CN1926058A - Method for making metal oxides - Google Patents

Abstract

A method of producing porous complex oxides includes the steps of providing a mixture of a) precursor elements suitable to produce the complex oxide; or b) one or more precursor elements suitable to produce particles of the complex oxide and one or more metal oxide particles; and c) a particulate carbon-containing pore-forming material selected to provide pore sizes in the range of approximately 7 nm to 250 nm, and treating the mixture to (i) form the porous complex oxide in which two or more of the precursor elements from (a) above or one or more of the precursor elements and one or more of the metals in the metal oxide particles from (b) above are incorporated into a phase of the complex metal oxide and the complex metal oxide has grain sizes in the range of about 1 nm to 150 nm; and (ii) remove the pore-forming material under conditions such that the porous structure and composition of the complex oxide is substantially preserved. The method may be used to produce non-refractory metal oxides as well.

Description

The manufacture method of metal oxide

Technical field

The present invention relates generally to the complex oxide material.Complex oxide is the oxide compound that comprises two or more different metal elements.They are applicable to multiple use, comprise as catalyzer and electronic material widely.In a preferred embodiment, the present invention relates to have the manufacture method of the porous complex oxide of improved high-temperature stability.On the other hand, the invention still further relates to the manufacture method of the non-refractory oxide of porous.

Background technology

Usually, the crystalline structure that comprises the oxide compound of several different metal elements compares such as Al ₂O ₃And SiO ₂The simple oxide complexity.In addition, in these complex compounds, realize generally unusual difficulty of phase purity (that is, exist the crystallization phases of wishing and do not have undesirable phase).This is because these complex crystals structures are very responsive to the variation of chemical ingredients.

Therefore, in order to realize even, the consistent performance very crucial to many application, must guarantee the homodisperse of element, this homodisperse causes wishing the complex oxide of purity.A kind of difficulty that occurs in the uniform distribution of realizing this element is the different modes that each element can show in treating processes.

For example, for various elements, precipitation and speed of reaction can change greatly, thereby cause segregation occurring in the method such as co-precipitation and collosol and gel processing.Different elements also may be very big to the response difference of temperature and atmosphere.For example, the many metallic elements that are used to form complex oxide have relatively low fusing point.If there is the atmosphere with enough reductibilities in heat treatment process, these elements can exist with the form of metal rather than oxide compound so, and can melt.This fusing can cause a large amount of formation of macrosegregation, impurity phase and the loss of surface-area.

Although these difficulties are arranged, still there are the various known methods that are used to make complex oxide in the art.

These methods comprise:

● " shaking baking (shake and bake) "

● co-precipitation

● thermal evaporation and sputtering technology

● polymkeric substance cooperates (complex) technology

● collosol and gel

Method is the most coarse also the simplest " to shake baking ".An example has been described in United States Patent (USP) 5932146.Comprise one or more different oxide powders of planting the element of needs respectively and mixed simply, grind and at high temperature fire then so that different element can be uniformly mixed by diffusion.The problem of this method is that starting material are very inhomogeneous; Therefore need very high sintering temperature to obtain homogeneity.Grind in the middle of also usually needing.High sintering temperature significantly reduces surface-area, and long sintering time, high temperature and middle the grinding cause very high processing cost.Make in this way even may not obtain the phase of some hope and purity mutually.

Coprecipitation method can be simple relatively metal oxide more uniform precursor is provided.At Applied Catalysis A:General, 235, the 79～92 pages, 2002 (Zhang-Steenwinkel, Beckers and Bliek) and J.of Power Sources, 86, the 395th～400 page, among 2000 (Morie, Sammes and the Tompsett) a plurality of examples have been described.These methods have because multiple element and very difficult shortcoming.Different elements are all with different velocity sedimentations, and therefore, for some materials, ununiformity is a subject matter, and still needs quite high sintering temperature.For example, people's such as Zhang-Steenwinkel method need surpass 800 ℃ temperature forming suitable crystallization phases, and people's such as Morie method needs 1000 ℃.In addition, realize that suitable precipitation and the necessary precipitation agent of chemical uniformity costs an arm and a leg usually.

The productions that relate to oxide film or coating of most of thermal evaporations and spraying technology more.These technology comprise the technology such as condensation of gas processing, chemical vapors condensation, plasma spraying and spray pyrolysis (spray pyrolysis).In these technology batch processing be the most important thing is spray pyrolysis (Messing etc., 1994).

Spray pyrolysis is the method that is used for making by the thermolysis of metal-salt or organo-metallic solution the powder of metal or oxide compound.These solution at first are transformed into aerosol by passing atomizing nozzle (atomisingspray nozzle) or ultrasonic transducer.Aerosol is splashed in the heating zone or on the heating surface then, and the enough heat of this heating zone or heating surface can cause the evaporation of solvent and the precipitation of metal or oxide compound subsequently.

Usually, in the spray pyrolysis process, be the elementary operation variable by changing temperature of reaction and vector gas composition change aerosol decomposition parameter.In addition, the solution performance such as the interpolation of precursor component, concentration or cosolvent may be most important for product component of realizing wishing and form.The limitation of spray pyrolysis method comprise be difficult to control the phase ratio, productivity is lower and form low-density hollow particle.

For relative simple oxidation thing, the polymkeric substance fitting method also can provide element distribution quite uniformly.At Key Engineering Materials, 206-213, the 1349-52 page or leaf has illustrated an example that is used for the La based perovskite among 2002 (Popa and the Kakihana).The subject matter of these methods is that the polymkeric substance of use is easy to the heat release burning.This can make difficult treatment.In addition, for the multielement compound, some elements can not cooperate with polymkeric substance, therefore can not obtain uniform element and distribute.

Sol-gel method generally needs careful control treatment condition to form uniform precursor.At J.Sol-Gel Science and Technology 25, the 147-157 page or leaf, 2002 (Mathur and Shen) and Chemistry of Materials 14, the 1981-88 pages or leaves have illustrated the example of the sol-gel method that is used for the La-Ca-Mn uhligite among 2002 (Pohl and the Westin).Collosol and gel is along with the complicacy increase of compound can become extremely difficult, and some elements are not suitable for sol-gel method.Collosol and gel generally is difficult to increase in proportion, and the starting material that need may be very expensive.

The U.S. Patent No. 6752979 of the applicant's name has illustrated the method for producing the complex metal oxide with equally distributed element.This method has been proved widely applicable different complex oxide.This method is by using low treatment temp to provide to have the mutually pure oxide compound of large surface area.

Except the uniform distribution of proofreading and correct crystal structure oxide and element, in many application, the hole of sintering intergranule that is present in oxide compound is very important for performance.For the application that requires good fluid (gas or liquid) migration, generally wish to have bigger, interconnected pores (＞about 1 μ m).For example, knownly can in oxide compound, provide macroporous method (for example United States Patent (USP) 4883497 and 6017647) for solid oxide fuel cell electrode.Great majority in these methods use various pore-forming materials, that is, in the stupalith can be by the molten material that goes or burn.Pore-forming material generally greater than 1 μ m so that can form the hole of this size.The hole of this size is too big, to such an extent as to can not increase the surface-area of material greatly.

Material with a large amount of fine porosity (＜about 7nm) generally shows high surface-area.High surface-area is useful for the application that utilizes surface property such as catalyzer.Constitute by the loose a large amount of very little particles that are deposited in together as fruit structure, can obtain little hole and high surface-area so.Various organic pore-forming agents also can be used for forming very little hole.Less hole generally is unable to bear higher temperature, therefore generally causes low high-temperature stability.

The hole of " centre " size range (about 7nm is to about 250nm) also is useful for improving fluid flow, and enough little of surface-area is made very big contribution.They have been believed to improve the high-temperature stability of some simple metal oxide compounds.United States Patent (USP) 6139814 has illustrated and has been used to make the method with the Ce base oxide that improves high-temperature stability.Though heat-staple reason is also uncertain, this patent infers that stability to small part is owing to there is the average pore size (example illustrates the average pore size of about 9nm) that is in " mesoscale " scope.The method of ' 814 comprises fibrous material that liquor with metal ion absorbs structure for example in the hole of filter paper.Liquid is become dry, and fire material to remove Mierocrystalline cellulose.Therefore, solid forms in cellulosic hole, and cellulosic hole is moulded solid.But this method has several shortcomings.Used very high organic: metal oxide ratio (reaching＞100: 1), this ratio causes the processing cost costliness together with the relative higher cost of suitable cellulose materials.With liquid-absorbent to such as the still process of a clumsiness that increases in proportion in the solid of paper.At last, for the uniform distribution of the different elements that produce more complicated material require, making the metal ion solution drying simply also is unfavorable to form solid.

