磷酸基功能化二氧化硅材料的制备、性能和应用

Preparation,Performance and Application of Phosphate-based Functionalized Silica Material

近些年来,二氧化硅材料因低密度、低毒性、良好的生物相容性、优良的化学与热稳定性以及优异的形貌与结构的可控性而具有巨大的应用价值。对其进行改性,引入有机功能基,从而制备功能化二氧化硅材料有助于进一步提高其性能并扩展其应用范围。因优异的性能与潜在的应用价值功能化二氧化硅材料引起了众多研究者们的关注,而磷酸基功能化二氧化硅材料是其中的一个研究热点。本文归纳了磷酸基功能化二氧化硅材料的研究进展,对其制备及应用作了相关介绍。磷酸基功能化二氧化硅的制备方法主要包括磷酸硅烷偶联法和后磷酸化法。在磷酸硅烷偶联法中,基于磷酸硅烷的引入,分为后嫁接法与共缩聚法,其中后嫁接法主要是采用磷酸硅烷对二氧化硅材料进行改性,在材料表面形成硅氧硅键以引入磷酸基团;共缩聚法主要是磷酸硅烷与其他硅烷共同水解缩合,形成硅氧硅网络以引入磷酸基团。后磷酸化法中,基于反应中所形成的化学键,主要分为硅氧磷键法、碳磷键法、碳氧磷键法,其中硅氧磷键法是通过磷酸或磷酸衍生物对二氧化硅材料表面的硅羟基进行改性,通过形成硅氧磷键引入磷酸基团。碳磷键法主要是对功能化的二氧化硅进行Arbuzov反应或Mannich反应形成碳磷键以引入磷酸基团。碳氧磷键法主要是磷化试剂对环氧基功能化的二氧化硅进行改性,通过环氧开环反应,以形成碳氧磷键的方式引入磷酸基团。凭借磷酸基团优异的络合能力、充足的酸性位点、优异的质子自脱离能力、良好的生物活性以及二氧化硅本身优异的性能,磷酸基功能化二氧化硅材料在吸附、催化、电导、生物医学等方面具有优异的性能与广阔的应用价值。最后本文对磷酸基功能化二氧化硅材料未来的发展进行了展望。

In recent years,silica materials have great application value due to their low density,low toxicity,good biocompatibility,excellent chemical and thermal stability,and excellent morphology and structure controllability.Modifying it and introducing organic functional groups to prepare functionalized silica materials will help to further improve its performance and expand its scope of application.Because of its excellent performance and potential application value,functionalized silica materials have attracted the attention of many researchers,and phosphate-based functiona-lized silica materials are one of the research hotspots.This article summarizes the research progress of phosphate-based functionalized silica materials,and introduces its preparation and application.The preparation method mainly includes phosphoric acid silane coupling method and post phosphorylation method.In phosphoric acid silane coupling method,based on the introduction of phosphoric silane,it is divided into post grafting method and copolycondensation method.The post grafting method is mainly through phosphoric silane to two modification of silicon oxide materials,forming Si-O-Si bonds on the surface of the material to introduce phosphoric acid groups.The copolycondensation method is mainly to hydrolyze and condense phosphoric silane and other silanes to form a silicon-oxygen silicon network to introduce phosphoric acid groups:post-phosphorylation based on the chemical bonds formed in the reaction,it is mainly divided into Si-O-P bonding method,C-P bonding method,and C-O-P bonding method.Among them,the Si-O-P bon-ding method uses phosphoric acid or phosphoric acid derivatives to affect silicon on the surface of silica materials.Hydroxyl modification introduces phosphoric acid groups by forming siloxyphosphorus bonds.The C-P bond method is mainly to perform Arbuzov reaction or Mannich reaction on functionalized silica to form C-P bond to introduce phosphoric acid groups.The C-O-P bond method mainly involves the modification of epoxy-functionalized silica with phosphating reagents,and the introduction of phosphoric acid groups in the form of C-O-P bonds through epoxy ring opening reaction.With the excellent complexing ability of phosphoric acid groups,sufficient acidic sites,excellent proton self-detachment ability,good biological activity and excellent performance of silica itself,phosphoric acid-based functionalized silica materials have excellent performance and broad application value in adsorption,catalysis,electrical conductivity and biomedicine.Finally,we looke forward to the future development of phosphate-based functionalized silica materials.