CN107026026A - A kind of method of controllable preparation redox graphene nano bar-shape β manganese dioxide aeroges - Google Patents

A kind of method of controllable preparation redox graphene nano bar-shape β manganese dioxide aeroges Download PDF

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CN107026026A
CN107026026A CN201710159572.8A CN201710159572A CN107026026A CN 107026026 A CN107026026 A CN 107026026A CN 201710159572 A CN201710159572 A CN 201710159572A CN 107026026 A CN107026026 A CN 107026026A
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mno
nano bar
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graphene
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郭新立
葛创
祝龙
刘园园
陈忠涛
赵丽
王小娟
张弘毅
张伟杰
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Southeast University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention provides a kind of method of controllable preparation redox graphene nano bar-shape β manganese dioxide aeroges.Mainly include the following steps that：1. using improving the solution that Hummers methods prepare graphene oxide and are configured to 2mg/ml.2. potassium permanganate and manganese sulfate controllable preparation nano bar-shape β MnO are utilized by hydro-thermal method2；2. by nano bar-shape β MnO2It is added in the graphene oxide solution configured and ultrasound makes manganese dioxide dispersed.Redox graphene nano bar-shape β MnO are self-assembled into 3. the mixed solution of dispersed graphene oxide and manganese dioxide is poured into reactor and carries out hydro-thermal reaction2Hydrogel.4. obtain redox graphene nanometer rods β MnO using freeze-drying method2Aeroge.Simple to operate, easily controllable, the nano bar-shape β MnO of the present invention2Addition reduce graphene film interlayer reunite simultaneously the higher electric conductivity of redox graphene can accelerate the transmission rate of electronics so as to play both cooperative effects, can as ultracapacitor electrode material.

Description

A kind of controllable preparation redox graphene-nano bar-shape β-manganese dioxide aeroge Method
Technical field
The present invention relates to a kind of two one-step hydrothermals controllable preparation redox graphene-nano bar-shape β-MnO2Aeroge Method, belongs to materials chemistry preparing technical field.
Background technology
Graphene be one kind by carbon atom with sp2What hydridization was formed has cellular crystal structure two-dimension nano materials, solely Special lattice structure makes it have excellent mechanics, optically and thermally electricity, performance.Graphene scene effect transistor, high frequency Had broad application prospects in terms of electronic device, transparent conductive film, composite, energy storage material, electrochemical sensor.
Preparing the method for graphene at present mainly has micromechanics stripping method, SiC epitaxial growth methods, oxidation-reduction method and change Learn vapour deposition process.The fault location and edge of graphene oxide are because with hydrophily is made it have containing functional group, while oxygen Not oxidized part has complete benzene ring structure and has hydrophobicity in graphite alkene.Therefore, graphene oxide has class Like the function that surfactant is dispersed.
Hydrophobic graphene, oxygen reduction fossil are gradually reduced under hydrothermal conditions with hydrophilic graphene oxide Adhesion enhancing between black alkene lamella ultimately forms the aeroge with three-dimensional structure.Aeroge have big specific surface area and The advantages of high conductivity.The conductive network of three-dimensional communication is conducive to reducing the transmission range of ion and improves the transmission speed of electronics Degree, thus graphene aerogel electrochemical field application widely.
Manganese dioxide has higher theoretical specific capacitance, is a kind of electrode material commonly used in ultracapacitor.Titanium dioxide Manganese has a variety of crystal structures, including α-MnO2、β-MnO2、γ-MnO2Deng.Different crystal structures makes manganese dioxide in electrification Learning aspect of performance has certain difference.Therefore, the controllable manganese dioxide pair for preparing different crystal structure, pattern, size Improve manganese bioxide electrochemical performance significant.Prepare at present the method for manganese dioxide mainly include liquid-phase precipitation method, Hydro-thermal method, electrochemical deposition method etc..Manganese dioxide crystallinity prepared by hydro-thermal method is high simultaneously can be by controlling the temperature of hydro-thermal With the manganese dioxide of the factor controllable preparation different crystal structure such as time.