At J.Porous Materials 7, the 435-441 pages or leaves, the method for the silicon-dioxide that is used to prepare the hole with about 10nm size range has been described among 2000 (Ermakova etc.).Various carbon are injected into silica gel, and drying is burnt then.By making the pore dimension that obtains increase in this way.When the thread carbon that plays katalysis is used as carbon source, obtain the thermostability that improves.Do not test by other, the thermostability of the hole that produces of carbon granule more spherical in shape.Regrettably, for forming many perovskite materials, particularly on commercial size, the sol-gel method of use is unfavorable.And injecting solid is a stupid method for increasing in proportion.Another problem is, the ratio quite high (being up to 30) of carbon material and oxide compound.This expense of increase making, reduce productivity and increase the weight of problem about the impurity element in the carbon.

United States Patent (USP) 4624773 has illustrated the method that is used for the catalytic cracking of hydrocarbon raw material.The part of this method is to make the aluminium-silicate material of the hole with preferred 100～600nm to improve the flowability that gas enters catalyzer.This method may further comprise the steps: make the gel of aluminum oxide and silicon-dioxide, and sneak into the reticulated carbon particle of the length with about 50～3000nm.After forming aluminium-silicate solid, carbon granule is burnt the hole of wishing size range with formation.This method requires to provide the smaller aperture in the aluminium-silicate zeolite structure of high surface area not influenced by burn-up process.

Be used for the more complicated material that gel technique that this method is used to form aluminium-silicate solid is unsuitable for the higher chemical uniformity of needs, particularly on commercial size.And to produce heat-staple surface-area needed greatly for the void ratio that gas fluidity maximization is produced.At last, carbon is strong reductant and is widely used in the mineral processing so that oxide compound is reduced into metal.Yet the oxide compound for aluminium and silicon is not like this, because these oxide compounds are very stable and be difficult to reduction, but the oxide compound of many other metals comprises the metal that generally is used for complex oxide, more may be by carbon reduction.The general reductibility of in Ellingham figure, representing different elements.Be difficult to reduction such as the oxide compound that is tending towards the figure bottom of Al, and reduce manyly easily vertical.Metal such as iron, nickel, cobalt, manganese, chromium and potassium is easy to reduction more than Al.Ellingham figure has also shown the reduction effect of the carbon monoxide in the reduction effect, particularly heat-treating atmosphere of carbon.

In the processing of complex oxide, particularly in the thermal treatment, the existence of metal may and/or can not form the oxide compound that needs with other element owing to segregation and produce serious difficulty mutually.Therefore, whether the close mixing of the carbon granule of unclear middle size and oxide precursor will allow the suitable development mutually of needs.And the existence of the oxide form that metal or other are reduced can increase the sintering degree greatly, thereby causes the heavy losses of surface-area and bad thermostability.

At J.of Materials Science 35 (2000), to have summarized in the 5639-5644 page or leaf and the example that carbon-based material is added problem relevant in the oxide precursor, this article has illustrated by using the Mierocrystalline cellulose of being burnt to form La _0.8Sr _0.2CoO ₃The method of material.It is found that if carbonic acid gas is not removed fast enough, carbonate can form and need higher calcining temperature to obtain phase purity thus so in matrix.

The GB2093816 that is worked out by Asia Oil Company Ltd and Mitsubishi Chemical IndustriesLtd has illustrated the method that is used to make porous refractory inorganic oxide product.GB2093816 provides by what following steps obtained has the void distribution of obvious peak value and the porous refractory inorganic oxide product that has 0.11cc/g or bigger void content (porosity) at radius 10nm to 50nm at diameter 10nm to 100nm: the mixture of the precursor of carbon black and refractory inorganic oxide and/or refractory inorganic oxide is shaped; Desciccate; In oxygen flow, it is fired and burn described carbon black simultaneously.

Clearly, GB2093816 is limited to manufacturing refractory inorganic oxide product.The typical refractory inorganic oxide that uses among the GB2093816 comprises the inorganic oxide such as aluminum oxide, silicon-dioxide, titanium oxide, zirconium white, Thorotrast, boron oxide (boria), zeolite and clay.The concrete instance that provides among the GB2093816 only illustrates the formation of the refractory inorganic oxide that adds aluminum oxide, silicon-dioxide, titanium oxide, silica alumina (silica alumina), boron oxide, zeolite, kaolin and sepiolite.

Except using precursor the embodiment 10 with formation titanium oxide of titanium tetrachloride as precipitin reaction, the example that provides among the GB2093816 all uses the solid particle starting material to obtain the mixed oxide product.The product of embodiment 10 is a titanium oxide, is not the blended oxide compound.

It is the carbon black of 15～300nm that GB2093816 uses mean diameter.GB2093816 also states, burns final firing temperature in the sooty step and be about 500 ℃ or higher, and [still], as long as porous refractory inorganic oxide product does not lose activity because of carrier or catalyzer, the upper limit is just unimportant.

The treatment condition of using among the GB2093816 can need relative high processing temperature to obtain to comprise the complex oxide matrix of metal mixture with parent material.In GB2093816, clearly disclose these treatment condition, thereby confirmed can not form the complex metal oxide phase.Therefore, the present inventor believes, in fact, the what is called that forms in GB2093816 is mixed inorganic oxide and is made up of the separation crystal grain or the particulate mixture of feed material, makes each crystal grain or particle only comprise a kind of in the feed material therein.Therefore, GB2093816 does not produce the complex metal oxide phase that comprises two or more different metals from forming the different precursor component of particulate.

Review to prior art shows that the manufacturing that lacks reliable and viable commercial has the method for size range for the complex metal oxide material of the hole of about 7nm～250nm.

For the complex oxide material with improved thermostability and the manufacture method of this material, also there is the intensive demand.

Summary of the invention

In first aspect, the invention provides a kind of method of making the porous complex oxide, this method comprises provides following mixture of ingredients:

A) be suitable for producing the precursor elements of complex oxide; Or

B) one or more plant precursor elements and one or more kind metal oxide particles to be suitable for producing the complex oxide particulate; With

C) select to be used to provide the particulate carbon-containing pore-creating material of the pore dimension of about 7nm～250nm,

And, mixture is handled, with

(i) form the porous complex oxide, in this porous complex oxide, from in the precursor elements of above-mentioned (a) two or more or from the precursor elements of above-mentioned (b) one or more plant with metal oxide particle in metal in one or more kinds be introduced in complex metal oxide mutually in, and this complex metal oxide has the grain-size (grain size) of about 1nm～150nm; With

(ii) under the condition of vesicular structure that keeps complex oxide basically and composition, remove the pore-creating material.

Different with the method described in the GB2093816, this method causes forming the metal oxide phase of the phase of the metal oxide particle that is used as feed particles in this processing of simple reflection (mirror), perhaps, produce the metal oxide phase that only comprises single refractory metal from precursor elements, method of the present invention produces complex metal oxide, described complex metal oxide is included in metal oxide and introduces in mutually from precursor or from precursor with as the complex metal oxide phase of two or more metals (in some embodiments, more than two kinds of metals) of the metal oxide particle of raw material.Should be appreciated that metal oxide comprises the matrix of metal oxide phase mutually, this matrix comprises the oxide structure that adds two or more metals.Suitably, these two or more metals be evenly distributed in whole complex metal oxide mutually in.

Suitably, form single phase complex metal oxide.But, the present invention also comprise form complex metal oxide mutually and one or more kinds of other metal oxide mutually, or form two or more complex metal oxide phases, comprise or do not comprise any other metal oxide phase.More suitably, each complex metal oxide of formation is phase pure phase (phase pure phase) mutually, that is, this phase only comprises the crystallization phases of hope and do not comprise undesirable crystallization phases.

