Method for exchanging interlayer anions of a layered double hydroxide

Abstract

The invention relates to a method for exchanging interlayer anions of a layered double hydroxide (LDH) with other anions whose affinity for the LDH is lower than the one of the starting interlayer anions, which comprises the successive steps of: (1) exchanging the starting interlayer anions of a layered double hydroxide with polyoxometalate anions in order to obtain a layered double hydroxide with polyoxometalate anions as interlayer anions, and (2) exchanging the polyoxometalate anions of the layered double hydroxide obtained in step (1) with other anions whose affinity for the LDH is lower than the one of the starting interlayer anions in order to obtain a layered double hydroxide with other anions as interlayer anions.

Claims

1. A method for exchanging starting interlayer anions of a layered double hydroxide (LDH) with other anions whose affinity for the LDH is lower than for the starting interlayer anions of the LDH, which comprises the successive steps of: (1) exchanging the starting interlayer anions of the layered double hydroxide with polyoxometalate anions in order to obtain a layered double hydroxide with polyoxometalate anions as interlayer anions, and (2) exchanging the polyoxometalate anions of the layered double hydroxide obtained in step (1) with other anions whose affinity for the LDH is lower than the one of the starting interlayer anions in order to obtain a layered double hydroxide with other anions as interlayer anions.

2. The method according to claim 1, wherein the exchanging step (1) is carried out in a solution containing oxometalate anions, whose pH is such that polyoxometalate anions are formed and the affinity of the LDH layers for the polyoxometalate anions is higher than its affinity for the starting interlayer anions.

3. The method according to claim 1, wherein the exchanging step (2) is carried out in a solution containing the other anions, whose pH is such that the polyoxometalate anions depolymerize to give oxometalate anions other than polyoxometalate anions and the affinity of the LDH layers for the said oxometalate anions is lower than its affinity for the other anions.

4. The method according to claim 1, wherein the LDH layers general formula is [M.sup.u.sub.l-x, M.sup.III.sub.x(OH).sub.2].sup.x, wherein: M.sup.u is selected from the group consisting of Ca.sup.2+, Mg.sup.2+, Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+Zn.sup.2+and 2.sup.Li+, +M.sup.III is selected from the group consisting of Al.sup.3+, Mn.sup.3+Fe.sup.3+, Co.sup.3+, Cr.sup.3+and Ni.sup.3+, and x is equal to the molar ratio of M.sup.III/ (M.sup.II+M.sup.III) and is comprised between 0 and 1.

5. The method according to claim 4, wherein M.sup.II is Mg.sup.2+and M.sup.III is Al.sup.3+.

6. The method according to claim 4, wherein x is comprised between 0.1 and 0.8.

7. The method according to claim 4, wherein x is comprised between 0.2 and 0.4.

8. The method according to claim 1, wherein the polyoxometalate is selected from the group consisting of polymolybdate, polytungstate, polyvanadate and mixtures thereof.

9. The method according to claim 1, wherein the starting interlayer anions are carbonates.

10. The method according to claim 9, wherein the layered double hydroxide is hydrotalcite.

11. The method according to claim 1, wherein the other anions are monovalent or multivalent, organic or inorganic anions.

12. The method according to claim 1, wherein steps (1) and (2) are followed by an additional step (3) of: exchanging the other anions of the layered double hydroxide obtained in step (2) with second anions, in order to obtain a layered double hydroxide with second anions as interlayer anions.

13. The method according to claim 12, wherein steps (1), (2) and (3) are performed at least a second time.

14. The method according to claim 12, wherein the second anions are identical to the starting interlayer anions.

15. A method for extracting anions contained in a solution, which comprises the steps of: (1) exchanging starting interlayer anions of a layered double hydroxide with polyoxometalate anions in order to obtain a layered double hydroxide (LDH) with polyoxometalate anions as interlayer anions, wherein the affinity for the LDH of the anions to be extracted is lower than for the starting interlayer anions, (2) placing the layered double hydroxide obtained in step (1) in the solution containing the anions to be extracted, and (3) extracting the anions contained in said solution by exchanging the polyoxometalate anions of the layered double hydroxide with the anions to be extracted.