Graphene aerogel is combined with the nano-manganese dioxide of controllable preparation can reduce the group between graphene sheet layer Coalescence and it the higher theoretical specific capacitance of the high conductivity and manganese dioxide of graphene is combined can play both collaborations Effect, has application prospect in ultracapacitor field.
The content of the invention
Goal of the invention：The invention provides a kind of controllable preparation redox graphene-nano bar-shape β-MnO2Aeroge Method.Graphene has high conductivity, excellent mechanical property, electric double layer capacitance the features such as and the poorly conductive of manganese dioxide But its theoretical electric capacity is high, both respective advantages performance cooperative effects can be given full play to by combining both, in super electricity Container electrode field has application prospect.
Technical scheme：To realize above-mentioned purpose, the present invention uses a kind of controllable preparation redox graphene-nanometer rods Shape β-MnO2Airsetting gluing method is：
1) prepares graphene oxide solution and is configured to 2-3mg/ml solution using improving Hummers methods；
2) prepares nano bar-shape β-MnO using potassium permanganate and manganese sulfate by hydro-thermal method2；
3) using the graphene oxide solution for preparing by nano bar-shape β-MnO2It is dispersed；
4) by step 3) dispersed good graphene oxide and nano bar-shape β-MnO2Mixing liquid carry out hydro-thermal it is anti- Hydrogel should be obtained；
5) freeze drier step of freeze drying 4 is utilized) obtained hydrogel obtains aeroge.
Wherein：
Described hydro-thermal method prepares nano bar-shape β-MnO2Temperature be 180 DEG C, time of hydro-thermal reaction is 3-12h.
Described graphene oxide and nano bar-shape β-MnO2Mixing liquid carry out hydro-thermal reaction temperature be 140-180 DEG C, the time of hydro-thermal reaction is 3-6h.
Described freeze temperature is -50 DEG C, and freeze-drying time is 12-24h.
Beneficial effect：Graphene oxide has amphipathic so as to the divergent function with surfactant-like.Aoxidize stone Black alkene can effectively disperse nano-manganese dioxide.Graphene can be reduced by the synergy of graphene and nano-manganese dioxide Reunion between lamella with stacking so as to maintain graphene big specific surface area and high conductivity the advantages of.By simple The hydrothermal temperature that adjustment prepares manganese dioxide can both obtain the nano-manganese dioxide of different crystal structure and pattern.Present invention tool Have the advantages that cost is low, easy to operate, time-consuming short.
Embodiment
A kind of two one-step hydrothermals controllable preparation redox graphene-nano bar-shape β-MnO of the present invention2The side of aeroge Method, is configured to 2mg/ml solution by the graphene oxide for improving the preparation of Hummers methods first and ultrasonic certain time makes its point Dissipate uniform.Then potassium permanganate and manganese sulfate controllable preparation nano bar-shape β-MnO are utilized by hydro-thermal method2.Afterwards by nanometer rods Shape β-MnO2Mixed with the graphene oxide solution prepared and ultrasonic certain time makes nano bar-shape β-MnO2In graphene oxide In be uniformly dispersed.Afterwards by graphene oxide and nano bar-shape β-MnO2Mixed homogeneous solution moves into reactor and carries out hydro-thermal Reaction obtains redox graphene/β-MnO of column2Hydrogel.Finally the hydrogel of acquisition is put into freeze drier It is lyophilized to obtain porous, structural integrity aeroge.Compared with other methods for preparing graphene-manganese dioxide composite material, this Invention can be by controlling the condition controllable preparation of hydro-thermal reaction to obtain the nano-manganese dioxide of specific crystal structure and pattern.Together When nano bar-shape manganese dioxide be dispersed between redox graphene lamella and effectively prevent between graphene sheet layer Reunion with stacking so as to being conducive to improving conductivity of composite material and specific surface area.
