzyme material with double enzyme activities, and preparation method and application thereof |
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| CN104998642A (en) * | 2015-07-23 | 2015-10-28 | 上海电力学院 | Preparation method for alcohol fuel zincode catalyst Pd-MnO2/GNRs |
| CN108671628A (en) * | 2018-05-08 | 2018-10-19 | 重庆鑫泽环保设备有限公司 | Filter fiber in waste gas treatment equipment and preparation method thereof |
| CN108671628B (en) * | 2018-05-08 | 2020-08-28 | 重庆鑫泽环保设备有限公司 | Filter fiber in waste gas treatment equipment and preparation method thereof |
| CN115011109A (en) * | 2022-07-26 | 2022-09-06 | 王卡 | Antibacterial platinum photocatalyst negative ion activated carbon filter cotton and preparation method thereof |
| CN115011109B (en) * | 2022-07-26 | 2023-11-14 | 王卡 | Preparation method of antibacterial platinum photocatalyst anion activated carbon filter cotton |
| CN115893473A (en) * | 2022-11-09 | 2023-04-04 | 福州大学 | Alcohol gas-sensitive material based on ZnO and activated carbon composite, and preparation method and application thereof |
| CN116058385A (en) * | 2022-11-18 | 2023-05-05 | 辽宁大学 | Palladium zinc oxide nano enzyme material with double enzyme activities, and preparation method and application thereof |
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Application publication date: 20130109 |