FR2838427A1 - Ordered mesoporous or mesostructure compounds based on an aluminium phase with cerium, titanium or zirconium oxide particles and an element in solid solution, useful as catalysts - Google Patents

Abstract

Mesostructured or ordered mesoporous compounds comprise a mineral phase of alumina in which crystalline particles of a compound of cerium, titanium or zirconium are dispersed, and presenting a chemical homogeneity such that the domains of heterogeneity are no more than 100 nm2. Independent claims are also included for the preparation of the material and its use.

Description

to be obtained by the process according to claim 15 or 16.

  ESOPOROUS COPYING COPRENESS TO AN ALUMINUM PHASE,

  OIL OF CER, TITLE OR ZIRCONIU, AND ONE

  ELEENT SOLUTION SOLED OF THESE PUMPS, METHOD OF

PREPARA TION AND USES.

  The pseudon inventon for oet a compoundA mAsosbucturA or mApoporous oonnA, homogen comprising a phase alumina, its pmcAdA of

prAparatlon and its uses.

  In the true sense of the word, the compos of maosopoulos are soils at the heart of the world, poms possAdan1 taB termAdl ent

  this is the case of the monomorphs of the type of zymes and this is macroscopic pores.

  MOREOVER, the "composite" composition of the system typically defines a compound that specifically compodes medium-sized compounds of 2 and 5 nm, as defined by the "mAps" method. Typically these compounds are compounds of amorphous or amorphous type. paracrystalline compounds in which the pores are generically distributed as a proportion of 8148101, 8C a dlstrlbutlon 1s lae de Is taiIle

pos.

  As far as the deschphon of this composition is concerned, it may be noted that this is the case, see 220, pp. 365-371 (1883) or encom in Jo / of ama 'Sonssa, 1, vol. 81, pp. 545-548 (1985), which are used for the purpose of injecting particles into the air, because they produce at least one dluslon peak in a radiation diRuslon diagram. of the type dlRusn by X-rays or by neuons.These diagrams of dlRuslon alinsi that their mode obiention son1 including dAcrlts in -0 4- <Scag (GlaNer and Krky - Academlc Pss London - 19821 the c of diRusn obseA in this type of program can be combined with a performance of the composite machine, which will be shown in the Dachlon system by the "spada hodeod" method of the program.

sys1Ame struurA.

  On the basis of these dadn # ions, we mean by "composA mAsosuurA" a compound having a pda breakpoint of pidon ent 2 and 50 nm. The sucture oanise psente in a 1el ma1Ahau will be dsnde 1 by the term

of sorostruure.

  As a result, muscle-dense compounds cause a case to accumulate as a result. In this case, there is a composite arrangement that involves a large spanning arrangement of the psen ma ss in their ructu, and that this is a good method of asso

  of a plc in a dlagram of dlRuslon.

  COMPos mAusosuus or MAsopoux oonnAs COMPRiNe mAre phase are known and psentent a gnd tAt, especially in the domne

  of the box, of the absorbance chemistry or of the membranaim.

  In addition to composting the mesosubuctus or maximus ordinates containing a monomle phase of alumina, from which at least one of the at least partially melanin-like particles of a compound of alumina, titanium or zimonium is present, there is a great deal of interest in the matter. of the catase. So as to adapt them to the same things, we tried to model them in the same way

amAHor ur c # A in s d domaes.

  1 There is a great need for prophetic medals

  amAlioes, for example for males with an improvement.

  We have obtained materials of this type of "dopAs", that is to say, including a malleable Alumment in the oxide layer, other than the mattematic AlaMe rmateur of the small padicle, in solid solutlon at the salt level of the CrAstaIln rAsaau. of paMule. In this case, even though it is possible to syhize some of the oxide particles that are very mature, especially of the ode type of Mum, lum, dimen sions and n, it is not necessary to the paMicus, in this case, contain elements that are soluble in soluon, can only synthesize doped oxides in the form of paduids of sufficient size, so that their use in a texturing process can lead to the conclusion of a process.

  the thermally stable mesosuction in a phase of alumina.

  The effect of the present invention is to meet the demands of these countries. Also the purpose of [invendon is to pose comps mAsosbuurAs or maopos oonnAs including a phase dlum minum [ne, su se queMe are spembes psb ms ms tes dopbes, ledk composA mAsoFuu

  a good homogeneous chemical.

  For this purpose, it is proposed that a component consisting of a mAbsosubu or mApsporous compound be included in a phase, provided that they are at least partially filled with a compound of cerium, titanium or roonium, and are composed of homogAnd # A chlmlque teMe that the Domalnes d'hArogAnditd are of more than 100 nm2, characteris en in the pslcules

  mpnne at least one soul in solon soaked in psKiles.

  Linvendon also offers a procAdA of pparston dudR composA.

  It was introduced as well as, unexpectedly, the introduction of massive dopant metal cells in solids in a variety of materials.

  mAsoruu may be severely falble tempArsture.

  In addition, the materials of the invention advantageously have a stabilized surface area, a high oxygen storage capacity (OSC), and

improved reducibility.

  Moreover, the advantage of the compounds according to the present invention is that, in addition to their high homogeneity, these compounds are thermally stable up to

  temperatures of about 600 C and even up to temperatures above 650 C.

  This stability is measured by comparison with the surface of a compound calcined prior to 500 C. By this is meant that when the compound is subjected to a heat treatment of 6 hours at the above-mentioned temperatures, it is observed, in addition to the preservation of the mesostructured nature, a relatively good maintenance of the specific surface area, that is to say that, following the heat treatment, the BET surface area of said compound does not generally vary by a factor exceeding 60%, this factor preferably remaining less than or equal to 50%, and advantageously less than or equal to 40%. The variation factor of the BET surface area to which reference is made is calculated by the ratio (Si-Sf) / (Si), where "Si" denotes the BET specific surface area measured after heat treatment at 500 ° C .; and o "Sf" refers to the BET specific surface area measured after

  heat treatment at 600 C or 650 C.