16. The method according to claim 15, wherein: the exchanging step (1) is carried out in a solution containing oxometalate anions, whose pH is such that polyoxometalate anions are formed and the affinity of the LDH layers for the polyoxometalate anions is higher than its affinity for the starting anions, and the pH of the solution in extracting step (3) is such that the polyoxometalate anions depolymerize to give oxometalate anions other than polyoxometalate anions and the affinity of the LDH layers for the said oxometalate anions is lower than its affinity for the anions to be extracted.

17. The method according to claim 15, wherein the LDH layers general formula is [M.sup.II.sub.i-x M.sup.III.sub.x(OH).sub.2].sup.x+, wherein: M.sup.II is selected from the group consisting of Ca.sup.2+, Mg.sup.2+, Mn.sup.2+, Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+, Zn.sup.2+and 2 Li.sup.+, M.sup.III is selected from the group consisting of Al.sup.3+, Mn.sup.3+, Fe.sup.3+, Co.sup.3+, Cr.sup.3+and Ni.sup.3+, and x is equal to the molar ratio of M.sup.III/(M.sup.II+M.sup.III) and is comprised between 0 and 1.

18. The method according to claim 15, wherein the polyoxometalate is selected from the group consisting of polymolybdate, polytungstate, polyvanadate and mixtures thereof.

19. The method according to claim 15, wherein the starting interlayer anions are carbonates.

20. The method according to claim 19, wherein the layered double hydroxide is hydrotalcite.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1a provides a schematic representation of the structure of a LDH, that consists of positively charged stacked layers with charge-balancing anions A.sup.n and water molecules located in the interlayer regions.

(2) FIG. 1b provides a schematic representation of the structure of a ZnAl LDH. Each layer of this hydrotalcite-like material is made of octahedral units that share edges to form infinite sheets. Each octahedral unit consist in a metal cation, either Zn.sup.2+ or Al.sup.3+, coordinated by 6 hydroxyl groups FIG. 2 shows the principle of the method for exchanging interlayer anions of a layered double hydroxide according to the invention, applied to a starting LDH in order to synthetize a LDH-X with X.sup.n anions as interlayer anions, via the preparation of a LDH-POM mediator. Both exchange steps are carried out in a solution containing the anions that are to be intercalated in the considered step, whose pH is such that the exchange is favored.

(3) FIG. 3a shows the evolution over time of ATR-IR (Attenuated Total ReflectionInfra Red) spectra of a LDH undergoing step (1) of the method according to the invention for exchanging interlayer anions. More precisely, the starting anions are carbonates, and the POM anions are polymolybdate anions. Carbonate and polymolybdate ions band are located at 1370 cm.sup.1 and 920 cm.sup.1, respectively. The LDH resulting from step (1) is referred below as LDH-Mo7.

(4) FIG. 3b displays only the initial (dashed line) and the final spectra (continuous black line), that is to say the spectra of the LDH before the exchange and at the end of the exchange respectively.

(5) FIG. 4 illustrates the Mo(VI) speciation in function of pH using MEDUSA software and the corresponding database.

(6) FIG. 5 corresponds to the Raman spectra of the commercial LDH undergoing step (1) of the method according to the invention (dashed line) and the resulting LDH-Mo7 (full line). Carbonate and heptamolybdate ions band are located at 1100 cm.sup.1 and 950 cm.sup.1, respectively.

(7) FIG. 6 shows the proof of the exchange of polymolybdate by methyl orange according to step (2) of the claimed method in a LDH-Mo7. Indeed, the solution that initially contains methyl orange has lost its orange coloration after being in contact with the LDH-Mo7, as one can see on the right-hand side of the picture, while the LDH has turned orange. On the left-hand side of the picture, one can see that the direct exchange of carbonates with methyl orange does not take place in the commercial hydrotalcite.

(8) FIG. 7 corresponds to the Raman spectra of the LDH-Mo7 undergoing step (2) of the method according to the invention (black line) and the resulting LDH having methyl orange as interlayer anions (grey line). Heptamolybdate and methyl orange ions band are located at 950 cm.sup.1 and above 1000 cm.sup.1, respectively.

(9) FIG. 8 shows the principle of the use of the method according to the invention for extracting anions.