Complex metal oxide can comprise two or more metals, such as being selected from two or more metals that ordination number is 3,4,11,12,19～32,37～51,55～84 and 87～103 metal.In one embodiment, two or more metals in the complex metal oxide can comprise at least a non-refractory metal, such as being selected from least a metal that ordination number is 3,4,11,19～21,23～32,37～39,41～51,55～84 and 87～103 metal.In this embodiment, metal oxide also can comprise other metal such as Ti, Al, Zr and Mg except that the non-refractory metal that comprises afore mentioned rules.

It is unexpected that the porous complex oxide that forms like this of finding show high-temperature stability with raising and volume of voids or the surface-area that increases greatly, the high-temperature stability of the raising in all 750 ℃ according to appointment～1000 ℃ temperature ranges.Complex oxide also suitably shows basically composition uniformly in each phase.The applicant is unexpected to be found, the complex oxide of the grain-size with above-mentioned scope of formation and the pore dimension of above-mentioned scope has and the high initial surface area that improves the combination of surface-area thermostability.

The applicant finds, if the grain-size of complex oxide greater than 150nm, material does not have enough surface-area so.Similarly, if pore dimension greater than about 250nm, can not obtain enough surface-area so behind high-temperature aging.If pore dimension less than about 10nm, can obtain high surface-area so, still, hole and surface-area therefore at high temperature can be not thermally-stabilised.

Different with GB2093816, method of the present invention can be used for forming non-infusibility complex metal oxide phase.The inventor is unexpected to be found, method of the present invention is not necessarily limited to make and is difficult to the reductive refractory oxide.On the contrary, all embodiment of GB2093816 produce the oxide compound phase of aluminum oxide, silicon oxide, titanium oxide, silica-alumina, boron oxide, zeolite, kaolin or sepiolite.All these metal oxide phase inertia are extremely strong, very are difficult to reduction with carbon.

Of the present invention aspect this in, the complex oxide of Xing Chenging can be any suitable type like this.Complex metal oxide can be uhligite mutually.Crystalline structure is that chemical formula is CaTiO ₃The crystalline structure of mineral " uhligite ".There are the different compounds that have perovskite crystal structure in a large number, comprise SrTiO ₃, YBa ₂Cu ₃O _xSemi-conductor and many La based perovskites of making catalyzer and being used as the electrode in the Solid Oxide Fuel Cell that is suitable for.The La based perovskite comprises LaMnO ₃, LaCoO ₃, LaFeO ₃And LaGaO ₃

Can be with different element substitutions in the oxide compound lattice, with the physicals that obtains to wish.For example, for uhligite, displacement can be in the A position (for example at LaMnO ₃In replace La with Sr) and/or the B position (for example at LaMnO ₃In replace Mn with Ni).Can on any one or two kinds of positions, carry out the displacement of multiple element, with the physicals of further adaptation application-specific.For example, uhligite composition (Ln has been described in the United States Patent (USP) useful to solid oxide fuel cell electrode 5932146 _0.2La _0.4Nd _0.2Ca _0.2) (Mn _0.9Mg _0.1) O ₃, wherein Ln is roughly La _0.598Nd _0.184Pr _0.81Ce _0.131Ca _0.002Sr _0.004

Exist for many other examples of complex oxide of the application and development of wide wide range, the present invention is equally applicable to them.

According to complex oxide to be formed, useful precursor elements can be any suitable type in mixture of the present invention.Can use the source of any proper metal and metallic cation.Can use metal and the mixture that comprises the metallic compound of one or more kinds in oxide compound, acetate (ester), carbonate (ester) and the nitrate (ester) etc.

Precursor elements or complex oxide and pore-creating mixtures of material can be any suitable type.Mixture can be solid-phase mixture, or forms solution or dispersion etc.

In one embodiment, as described below, precursor elements and pore-creating material can be mixed to form solid-phase mixture, form complex oxide by suitable thermal treatment subsequently.

In another embodiment, can form the oxidase complex composition granule, and the pore-creating material is mixed with the oxidase complex composition granule to form mixture from suitable precursor elements.

The mixture of solution or dispersion form can be provided alternatively.For example, can at first form solid-phase mixture, then it is distributed to or dissolve in the appropriate solvent.

In another embodiment, can at first in solution, form the precursor elements mixture, and subsequently the pore-creating material be added in the solution.Scheme as an alternative, precursor elements and at least a portion pore-creating material can be mixed to form solid-phase mixture and dissolve in the mixture of appropriate solvent.

The most suitably, the part of precursor elements formation and pore-creating material and metal oxide particle (if use) blended solution.

Under the situation that forms dispersion or solution, can use any appropriate solvent.Though can use the inorganic and organic solvent such as acid (for example, hydrochloric acid or nitric acid), ammonia, alcohol, ether and ketone, water is preferred solvent.

This mixture can preferably comprise tensio-active agent.This tensio-active agent can be any suitable type.The tensio-active agent of having found to license to the type of explanation among applicant's the International Patent Application Publication No. WO 02/42201 is suitable, incorporates the full content of this patent into this paper by reference.

Some examples comprise: Brij C ₁₆H ₃₃(OCH ₂CH ₂) ₂OH is called C ₁₆EO ₂, (Aldrich); Brij 30, C ₁₂EO ₄, (Aldrich); Brij 56, C ₁₆EO ₁₀, (Aldrich); Brij 58, C ₁₆EO ₂₀, (Aldrich); Brij 76, C ₁₈EO ₁₀, (Aldrich); Brij78, C ₁₆EO ₂₀, (Aldrich); Brij 97, C ₁₈H ₃₅EO ₁₀, (Aldrich); Brij 35, C ₁₂EO ₂₃, (Aldrich); Triton X-100, CH ₃C (CH ₃) ₂CH ₂C (CH ₃) ₂C ₆H ₄(OCH ₂CH ₂) _xOH, x=10 (av), (Aldrich); TritonX-114, CH ₃C (CH ₃) ₂CH ₂C (CH ₃) ₂C ₆H ₄(OCH ₂CH ₂) ₅OH (Aldrich); Tween 20, poly-(ethylene oxide) (20) sorbitan monokayrate (Aldrich); Tween 40, poly-(ethylene oxide) (20) sorbitan-monopalmityl ester (Aldrich); Tween 60, poly-(ethylene oxide) (20) anhydrosorbitol monostearates (Aldrich); Tween, poly-(ethylene oxide) (20) dehydrating sorbitol monooleates (Aldrich) are (Aldrich); With Span 40, sorbitan-monopalmityl ester (Aldrich), Terital TMN 6, CH ₃CH (CH ₃) CH (CH ₃) CH ₂CH ₂CH (CH ₃) (OCH ₂CH ₂) ₆OH (Fulka); TergitalTMN 10, CH ₃CH (CH ₃) CH (CH ₃) CH ₂CH ₂CH (CH ₃) (OCH ₂CH ₂) ₁₀OH (Fulka); Have with two primary hydroxyls end capped (hydrophobic) and gather (EO-PO-EO) segmented copolymer of sequence of poly-(ethylene oxide) that (propylene glycol) nuclear is the center-poly-(propylene oxide)-poly-(ethylene oxide); Pluronic L121 ( _Mav=4400), EO ₅PO ₇₀EO ₅(BASF); Pluronic L64 ( _Mav=2900), EP ₁₃PO ₃₀EO ₁₃(BASF); Pluronic P65 ( _Mav=3400), EP ₂₀PO ₃₀EO ₂₀(BASF); Pluronic P85 ( _Mav=4600), EO ₂₆PO ₃₉EO ₂₆(BASF); PluronicP103 ( _Mav=4950), EO ₁₇PO ₅₆EO ₁₇(BASF); Pluronic P123 ( _Mav=5800), EO ₂₀PO ₇₀EO ₂₀(Aldrich); Pluronic F68 ( _Mav=8400), EO ₈₀PO ₃₀EO ₈₀(BASF); Pluronic F127 ( _Mav=12600), EO ₁₀₆PO ₇₀EO ₁₀₆(BASF); Pluronic F88 ( _Mav=11400), EO ₁₀₀PO ₃₉EO ₁₀₀(BASF); Pluronic 25R4 ( _Mav=3600), PO ₁₉EO ₃₃PO ₁₉(BASF); Have and be attached on the quadrol nuclear and by four hydroxy-end capped EO of secondary _n-PO _mChain (perhaps, on the contrary, four PO _n-EO _mChain) star diblock copolymer; Tetronic 908 ( _Mav=25000), (EO ₁₁₃PO ₂₂) ₂NCH ₂CH ₂N (PO ₁₁₃EO ₂₂) ₂(BASF); Tetronic 901 ( _Mav=4700), (EO ₃PO ₁₈) ₂NCH ₂CH ₂N (PO ₁₈EO ₃) ₂(BASF); With Tetronic 90R4 ( _Mav=7240), (PO ₁₉EO ₁₆) ₂NCH ₂CH ₂N (EO ₁₆PO ₁₉) ₂(BASF).