  By specific surface is meant for the whole of the description, the surface

  specific B.E.T. determined by nitrogen adsorption according to ASTM D 3663-78 established from the method BRUNAUER - EMMETTTELLER described in

  Periodical "The Journal of the American Chemical Society, 60, 309 (1938)".

  Other advantages and features of the present invention will be apparent

  clearly on reading the description and examples given purely

  illustrative and not limiting, which will follow.

  First of all, the subject of the invention is an ordered mesostructured or mesoporous compound comprising a mineral phase of alumina in which at least partially crystalline particles of a cerium, titanium or zirconium compound are dispersed. a compound having a chemical homogeneity such that the domains of heterogeneity are at most 100 nm 2, characterized in that the particles

  comprise at least one element M in solid solution in said particles.

  As regards the alumina phase or mineral matrix, alumina is understood to mean Al (OH) 3 aluminum hydroxides, AlO (OH) aluminum oxyhydroxides or Al2O3 aluminum oxides. Within this mineral phase are dispersed at least partially crystalline particles of a compound of cerium, titanium, or zirconium. These particles of cerium, titanium and zirconium are particles of nanometric size. It should be noted here that the mineral phase or matrix does not completely encompass the nanometric-sized particles that it contains. In this case, the mineral phase is a role of 1 year in 1m the padules don1 at least one blade of the pacifier is thus accessible and clear of phase mindle. Alnesi, at least one padie padic is in conts with the psKies constuant [space teFne accesslble by a gas phase notamme, maMsu. We use the term pab in the deschphon steps as phase llante in the se1 of the mineral phase. Psr "nanomaterial dimenslon" means, in the sense of the present venom, the parametric morphology sphinchales or mpe of which at least 50 of popuÉon possade a medium amma comp1 en 1 m 10 nm e1 pmn usn 6nm, a --on gnul-that of = l of pn monodpem ld for the deslon, the #s of the padules

  son1 measured by mmscop dronue 1mosmissn (ET).

  In the same way, the 1st "nanomaterial dimenslon padules" can also be used according to the invention to describe rod-type, barton-type rods, the condition that for at least 50 of the populatlon of these palms, the average L-diametral diameter is fully contained. 1 and 10 nm and ngueur does not exceed 100 nm, with a granumrue rApaM # of these padicus prence monodisperse. The impregnated padules within the alumina matrix are dlamAbe pads of 30 nm in length. The components of adum, t # ane or

  zircorlum of the padicles are mainly oxides.

  The same phase is also carried out by a combination of nanomaterial transfer probes. In this case, the slumine or pm pulldown variables = 1 of the mposs pshicus

  of ahum, titanium or rconium, for example from 1 to 5 nm.

  As far as the structure of the composition of the inntlon is concerned, this one is one of the pars ms which can

  dh phas d fields of dlmensn nanomdque padules.

  Sntageusement s paro mlndrales can consenludes by dames of lnte phase possessing a Apaseur us l compae leur the domnes

nanomAque mens pscus.

  These params reveal a porous volume with access to the sucks of the padicus of nanomate of the compound of cAhum, of rconIum or of

  Utane by a gas phase or a luide phase.

  The nanomrous padicus based on the compounds of the compounds mentioned in the present invention are crystalline, crystalline magnes, in which the maleic oxide generally has a viscosity of about 20% by weight. 30 cent in volume. The degree of volume distribution of a given metal oxide, which corresponds to the thickness of the nanomaterials of the material of the invention, can be determined by the ratio of the peak to the diameter measured by the diiron for a sample of the compound according to US Pat. lnventlon al of the same plc of dlRralon measured for an Achan1110n 1Amoin said oxide state 101aIlIl chstaIA, corUg of absorbent coefficients of the corresponding oxides. The presence of these particles, which can be analyzed in the same way as in the phase of the process, can be compared with that of the system with a total of about 12% of the total weight of the cells, and is generally less than 0% by volume. less than 30 by volume, this total global volumetric flow rate was calculated by multiplying the number of cracks in a given volumetric time [M lnA expArm m entalem nt for pshi cu s, based on the above the material of the material which is occupied by the said particles. More particularly, the composition according to the invention refers to a global crystallization rate in the volume of at least 50 and more preferably at least 60 mol%. Crystalline crystals of a material suitable for the purpose of the invention. We mean the tsux of cMstsIinKA specific to the struval paro, which globally takes into account the ls Is cMstaIlnkA AventueIe of the mind phase of slumine or usnte cMan phase of the nanomMcs mensculum psules lnuses in usnte phase. To this set it was therefore necessary to remember that MatAMsu, in the sense of Unvendon, corre- sponds to a microscopic oste- sone, particularly by diRmion (for example by large-scale X-ray disintegration, which is used to prevent a macroscopic infection, for example). Ia

mAsoruum of the matAMal.

  The minute phase of the material is an important step in the future of the nanomedical process, which is conside- red only once.

  a minéral phase, smorphe psleMement chstsIlre, slumlne consl1ude.

  The essential characteristic of the invention is that it contains a solution in solution in the constituent molecule of the atom, ie in chlorine dioxide, zirconium, and / or titanium. This AlAment is the Catabolic State, generally in solid solution of the substitution eVou lnsedion, within the struure

Crystalline is Psicicle.

  A solid solution in solution of the substance is understood to mean the presence of this substance as a cation, a cation of an injection or a substitution, within the oxide of the substance of the cell, and the role of the cell itself. A crystalline reactor, the AlAment cell line, generally having a molar mass of 50 mol of the total amount of metal salts peroxide in the oxide, that is, that the solid solution cation is predominantly a catabolite. It has a minor content relative to the constitutive cations of the metal oxide when it is incorporated in solid solution, the content of this cation of the element M possibly being up to 50% in certain cases. A crystalline oxide incorporating cations in solid solution retains the structure of the crystalline oxide in pure form, slight modifications of the mesh parameters can however be observed, for example in accordance with the law of Vegard. A crystalline oxide incorporating cations in solid solution thus generally has an X-ray diffraction pattern similar to that of the mixed oxide

  pure, with a more or less significant shift of the peaks.