(10) FIG. 9 illustrates the W(VI) speciation in function of pH using MEDUSA software and thermodynamic data from literature [Cruywagen, Adv. Inorg. Chem. 2000, 49, 127-182; Cruywagen et al. J. Chem. Soc., Dalton Trans. 1987, No. 7, 1701-1705].

(11) FIG. 10 corresponds to the normalized IR-ATR spectra of the LDH-Ibu sample resulting from step (2) and having Ibuprofen as interlayer anions (dark line), and of the resulting LDH after the same sorption protocol applied on a commercial carbonated LDH (grey line). According to the literature [Mara L et al. Journal of Colloid and Interface Science. 351 (2010) 134-139], the bands at 1545 cm.sup.1 and 1360 cm.sup.1 (dark line) correspond to the asymmetric and symmetric modes of the carboxylate group of the ibuprofen respectively.

(12) FIG. 11 corresponds to the normalized IR-ATR spectra of the LDH-Pic sample resulting from step (2) and having Picloram as interlayer anions (black line), and of the resulting LDH after the same sorption protocol applied on a commercial carbonated LDH (grey line). According to the literature [Luis H et al. Quim. Nova, Vol. 38, No. 1, 71-76, 2015], the band at 1600 cm.sup.1 and the bands in the range of 1300-1550 cm.sup.1 (dark line) correspond to the carbonyl stretching vibration and CC pyridine ring vibrations respectively of Picloram molecule.

(13) FIG. 12 corresponds to the normalized IR-ATR spectra of the LDH-Pic sample resulting from step (2) and having Picloram as interlayer anions (black line), and of the LDH-Pic-Des sample after exchange of Picloram (grey line) in the LDH-Pic in rainwater conditions. The bands corresponding to the Picloram vibration are not present (grey line), that indicates the release of Picloram under rainwater conditions.

DETAILED DESCRIPTION AND ADDITIONAL EMBODIMENTS

(14) The present invention concerns a method for exchanging interlayer anions of a layered double hydroxide (LDH) with other anions whose affinity for the LDH is lower than the one of the starting interlayer anions, which comprises the successive steps of: (1) exchanging the starting interlayer anions of a layered double hydroxide with polyoxometalate anions in order to obtain a layered double hydroxide with polyoxometalate anions as interlayer anions, and (2) exchanging the polyoxometalate anions of the layered double hydroxide obtained in step (1) with other anions whose affinity for the LDH is lower than the one of the starting interlayer anions in order to obtain a layered double hydroxide with other anions as interlayer anions.

(15) In the context of the present invention, layered double hydroxide refers to inorganic materials that consist of positively charged stacked layers with charge-balancing anions located in the interlayer regions. They can be described with the general formula [M.sup.II.sub.1-xM.sup.III+.sub.x(OH).sub.2].sup.x+A.sup.n.sub.x/n.mH.sub.2O where: M.sup.II and M.sup.III represent metal cations of valence z and 3 respectively, with z being generally equal to 1 or 2, x corresponds to the molar ratio of M.sup.III/(M.sup.II+M.sup.III) and also the net charge carried by a layer, A.sup.n stands for the interlayer anion of valence n, and m is a positive number.
M.sup.II can be selected from the group consisting of Ca.sup.2+, Mg.sup.2+, Mn.sup.2+, Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+, Zn.sup.2+ and 2Li.sup.+.
M.sup.III can be selected from the group consisting of Al.sup.3+, Mn.sup.3+, Fe.sup.3+, Co.sup.3+, Cr.sup.3+ and Ni.sup.3+.
x can be comprised between 0 and 1, preferably between 0.1 and 0.8 and more preferably between 0.2 and 0.4.

(16) Preferably, z is equal to 2, and the LDH can be described with the general formula [M.sup.2+.sub.1-xM.sup.3+.sub.x(OH).sub.2]A.sup.n.sub.x/n.mH.sub.2O where: M.sup.2+ and M.sup.3+ represent metal cations of valence 2 and 3 respectively, x corresponds to the molar ratio of M.sup.3+/(M.sup.2++M.sup.3+) and also the net charge carried by a layer, A.sup.n stands for the interlayer anion of valence n, and m is a positive number.
M.sup.2+ can be selected from the group consisting of Ca.sup.2+, Mg.sup.2+, Mn.sup.2+, Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+ and Zn.sup.2+.
M.sup.3+ can be selected from the group consisting of Al.sup.3+, Mn.sup.3+, Fe.sup.3+, Co.sup.3+, Cr.sup.3+ and Ni.sup.3+.
x can be comprised between 0 and 1, preferably between 0.1 and 0.8 and more preferably between 0.2 and 0.4.