Above-mentioned glass or plastic containers.Spendable other tensio-active agent comprises:

Anion surfactant:

Alcohol ethoxy carboxylicesters (Alcohol Ethoxycarboxylate) (R-(O-CH2-CH2) x-O-CH2-CH2-OH) (NEODOX AEC)

Alkyl ethoxy carboxylic acid (R-(O-CH2-CH2) x-O-CH2-CO2H) (EMPICOL C)

Sodium lauryl sulphate CH ₃(CH ₂) ₁₁OSO ₃NA

Several manufacturerss are arranged.Sigma is an example.

Cats product:

Cetyltrimethylammonium chloride (Cetyltrimethylammonium chloride) CH ₃(CH ₂) ₁₅N (CH ₃) ₃Cl Aldrich

Cetrimonium bromide (Cetyltrimethylammonium bromide) CH ₃(CH ₂) ₁₅N (CH ₃) ₃BT Aldrich

Cetylpyridinium chloride (Cetylpyridinium chloride) C ₂₁H ₃₅NCl Sigma

It is exhaustive that this inventory should not be considered to.

The pore-creating particle can be any suitable type.Particle should have suitable size to produce the pore dimension in " intermediate range " (for example, pore diameter is about 7nm-250nm, preferred 10nm-150nm).Can use about 7nm to 300nm, preferably about 10nm to 150nm, the pore-creating particle of 10nm to 100nm more preferably from about.Preferred carbon granule, more preferably carbon black pellet.

By providing and prevent zone that one or more precursors and metal oxide particle are resident and at subsequent removal pore-creating particle forming the complex metal oxide phase time, the carbonaceous particles as pore-forming material in the method for the present invention is considered to promote wish the formation of the hole of size range.Therefore, need nano level pore-creating particle.Should with this method with use porous carbonaceous matrices (such as filter paper or activated carbon) to absorb liquid phase front body mixture and to distinguish in other method of subsequent removal matrix.The size of the matrix that uses in these methods is generally than the big several magnitude of using among the present invention of pore-creating particle.These existing methods are difficult to exceed laboratory scale.

In particularly preferred embodiment of the present invention, use carbon black as the pore-creating particle.

Preferably remove the pore-creating particle by thermal treatment.

Forming the required composition of complex oxide should be evenly dispersed to form the mixture of precursor elements.Can mix each element by any appropriate means commonly known in the art.Also should comprise high-speed shearing device, ultrasonic device, roller crusher, ball mill and sand mill etc. by using method commonly known in the art, with the pore-creating particles dispersed in mixture.The applicant finds that the carbon containing pore-creating particulate in this stage better disperses to cause more carbon containing pore-creating particle to mix closely with precursor, and makes more hole be in the size range of hope thus.In another preferred embodiment, with liquid mixing before, by vacuum from carbon containing pore-creating particle removal air.Then by using dispersing method that liquid is mixed with carbon.This cause the better dispersion of carbon granule in solution, more carbon granule in precursor close mixing and more be in hole in the preferred size range.

The pore-creating particle can be contained in the mixture before disperseing in whole or in part.

In order to form the processing that processing that complex oxide carries out mixture can provide any suitable type with basic complex oxide of forming uniformly.

In one embodiment, therefore the formation of porous complex oxide can comprise two basic steps:

1. produce the particle that the mixture by complex oxide or complex oxide precursor elements and carbon granule constitutes.

2. to heat-treating from the particle of step (1), with under the situation of body before use in the past body form the oxide compound phase of wishing, and remove (for example, burning) carbon granule basically to produce hole.

Step (1) and (2) can take place successively or simultaneously.

In step 1, the element in the oxide precursor should be evenly dispersed.If they are not evenly dispersed, so need very high temperature with the homodisperse element and form appropriate phase, this temperature may reduce the quantity of hole and reduce its size, or eliminates hole fully.If element is inhomogeneous basically, can not obtain the phase and/or the phase purity and the crystal grain that is in the appropriate size range that need so.

In the carbon granule at least some should preferably be mixed with oxide compound or oxide precursor closely.If there is not carbon granule to mix closely with oxide compound or oxide precursor, opposite carbon granule can not form the hole of appropriate size so only wherein not exist the megalump of oxide compound or oxide precursor to exist.Can select pore dimension and volume of voids to the size of carbon granule and these particulate volumes to adapt to hope.

If the carbon granule of appropriate size can be added in the method, make in the carbon granule at least some mix closely and this method can produce the oxide compound with appropriate grain-size, just can use any method that is suitable for producing equally distributed basically oxide compound of element or oxide precursor in the method for the invention with precursor.

Therefore, in a preferred embodiment of the invention, this method also comprises following preliminary step: the solution of the complex oxide precursor elements that comprises metallic cation, source and nonionic, positively charged ion or the anion surfactant of carbon granule are provided; Mixing solutions, tensio-active agent and carbon granule, so that form surfactant micelle, and mixture forms basically dispersion uniformly; And heated mixt, under the condition of removing carbon granule basically, to form complex metal oxide.

In another preferred embodiment, can prepare oxide precursor according to the method for explanation in the U.S. Patent No. 6752979 that licenses to the applicant, be incorporated herein it all openly as a reference.This method may further comprise the steps:

A) preparation comprises the solution that one or more plant metallic cation;

B) making that forming surfactant micelle in the solution will mix with tensio-active agent from the solution of step (a) under with the condition that forms micella liquid thus; With

C) heating is from above-mentioned steps b) micella liquid, to form metal oxide, this heating steps occurs in a certain temperature and continues for some time, removing tensio-active agent and to form metal oxide particle thus with unordered pore texture,

In a preferred embodiment of the invention, carbon black pellet is added to from a) solution or from b) mixture, and (burning) carbon black pellet is also removed in thermal treatment basically.Preferably before mixing, carbon granule is added in the solution of step a).

In another preferred embodiment, mix with the cationic solution in carbon granule and the step a) or from the mixture of step b) or both by aforesaid method.Preferably by high speed shear, sonication, add particulate before the liquid find time (vacuuation) or their combination to, carbon black pellet is distributed in initial soln and/or the solution-surfactant mixture.

In another preferred embodiment, can provide the mixture of complex oxide and carbon granule by carbon granule is mixed with the oxidase complex composition granule, the oxidase complex composition granule has close with the target grain-size or less than the size range of target grain-size.

Scheme perhaps in addition, can form complex oxide by utilizing method as known in the art as an alternative.Can be by utilizing polymkeric substance companion method, coprecipitation method or sol-gel method, thermal evaporation, hydrothermal method or any other appropriate means or their combination results complex oxide.In United States Patent (USP) no 6139816 (Liu etc.), United States Patent (USP) no 5879715 (Higgens etc.), United States Patent (USP) no 5770172 (Linehan etc.), United States Patent (USP) no 5698483 (Ong etc.), United States Patent (USP) no 6328947 (Monden etc.), United States Patent (USP) no 5778950 (Imamura etc.) and U.S. Patent Application Publication No. 2005/0008777 (McCleskey etc.), provide the example of these methods.Here all openly incorporate above-mentioned patent of mentioning and patent application into this paper by cross reference.The method of a first aspect of the present invention is specially adapted to make the method for metal oxide, wherein will comprise one or more solution of planting precursors with tensio-active agent or mixed with polymers and generally handling with the formation complex metal oxide by heating subsequently.

Can implement heat treatment step in the method for the present invention by using any suitable equipment as known in the art, for example, tubular type, belt or retort furnace, fluid bed furnace, multiple hearth furnace, rotary calciner, add hot basal body (heated substrate), thermospray (thermal spray), spraying calcining furnace etc.