  Generally, the element M is chosen from rare earths and transition metals that can be integrated in cationic form in solid solution within said particle. However, the metal M may be chosen more specifically depending on the nature of the metal oxide of the particle in which it is integrated in solid solution. It will be noted that the quantity of metal M that can be introduced into solid solution within the oxide depends on the nature of said metal M and the nature of the element

constituent of said oxide.

  Thus, when the particle is composed of cerium oxide, the element M present in solid solution may, in general, be selected from rare earths other than cerium. In this case, the metal M may be more particularly lanthanum, yttrium, neodymium, praseodymium, dysprosium or europlum. The element M may also be chosen from transition metals that can be integrated in cationic form in solid solution in a cerium oxide, in particular zirconium, manganese and titanium. When the doping metal M represents zirconium or a rare earth other than cerium, the quantity of cations of the metal M that can be integrated into solid soil can represent a value such that the molar ratio M This amount of at most 1. When the dopant metal M represents titanium, the amount of titanium that can be incorporated in solid solution can represent a value such that the molar ratio Ti / Ce

not more than 0.5.

  When the particle is made of zirconium oxide, the metal M present in

  Solid solution can be selected from cerium and rare earths other than cerium.

  In this case, M may advantageously be cerium, lanthanum, yttrium, neodymium, praseodymium, dysprosium or europlum. M may also be chosen from transition metals that can be integrated in cationic form in solid solution in a zirconium oxide. When the dopant metal M represents cerium or another rare earth, the quantity of cations of metal M that can be integrated in solution

  solid may represent a value such that the molar ratio M / Zr is at most 1.

  When the particle is made of titanium oxide, the metal M present in the cationic state in solid solution can also be chosen from rare earths, transition metals that can be integrated in solid solution in an oxide of ititane. The machine can be used more mangandse, autain, vanadium,

  nioblum, molybdAne or antimony.

  Finally, according to a mode of alumina, AlAlmen is cholsl parml the rm, the 1hane, the zlmonm, the mangandse, the hane, the pmsodyme and ndodyme, said 61Amen1 61ant dimnt of the constituting AlAment of the oxide of the

  padium (cerium oxide, zirconium oxide or titanium oxide).

  According to a varactor of inntlon, the paiculum may be responsible for the removal of malignant cells or an alkaline or alkaline earth metal and alkaline or alkaline-earth metal clusten and / or crystallites of these same elements, cations or clusters or crystallites, and thus, in a homogeneous manner, sucks the oxide of the oxide. They can be used in the case of alkali or alkaline earth metals, hydroxides, carbonates, hydrocarbonates or salt salts. It is understood to mean an entanglement of about 2 nm, from 1 nm to 1 nm, at the pH of the ml of the molecule, to a state of oxidase O, or to a state of higher odds (this is usually base of species oxides eV0 hydroxides of the evil, eg polyatomic ends to which the atoms of the metal are mutated to each other by bridges -O- or -OH-, each of the atoms of the mAtal may be 6 one or usum groups - This can be particularly the case where the rat is roonum, manganese, or still a ram (lanthanum, I'rm, nodymium, psodyme, dyspslum or Leuroplum). The crystals of an alkaline or aanodous metal are available on the basis of the volume of the monomer as this is the equivalent of that quantity under this system, expcbed in my terms by reference to x moles of the oxide or oxides constud and mal, e compdse

genuinely 2 and 30.

  Ps padicuHAmment ladk composA ps a homogenY # A chemlque teMe that _n. By homogany, only the h-gAnA so ns of us x nm2, we mean a compound that represents a chiral homogAnAkA on a pacemaker of x nm to mns. For example, by HomogAnA ################################################################################################################ A compound which exhibits a homogenous ## EQU1 ## a sucks at least 10 nm × mml_. What is the name of the person in the picture?

  produCtS from llnvenDon enReer sucking areas of 100 nm2.

  These homogenous caradhomes were analyzed by ET-EDS analysis. Ps padicullArmen1, the domain of hA1AmgAnAi16 was measured by the sperm endoscopic analysis method (EDS) using a microsolid microsolution of 1mnsmlssn (ET) on uRramro10mes sections. These analyzes include a sample of a source of 300 (conOrmeO e1 kamiom10mes cuts possAden1 an Apaseur 80

nm, nm.

  In a mode of aNson p, the mposA sen ln ln a small phase can be enumerated dlumlre his sonl dlspembes humus pa In the case of the cAhum are psen in quantd He that ppod oml Ra = Al / (Ce + Al) is at ps 50, of

presence 25.

  The compound according to Pvendon advantageously has a structure mAsosbuurde of which [CompaS global paseur compound is compdse between 2 and

10 nm.

  The compound according to P [nvenNo advantageously has a sucture mAsopouse compodan1 poms 1He compdse en1m 2 12 nm, prence 3g. The compound according to Cvendon is advantageously a method that is locally present at one or more of the selected osmosis (s) among: - mAsoruus mAbsuids of symmetrical hexagons P63 / mmc, of hexagonal symmetrical P8mm, of cubic symmetry TUdimensnneMe Is3d , Im3m or Pn3m or - the mAsoruus of type vAsloulaires or lamellar,

  the mAostructus of the vermulculan type.

  In terms of the dADnklon of these symmetric dies and structures, it is possible to refer, for example, Chemical atebals, voL9, N 12, pp. 2685-2886 (1997) or Natur voL 398, pp.223-226 0999) or in Science Vol 269, pp 1242-1244 g95) Dube pad, s composs of [sellon psentent a good abORA in temperature a sudace spAcKue eve1 advantageously supdeum mm3, pmnce supdeum 900mm3, and encom us pmeement

  1200m2m suprure for a 1empAratum of cainadon of 6 hours 400 C.

  This sucks spAclflque expressed in m2 / cm es1 obtained by multiplying the suck gAndrament measured in m2 by dens # A of matAMau compound. For a compound donating nanometeous particles, it is based on a compound of adum,

  THIS IS SAMPLE EXCLUSIVE FOR 100 m.