A. Hummers methods are improved and prepare graphene oxide：
0.3g graphite is weighed to be thoroughly mixed with 6g potassium permanganate.Measuring tank measures the 36ml concentrated sulfuric acids and 4ml phosphoric acid is abundant It is well mixed.The mixture of potassium permanganate and graphite is added in the mixed liquor of the concentrated sulfuric acid and phosphoric acid and 50 DEG C of stirrings afterwards 12h obtains graphite oxide.1ml hydrogen peroxide is taken afterwards and adds in 50ml deionized waters and is put into refrigerator makes ice cube.Will system Standby graphite oxide, which is added in frozen water, to be obtained orange solution and stands 3 days.The sediment centrifugation obtained and ultrasound will be stood Obtain graphene oxide.The solution and ultrasonic disperse that the graphene oxide of acquisition is configured into 2-3mg/ml are uniform.
B. hydro-thermal method controllable preparation nano bar-shape β-MnO2：
Weigh 158mg potassium permanganate and 253mg manganese sulfates are dissolved in 25ml deionized waters respectively.Liquor potassic permanganate is fallen Enter in manganese sulfate solution and stir 2-5 minutes.Mixed solution is moved into 100ml reactors and carries out hydro-thermal reaction.Hydro-thermal The temperature of reaction is 180 DEG C, and the time of hydro-thermal reaction is 3-12h.Finally by 60 DEG C of bakings after the product centrifugation for several times of hydro-thermal reaction Dry 8h obtains nano bar-shape β-MnO2。
C. hydro-thermal method prepares redox graphene/β-MnO2Hydrogel：
Take 10-30mg nano bar-shape β-MnO2It is dissolved in 25ml 2-3mg/ml graphene oxide solution and ultrasound 2-4h Manganese dioxide is set to be uniformly dispersed in the solution.Finely dispersed solution after mixing is moved into 50ml reactors and carries out hydro-thermal reaction Obtain hydrogel.The temperature of hydro-thermal reaction is 140-180 DEG C, and the time of hydro-thermal reaction is 3-6h.
D. freeze-drying obtains redox graphene/β-MnO2Aeroge：
Hydrogel is put into freeze drier and carries out lyophilized acquisition aeroge.Freeze temperature is -50 DEG C, and freeze-drying time is 12-24h。
Embodiment 1：
(1) 0.3g graphite is weighed to be thoroughly mixed with 6g potassium permanganate.Measuring tank measures the 36ml concentrated sulfuric acids and filled with 4ml phosphoric acid Divide well mixed.The mixture of potassium permanganate and graphite is added in the mixed liquor of the concentrated sulfuric acid and phosphoric acid and 50 DEG C of stirrings afterwards 12h obtains graphite oxide.1ml hydrogen peroxide is taken afterwards and adds in 50ml deionized waters and is put into refrigerator makes ice cube.Will system Standby graphite oxide, which is added in frozen water, to be obtained orange solution and stands 3 days.The sediment centrifugation obtained and ultrasound will be stood Obtain graphene oxide.The solution and ultrasonic disperse that the graphene oxide of acquisition is configured into 2-3mg/ml are uniform.
(2) weigh 158mg potassium permanganate and 253mg manganese sulfates are dissolved in 25ml deionized waters respectively.Potassium permanganate is molten Liquid is poured into manganese sulfate solution and stirred 2-5 minutes.Mixed solution is moved into 100ml reactors and carries out hydro-thermal reaction. The temperature of hydro-thermal reaction is 180 DEG C, and the time of hydro-thermal reaction is 3h.Finally by 60 DEG C of bakings after the product centrifugation for several times of hydro-thermal reaction Dry 8h obtains nano bar-shape β-MnO2。
(3) 10mg nano bar-shape β-MnO are taken2It is dissolved in 25ml 2-3mg/ml graphene oxide solution and ultrasound 2-4h Manganese dioxide is set to be uniformly dispersed in the solution.Finely dispersed solution after mixing is moved into 50ml reactors and carries out hydro-thermal reaction Obtain hydrogel.The temperature of hydro-thermal reaction is 140 DEG C, and the time of hydro-thermal reaction is 6h.
(4) hydrogel is put into freeze drier and carries out lyophilized acquisition aeroge.Freeze temperature is -50 DEG C, when freezing Between be 12h.