Do not have connected individual particle if oxide compound or oxide precursor comprise, thermal treatment should make and form some connections before carbon burnouts between particle so.If do not form this network before carbon burnouts, hole is with collapse so.

Thermal treatment is removed (" burning ") carbon then with the generation hole, and oxide precursor is transformed into the crystal structure oxide of hope.

Heating steps causes the formation of metal oxide and particulate pore texture.Handle differently with the prior art that is used to produce complex metal oxide, method of the present invention only suitably needs the relatively low temperature that applies.In fact, in the cut-and-try work of carrying out so far, find that it is suitable being lower than about 350 ℃ temperature that applies.The highest temperature that applies that reaches in step (c) preferably is no more than about 750 ℃, more preferably no more than about 650 ℃, and most preferably from about 300～350 ℃.

Heating steps can comprise and is heated rapidly to the highest desired temperature, maybe can comprise the thermal treatment mechanism of more accurate control.

Therefore, in another preferred embodiment of the present invention, heat treatment step may further comprise the steps:

Make dispersion experience heat treatment cycle curve to reach the top temperature of hope in the given time.

For example, can in controlled atmosphere, implement heating steps.Heating steps can comprise and is heated to drying temperature (generally being lower than the boiling temperature of mixture) with drying composite, is slowly to be warmed up to the highest temperature that applies then, perhaps be then finally reach the highest apply temperature before series be incremented to medium temperature.The time length of heating steps can extensively change, and makes that the preferred time in the step (c) is 15 minutes～24 hours, and more preferably 15 minutes～2 hours, most preferably 15 minutes～1 hour.

The scope of heat treatment cycle curve can be about 100 ℃～750 ℃, and preferred about 100 ℃～650 ℃, more preferably from about 100 ℃～300 ℃.The heat treatment cycle curve that should be appreciated that selection will depend on the concrete composition of the complex oxide of handling.

Preferably under the oxygenation condition, heat-treat step.This can realize by suitable air-flow is provided in thermal environment.

In preferred embodiments, thermal treatment should promote oxygen to infiltrate in the particle in the carbon stage of burning.Preferred equipment comprises fluid bed furnace etc.Less oxide compound or oxide precursor/carbon granule size also promotes the infiltration of oxygen.The applicant finds that the better infiltration of oxygen can cause better thermostability.Be not limited to any specific theory, the applicant believes that better oxygen infiltration causes the removal more completely of carbon under lower temperature, and keeps the stronger atmosphere of oxidisability thus.Less oxygen cause carbon under higher temperature delay and such as the catching of the reducing gas of carbon monoxide, thereby cause the very high environment of reductibility.This can cause some metals to form and this metal is remained into very high temperature, and this can cause the loss of sintering and surface-area.Can promote the oxygen infiltration by oxide compound is moved with respect to oxygen-containing atmosphere, also increase the rate of diffusion that oxygen enters oxide compound thus with the thickness that reduces oxide compound frictional belt on every side thus.In fluid bed furnace or flow through therein that to handle oxide compound in the stove of oxygen-containing atmosphere be suitable.

And, preferably allow at lesser temps, for example at about 100～750 ℃, preferred about 100～650 ℃, more preferably from about 100～300 ℃ temperature is burnt the thermal treatment of carbon.Burn under fully high temperature and can cause the no control heat release of carbon to be burnouted, this seriously reduces surface-area.And the applicant believes that carbon remains into higher temperature and reduces high-temperature stability by above-mentioned mechanism.

For fear of departing from the desired temperature curve of burning step, should keep burning the accurate control of step.For example, can use the accurate supervision of the temperature in the burn-up process.If observe undesirable rising (expression is because the increase of the heat release rate of combustion of carbon causes excess energy to produce) of temperature, so can be by reducing the dividing potential drop of oxygen, the atmosphere of stove is supplied with in control.A kind of mode that realizes this result is to inject extra nitrogen or other torpescence or nonreactive gas.This not only reduces the dividing potential drop of oxygen, also is used to cool off stove.Owing in the burn-up process of the carbon that comprises pore-forming material, also wish to keep oxidizing atmosphere, therefore, only when requiring rapid response temperature to depart from or obviously depart from and must reduce or stop the oxidation of carbon rapidly the time (for example, reason for secure context), should use the method for this controlled temperature.Scheme can provide additional cooling as an alternative.Do not pay close attention to the temperature in the burn-up process, and, can obtain satisfied result yet by the temperature in the burn-up process being remained on below the top temperature of regulation.The top temperature of regulation can change greatly according to the specific complex metal oxide that is forming.As another replacement scheme, can under the quality control protocol of operational condition of stipulating (cold) and any substandard product of refusal that keeps, operate method of the present invention such as oxygen gas flow rate and stove.Test that can be by product or determine the existence of substandard product by the surveillance technology that monitors one or more operating parameters and refusal forms any product when the specialized range of one or more parameter value of deflecting away from.For example, can use simple thermopair to monitor the top temperature that reaches in this procedure, and, if top temperature surpasses the maximum value of regulation, product can be rejected so, perhaps, in treating processes red heat if visual inspection shows mixture or product, product can be rejected so.

In a second aspect of the present invention, porous complex oxide material is provided, wherein, this complex oxide bill of material reveals high-temperature stability and comprises the oxide components of being represented by following general formula:

A _1-xB _xMO ₃

Here,

A is the mixture of lanthanon;

B is divalence or monovalent cation;

M is that to be selected from ordination number be 22～32,40～51 and 73～83 the element or the mixture of multiple element; And

X is the number in scope 0.1≤x≤0.5.

The complex oxide material is preferably made by the method for a first aspect of the present invention.

The complex oxide material can be suitable phase (for example, single-phase or heterogeneous), and the initial surface area of the phase that this is suitable is greater than about 15m ²/ g is preferably greater than about 20m ²/ g is more preferably greater than about 30m ²/ g, in air at the surface-area of timeliness after 2 hours under 1000 ℃ the temperature greater than about 5m ²/ g is more preferably greater than about 10m ²/ g is most preferably greater than about 15m ²/ g.

The complex oxide material can show basically composition uniformly.

The complex oxide material can comprise perovskite material.

The complex oxide material generally can show about 2～150nm, the average grain size of preferred about 2～100nm, and have about 7～250nm, the pore dimension scope of preferred about 10～150nm.But the average crystal grain of complex oxide material and pore dimension can change according to the specific complex oxide of selecting.

For example, for CeZrO ₂The complex oxide material of type, average grain size can preferably drop on the lower end of this scope, for example, and at about 2～50nm, 2～10nm more preferably from about, hole is at about 7～50nm, more preferably in the scope of about 7～30nm.

The complex oxide material of lanthanum manganate type can show about 2～100nm, the average grain size of 2～30nm more preferably from about, and hole is at about 15～200nm, more preferably in the scope of about 15～150nm.

More preferably, the complex oxide material can show dispersive pore dimension scope basically.

In the third aspect, the invention provides a kind of method that is used to make the non-refractory metal oxide of porous, this method comprises provides following mixture of ingredients:

A) one or more that are suitable for producing non-refractory metal oxide are planted precursor elements, and the particle of non-refractory oxide is as the oxide particle of the precursor of non-refractory oxide or two or more the mixture in them; With

B) select to be used to provide the particulate carbon-containing pore-creating material of the pore dimension of about 7nm～250nm,

And, this mixture is handled, with

(i) form the non-refractory metal oxide of porous, and this non-refractory metal oxide has the grain-size of about 1nm～150nm; With

(ii) remove the pore-creating material under the condition of the vesicular structure keep non-refractory metal oxide basically and composition making.

Suitably, in above step (i), will from the precursor elements of above (a) one or more plant to add non-refractory metal oxide mutually in.

One or more plant precursor elements can comprise comprise be selected from ordination number be one or more of 3,4,11,19～21,23～32,37～39,41～51,55～84 and 87～103 metal plant metals one or more plant metallic compounds.One or more plant metallic compound can be oxide compound, acetate (ester), carbonate (ester) and nitrate (ester) etc.