  In the particular case of a material consisting of a binder phase of alumina and cerium oxide particles and in which M is titanium, this surface may be at least 100 m 2 / g, more particularly from less 125m2 / g and even more

  especially at least 1 50m21g.

  The pore volume of the materials of the invention is generally at least 0.10 cm 3 / g, more particularly at least 0.15 cm 3 / g and even more particularly

at least 0.20cm3 / g.

  One of the advantages of the materials of the invention based on cerium oxide particles is their reducibility. This "reducibility" of a material according to the invention can be demonstrated by treating the material with hydrogen and by analyzing the degree of conversion of the cerium to the IV oxidation state initially present, in cerium at room temperature. oxidation state lil in the material obtained after the treatment, according to the overall reaction below: 2 CeO 2 + H 2 Ce 2 O 3 + H 2 O The reducible nature of a material according to the invention can thus be quantified in particular by the measured conversion rate. at the end of a protocol called "TPR", explained below: - in an AMI-1 Altamira type apparatus equipped with a silica reactor, is placed at temperature amblante (generally between 1 5 C and 25 C) 100 mg sample of the solid to be tested, under a gaseous flow of a 10% hydrogen / argon mixture

  hydrogen at a rate of 30 mL per minute.

  a rise in temperature up to 900 ° C is carried out at the rate of a constant temperature rise gradient of 10 ° C. per minute. Using a thermal conductivity detector at 70 mA, the amount of hydrogen captured by the material is determined from the missing surface of the hydrogen signal from the basic line to

  the ambling temperature at the baseline at 900 C.

  At the end of such a test, a conversion rate of the initially present cerium IV species which is at least 30% is generally measured, this conversion ratio advantageously being at least 40%, more preferably at least

equal to 50%.

  It should also be noted that the peak of cerium reduction determined by the above protocol is centered on temperatures of at most 450 ° C., preferably

  at most 400 C and even more preferably at most 375 C.

  The method according to the invention will now be described.

  The process for preparing the product according to the invention comprises the following steps: 1) forming an aqueous mixture comprising: a collodal alumina dispersion; - to the mos a agent teunt - a smion coU-s in mposA of Mum, 1ne or um in which the oomposA of rm, lane or monme nionnaNSA by an agen1 succe of form X / -Y in IsqueMe: (s) X is a comexant member of the caton of the compound of Ahum, Kane or zonium of the coastal area; (b) A ss 1 a pe kyUindai sump or mA y es1 a glyndine or hydroxyl ss II-alumina alumina of the mposA of adum, Dane or ziroorlum praansananan conductivity lnrr 25mS / cm: 2) imine lsu m alange p 3) All the same, let us know the material obtained from a solution of AlAlmen1 that has a concentration of at least 61% in the range of 2 months: - (b) we ca [ the mother has not put in contact with a temperature of not more than 500 C - (c) we have renewed the case of the apes (s) e1 (b) up to 1btenDon

  dn mdau psentan1 1eneur desired in Amen1.

  Also, the key dates for step 1 are as follows: ## EQU1 ## ## EQU1 ## ############################################################################# -58 (noismmen1 for spelon coUdale umlre1 These sperons can be used to reduce the amount of powder powders obtained by high-level synthesis procedures of the type of chlorus combustons used in a known nsmm. As in the past, the concentrates in palms in the dilspersons

  According to the invention, expressed in moles of water above 1.

  The colloidal alumina solution has a pH of between 3 and 6. Furthermore, it is preferable to use a colloidal dispersion of alumina which is not soluble.

  psicus or coNoes es1 contains 1 nm and 5 nm.

  The distribution of a compound of alumum, titanium or zirconium may result in the production of psikicus or medium-sized compounds.

in1 3 nm 8 nm.

  Colloidal alumina dispersions of acrylate, titanium or zirconium compound are used by the ultrafiltration technique to purify it by means of a high flow rate over a range of pH values. on pH 2 and 5 decenters a concenaton in cshon of 1. This measure is measured in

  these condions are alnsn [um 25mS / cm, lavishly inrieu 8mS / cm.

  The first step of the Atape (1) is an aqueous medium, but it can also be a hydro-alcoholic mill, and in this case an aqueous solution of ethanol. The mixing agent from step 1 comprises at least one texturizing agent. This tiding agent, which is used in the mange, is an amphiphilic compound of the tenslactic type, especially a copolymer. The essential characteristic of this compound is that it is sus- ceptible of transient chromatic phases in the active, conditional mixture, a mindra mat- ter possessing a mAbsosumum for me with the LCT tetracycline: (Uqu Cdst Templatlng) . However, in addition to a new texturion that has a better conductive effect, an increase in the parser obtained and therefore an improvement in the stability of the final structure, the uddering agent in the Univans procadas is of gon prAfArent a compound

  no chaA in the condAns of me in uv pcAdA.

  -geuseme, lge unt sen N_ndon e a tenslf not naked of pe copomAre, and particular choi among the squencAs copomAres of pe pe

diblock or tribToc.

  Preferably, in the case of aqueous or hydrochloric acid processes, a non-polar peomethylated copolymer, and more preferably a poly (AthylAne) -poly (propylene oxide) -polyester copolymer ( AthylAne oxide) said PEO-PPO-PEO (also called A (EO) (PO \ (EO of the pe of those dachts including by Zhao et al In Journal of AmeMcan Chemical Socly, I. 12O, pp. 60-6036 OS8t As a matter of fact, it is also possible to use non-ionic surfactants such as poly (AthylAne oxide) salts (EO / CY as made by Arh under the names of maues BU or en1 or non-ionic taching of all commercially

by Uka under the name of Maue Span.

  Texturizing lye may also be a polyca (AthylAne) squencA copolymer

  poly (isopropAne) or a polycaprolene poly (AthylAne oxide) copolymer.

  According to the invention, the colloidal dispersion of the acrylate, titanium or zirconium compound is caratolys in that the compound of alumina, titanium or zirconium is dissolved by a glucose-reducing agent (AY). also be under b within the dispemion.

