Straightforward solid-phase modification of TiO2 with propylphosphonic acid via manual grinding and shaker mixing: enhancing modification degree by thermal control while improving atom economy†

Grafting organophosphonic acids (PAs) on metal oxides has shown to be a flexible technology to tune the surface properties of metal oxides for various applications. The solvents applied in the commonly used synthesis method have associated impeding effect on tailoring the resulting modification degree. In this work, an alternative solid-phase manual grinding method is proposed that (i) is straightforward, (ii) can achieve controllable and higher modification degree, and (iii) excludes the use of solvent during the synthesis. Specifically, propylphosphonic acid (3PA) was grafted onto titania by manual grinding, and different modification degrees were obtained by varying the duration of the post-synthetic thermal treatment. Importantly, the solid-phase method can achieve a modification degree that is 25.0% higher than the maximal modification degree reached by the liquid-phase method, while its atom utilization efficiency is 4.8 times (toluene-based) or 7.5 times (water-based) that of the liquid-phase method.