(17) The LDH layers general formula is thus [M.sup.II.sub.1-xM.sup.III.sub.x(OH).sub.2].sup.x+, wherein: M.sup.II and M.sup.III represent metal cations of valence z and 3 respectively, with z being generally equal to 1 or 2, preferably 2, and x corresponds to the molar ratio of M.sup.III/(M.sup.II+M.sup.III) and also the net charge carried by a layer.
M.sup.II can be selected from the group consisting of Ca.sup.2+, Mg.sup.2+, Mn.sup.2+, Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+, Zn.sup.2+ and 2Li.sup.+.
M.sup.III can be selected from the group consisting of Al.sup.3+, Mn.sup.3+, Fe.sup.3+, Co.sup.3+, Cr.sup.3+ and Ni.sup.3+.
x can be comprised between 0 and 1, preferably between 0.1 and 0.8 and more preferably between 0.2 and 0.4.

(18) In particular, M.sup.II can be Mg.sup.2+ and M.sup.III can be Al.sup.3+.

(19) The interlayer anion A.sup.n according to the invention may be the starting anion, a polyoxometalate anion, another anion, or a second anion.

(20) The starting interlayer anions according to the invention are the anions that are originally located in the interlayer regions of the starting LDH.

(21) In the method according to the present invention, any starting anions can be used. In particular, the starting anions may be monovalent or multivalent, organic or inorganic. In a preferred embodiment, the starting anions are carbonates.

(22) In a most preferred embodiment, the starting layered double hydroxide is hydrotalcite.

(23) In the context of the present invention, polyoxometalate anions, abbreviated POM, refers to polyatomic anions, that contain three or more transition metal oxyanions linked together by shared oxygen atoms, notably 5 or more, in particular 7 or more.

(24) The transition metal is usually a group 6 metal such as molybdenum (Mo) or tungsten (W), or a group 5 metal like vanadium (V), niobium (Nb) or tantalum (Ta), in their higher stable oxidation states. It can also be a mixture of these atoms. Preferably, it is Mo, W, or V.

(25) A POM can be described with the general formula [M.sub.mO.sub.y].sup.p, where y and p are positive numbers, and m is greater than or equal to 3, notably greater than or equal to 5, in particular greater than or equal to 7.

(26) A POM can also contain a main group metal, and if so is referred to as a hetero-polyoxometalate, that can be described with the general formula [X.sub.xM.sub.mO.sub.y].sup.p where x, y and p are positive numbers, m is greater than x and greater than or equal to 3, notably greater than or equal to 5, in particular greater than or equal to 7. X can be phosphorus (P) or silicon (Si).

(27) In both formulas above, M can be a group 6 metal such as molybdenum (Mo) or tungsten (W), or a group 5 metal like vanadium (V), niobium (Nb) or tantalum (Ta), in their higher stable oxidation states, or a mixture of these atoms. Preferably, M corresponds to one type of atom, such as Mo, W, or V.

(28) POMs are characterized by very high negative charge (p in the formulas above), usually superior or equal to 2, preferably superior or equal to 3, more preferably superior or equal to 5, and present thus an important affinity for the positively charged layers of a LDH.

(29) In a preferred embodiment, the polyoxometalate involved in the method according to the invention is selected from the group consisting of polymolybdate, polytungstate, polyvanadate and mixtures thereof.

(30) POMs mostly form at acidic pH, and tend to depolymerize to give the corresponding oxometalate anions, whose charge is lower than the one of the initial POM (in terms of absolute value), and is preferably inferior or equal to 2, when the pH increases (FIGS. 4 and 9).

(31) In the context of the present invention, oxometalate anions, refers to oxyanions containing at least a transition metal atom, including POM.

(32) The other anions according to the invention are the anions that are exchanged with the polyoxometalate anions during step (2). They are also different from the starting interlayer anions.