  This surfactant is an organic compound in which A is an optionally substituted linear or branched alkyl group, which may for example comprise from 1 to 12

  carbon atoms, preferably between 2 and 8 carbon atoms.

  Function X is a complexing function of the metal cation of the colloidal dispersion of the cerium, titanium or zirconium compound. By complexing function is meant a function which allows the formation of a complexing bond between the colloid cation, for example the cerium cation, and the surfactant. This function can be a function of the phosphonate type pO3 2-, or phosphate pO42-,

  carboxylate -CO2-, or sulfate -SO42-, sulfonate SO32 for example.

  Function Y is an amine or hydroxy function. It may be an amine function of the type UNH2, b1NHR2, or L1NR3R2, or [: NH4 +, R2 and R3, which may be identical or different, denoting a hydrogen or an alkyl group comprising from 1 to 8 carbon atoms. It can also be an OH function. OH-functional agents include, for example, glycolic acid, gluconic acid, lactic acid, acid and the like.

  hydroxybenzoic acid, the disodium phosphate of glycerol.

  Among the surfactants which are particularly suitable for the invention it is possible to

  mention the amino acids, and especially the aliphatic amino acids.

  In particular, mention may be made of the amino acids constituting the proteins of structure R 0 CH (NH 2) 1 COOH where R is an aliphatic radical. As an example we can

  mention leucine, alanine, valine, isoleucine, glycine, lysine.

  The preferred surfactant according to the invention is amino hexanoic acid.

  Advantageously, the amount of surfactant used to functionalize the compound of this dispersion is expressed by the ratio Rb, determined by the following formula: Number of moles of function X Rb = Number of moles of cerium oxide, titanium oxide or zirconium

  The ratio Rb is advantageously between 0.1 and 0.5.

  Preferably, the functionalization of the cerium, titanium or zirconium compound is carried out by contacting a dispersion of said compound with the agent

of surface.

  According to a preferred variant of the invention, the colloidal dispersion of starting alumina may also be a dispersion in which the alumina colloids may be functionalized with a XAY surfactant, which is identical to or different from the surfactant. of the colloidal dispersion of the cerium, zirconium or titanium compound. Preferably, removal of the surfactant molecules is carried out

  optionally free by washing by ultrafiltration.

  The rmn of the [Atape 1] pdA mange sen [venton is 11 by simply putting in contact with the constituents of the alange aluminium dispersion, Fagen11extuFant dlspers [on coNoldale fonionnalise according to the method d'Achte plus

  above. This simple setting in conta is in milleux aqueous or hydroalcoholic.

  The conditions of operation of step 1) are such that they can be obtained from the machine 1) a food that has a condul (measured as a comfort of 1) that is preferably 25mS / us. cm. As a result, the temperature of the mixture (measured in the same condlons) will be from

- 8 m.

  To conduct a course of study, colloidal elections are held

presenting this conduivitA.

  The colloidal and agglomerative dyes are used in quantities such as the ratio of glue volume to colloid volume. The volume of the nutrient unit is comprised of 0, 1, 1, 0, and 1 plus 1 and 0.1, respectively. By means of coefficients it is meant to obtain in dlsan1 the mass of the coMoTdes prAsents in the dlspemns by denskA 1houohque of the coNoTdes e1 by volume of Pagen1 reducing the value held by saying the

  mass of lgent tum by the density of I-.

  The second stage of the PCAdA is lmlner at mns in the Ceau of the dApad mix. This can be done by Avapontion lk Ob or under fume hood, e1 from room temperature. Advantageously, it can be carried out in an aqueous layer with a thickness of less than 5 mm. We

  can also fal a dry-atomaton in tempAratu.

  The third step of the procedure for the preparation of the compound of the invention

imir lge um.

  This Atape can be especially 6th by a German element. In this case, the heat treatment is advantageously at a temperature rise of 0.2 ° C per ml and 3 ° C per minute, and preferably after a temperature increase of about 0.5%. 'C per minute and 2'C per mute, to avoid damaging the matAMau. This temperature rises in temperature is generally 6% up to a tempeRing rate of lenabon

  until it reaches a condensing temperature of 300 ° C to 1800 ° C.

  Because of this, the use of a single element by the M uw of M g ust assumes an unloaded amphiphic compound, which induces a teran ummary agent that is

allow this type of Allminatlon.

  In an unfortunate manner, the request of the successor at step 3 may furthermore be subject to a supplementary heat seal, and in particular to a caimon. The purpose of this additional optional heat treatment is to increase the crystallinity of the material obtained, and to limit the quantities such as nitrate anions and agents.

of sucks.

  The quaRlAme Atape of the PMcAdA conste puts in contact the matAMau obtained

  1Q to the pcAdent steps of the procAdA with an element of the element.

  The solutlon of AlAment used in the case of procAdA is usually an aqueous solution of salts of this AlAment. Inosylic acid salts such as nitrates, sultines or chlorides can be used. It is also possible to use the salts of oily acids and especially salts of saturated allphatic carboxylic acids or salts of hydroxycarbolic acyls. By way of examples, it is possible to form rimes, acatates, proponates, oxalates or clttes. however, it is necessary to use an aqueous solon or h-al = ue mpnant

  badly done, or in any other way, gAnAMment in mHu sol-

  anhyd, containing a metal oxide.

  When the AlAment is t # ane, one can uSEUser more padicuRArement an alkoxide

  of titanium in milled hydrochloric acid.

  The soluton which is in contact with the material has a concentration in this element which is not more than 2, but not more than 1.2. More concentration is needed to prevent a solid solution from

  AlAment in the constituting oxide of the paiculum.

