CN103691428A - Preparation method of carbon-supported noble metal catalyst - Google Patents
Preparation method of carbon-supported noble metal catalyst Download PDFInfo
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- CN103691428A CN103691428A CN201310731219.4A CN201310731219A CN103691428A CN 103691428 A CN103691428 A CN 103691428A CN 201310731219 A CN201310731219 A CN 201310731219A CN 103691428 A CN103691428 A CN 103691428A
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Abstract
The invention relates to a preparation method of a carbon-supported noble metal catalyst, and a noble metal precursor-loaded carrier obtained by an impregnation method is reduced by cold plasmas under atmospheric pressure to obtain the high-performance carbon-supported noble metal catalyst. The method specifically comprises the following steps: (a) loading the active ingredients of a required noble metal precursor to a carrier by the impregnation method, and drying; (b) putting a catalyst obtained from the step (a) into a discharge region, taking pure hydrogen or hydrogen-containing inert gas as working gas, and reducing the carrier by the cold plasmas under the atmospheric pressure. If needed, the step (c) of performing heat treatment on the catalyst in the step (b) in a hydrogen or inert atmosphere can be performed. The method for preparing the carbon-supported noble metal catalyst by the cold plasmas under the atmospheric pressure has the characteristics of simple process, environmental friendliness and the like; the catalyst performance can be remarkably improved.
Description
technical field:
The present invention relates to a kind of preparation method of charcoal supported noble metal catalyst, the method is to utilize the preparation of atmosphere cold plasma to charcoal supported noble metal catalyst, belongs to charcoal supported noble metal catalyst preparation field.
background technology:
Charcoal supported noble metal catalyst has a wide range of applications at chemical industry, the energy and field of Environment Protection.For example, Pt/C catalyst is widely used aspect fuel cell, has catalytic activity high, stable chemical performance, the advantage such as exchange current density is large.Au/C and Pd/C catalyst are at glucose oxidase, and the fields such as hydrogenation reaction have a wide range of applications.The preparation of charcoal supported noble metal catalyst adopts infusion process and chemical preparation conventionally.Infusion process is simple to operate, but Kaolinite Preparation of Catalyst activity is often active poor.Chemical reduction method can be prepared high performance charcoal supported noble metal catalyst conventionally, but it need to use poisonous and hazardous chemical reagent conventionally, and environment is unfriendly.In addition, liquid phase reduction is prepared Pd/C catalyst, often adopts solvent dehydration method, dangerous, consuming time, environment is unfriendly.Oven drying easily causes metal Pd aggregated particle size to become large, dispersed variation, and then cause active decline.If the charcoal supported noble metal presoma that can prepare simple infusion process carries out simple process, prepare high performance charcoal supported noble metal catalyst, will there is important using value.
Cold plasma is a kind of non-equilibrium thermodynamics plasma, at room temperature just can realize decomposition, reduction, regeneration and the modification of catalyst.Preparation method compares with traditional catalyst, and cold plasma is a kind of environmentally friendly preparation method, has the features such as manufacturing cycle is short, can prepare fast high performance catalyst.The people such as Liu Changjun have reported and have adopted plasma deoxidization in low termprature to prepare the method for load type metal catalyst, metal ion can be reduced into metal simple-substance in patent (patent publication No.: CN1539553, CN1647858, CN1739854, CN102151586).But it carries out conventionally under low pressure, be unfavorable for scale amplification.And in its patent, emphasize electron reduction, be difficult to realize reducing metal ion under atmospheric pressure.The people such as Wang Qi are in patent (patent publication No.: reported a kind of method of preparing Graphene platinum nano composite material with argon plasma CN102698741).The method can effectively be prepared the graphene-based platinum nano composite material being evenly distributed, but it need to carry out under low pressure.The people such as Hu Haoquan are in patent (patent publication No.: reported CN101602017) and utilized low temperature plasma to prepare the carrier of load type metal catalyst and the method for active component, but wherein do not related to the research of direct-reduction load type metal ion on carrier simultaneously.
Summary of the invention
Problem in view of prior art existence, the object of the invention is to provide a kind of preparation method of charcoal supported noble metal catalyst, the method is that infusion process is carried out to simple process, is a kind of method that can utilize atmosphere cold plasma to prepare high-performance carbon supported noble metal catalyst.
To achieve these goals, the technical solution adopted in the present invention is a kind of preparation method of charcoal supported noble metal catalyst, and its course of work is as follows:
A. by infusion process, required noble metal precursor body is loaded on charcoal carrier, room temperature is placed 2-24 h, at 60-110
oc is dried 2-24 h.