Embodiment 2：
(1) is same as scheme 1, process (1).
(2) weigh 158mg potassium permanganate and 253mg manganese sulfates are dissolved in 25ml deionized waters respectively.Potassium permanganate is molten Liquid is poured into manganese sulfate solution and stirred 2-5 minutes.Mixed solution is moved into 100ml reactors and carries out hydro-thermal reaction. The temperature of hydro-thermal reaction is 180 DEG C, and the time of hydro-thermal reaction is 6h.Finally by 60 DEG C of bakings after the product centrifugation for several times of hydro-thermal reaction Dry 8h obtains nano bar-shape β-MnO2。
(3) 20mg nano bar-shape β-MnO are taken2It is dissolved in 25ml 2-3mg/ml graphene oxide solution and ultrasound 2-4h Manganese dioxide is set to be uniformly dispersed in the solution.Finely dispersed solution after mixing is moved into 50ml reactors and carries out hydro-thermal reaction Obtain hydrogel.The temperature of hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 4h.
(4) hydrogel is put into freeze drier and carries out lyophilized acquisition aeroge.Freeze temperature is -50 DEG C, when freezing Between be 16h.
Embodiment 3：
(1) is same as scheme 1, process (1).
(2) weigh 158mg potassium permanganate and 253mg manganese sulfates are dissolved in 25ml deionized waters respectively.Potassium permanganate is molten Liquid is poured into manganese sulfate solution and stirred 2-5 minutes.Mixed solution is moved into 100ml reactors and carries out hydro-thermal reaction. The temperature of hydro-thermal reaction is 180 DEG C, and the time of hydro-thermal reaction is 12h.Finally by 60 DEG C after the product centrifugation for several times of hydro-thermal reaction Dry 8h and obtain nano bar-shape β-MnO2。
(3) 20mg nano bar-shape β-MnO are taken2It is dissolved in 25ml 2-3mg/ml graphene oxide solution and ultrasound 2-4h Manganese dioxide is set to be uniformly dispersed in the solution.Finely dispersed solution after mixing is moved into 50ml reactors and carries out hydro-thermal reaction Obtain hydrogel.The temperature of hydro-thermal reaction is 180 DEG C, and the time of hydro-thermal reaction is 3h.
(4) hydrogel is put into freeze drier and carries out lyophilized acquisition aeroge.Freeze temperature is -50 DEG C, when freezing Between be 24h.

Claims (4)

1. a kind of controllable preparation redox graphene-nano bar-shape β-manganese dioxide airsetting gluing method, it is characterised in that the party Method uses two one-step hydrothermals, comprises the following steps that：
1) prepares graphene oxide solution and is configured to 2-3mg/ml solution using improving Hummers methods；
2) prepares nano bar-shape β-MnO using potassium permanganate and manganese sulfate by hydro-thermal method2；
3) using the graphene oxide solution for preparing by nano bar-shape β-MnO2It is dispersed；
4) by step 3) dispersed good graphene oxide and nano bar-shape β-MnO2Mixing liquid carry out hydro-thermal reaction acquisition Hydrogel；
5) freeze drier step of freeze drying 4 is utilized) obtained hydrogel obtains aeroge.
2. controllable preparation redox graphene according to claim 1-nano bar-shape β-MnO2Airsetting gluing method, it is special Levy and be that described hydro-thermal method prepares nano bar-shape β-MnO2Temperature be 180 DEG C, time of hydro-thermal reaction is 3-12h.
3. controllable preparation redox graphene according to claim 1-nano bar-shape β-MnO2Airsetting gluing method, it is special Levy and be described graphene oxide and nano bar-shape β-MnO2Mixing liquid carry out hydro-thermal reaction temperature be 140-180 DEG C, the time of hydro-thermal reaction is 3-6h.
4. controllable preparation redox graphene according to claim 1-nano bar-shape β-MnO2Airsetting gluing method, it is special Levy and be that described freeze temperature is -50 DEG C, freeze-drying time is 12-24h.
