1. Bilateral Project, Modul III, Funded by ANCS, Program PN II ‘Capacities’ Romania - India Contract no. 213 / 23.03.2009 „Development of sol-gel derived high purity aluminas for catalytic applications” Director: Dr. Maria Crisan Period: 23.03.2009 - 30.11.2009

2. ROMANIAN PARTNER InstitutionINSTITUTE OF PHYSICAL CHEMISTRY “ILIE MURGULESCU”, ROMANIAN ACADEMY AdressSplaiul Independentei, nr. 202, Bucharest, 060021, Romania Phone/fax/e-mail+40213167912 / +40213121147 / mcrisan@icf.ro, msidcrisan@yahoo.commcrisan@icf.ro Project leader Dr. Maria Crisan FOREIGN PARTNER Institution INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD, INDIA Adress Phone/fax/e-mail tel: 0091-40-27193165, fax: 0091-40-27160921, e-mail: durgakumari@iict.res.in Project leader Dr. V. Durga Kumari

3. INSTITUTE OF PHYSICAL CHEMISTRY “ILIE MURGULESCU” Dr. Maria Zaharescu Dr. Maria Crişan Dr. Mălina Răileanu Dr. Măriuca Gartner Dr. Dorel Crişan Dr. Nicolae Dragan Dr. Ana Brăileanu Dr. Luminiţa Predoana Drd. Silviu Preda Research teams ROMANIAN PARTNER FOREIGN PARTNER INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD, INDIA Dr.V.Durga Kumari Dr. M.Subrahmanyam Drd.J.Krishna Redd

4. PROJECT DESCRIPTION The aim of the proposed project is the development of sol-gel based alumina materials for catalytic applications. The unique and well- known advantage of the sol-gel process offers a beneficial alternative to the use of traditional alumina obtained by dehydration or pyrolysis of the hydrates, for catalytic process. The results obtained will give the possibility to optimize the sol-gel reactions starting from commercially available aluminium alkoxides in order to obtain nanopowders with pre-determined structure and properties. According to these results, the best materials will be recommended for catalytic applications.

5. PROJECT JUSTIFICATION Active aluminas with high surface area are well known for their use as adsorbents, catalysts, desiccants, coatings, soft abrasives and advanced polycrystalline ceramics. Reactive aluminas do not occur naturally and generally are prepared by the thermal transformation of aluminium hydroxides and alumina gels. Dehydration or pyrolysis of the hydrates results in a particulate oxide. A sol-gel process makes possible to produce a new active alumina, in transparent monolithic form, at low temperature. In the last years, the sol- gel process provides a new approach to the preparation of oxide materials and offers many advantages for making catalysts. Since homogeneous mixing can be made at the molecular scale, the chemical reactivity of the oxide surface can be greatly enhanced; thus powders with high surface area and optimized pore size distribution can be obtained. A real masterly of the sol-gel process would require an emphasis which relates chemical reactivity of the precursors to gel formation and powder morphology. The catalyst can be prepared from a homogeneous solution which includes not only the metal oxide support precursor, but also the metal precursor used as dopant. So, the sol-gel process offers many advantages for making catalysts with a uniform distribution of the active phase in the support, offering a beneficial alternative to the use of traditional aluminas obtained by dehydration or pyrolysis of the aluminium hydrates. This study will investigate the effect of Ni-modified ()-Al 2 O 3 prepared by sol-gel method on the structural and functional properties of the final catalyst. A comparative study with sol-gel pure alumina was realized. By physical-structural studies (XRD, FT-IR, BET surface area measurements and SEM), the changes induced by the introduction of the Ni precursor, before and after aluminium alkoxide hydrolysis will be highlighted.

6. Diagram of project execution Project budget Year 2009: 2 381 lei YearStage description (activities)Partner 2009 Experiments of based alumina materials (pure and Ni-doped) obtained by sol-gel method. Structural and textural characterization of synthesized materials. Romanian Catalytic test of the obtained catalysts in the test reaction.Indian

7. RESULTS Pure and Ni-doped Al 2 O 3 sol-gel nanopowders were prepared by controlled hydrolysis-condensation of aluminium isopropoxide. The influence of introduction of the Ni dopant (before and after hydrolysis) on the nanopowders structure was established. The introduction of Ni at the beginning of the reaction favours ()-Al 2 O 3 crystallization. When Ni is added at the end of reaction, it delays the alumina crystallization and induces the disorder of the lattice. This fact was confirmed by the structural parameter values (small crystallite sizes and high internal strains). The obtained catalysts were tested for glycerol reforming to generate H 2 for fuel cell applications. These results are in agreement with the structural data. Some evaluation results of Ni-doped alumina combined with TiO 2 in photocatalytic glycerol reforming reaction for hydrogen generation have been included. Ni added to the sol after hydrolysis of alumina precursor and physically combined with TiO 2 ensures the synergistic performance. The results of the researches made the object of the paper: “Some structural and textural properties of sol-gel based alumina powders with catalytic applications”, authors: M.Crişan, M.Zaharescu, V.Durga Kumari, M.Subrahmanyam, D.Crişan, N.Drăgan, M.Răileanu, J.Krishna Reddy, A. Rusu and S.Preda, which has been presented at the XV th International Sol-Gel Conference, held in Porto de Galinhas Pernambuco/Brazil- August 23-27, 2009. The paper will be published in Journal of Sol-Gel Science and Technology.