Different with a first aspect of the present invention, the method for a third aspect of the present invention comprises and is formed on oxide compound and only has the regulation grain-size of a kind of metal (that is, not being complex oxide) and the porous metal oxide of pore dimension in mutually.But a third aspect of the present invention is limited to the non-refractory metal oxide of formation.Because existing, carbon containing pore-creating particulate is considered to cause the non-refractory metal oxide of reduction in removing pore-creating particulate step, this can destroy or damage basically the metal oxide phase certainly, and therefore can form this non-refractory metal oxide by this way is very unexpected result.But the present inventor finds that the method for a third aspect of the present invention in fact can form this non-refractory metal oxide.

In one embodiment, the method for a third aspect of the present invention provides precursor elements as solution or dispersion.For example, can at first form solid-phase mixture and disperse then or dissolve in the appropriate solvent.

In one embodiment, precursor elements and pore-creating material can be mixed, and be as described below subsequently to form solid-phase mixture, forms oxide compound by suitable thermal treatment.

In another embodiment, can form oxide particle, and the pore-creating material mixes with oxide particle to form mixture from suitable precursor elements.

Optionally provide mixture with solution or the outstanding liquid that wafts.For example, solid-phase mixture can at first form and disperse then or dissolve in the appropriate solvent.

In another embodiment, can at first in solution, form precursor elements, subsequently the pore-creating material be added in the solution.Scheme as an alternative, at least a portion of precursor elements and pore-creating material can be mixed to form solid-phase mixture, and mixture is dissolved in the appropriate solvent.

Under the situation that forms dispersion or solution, can use any appropriate solvent.Though can use the inorganic and organic solvent such as acid (for example, hydrochloric acid or nitric acid), ammonia, alcohol, ether and ketone, water is preferred solvent.

The method of a third aspect of the present invention is specially adapted to make the method for metal oxide, in the method, comprises one or more solution of planting precursors with tensio-active agent or mixed with polymers and generally be heated with the formation metal oxide by heating subsequently.

The further feature of the embodiment of a third aspect of the present invention is as with reference to each embodiment explanation of the present invention like that, and, for convenience and concisely, do not need to illustrate again.

The method of a third aspect of the present invention has been used to make the cupric oxide with bigger specific surface area.Also make other oxide compound by the method for a second aspect of the present invention, no matter be complex oxide or the oxide compound that comprises single metal species.

Of the present invention first and the method for the third aspect be particularly suitable for making metal oxide powder.

Description of drawings

Fig. 1 represents to be heat-treated to after 650 ℃, the pore size distribution of the material of preparation in the example 1 and 2.

Fig. 2 represents for embodiment 18～22, the surface-area and the La that obtain after the thermal treatment of 650 ℃ and 800 ℃ ₂O ₃Relation between the content.

Fig. 3 represents for embodiment 18～22, the volume of voids that obtains after 650 ℃ thermal treatment and La ₂O ₃Relation between the content.

Fig. 4 a and Fig. 4 b represent a) without carbon (embodiment 28) with b) with the XRD figure case that is heat-treated to 450 ℃ Ce0.45Zr0.45La0.10x of carbon (example 29) preparation.

Fig. 5 a and Fig. 5 b represent a) without carbon (embodiment 28) with b) with the XRD figure case that is heat-treated to 800 ℃ Ce0.45Zr0.45La0.10x of carbon (example 29) preparation.

Embodiment

Embodiment 1

Prepare La according to following method _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃By restraining La (NO with 149 ₃) ₃6H ₂O, 18.2 gram Sr (NO ₃) ₂, 6.86 gram Pd (NO ₃) ₂XH ₂O, 2.04 gram NiCO ₃With the gram of 138.3 in the aqueous solution that contains 233g/L Mn Mn (NO ₃) ₂Dissolve in by 135 gram water and 12 gram HNO ₃(70%) in the solution of Gou Chenging, preparation solution.This solution of 119 grams is mixed with 72 gram Brij, 30 tensio-active agents.This mixture slowly is heated to 300 ℃.Then in having the tube furnace of air-flow under the temperature of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 600 ℃ and 650 ℃ with dried product thermal treatment 0.5 hour.

XRD shows that this material is single-phase uhligite.The surface-area that obtains after this thermal treatment is 17.8m ²/ g.Fig. 1 represents pore size distribution.TEM shows that average grain size is about 50nm.After 2 hours, surface-area is 6.9m in thermal treatment under 1000 ℃ the temperature ²/ g.

Embodiment 2

Except with before tensio-active agent mixes with carbon blacks (Cabot Monarch 1300, average initial particle size 13nm, DBP oil number 100cc/g, the nitrogen surface area 560m of magnetic stirrer with 16.15 grams ²/ g) with outside solution mixes, prepare La in the mode identical with embodiment 1 _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃(shearer) disperses this solution/carbon black stock by high-speed shearing machine, then it mixed with tensio-active agent, and then disperses.Apply the thermal treatment identical with embodiment 1.

XRD shows that this material is single-phase uhligite.The surface-area that obtains after thermal treatment is 24.7m ²/ g.Fig. 1 represents pore size distribution.TEM shows that average grain size is about 50nm.After 2 hours, surface-area is 10.04m in thermal treatment under 1000 ℃ the temperature ²/ g.

It should be noted that the sooty adding provides significantly bigger hole, and material is at high temperature more stable.

Embodiment 3

Except thermal treatment comprises under the temperature that the material that will be heated to 300 ℃ is placed directly in 1000 ℃, prepare La in the mode identical with embodiment 2 _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃After 2 hours, surface-area is 1.9m in thermal treatment under 1000 ℃ the temperature ²/ g.

This example shows, carbon black added itself be not enough to provide high-temperature stability in the uhligite.The heat-treat condition of using in the present embodiment causes the destruction of the surface-area of material.According to supposition, the bigger temperature step change of using in the present embodiment causes burning carbon from oxide compound uncontrollablely, and this causes the regional area of excessive temperature.This is assumed that sintering and the reduction that causes metal oxide.In other words, the composition of metal oxide and pore texture are not held in the process that carbon is burnt.

Embodiment 4

Except in pipe furnace, not having the air-flow, prepare La in the mode identical with embodiment 3 _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃Remaining program is identical.

XRD shows that material is the uhligite phase.The FWHM of the peak value among halfwidth of peak value (FWHM) and the embodiment 1 and 2 is close, shows grain-size close (that is about 50nm).The surface-area that obtains after this thermal treatment is 22.1m ²/ g.After 2 hours, surface-area is 9.1m in thermal treatment under 1000 ℃ the temperature ²/ g.

Result (the 10.2m of this result and embodiment 2 ²/ comparison sheet g) is understood the beneficial effect of increase oxygen in thermal treatment.The inventor believes that less oxygen provides reductive condition in stove, and this can cause forming metal in material.This can cause sintering and in the minimizing of surface-area and hole.

Embodiment 5～8

Use the carbon blacks (Raven 850) of different amounts, prepare La in the mode similar to embodiment 2 _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃

XRD shows that this material is the uhligite phase, and peak F WHM is close with embodiment 1 and 2.

Surface-area, void content and pore size distribution are shown in Table 1, and obviously depend on the sooty amount of use.

Table 1

Embodiment	Sooty amount (g)	Surface-area (m at 650 ℃ 2/g)	2～200nm diameter void content (cc.g)	10～200nm diameter void content (cc.g)	50～200nm diameter void content (cc.g)
						5	8	37	0.22	0.2	0.1
6	16	44	0.33	0.31	0.18
						7	32	44	0.34	0.32	0.22
8	48	51	0.41	0.39	0.25

Embodiment 9～11, use different sooty La _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃Embodiment

Expression uses dissimilar carbon black pore-forming materials to from complex oxide La _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃The embodiment of the surface-area that obtains and the influence of pore texture.

Except using dissimilar carbon blacks, form oxide compound by using the method described in the embodiment 2.

XRD shows that all compounds are perovskite structure, and peak F WHM is close with embodiment 1 and 2, shows that grain-size is about 50nm.The results are shown in the table 2 of surface-area that obtains and pore texture.