  The mlse in conta can be fm by imming the damat mAsoruurA mAsoruurA within a solution including l'AlAment puls while submitting the medium onu a ce-gadon. CAnAmleme, the glon e aUse, mison of 2000 5000 rounds per minute, during a due no exChanTing gAnArament not 3Q minutes. According to a padiculler mode of alisation, the alament of the AlAment with compound of cAdum, tRane or rcorlum is # by a dry imprAgnaBon. Limit dry to the product to impregnate an aqueous component of a component that is equal to the louse of the impurity medium. The solid obtained from phase (a) of the test procedure is then submitted to a lon. Cainion (phase of the fourth stage) is usually de-weded to initiate an injection into the padular mass of ALAment cells in solid soluton with the aid of the constituting oxide of the padicle. A temperaTure at the Agale 300 ° C, this temperaTuratY at the time of treatment is 350 ° C and is preferably 400 ° C and advantageously 500 ° C. Higher temperatures are not required for this purpose. An aggression of the cations of the AlAment to the salt of the oxide of the paiculum In this connection, it is suggested that the PCAdA of the present invention allows, surprisingly, the inclusion of metal catlons in solid insulin solution. and or of substituting for the salt of the alkali of the temperature, which can be achieved in particular by obtaining mAbsosuus mammals, which can be used in the presence of very high sphacks. TEMPERATURE GAUGE, AN INNOVATIVE ENVIRONMENTAL TEMPERATURE 1 5 and 95 ° C., a final temperature of 350 ° C. and 1000 ° C., advantageously with a temperature increase of 0.5 ° C. per minute 2 ° C. per minute, with one or more steps in the middle of the intermediate temperatures, of the first time between 350 and 600 C, for a variable fee, generally between 1

hour and 24 hours.

  In this case, the procedure of the Unvendon may include a stage of salvage, prior to step 4) (b) of cainaNon. In this case, this preliminary drying is generally conducted by the slowest possible gon, especially to increase the naked exchanges. At this point, drying is often carried out at a temperature of 15 ° C and 80 ° C, initially at a temperature of 50 ° C, preferably 40 ° C, and advantageously at room temperature. This drying can be carried out under nitrogen (Argon) or under oxidizing atmosphere (ak, oxygen) in the compounds present in the material. In the case where the disease is severe in the middle of the

  Preferably, the drying is conducted under atmospheric water-free conditions.

  According to an advantageous mode of optimization, PlnvenNon's procAdA can compnd, su # e to the Attes 4) (a) 4) (b, one or more of the contacalnaton tdeum meMant in uv of the Steps of pe 4) (a) and 4) (b), condes on the demand obtained from the prAcAdent cycle. By implementing this type of process in order to improve the effectiveness of the process, a very good proportion of solids is solved in solutlon, which is applied to the salt of the oxide flasks. The panting of these cycles is to the extent of producing the desired neuron in the blood. It is possible to increase the number of patients in contact with the implant using doping agents of the distinous type, whereby little can be used to produce doped substances by usuAl elements.

mAtalTiq ues in soil and soil.

  For the sake of high values in the air in which cabons, duals, or ducts of the metal or of a metal or alkaline medium are dispersed the sucks of the constituting oxide of the material, solutions of this AlAment (or alcallos) are used. or alcalino-termux) concentratlons eves, for example from to 1,5 m or new phase of mlse in conta with this sat s saton satutlon of the constuff ode of the matédau under rme de

Solid solutlon by this AlAment.

  Finally, the inventlon also concerns the use of the compound mAsostruurA or mAsopoux oonnd sen [unsend and the product # obtained by pcAdA sen UnvenDon as a catasor or as a suppod of a catasor notably for post

automobile combuion.

  The following examples illustrate the invention without letting the poise.

EXEPLES

  1) Preparation of a compound of nanoparticles of adum in a mixture of alumina # OH with a ratio of (I / Ce) = (04 / 0.9) mw = 0.2

1 - _

  The following is a description of the application of the present invention to the present invention, which is described in US Pat.

cAMum is 65 by weight.

  300 g of water are added to 500 g of Mum spemab.

  Puls on an ultraturax dispersion for 15 minutes at 4500 rpm.

  The speron is cenhuge for 15 minutes rson of 4500 rpm / m on rAcupAre

a wet ass.

  In the wet end, one or 200 g of water of Amindlde, the same type of dspeion aps addition of water Atant of 300 ml. Aps homogAndisatlon I'ultratumx for 15 minutes, the d ~ speron is cenhuge for 45 minutes 4500 t / m On cupA a Cut Again we cut this wet cut of lau dAmArabse iusqu a total vome of 600 ml. After homogenization, a clear colloidal dispersion is obtained, which is then passed through 330 mL of water of ammonia up to a volume of 600 mL. Up to 200 mL is obtained after [min. u of spemn of dens # A 1, O2, the concenaJon

  CeO2 molaim is 5.69 or 2.05 mol / kg.

  The functionalization of the sucks of CeO nanoparticles was carried out in the following manner: To 400 g of spathecine, prepared as before, an additive solution of 30.0 g of magnesium hydroxide in 400 ml of water was added. It is lambed under a tempatum agantum for 16 hours. The pH is 4.6. The decline is again achieved by adding two volumes equivalent of Amindralise water. Concentrate to 500 ml. The dlspersion

thus obtained is 2.08 mol / l.

  Aps dilution with 1ml water, the pH of the dsperslon is 4.3 and the

Spectrum nduivi of 15 mm.

  1 - 2) Aqueous column of aluminum hydroxide hydrate (Al (OH) S) of nanomaterial dimensions: A co-literal distribution of aluminum hydroxide is prepared according to the optical method below. : In a doubtful air, a Juni dmee dghlon a condenseup

  150 g of aluminum salt AlCl, CHO are added to 150 g of water under stirring.

  After decantation, 154 ml of NH 3 OH were added to the room temperature.

- P dne g ^ - l d - g _.

  The meu meu alonnel matte G5 C for 18 hours.

  After the precipitation, the pH is pH 6, Og.

  The sponge is placed in a beaker that has a pH gradient of one pH ion spore. After a few hours, you can take a hydrolysaccharide to reduce the pH of the pH 4 dye.

agita110n an hour more.

  Spen e l par 4 is its lume by 1Rn dAmlndl6e

on membranes of 3 KD.

  The dispersion is concentrated by filtration and determination of the dry extract by

  calcination of a 1000 ° C aliquot indicates a concentration of 1.1 mol in Al.