(33) Their affinity for the LDH layers is inferior to the one of the starting anions. This means that the direct exchange of the starting interlayer anions of the LDH with the other anions is not possible. The affinity of an anion depends in the first place on its charge (the more negative the species to exchange, the higher its affinity towards LDHs) then on its geometry which can allow a stabilization by H-binding [Prasanna and Vishnu Kamath, Ind. Eng. Chem. Res. 48, 6315-6320 (2009)].

(34) The other anions may be monovalent or multivalent, inorganic anions (NO.sub.3.sup., halides, etc.) or organic anions (drugs as Ibuprofen or Naproxen, agrochemicals as Picloram or Glyphosate, etc.).

(35) By exchange is meant in the present invention that at the microscopic scale, a given anion (starting, polyoxometalate or other anion) is replaced by another anion (polyoxometalate, other anion or second anion). At the macroscopic scale, the exchange may or may not be total, but at least some of the anions have been exchanged.

(36) The duration of the anion exchange according to the invention can range from 1 hour to 3 days, notably from 8 to 30 hours.

(37) In a preferred embodiment, the exchanging step (1) is carried out in a solution containing oxometalate anions, such as an aqueous solution, whose pH is such that polyoxometalate anions are formed and the affinity of the LDH layers for the polyoxometalate anions is higher than its affinity for the starting anions.

(38) In particular, the solution containing the oxometalate anions has a pH between 4 and 6, notably about 5.

(39) The oxometalate anions concentration in the solution can range from 0.1 mM to 1 M, notably from 1 mM to 0.1 M, more particularly from 1 mM to 10 mM.

(40) In another preferred embodiment the exchanging step (2) is carried out in a solution containing the other anions, such as an aqueous solution, whose pH is such that the polyoxometalate anions depolymerize to give oxometalate anions other than polyoxometalate anions and the affinity of the LDH layers for the said oxometalate anions is lower than its affinity for the other anions.

(41) In particular, the pH of the solution containing the other anions is higher than 6, notably higher than 6.5. The pH of the solution containing the other anions can in particular have a pH between 6 and 13, such as between 6 and 9. More particularly, the pH of the solution containing the other anions has a pH between 6.5 and 13, such as between 6.5 and 9.

(42) Preferably, the charge of the oxometalate anions is lower than the one of the initial POM (in terms of absolute value), and is preferably inferior or equal to 2.

(43) The other anions concentration in the solution can range from 0.1 mM to 1 M, notably from 1 mM to 0.1 M, and more preferably from 1 mM to 10 mM.

(44) The method according to the present invention allows an easy access to LDHs with various types of interlayer anions.

(45) Depending on the envisioned further applications of the LDH resulting from the method according to the invention, the other anions may be catalysts, drugs, biomolecules, anti-corrosive agents, etc.

(46) The LDH resulting from the method according to the invention can be in various forms, such as powder, fixed-bed column, monolithic or hybrid polymer-LDH forms, or also be part of a composite material.

(47) The method according to the present invention can be used also for the extraction of the other anions. In this case, steps (1) and (2) are advantageously followed by an additional step (3) of:

(48) (3) exchanging the other anions of the layered double hydroxide obtained in step (2) with second anions, in order to obtain a layered double hydroxide with second anions as interlayer anions.

(49) The second anions refers to the anions that are exchanged in place of the other anions during step (3), when present.

(50) The second anions may be monovalent or multivalent, organic or inorganic anions.

(51) Preferably the second anions are identical to the starting anions, and the method according to the invention can be used for extracting the other anions from a solution, and allows the regeneration of the starting LDH, that can hence be reused for at least another cycle.

(52) Most preferably, the starting and second anions are carbonates.

(53) Therefore, the present invention also relates to the use of a method for extracting other anions contained in a liquid medium. Step (2) of the method is performed in a solution containing the other anions, whose pH is adjusted so that polyoxometalate anions depolymerize to give oxometalate anions other than polyoxometalate anions and the affinity of the LDH layers for the said oxometalate anions is lower than its affinity for the other anions.

(54) The other anions are afterwards exchanged in step (3) of the method with second anions.

(55) Preferably, the second anions are identical to the starting anions, and more preferably are carbonates, so that the LDH obtained at the end of step (3) can be recycled and used for performing at least another cycle of steps (1), (2) and (3) (FIG. 8).