Table 2

Embodiment	Carbon black			Surface-area m 2/g		Void content cc/g
										Type	Particle size (nm)	Oil number (cc/g)	650℃	1000℃	3-200nm	＞10nm	＞50nm
9	Monarch 280	45	137	25	11.3	0.17	0.16	0.10
									10	Monarch 1300	13	100	23	9.8	0.22	0.21	0.14
11	Mogul L	24	62	32	12.0	0.25	0.23	0.16

Embodiment 12～13

In embodiment 12～13,, prepare La in the mode identical respectively with embodiment 1 and 2 (do not have carbon and carbon is arranged) except with polyoxyethylene glycol (molecular weight 4000) the substitution list surface-active agent _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃XRD shows uhligite phase and a spot of impurity peak value example 12.Surface-area and void content are shown in Table 3.Obviously, the adding of carbon has increased more macroporous quantity.

Table 3

Embodiment	Surface-area m 2/g	Void content cc/g
						650℃	3-200nm	＞10nm	＞50nm
12	17.5	0.12	0.105	0.04
					13	31.7	0.22	0.2	0.15

Embodiment 14～15

Prepare La by chemical coprecipitation technique _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃, implement embodiment 14 and 15 with carbon (Monarch 1300 of 17.8g) or without carbon.Prepare solution in the mode identical with embodiment 1.Dissolve in another solution of preparation in 960 water that restrain by ammonium oxalate with 55g.Make up these solution in the stirred vessel to produce throw out by lentamente each solution being added to.With throw out flushing, filter and dry under～100 ℃ temperature, heat-treat in the mode identical then with embodiment 1.

XRD shows uhligite phase and some peaks that separate.Surface-area and void content are shown in Table 4.

Obviously, carbon to the influence of void distribution much smaller than observed in the embodiment that uses tensio-active agent and polyoxyethylene glycol.Be not limited to any specific theory, the inventor believes that the big liquid volume that co-precipitation often needs causes very dispersive precipitate particles and carbon granule.This can make that carbon granule fully is distributed to the hole of wishing with generation between the throw out becomes very difficult.

Table 4

Embodiment	Surface-area m 2/g	Void content cc/g
						650℃	3-200nm	＞10nm	＞50nm
14	19	0.105	0.09	0.025
					15	17	0.115	0.11	0.06

Embodiment 16～21, use dissimilar sooty Ce _0.54Zr _0.37La _0.03Pr _0.06O _xEmbodiment

These embodiment represent to use dissimilar carbon black pore-forming materials to from complex oxide Ce _0.54Zr _0.37La _0.03Pr _0.06O _xThe surface-area that obtains and the influence of pore texture.

By an amount of cerous nitrate, zirconium carbonate, lanthanum nitrate and praseodymium nitrate being dissolved in water/salpeter solution prepared composition Ce _0.54Zr _0.37La _0.03Pr _0.06O _xOxide compound.Use high-speed shearing machine with the carbon black dispersion of 33 grams in solution, add the Erunon LA4 tensio-active agents of 70 grams and dispersed mixture once more.This mixture slowly is heated to 300 ℃.Then in having the pipe furnace of air-flow under the temperature of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 600 ℃ and 650 ℃ with dried product heat treated 0.5 hour.

XRD shows that this sample is single-phase, and TEM shows that after being heated to 650 ℃, the average grain size of Zhi Bei material is 5～10nm in these embodiments.Other embodiment shows similar XRD peak F WHM, shows to have close grain-size.

Use the surface-area and the void content of different sooty samples to be shown in the following table 5 with sooty particle size and oil suction value.Also be illustrated in the surface-area that thermal treatment obtained after 2 hours under 1000 ℃ the temperature among the figure.

Table 5

Embodiment	Carbon black			Surface-area m 2/g		Void content cc/g
										Type	Particle size (nm)	Oil number (cc/g)	650℃ (cc/g)	1000℃	3-200nm	＞10nm	＞50nm
12	Monarch 280	45	137	101	13.9	0.3	0.2	0.12
									13	Raven 2500	13	65	112	17	0.41	0.32	0.14
14	Raven 1190	21	62	116	18.4	0.43	0.33	0.17
									15	Raven 410	101	68	108	12.7	0.28	0.175	0.09
16	Raven 850	34	75	110	19.5	0.38	0.33	0.15
									17	Raven 460	67	61	99	18.3	0.40	0.3	0.17

The carbon black change pore texture and the surface-area that can have obviously, the different shape feature by use.

Embodiment 22～26 has the example of excessive La content

Prepare La in the mode similar to the embodiment of front _0.8Sr _0.2Mn _0.9Ni _0.04Pd _0.06O ₃+ La ₂O ₃Material.La ₂O ₃Amount between 2.5wt% and 20wt%, change.XRD shows that uhligite adds mutually because the excessive La that increases ₂O ₃The La of increasing amount ₂O ₃Phase.Fig. 2 and Fig. 3 are illustrated in surface-area and the La that obtains after 650 ℃ and the 800 ℃ of following thermal treatment ₂O ₃Relation between the content.

This embodiment shows, by adding second phase of different amounts, can change the pore texture of oxide components.

Embodiment 27 excessive CeO ₂(7b)

Prepare La in the mode similar to embodiment 1 _0.8Sr _0.2Ni _0.04Pd _0.06Mn _0.9O ₃The CeO of+10wt% ₂Special this composition of selecting is to provide mutually and independently CeO of uhligite ₂Phase (this excessive CeO ₂Amount can not join uhligite mutually in).XRD shows that this material is uhligite phase and CeO ₂The surface-area that obtains is 28.9m ²/ g, and the volume of the hole of 3nm～200nm is 0.26cc/g, is about 0.25cc/g in 10nm～200nm void content, and be about 0.175cc/g at 50nm～200nm.After 2 hours, surface-area is 11.7m in thermal treatment under 1000 ℃ the temperature ²/ g.

Embodiment 28 and 29 Ce by the hydrothermal method preparation _0.45Zr _0.45La _0.1O _x

Prepare Ce by the similar hydrothermal method of currently known methods that uses and similar compound is used _0.45Zr _0.45La _0.1O _x

The cerium ammonium nitrate (IV) of 49.3 grams, the zirconium carbonate of 27.4 grams and the lanthanum nitrate of 8.66 grams are dissolved in the solution that comprises 940 gram water and 63 gram nitric acid (70%).Under about 95 ℃ temperature with about 24 hours of this mixture heating up, thereby throw out is formed.Add the ammonia solution (%) of 150ml at last, and, with the throw out flushing, by filtering separation and dry under about 100 ℃ temperature.Implement thermal treatment then.From 150 ℃ of intensifications, be incubated 0.5 hour at 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃ and 450 ℃ successively.Surface-area after this thermal treatment is 145m ²/ g.Void content is shown in Table 6, and XRD is shown among Fig. 4.

Comparative example 29

Except Raven 850 carbon blacks with 32 grams add in the solution and disperse with high-speed shearing machine, prepare Ce in the mode identical with embodiment 28 _0.45Zr _0.45La _0.1O _xImplement hydro-thermal heating and thermal treatment then in an identical manner.The surface-area of this sample is about 100m ²/ g.Void content is shown in Table 6, and XRD is shown among Fig. 4.Compare with embodiment 28, the adding of carbon has increased macroporous volume as can be seen.But XRD shows, the adding of carbon has caused having the rich cerium dioxide that separates a little and the formation of rich zirconium white oxide compound mutually.This is confirmed that by bimodal the peak that separates is to CeO ₂And ZrO ₂Peak moves.Therefore, carbon has influenced the hydrothermal deposition process, thereby causes the remarkable separation of different element kinds and increase void content.Clearly show that this effect in Fig. 5, this Fig. 5 shows and to have applied 800 ℃, the XRD of two exemplary compounds of the additional heat treatment of 0.5h.

Table 6

Embodiment	Surface-area m 2/g	Void content cc/g
						650℃	3-200nm	＞10nm	＞50nm
28	145	0.2	0.04	0
					29	100	0.39	0.31	0.15

Embodiment 30～32 CuO

Embodiment similar methods by use and front prepares CuO.Embodiment 30 slowly is heat-treated to 350 ℃, wherein is incubated 0.5 hour at 150 ℃, 200 ℃, 250 ℃, 300 ℃ and 350 ℃.Embodiment 31 is also in a similar fashion by thermal treatment, but according to observations, this sample is seriously overheated in heat treatment process, thereby in the zone of the temperature of expression sample experience far above 350 ℃ rubescent (red glow).Embodiment 32 is subjected to slower thermal treatment, has at 1 hour additional step of 225 ℃ of insulations.Find that this thermal treatment generation has the more material of consistent performance, and do not observe elevated temperature excursions.