  It is u by dhuton by the dAminAmlbe concentn of spelon 1

in Al.

  The pH is 4.65 and the conductivity is 4.5 mS / cm. Cryo electron transmission microscopy, we visualize nanoparticles with a diameter of 3 nm

perfectly individualized.

  1 - 3) Preparation of the Mesostructured Material In a beaker, 200 g of water are poured, followed by 6.10 g of Pluronic P 123. This Pluronic P 123 compound is an amphiphilic copolymer of the triblock block type type from the company. BASF having the structural formula HO (CH 2 CH 2 O) 20 (CH 2 CH (CH 3) O) 70 (CH 2 CH 2 O) 20H and an average molecular weight of

  5750 g / mole. The resulting mixture was stirred for two hours.

  56.3 ml of the colloidal dispersion of cerium oxide at 1M previously described and 6.3 ml of the colloidal dispersion of aluminum hydroxide 1M previously described were then added simultaneously. Stirring was continued for 15 minutes. The dispersion obtained was then placed in glass petri dishes and was

  subjected to evaporation at 20 C for 5 days in a fume hood.

  The dry product was then transferred to alumina pods. The product was calcined at 500 ° C. with a rise in temperature of 1 ° C./min and a plateau of 6 hours. The quantities of amphiphilic copolymer and colloidal dispersion thus used

check the ratio = 0.2.

  Observation by transmission electron microscopy of the material obtained at the end

  from these different stages, the existence of a texture appears.

  In addition, the plot of the BET nitrogen adsorption - desorption curves shows a

  monodisperse distribution of pore size.

  The specific surface area of the material was determined equal to 200 m 2 / g for the calcined product at 400 ° C. 6 h, ie 1360 m 2 / cm 3. The specific surface of the material was determined to be 158 m 2 / g for the product.

  calcined at 500 C 6h or 1075 m2 / cm3.

  The specific surface of the material was determined equal to 110 m 2 / g for the product calcined at 600 C 6h or 748 m 2 / cm 3. Moreover, the average pore size for these different products was determined.

equal to 7 nm.

  The pore volume determined by BET nitrogen is vp = 0.33 cm3 / g. By diffraction of

  X-rays, we observe lines characteristic of the CeO2 structure.

  2) Comparison of the dams: 2 - 1) PrApa [a DACA mAsoru mat: 43- CO d +) A sotn of NO, 1,2 in ppae by add # lon 54,8 ml of solution of Zr (NO 2.1g in Zp of Density # A 1,368 and 270 g) in zirconium oxide

  contained in Ammonia water (up to 100 cc volume).

  The impregnation of 12 g of the magnesium oxide, obtained in Step 1 - 3) pcAden, Al (OH) 2 O ((I: Ce) = (0: 0, g), is measured 66 mimes of Ce 7, 2 millimoles Al), calClnA 400 C for 6 hours per 8.16 cm of solut [on solution of Zrcorlum nltrate palablly pparde 1.2 in Zr (or 9.8 mlllimoles of Z0.Le mppod mol e) is om Agal 0J The pdu # e sAchA tempAtu ama nu, pu C to 8 h-. It is heated to 400 ° C. with a temperature of 1 ° C./min and an oven.

6 hours.

  The impregnation operation of the chemical treatment was then renewed. The rappod

  Final molaim (Z Ce) is equal to 0.3.

* By X-ray dlaion, one obtains a padicu spec 1s close to this one of adum pu acs from the 1AgAmmen1 dAcalAs vem the short distances (paramaLs of maiMe of 5,40 A) and the presence of ZrO quadraque in PAs

propolons.

  By tracA hermes adsorion-dsorlon, the subricate is derminde 1 ^

  A porous membrane centered on an 8 nm pomate is observed.

  The porous v e dAtermind Agal 26 cm.

  After 1 TPR test, a low temperature of 1 ° C is obtained at a temperature of 350 ° C. The percentage of rAdui16 intAg up to 700 C is 64. 2 - 2) PrAparaton dn mAsosbuu dopA prsodymeu mat: 44O - CO d75 + A soluton of Pr (NO 1.21 in Pr is prepared by addRion 51, g ml of soluton of Pr (NO \ 2.91 in Pp of dens # A 1.73 and 28.6 in prasodyme oxide contained , as a result of soc16 Rhod Terres rams, by AmArlse water

  to obtain a final volume of 125 cm3.

  10 g of the mApsopharous product, described in CAlape 1 - 3), was prepared. (I: C = (0.1: 0, g) sok 55 mHUmoles Ce, 6 mimics Alt calnA 400 C Using 6 hours per 6.8% of solids from prasodymium nitrate solution palablemen1 prApae 1.21 to Pr (so # 8.23 mmol of PO, the molar ratio (PCe) is equal to 0.15. sAchA ambient temperature 16 hours, for 80 hours, 8 hours, then the product under the atmosphere at 400 ° C with a temperature rise of 1 ° C

/ mn e1 a paber of 6 hours.

  LopArlon impregnated with a new model. The ppod

  Molar molar (P Ce) es1 alo Agal O, 3.

  By X-ray diffraction, one obtains a spere of the media that is close to that of an oxide of the pupum with psAs gAmmen1 dAcalAs towards the larger ones.

  substances (5.45 A range of parameters).

  By 1cA of other adsorpon-dsorpton, the suck spAcKue es1 dermlnde Aga5112m2.

  A woman is found on a 7-nm dot.

  The porous porous material was equal to 29 cm3.

  2 - 3) Preparation of Acetate DHA Amylosolate: YOJ-COOP A solution of acidified ammonium hydroxide is prepared by dissolving 20, 65 g of Tl (OBu), 23.45 of TiO in 15 cm 3 of Alcohol, e1 8 cm HNO 15 which was filled 50 cmS with iodine We impregnate the impgnation of 4 g of the product mAsopoux, obtained 1'ape 1 - 3) prevAcente, Al (OH) -CeO: (( Al: Ce) mO = (0.1: 0, g), ie 22 m [Ce lmoles], CaCl2 400 C suspended by 2.72 cm of pre-bleached olive oil solution (sO 3, 26 mlmol of T0, the mopoM molake (Ti / Ce) is then equal to 0.15, the product is sAchA 1empAratum amante pendan1 16 heus, or 80 C for 8 heus.They are cured by the pduk under atmosphere r 400 C with a mounting in

  1emperature of 1 C / min and a PaHer of 6 hours.