(56) The examples that follow illustrate the invention without limiting its scope in any way.

EXAMPLES

(57) 1. Preparation of LDHs Exchanged with POMs (Step (1))

(58) A commercial carbonated hydrotalcite (Mg.sub.6Al.sub.2(CO.sub.3)(OH).sub.16.4H.sub.2O; Sigma-Aldrich, ref. 652288) has been used. The experimental procedure consisted in stirring a 3.3 g/L suspension of LDH in a 10.sup.2 M molybdate sodium aqueous solution (200 mL). A pH value of 5 was imposed by addition of small volumes (approximately 50 L) of HNO.sub.3 using an automatic titrator (Metrohm, software Tiamo). This addition was performed in 1 hour, then the suspension was stirred at a stabilized pH during 19 hours.

(59) The exchange has been followed by recording ATR-IR spectra of suspension aliquots after different durations. The procedure consisted in filtrating 5 ml of the suspension, followed by rinsing with 3 ml of deionized water, then resuspension in 1 ml of water. Then, 1 L of this suspension was dried on the Attenuated Total Reflection element to get the spectrum: the decrease of the carbonate ion band was found to be correlated to the growth of the polymolybdate band (FIGS. 3a and 3b). In these conditions (pH, concentration), molybdate forms a highly-charged heptamer, namely Mo.sub.7O.sub.24.sup.6 (in different protonation states, as it can be seen in FIG. 4). This fully-deprotonated species, present at low concentration, has a high affinity towards LDH, much higher than the one of carbonate ions. After the exchange step, the solid was filtered, rinsed by HNO.sub.3 pH 4 to keep molybdate ion as a heptamer, then dried in a silica gel filled dessicator.

(60) The solid obtained after this step has been characterized by micro-Raman spectroscopy (FIG. 5), and the results confirmed that a LDH with Mo.sub.7O.sub.24.sup.6 interlayer anions has been obtained, in agreement with literature [Ciocan et al. Catal. Today 2012, 198 (1), 239-245]. The solid is referred as LDH-Mo7 in the following.

(61) 2. Preparation of LDHs Exchanged with Other Anions (Step (2))

(62) 2.1. With Methyl Orange

(63) The exchange of methyl orange has been chosen to demonstrate the POM mediator way to intercalate low-affinity anion. This ion is characterized by only one negative charge (sulfonate). It is easily titrated by spectrophotometry due to its orange color.

(64) ##STR00001##

(65) The exchange has been performed by mixing 4.6 mg of LDH-Mo7 in 30 ml of 9 mM methyl orange solution under a nitrogen flux to avoid CO.sub.2 dissolution. pH has been increased from 5.7 to 6.8 using sodium hydroxide. The total duration of the experiment was 24 h. A blank has been performed using the same protocol with commercial (carbonated) LDH. After the exchange, the solids have been filtered and rinsed with 2 ml of deionized water. In FIG. 6, a picture of solutions and solids after reaction are shown.

(66) The commercial LDH remained white, while LDH-Mo7 became orange. Solutions have been analyzed by spectrophotometry: no decrease of methyl orange concentration has been observed for the solution of the experiment with commercial LDH, while a decrease by 57% has been measured for the solution of the experiment with LDH-Mo7. Analyses by micro-Raman (FIG. 7) have shown the presence of methyl orange band in the solid, along with the disappearance of polymolybdate bands.

(67) These analyses demonstrate that the LDH with methyl orange anions has been prepared with the process according to the invention, which is not possible by a direct exchange step with a carbonated LDH, due to the low affinity of the methyl orange anion for the layers in comparison to carbonate.

(68) Uptake of methyl orange was achieved because the pH has been chosen beyond the stability domain of heptamolybdate (FIG. 4). Around pH 6.7, the depolymerization of heptamolybdate takes place, and methyl orange can enter the LDH structure.

(69) 2.2. With Ibuprofen or Picloram

(70) Two organic molecules have been chosen to demonstrate the application fields of POM mediator way to intercalate low-affinity anion in LDH, i.e. ibuprofen and picloram.