B. the catalyst of step a gained is put into atmospheric pressure plasma reactor and reduce, using the inert gas of pure hydrogen or hydrogen as working gas, the alternating voltage peak-to-peak value of electric discharge is 0.5-40 kV, and the recovery time is 6-120 min.
According to catalyst, use needs, the present invention also can comprise step c roasting: catalyst roasting 0.5 ~ 6 h in hydrogen or inert gas that step b is obtained, temperature is 200 ~ 500
oc.
Described noble metal is a kind of in Pd, Pt, Au, Ag, Ir or Ru.
In described noble metal, precious metal ion generally loads on carrier by the loading of 0.1-10%.
Described charcoal carrier can be a kind of in active carbon, Graphene, CNT or nano carbon fiber.
Described atmosphere cold plasma is atmospheric dielectric barrier discharge cold plasma, atmospheric radio-frequency discharging cold plasma, or a kind of in Atomospheric pressure glow discharge cold plasma.
Described working gas is hydrogen, or hydrogen and argon gas, or the mist of hydrogen and helium.
Beneficial effect of the present invention is: the method is that infusion process is carried out to simple process, utilizes atmosphere cold plasma to prepare fast noble metal catalyst, has environmental friendliness, the short feature of manufacturing cycle.
figure of description
Fig. 1 is the XRD spectra of the Pd/C catalyst of preparation.
Fig. 2 is the active testing curve of the Pd/C catalyst of preparation.
The specific embodiment
below in conjunction with embodiment, the present invention is described in detail.
embodiment 1:
With 30%HNO
340-60 order active carbon after pretreatment 5 h is carrier, dipping H
2 pdCl
4 solution (content of metal Pd is 5%), standing 12 h, 100
oc is dried 2 h.Get this sample of 0.3 g and put into plasma reactor, the mist of hydrogen and argon gas of take is working gas (total gas flow rate 100 mlmin
-1, the ratio of hydrogen and argon gas is 1:1), adopt atmospheric dielectric barrier discharge cold plasma to reduce, regulating simple alternating current discharge voltage peak-to-peak value is 36 kV, the recovery time is 6 min, and then under hydrogen atmosphere 300
oc roasting 2 h, obtain 5% Pd/C catalyst.The XRD spectra of the Pd/C catalyst obtaining, as shown in Figure 1.
As shown in Figure 1, the load type palladium ion fast restore that plasma method can be prepared infusion process is Metal Palladium simple substance.Get this sample of 10 mg, put into the reaction tube that internal diameter is 4 mm, pass into 20 mlmin
-1cO calibrating gas (CO:O
2 : N
2 =1:20:79), carry out the test of CO oxidation activity, result represents as Fig. 2.
As seen from Figure 2, plasma method is prepared sample to have obvious carbon monoxide oxidation active.
Above-described embodiment is a kind of of embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other are any does not run counter to the change of doing under Spirit Essence of the present invention and principle and all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (7)
1. a preparation method for charcoal supported noble metal catalyst, is characterized in that comprising the steps: that a. loads to required noble metal precursor body on charcoal carrier by infusion process, and room temperature is placed 2-24 h, at the dry 2-24 h of 60-110 oC; B. the catalyst of step a gained is put into atmospheric pressure plasma reactor and reduce, using the inert gas of pure hydrogen or hydrogen as working gas, the alternating voltage peak-to-peak value of electric discharge is 0.5-40 kV, and the recovery time is 6-120 min.
2. as the preparation method of a kind of charcoal supported noble metal catalyst affiliated in claim 1, it is characterized in that comprising step c roasting, described step c roasting is catalyst roasting 0.5 ~ 6 h in hydrogen or inert gas that step b is obtained, and temperature is 200 ~ 500
oc.
3. as the preparation method of a kind of charcoal supported noble metal catalyst under in claim 1, it is characterized in that described noble metal is a kind of in Pd, Pt, Au, Ag, Ir or Ru.
4. as the preparation method of a kind of charcoal supported noble metal catalyst affiliated in claim 3, it is characterized in that in described noble metal, precious metal ion generally loads on carrier by the loading of 0.1-10%.
5. as the preparation method of a kind of charcoal supported noble metal catalyst under in claim 1, it is characterized in that described charcoal carrier can be a kind of in active carbon, Graphene, CNT or nano carbon fiber.
6. as the preparation method of a kind of charcoal supported noble metal catalyst affiliated in claim 1, it is characterized in that described atmosphere cold plasma is atmospheric dielectric barrier discharge cold plasma, atmospheric radio-frequency discharging cold plasma, or a kind of in Atomospheric pressure glow discharge cold plasma.