  By X-ray diffraction, we observe a spectra of the truncated trellis close to Celia Sun oxide of curium pug with pica gas lAgAmen1 dAcalAs vets at small distances by adsorpon-dsorphon bothermes, is surface spAciue es1 dA1ermlnde

Agate 165 may.

  We observe a pM # n pouse center on a gamma pores of 7 Am.

  The lice volume was found to be 0.32 cm / g.

Claims (16)

  An ordered mesostructured or mesoporous compound comprising a mineral phase of alumina, in which at least partially crystalline particles of a cerium, titanium or zirconium compound are dispersed, said compound having a chemical homogeneity such that the domains of heterogeneity are at most 100 nm 2, characterized in that the particles comprise at least one element M in   solid solution in said particles.   2- compound according to claim 1 characterized in that it has a rate of   overall crystallinity by volume of at least 10% by volume.   3- compound according to one of the preceding claims characterized in that it presents   a chemical homogeneity such that the domains of heterogeneity are at most 25 1 5 nm2.   4- compound according to one of the preceding claims characterized in that said   element M is selected from the rare earths and transition metals likely to   can be integrated in cationic form in solid solution within said particle.   - compound according to one of the preceding claims characterized in that said   the element M is chosen from cerium, titanium, zirconium, manganese, lanthanum, praseodymium and neodymium, said element M being different from the element constituent of said particle.   6. Compound according to one of the preceding claims characterized in that   comprises particles of a cerium compound and in that the element M is chosen   among rare earths and zirconium, the molar ratio M / Ce is at most 1.   7- compound according to one of the preceding claims characterized in that   comprises particles of a cerium compound and in that the element M is titanium   and in that the Ti / Ce molar ratio is at most 0.5.   8- Compound according to one of the preceding claims, in which the particles are   doped cerium particles and where alumina and cerium are present in an amount such that the atomic ratio Ra = Al / (Ce + Al) is at most 50%, preferably not more than 25%.   G-ComposA is based on the preceding sales, characterized in that the overall value of the components of the compound mA.subhasu is computed in 1 2 e110 nm. 10- ComposA according to rune vendacLons prAcAdentes carac16hsA in that the padicus spembes in the phase m son1 palcus amAt 3 nm nm. 11- ComposA sen ls of the vendadons pcAdentes caraNsA in qull compoe   poms of 18 cm in 12 nm, 30 nm in diameter.   12- ComposA refers to the vendaBons pcAdentes camAhsA in which at the locame one or usum mAsoum (oieO pa: - mausosuus mausopouses of symde hexagona 1hdimensnne mee P6mc, symA1de Hexagona dlmensnnee P6mm, symme cube 1ddimensnnee 13d, Im3m or Pn3m; - the mesostruus of type s [culais or lamellais, - the vermiculalms mAsostructures.   13- PcAdA de pamadion du pdu # s saladrons 1 12 carac1AhsA in that it includes the Sweaty Steps: 1) a watery meal is formed comprising: - a colloidal alumlle diple; at least one agenextext1; - a coLloal dlspem of a compound of cArrlum, titanium or lrconlum in which m of dum, ne or um nchonnaNsA by a sane agent of rme XAY in Isque # e: d) X es1 a comexante nchon The composition of the compound of adum, tRane or zircorlum of the colloidal dispelon is as follows: e) A is a gupemen1 of the alkylindalre type or mlfA; Y is a gum amine or hydroxy; The diameters of the aluminum, ammonia, or ammonium compound were 25 mm; 2) feeding the water of the mixture pci16; 3) the extension is determined; 4) - (a) the ammonia obtained with a solution of the AlAment that has a concentration of at least 2 mo in concentration is reported; - (b) calcining the material obtained after this contacting with said solution at a temperature of at most 500 C; (c) where appropriate, the steps (a) and (b) are repeated until a material having the desired content of element M is obtained.Method according to claim 13, characterized in that one uses a dispersion   colloidal alumina whose pH is between 3 and 6.   - Method according to one of claims 13 to 14 characterized in that one uses   a colloidal alumina dispersion whose colloids have a size between 1 and nm.   16- Method according to one of claims 13 to 15 characterized in that one uses a   texturing agent which is a nonionic surfactant of copolymer type, and in particular   chosen from block copolymers of the diblock or triblock type.   17- Method according to one of claims 13 to 17 characterized in that one carries out the   contacting the element M with the cerium, titanium or zirconium compound by dry impregnation.   18- Method according to one of claims 13 to 18 characterized in that one uses   a colloidal dispersion of a cerium, titanium or zirconium compound in which the amount of surfactant is expressed by the ratio Rb (Rb = number of moles of function X / number of moles of cerium oxide, titanium or zirconium), which is between 0.1 and 0.5.   19- Method according to one of claims 13 to 18 characterized in that one uses a   surfactant which is an amino acid, more particularly an aliphatic amino acid.   - Method according to one of claims 13 to 19 characterized in that one forms, to   step 1), a mixture whose conductivity, measured at a concentration of 1M, is not more than 25 mS / cm.   21- Method according to one of claims 13 to 20 characterized in that one uses the   colloidal dispersions and the texturizing agent in amounts such that the ratio (+ = volume of the colloTdes / volume of the collodes + volume of the texturing agent) is included   between 0.1 and 0.6, and more particularly between 0.1 and 0.4.   22- PodA salon one of the 13 13 cara6hsA claims in that we revise nlonnabsaBon of the compound of Swum, Mane or anonym by Mae in congas   a spele alla dude Impose _c the sump agent.   23- Use of the product Menu salon one of the Syndications 13 of the prodult obtained by the pcAdA salon [one of the vendadons 13 22 comma cataseur or