(71) The incorporation of drug anions as ibuprofen in LDH presents a wide range of pharmaceutical applications. In this case, the release mechanisms of drugs consist in its dissolution at low pH values (pH around 1.2 in the gastric fluid). Ibuprofen is characterized by a low hydrophobicity at high pH and a negative charge (carboxylate). The solid obtained after this exchange is referred as LDH-Ibu in the following.

(72) ##STR00002##

(73) The incorporation of herbicid as picloram in LDH presents a wide range of phytosanitary applications. In this case, the release mechanism of herbicide is by anions exchange, at moderately low pH values (pH between 4 at 5.5 corresponding to rainwater pH), in presence of competitive anions such as carbonate. Picloram is characterized by a negative charge (carboxylate) at neutral to basic pH. The solid obtained after this exchange is referred as LDH-Pic in the following.

(74) ##STR00003##

(75) In both cases, the preparation of the molecule-laden LDHs has been performed by two consecutive exchange steps of ibuprofen or picloram on LDH-Mo7. The first sorption has been performed by mixing 6.6 mg of LDH-Mo7 in 20 ml of 0.13 M ibuprofen solution, or by mixing 6.6 mg of LDH-Mo7 in 20 ml of 50 mM picloram solution. Sorptions were performed under a nitrogen flux to avoid CO.sub.2 dissolution. pH has been increased from 5.7 to 12 using sodium hydroxide. The total duration of the experiments was 24 h. After the first exchange, the solid has been centrifuged, sonicated and washed with 2 ml of deionized water twice. Then, the second sorption has been performed with the same experimental conditions as previously, for the two organic molecules respectively: the solid from the first sorption has been mixed in 20 ml of 0.13 M ibuprofen solution, or in 20 ml of 0.13 M picloram solution, under a nitrogen flux at pH 12 during 24 h. The resulting solid has been rinsed in the same way as previously described. Blanks have been performed using the same protocol with commercial (carbonated) LDH.

(76) ICP-OES analysis and IR-ATR (InfraredAttenuated total reflection) spectra have been performed on the three solids: LDH-Mo7, LDH-Ibu, LDH-Pic. Analyses by IR-ATR have shown the presence of Ibuprofen (FIG. 10) or Picloram (FIG. 11) bands in the solid (black lines), along with the disappearance of polymolybdate bands. No appearance of Ibuprofen or Picloram bands are observable in the experiment with carbonated LDH. The resulting remaining amounts of molybdate ions, after Picloram or Ibuprofen sorption, is shown in the table below.

(77) TABLE-US-00001 Sample LDH-Mo7 LDH-Ibu LDH-Pic Mass percentage of 49.1 0.2 1.0 Molybdate in sample Mass percentage of 0 39 44 organic molecule

(78) The exchange of molybdate is almost total, 99.6% and 98% of molybdate are desorbed during Ibuprofen and Picloram exchange steps respectively. The theoretical amounts of organic molecules have been calculated from residual heptamolybdate amount and positive charge of the LDH, assuming carboxylated molecules (monoanions). The resulting solid contents a high amount of molecules, as expected.

(79) These results demonstrate that the LDH with Picloram or Ibuprofen anions has been prepared with the process according to the invention, which is not possible by a direct exchange step with a carbonated LDH, due to the low affinity of theses organic anions for the layers in comparison to carbonate. These examples illustrate the large application fields of POM mediator way to intercalate anions of interest.

(80) 3. Release of Picloram and Ibuprofen Molecules from LDH-Pic and LDH-Ibu

(81) The release of Ibuprofen would occur by dissolution of the LDH-Ibu at acidic pH (pH around 1.2 corresponding to the gastric fluid). The release step of Picloram in soils would be a leaching by the rainwater by anionic exchange with carbonate ions. Experimentally, the exchange has been performed by mixing 6.6 mg of LDH-Pic, in 20 ml of 151 M carbonate solution at pH 5. The total duration of the experiments was 24 h. Then, the solid has been centrifuged, sonicated and washed with 2 ml of deionized water twice time. FIG. 12 shows the comparative band of the same LDH-Pic sample before (black line) and after (grey line) the release of picloram in rainwater conditions. Analyzes by IR-ATR have shown the disappearance of Picloram bands in rainwater conditions, corresponding to a total release of Picloram molecules, replaced by carbonate ions.