7. as the preparation method of a kind of charcoal supported noble metal catalyst affiliated in claim 1, it is characterized in that described working gas is hydrogen, or hydrogen and argon gas, or the mist of hydrogen and helium.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707599A (en) * | 2015-03-03 | 2015-06-17 | 江苏丽港科技有限公司 | Preparation method for palladium-carbon composite catalyst |
| CN107775014A (en) * | 2017-09-06 | 2018-03-09 | 深圳先进技术研究院 | A kind of method that atmosphere cold plasma prepares noble metal/graphene composite nano material |
| CN109745969A (en) * | 2018-12-20 | 2019-05-14 | 西安交通大学 | A kind of carbon carries super-small precious metal nano-particle catalyst and preparation method |
| CN110918028A (en) * | 2019-12-06 | 2020-03-27 | 大连海事大学 | Device and method for preparing metal catalyst by using plasma |
| CN111450866A (en) * | 2020-05-08 | 2020-07-28 | 中国科学院长春应用化学研究所 | Method for preparing catalyst by solid-state electroreduction |
| CN112452323A (en) * | 2020-11-26 | 2021-03-09 | 高化学（江苏）化工新材料有限责任公司 | Preparation method and application of double-activity-center propane dehydrogenation catalyst |
| CN113648993A (en) * | 2021-08-16 | 2021-11-16 | 大连大学 | Method for preparing graphene oxide supported palladium by using liquid-phase atmospheric pressure cold plasma |
| CN113828303A (en) * | 2021-09-15 | 2021-12-24 | 江南大学 | High-value utilization method of precious metal waste catalyst |
| CN114797464A (en) * | 2022-06-01 | 2022-07-29 | 宁波工程学院 | Device and method for online elimination of CO based on plasma technology |
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| CN1647858A (en) * | 2004-12-01 | 2005-08-03 | 天津大学 | Method for reducing loaded metal catalyst using low temperature plasma |
| US20080019893A1 (en) * | 2004-08-13 | 2008-01-24 | Nec Corporation | Method For Manufacturing Metal Loading Carbon Material |
| US20080039315A1 (en) * | 2004-11-16 | 2008-02-14 | Jun Ma | Methods of preparing supported catalysts from metal loaded carbon nanotubes |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707599A (en) * | 2015-03-03 | 2015-06-17 | 江苏丽港科技有限公司 | Preparation method for palladium-carbon composite catalyst |
| CN107775014A (en) * | 2017-09-06 | 2018-03-09 | 深圳先进技术研究院 | A kind of method that atmosphere cold plasma prepares noble metal/graphene composite nano material |
| CN107775014B (en) * | 2017-09-06 | 2020-05-22 | 深圳先进技术研究院 | Method for preparing noble metal/graphene composite nano material by using atmospheric pressure cold plasma |
| CN109745969A (en) * | 2018-12-20 | 2019-05-14 | 西安交通大学 | A kind of carbon carries super-small precious metal nano-particle catalyst and preparation method |
| CN110918028A (en) * | 2019-12-06 | 2020-03-27 | 大连海事大学 | Device and method for preparing metal catalyst by using plasma |
| CN111450866A (en) * | 2020-05-08 | 2020-07-28 | 中国科学院长春应用化学研究所 | Method for preparing catalyst by solid-state electroreduction |
| CN111450866B (en) * | 2020-05-08 | 2023-08-29 | 中国科学院长春应用化学研究所 | Method for preparing catalyst by solid-state electroreduction |
| CN112452323A (en) * | 2020-11-26 | 2021-03-09 | 高化学（江苏）化工新材料有限责任公司 | Preparation method and application of double-activity-center propane dehydrogenation catalyst |
| CN113648993A (en) * | 2021-08-16 | 2021-11-16 | 大连大学 | Method for preparing graphene oxide supported palladium by using liquid-phase atmospheric pressure cold plasma |
| CN113648993B (en) * | 2021-08-16 | 2023-09-01 | 大连大学 | Method for preparing graphene oxide supported palladium by using atmospheric pressure cold plasma in liquid phase |
| CN113828303A (en) * | 2021-09-15 | 2021-12-24 | 江南大学 | High-value utilization method of precious metal waste catalyst |
| CN114797464A (en) * | 2022-06-01 | 2022-07-29 | 宁波工程学院 | Device and method for online elimination of CO based on plasma technology |
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Application publication date: 20140402 |