The XRD of all material all shows to have only the CuO phase.The surface-area and the void content that obtain are listed in the table 7.

Table 7

Embodiment	Surface-area m 2/g	Void content cc/g
						650℃	3-200nm	＞10nm	＞50nm
30	95	0.2	0.11	0.04
					31	57.4	0.13	0.1	0.04
32	130	0.25	0.18	0.065

Surprisingly, these embodiment show, utilize the method for the present invention of appropriate heat treatment can produce thermo-sensitive material by use.

Should be appreciated that in this specification sheets the present invention open and that limit expand in the literary composition mention among the figure or conspicuous various single feature in two or more all alternative combinations.All these are different constitutes various substituting aspect of the present invention.

It is also understood that the term that uses in this specification sheets " comprises " (or its grammatical variants) and is equal to " comprising ", and should not be regarded as getting rid of the existence of other element or feature.

Claims (33)

1. method that is used to make the porous complex oxide, this method comprises provides following mixture of ingredients:

A) be suitable for producing the precursor elements of complex oxide; Or

B) one or more plant precursor elements and one or more kind metal oxide particles to be suitable for producing the complex oxide particulate; With

C) select to be used to provide the particulate carbon-containing pore-creating material of the pore dimension of about 7nm～250nm,

And, mixture is handled, with

(i) form the porous complex oxide, in this porous complex oxide, from in the precursor elements of above-mentioned (a) two or more or from the precursor elements of above-mentioned (b) one or more plant with metal oxide particle in metal in one or more kinds enter into described complex metal oxide mutually, and this complex metal oxide has the grain-size of about 1nm～150nm; With

(ii) under the condition of vesicular structure that keeps described complex oxide basically and composition, remove the pore-creating material.

2. the method for claim 1 is characterized in that, forms single-phase complex metal oxide.

3. the method for claim 1 is characterized in that, forms the phase of complex metal oxide and one or more of other metal oxide and plants mutually.

4. the method for claim 1 is characterized in that, forms two or more complex metal oxide phases that have or do not have any other metal oxide phase.

5. the method for claim 1 is characterized in that, each complex metal oxide of formation is the phase pure phase mutually.

6. the method for claim 1 is characterized in that, the pore-creating particle has the particle size of about 7nm～300nm.

7. method as claimed in claim 6 is characterized in that the pore-creating particle has the particle size of about 10nm～150nm.

8. method as claimed in claim 6 is characterized in that the pore-creating particle has the particle size of about 10nm～100nm.

9. the method for claim 1 is characterized in that, the pore-creating particle is the sooty particle.

10. the method for claim 1 is characterized in that, each component that is used to form complex oxide is evenly dispersed to form the mixture of precursor elements.

11. method as claimed in claim 10 is characterized in that, disperses the pore-creating particle by the method that is selected from high speed shear, ultrasonic mixing, rolling, ball milling or sand milling in mixture.

12. the method for claim 1 is characterized in that, before forming mixture, removes air by vacuum from carbon containing pore-creating particle.

13. the method for claim 1, it is characterized in that, this method may further comprise the steps: the solution that the complex oxide precursor elements that comprises metallic cation is provided, the source of carbon granule and nonionic, positively charged ion or anion surfactant, mix described solution, tensio-active agent and carbon granule, to form mixture, make and form surfactant micelle, and mixture forms basically dispersion uniformly, heated mixt is to form complex metal oxide under the condition of removing carbon granule basically.

14. method as claimed in claim 13 is characterized in that, this method may further comprise the steps:

A) preparation comprises the solution that one or more plant metallic cation;

B) making that in solution forming surfactant micelle will mix with tensio-active agent from the solution of step (a) under with the condition that forms micella liquid thus; With

C) heating is from above-mentioned steps b) micella liquid, to form metal oxide, heating steps carries out for some time in a certain temperature, removing tensio-active agent and to form metal oxide particle thus with unordered pore texture,

Wherein, carbon black pellet is added to from a) solution or from b) mixture in, and (burning) carbon black pellet is also removed in this thermal treatment basically.

15. method as claimed in claim 14 is characterized in that, before mixing, carbon granule is added in the solution of step a).

16. the method for claim 1 is characterized in that, treating mixture comprises mixture heating up to about 100 ℃～about 750 ℃ temperature with the step that forms complex metal oxide and remove carbonaceous particles.

17. method as claimed in claim 16 is characterized in that, described temperature falls into about 100 ℃～about 650 ℃ scope.

18. method as claimed in claim 16 is characterized in that, described temperature falls into about 100 ℃～about 300 ℃ scope.

19. the method for claim 1 is characterized in that, one or more in heat treatment step in controlled temperature, rate of cooling or the oxygen partial pressure is with the reduction of the complex metal oxide in the removal process that minimizes or avoid carbonaceous particles.

20. method as claimed in claim 19 is characterized in that, controls described temperature, makes to be no more than specific top temperature in the removal process of carbonaceous particles.

21. the method for claim 1 is characterized in that, it is two or more metals of 3,4,11,12,19～32,37～51,55～84 and 87～103 that described metal oxide comprises ordination number.

22. the method for claim 1 is characterized in that, described mixture comprises liquid ingredient.

23. method as claimed in claim 22 is characterized in that, one or more kinds in the precursor elements are dissolved in the liquid ingredient.

24. method as claimed in claim 23 is characterized in that, described mixture also comprises polymkeric substance.

25. comprising, a method that is used to make the non-refractory metal oxide of porous, this method provide following mixture of ingredients:

A) one or more that are suitable for producing non-refractory metal oxide are planted precursor elements, the particle of non-refractory oxide, and as the oxide particle of the precursor of non-refractory oxide, or two or more the mixture in them; With

B) select to be used to provide the particulate carbon-containing pore-creating material of the pore dimension of about 7nm～250nm,

And, this mixture is handled, with

(i) form the non-refractory metal oxide of porous, wherein this non-refractory metal oxide has the grain-size of about 1nm～150nm; With

(ii) remove the pore-creating material under the condition of the vesicular structure keep non-refractory metal oxide basically and composition making.

26. method as claimed in claim 25, it is characterized in that, described one or more plant precursor elements comprise comprise be selected from ordination number be one or more of 3,4,11,19～21,23～32,37～39,41～51,55～84 and 87～103 metal plant metals one or more plant metallic compounds.

27. method as claimed in claim 26 is characterized in that, described one or more kind metallic compounds are metal oxide, acetate (ester), carbonate (ester) or nitrate (ester).

28. method as claimed in claim 25 is characterized in that, provides described precursor elements as solution or dispersion.

29. method as claimed in claim 28 is characterized in that, forms precursor elements in solution, and subsequently the pore-creating material is being added in the solution.

30. method as claimed in claim 28 is characterized in that, with precursor elements and at least a portion pore-creating material mixing, forming solid-phase mixture, and mixture is dissolved in the appropriate solvent.

31. method as claimed in claim 25, it is characterized in that, this method may further comprise the steps: the solution of the complex oxide precursor elements that comprises metallic cation, source and nonionic, positively charged ion or the anion surfactant of carbon granule are provided, mix described solution, tensio-active agent and carbon granule, to form mixture, make and form surfactant micelle, and mixture forms basically dispersion uniformly, heated mixt is to form complex metal oxide under the condition of removing carbon granule basically.

32. method as claimed in claim 31 is characterized in that, this method may further comprise the steps:

Preparation comprises one or more solution of planting metallic cation;

Making that in solution forming surfactant micelle will mix with tensio-active agent from the solution of step (a) under with the condition that forms micella liquid thus; With

Heating is from above-mentioned steps b) micella liquid, to form metal oxide, heating steps carries out for some time in a certain temperature, removing tensio-active agent and to form metal oxide particle thus with unordered pore texture,

Wherein, add carbon black pellet to solution, and (burning) carbon black pellet is also removed in thermal treatment basically from (a).

33. method as claimed in claim 25 is characterized in that, in step (i), will from the precursor elements of step (a) one or more plant to add non-refractory metal oxide mutually in.

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