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用于磷酸盐水解的铈基固相催化剂作为下一代纳米结构的新工具。

Ce-based solid-phase catalysts for phosphate hydrolysis as new tools for next-generation nanoarchitectonics.

作者信息

Komiyama Makoto

机构信息

Research Center for Advanced Science and Technology (RCAST), The University of Tokyo, Tokyo, Japan.

出版信息

Sci Technol Adv Mater. 2023 Sep 8;24(1):2250705. doi: 10.1080/14686996.2023.2250705. eCollection 2023.

Abstract

This review comprehensively covers synthetic catalysts for the hydrolysis of biorelevant phosphates and pyrophosphates, which bridge between nanoarchitectonics and biology to construct their interdisciplinary hybrids. In the early 1980s, remarkable catalytic activity of Ce ion for phosphate hydrolysis was found. More recently, this finding has been extended to Ce-based solid catalysts (CeO and Ce-based metal-organic frameworks (MOFs)), which are directly compatible with nanoarchitectonics. Monoesters and triesters of phosphates, as well as pyrophosphates, were effectively cleaved by these catalysts. With the use of either CeO nanoparticles or elegantly designed Ce-based MOF, highly stable phosphodiester linkages were also hydrolyzed. On the surfaces of all these solid catalysts, Ce and Ce coexist and cooperate for the catalysis. The Ce activates phosphate substrates as a strong acid, whereas the Ce provides metal-bound hydroxide as an eminent nucleophile. Applications of these Ce-based catalysts to practical purposes are also discussed.

摘要

本综述全面涵盖了用于生物相关磷酸盐和焦磷酸盐水解的合成催化剂,这些催化剂在纳米结构与生物学之间架起桥梁,以构建它们的跨学科杂化物。20世纪80年代初,人们发现铈离子对磷酸盐水解具有显著的催化活性。最近,这一发现已扩展到与纳米结构直接兼容的铈基固体催化剂(CeO和铈基金属有机框架(MOF))。这些催化剂能有效裂解磷酸盐的单酯和三酯以及焦磷酸盐。使用CeO纳米颗粒或精心设计的铈基MOF时,高度稳定的磷酸二酯键也能被水解。在所有这些固体催化剂的表面,Ce(III)和Ce(IV)共存并协同催化。Ce(IV)作为强酸活化磷酸盐底物,而Ce(III)提供与金属结合的氢氧化物作为优良的亲核试剂。本文还讨论了这些铈基催化剂的实际应用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d0e/10494760/8ec849d33f05/TSTA_A_2250705_UF0001_OC.jpg

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