CN201710159572.8A 2017-03-17 2017-03-17 A kind of method of controllable preparation redox graphene nano bar-shape β manganese dioxide aeroges Pending CN107026026A (en)

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CN108455573A (en) * 2018-02-02 2018-08-28 贵州大学 A kind of preparation method of the loose stratiform graphene aerogel of tearing bread-like
CN108905910A (en) * 2018-07-05 2018-11-30 平顶山学院 A kind of three-dimensional redox graphene/MnO2Composite material and preparation method
CN110707319A (en) * 2019-09-27 2020-01-17 上海应用技术大学 Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof
CN110739159A (en) * 2019-10-14 2020-01-31 北京化工大学 Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite materials for super capacitor
CN112349909A (en) * 2020-11-06 2021-02-09 常州大学 Zinc-ion battery positive electrode composite material and preparation method and application thereof
CN112441620A (en) * 2020-11-23 2021-03-05 广东工业大学 Alpha-type manganese dioxide with pore channels filled with hydrogen ions and preparation method thereof
CN112635706A (en) * 2020-12-30 2021-04-09 蜂巢能源科技有限公司 Preparation method of graphene-manganese dioxide nanorod-shaped negative electrode material
CN113213543A (en) * 2021-05-13 2021-08-06 陕西科技大学 MnO (MnO)2/V2O3Process for preparing nano composite material
CN114733517A (en) * 2022-06-09 2022-07-12 中国环境科学研究院 Preparation method and application of novel photocatalytic material for efficiently removing refractory organic matters
CN114974912A (en) * 2022-06-27 2022-08-30 盐城工学院 Preparation method of nano transition metal oxide-porous carbon composite electrode material
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CN108455573A (en) * 2018-02-02 2018-08-28 贵州大学 A kind of preparation method of the loose stratiform graphene aerogel of tearing bread-like
CN108455573B (en) * 2018-02-02 2021-04-20 贵州大学 Preparation method of hand-tearing bread-shaped loose laminar graphene aerogel
CN108404822A (en) * 2018-04-12 2018-08-17 吉林大学 A kind of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel and preparation method thereof
CN108905910A (en) * 2018-07-05 2018-11-30 平顶山学院 A kind of three-dimensional redox graphene/MnO2Composite material and preparation method
CN108905910B (en) * 2018-07-05 2021-03-16 平顶山学院 Three-dimensional reduction graphene oxide/MnO2Composite material and preparation method thereof
CN110707319A (en) * 2019-09-27 2020-01-17 上海应用技术大学 Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof
CN110739159A (en) * 2019-10-14 2020-01-31 北京化工大学 Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite materials for super capacitor
CN112349909A (en) * 2020-11-06 2021-02-09 常州大学 Zinc-ion battery positive electrode composite material and preparation method and application thereof
CN112441620B (en) * 2020-11-23 2023-05-16 广东工业大学 Alpha-type manganese dioxide with hydrogen ion filled pore canal and preparation method thereof
CN112441620A (en) * 2020-11-23 2021-03-05 广东工业大学 Alpha-type manganese dioxide with pore channels filled with hydrogen ions and preparation method thereof
CN112635706A (en) * 2020-12-30 2021-04-09 蜂巢能源科技有限公司 Preparation method of graphene-manganese dioxide nanorod-shaped negative electrode material
CN113213543A (en) * 2021-05-13 2021-08-06 陕西科技大学 MnO (MnO)2/V2O3Process for preparing nano composite material
CN114733517A (en) * 2022-06-09 2022-07-12 中国环境科学研究院 Preparation method and application of novel photocatalytic material for efficiently removing refractory organic matters
CN114974912A (en) * 2022-06-27 2022-08-30 盐城工学院 Preparation method of nano transition metal oxide-porous carbon composite electrode material
CN116453874A (en) * 2022-11-30 2023-07-18 湖南金阳烯碳新材料股份有限公司 Graphene carbon nanocomposite and preparation method and application thereof
CN116272962A (en) * 2023-03-21 2023-06-23 张永生 Catalytic material for treating automobile exhaust

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