Water-Stable, Nonsiliceous Hybrid Materials with Tunable Porosity and Functionality: Bridged Titania-Bisphosphonates,Chemistry of Materials

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Water-Stable, Nonsiliceous Hybrid Materials with Tunable Porosity and Functionality: Bridged Titania-Bisphosphonates
Chemistry of Materials ( IF 7.2 ) Pub Date : 2020-03-23 , DOI: 10.1021/acs.chemmater.9b05095
Yanhui Wang ₁ , Johan G. Alauzun ₁ , P. Hubert Mutin ₁

Affiliation

Combining the properties of organic and inorganic moieties with high surface areas and pore volumes offers endless possibilities to design materials adapted to a wide range of advanced applications. The vast majority of mesoporous hybrid materials are siliceous materials, and developing low-cost synthetic methodologies leading to water stable nonsiliceous hybrid materials with controlled texture and functionality is essential. We report here an original strategy for the synthesis of mesoporous bridged titania-bisphosphonate hybrids based on a one-step, templateless nonhydrolytic sol–gel route. The reaction of Ti(OⁱPr)₄ and a rigid bisphosphonate ester in the presence of Ac₂O leads to the formation of TiO₂ anatase nanorods cross-linked by fully condensed bisphosphonate groups. The porosity can be readily adjusted over a wide range by changing the reaction conditions, and very high specific surface areas (up to 720 m² g^–1) and pore volumes (up to 1.85 cm³ g^–1) can be reached. The texture is stable in aqueous media between pH 1 and pH 12. Furthermore, accessible functional organic groups can be easily incorporated using either functional bisphosphonates or easily available monophosphonate compounds. The accessibility of bipyridyl organic groups was checked by Cu²⁺ adsorption from aqueous solutions. The unique combination of texture, functionality, and stability displayed by bridged titania-bisphosphonates makes these promising materials complementary of other hybrid materials such as organosilicas, MOFs, or mesoporous metal phosphonates.

中文翻译：

具有可调孔隙率和功能的耐水，非硅质杂化材料：桥接的二氧化钛-双膦酸盐

将有机和无机部分的特性与高表面积和孔体积相结合，为设计适合多种高级应用的材料提供了无限可能。绝大多数介孔杂化材料是硅质材料，开发低成本的合成方法以形成具有受控质地和功能的水稳定性非硅质杂化材料至关重要。我们在此报告了一种基于一步法，无模板的非水解溶胶-凝胶路线的介孔桥接二氧化钛-双膦酸酯杂化物合成的原始策略。Ti（O ⁱ Pr）₄和刚性双膦酸酯在Ac ₂ O存在下的反应导致TiO ₂的形成锐钛矿型纳米棒通过完全缩合的双膦酸酯基团交联。通过改变反应条件，可以很容易地在宽范围内调节孔隙率，并且可以实现非常高的比表面积（最大720 m ² g ^–1）和孔体积（最大1.85 cm ³ g ^–1）。在pH 1和pH 12之间的水性介质中，质地稳定。此外，可以使用功能性双膦酸酯或容易获得的单膦酸酯化合物轻松掺入可及的官能有机基团。Cu ²⁺检查联吡啶有机基团的可及性从水溶液中吸附。桥接的二氧化钛-双膦酸酯显示出的质地，功能和稳定性的独特组合，使这些有前途的材料成为有机硅，MOF或中孔金属膦酸酯等其他杂化材料的补充。

更新日期：2020-04-23

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