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We report surface modification of TiO 2  colloids with amino phosphonic and carboxylic acids that covalently bind to the surface of TiO 2  and at the same time chelate copper ions and attach them to the colloid surface. Correlation of the structural (FTIR and XAFS), dynamic (EPR), and redox (CV) properties of surface modified TiO 2  colloidal particles has provided principles for the design of an optimal surface modifier for the reduction of Cu 2+  ions. The change in the oxidation state of copper was determined by XAFS spectroscopies. It was found that the surface modifier must contain a carboxyl group to effectively bind to the colloid surface and at the same time bind metallic ions. Alanine adsorbs the largest quantities of Cu 2+  ions in the dark due to the existence of a stable complex that bridges surface Ti and Cu 2+  ions through the carboxyl group. In this way Cu 2+  becomes covalently linked to the particle surface, and the reduction occurs more effectively than without surface modifiers. In the presence of a current doubling agent, the reduction of copper was doubled. We found with XANES that in the case of surface modification with amino phosphonic or carboxylic acids all reduced copper has Cu-Cu distances consistent with the metallic form of copper. A simple photo-nano-lithography device producing conducting patterns is demonstrated.

Photoreduction of Copper on TiO 2 Nanoparticles Modified with Polydentate Ligands