Process for preparing materials by grafting halogenated phosphorus-containing groups onto an inorganic surface

A grafting process for preparing a hybrid organic-inorganic material (HOIM) with phosphorus-containing bonds between the surface of a solid inorganic substrate containing at least one element M and one or more organic groups, said bonds being of the covalent M-O-P-R type, said process comprising

• a) pretreating solid inorganic substrate, to remove residual water comprising heating said substrate to a temperature in the range of 20° C. to 300° C. at an absolute gas pressure in the range of 0.01 Pa to 0.2 MPa and for a period in the range of 1 to 20 hours,
• b) contacting resultant pretreated inorganic substrate with an anhydrous organic solution of a precursor for said organic group or groups, wherein said precursor is constituted by at least one organophosphorus acid chloride with formula RxP(O)Xy in which x=1or 2, y=3-x, X being chlorine and R designating at least one organic alkyl, aryl or aryl-alkyl group to produce covalent M-O-P-R bonds between the organic and inorganic phases;
• c) filtering and washing the solid obtained in step b);
• d) heat treating the solid obtained in step c) at a temperature in the range 25° C. to 500° C., at an absolute air pressure in the range of 0.01 Pa to 0.2 MPa in which M is selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IA, IIA, IIIA, IVA, VA, the lanthanides and actinides of the periodic table, and
• wherein the process avoids the formation of lamellar phases in the surface of the inorganic substrate.