一种基于菲咯啉的多孔有机聚合物，用于铱催化的二氧化碳加氢成甲酸酯<a href="#fn1" title="提供电子补充信息（ESI）。参见DOI：10.1039 / c9ta03807h">†</a>,Journal of Materials Chemistry A

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一种基于菲咯啉的多孔有机聚合物，用于铱催化的二氧化碳加氢成甲酸酯 †
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2019-05-14 00:00:00 , DOI: 10.1039/c9ta03807h
Gunniya Hariyanandam Gunasekar _{1,

2,

3,

4} , Sungho Yoon _{4,

5,

6,

7}

Affiliation

菲咯啉单元代表配位化学中最重要的配体骨架之一。在非均相催化领域，构建在聚合物骨架中具有非反应性官能团的基于菲咯啉的多孔有机聚合物是一个非常具有挑战性的目标，因为它将为掺杂分子催化模块并产生单点，稳定和多孔的非均相提供一个新颖的平台。催化实体，适用于广泛的催化应用。在这方面，一个独特的策略来构建菲咯啉基多孔有机聚合物（苯-POP），无其他反应性/聚合物骨架已被设计为在第一时间协调的官能团，并合成通过BET表面积为560 m ² g ^-1的溶剂编织的Friedel-Crafts聚合方法。明确定义和隔离的phen-POP的phen位点可作为通过N–N配位键固定过渡金属催化剂的平台。phen-POP用氯化铱（III）的合成后金属化提供了最活跃的活性（初始周转频率为40 000 h ^-1），简单且选择性的非均相Ir催化剂，用于CO ₂加氢成甲酸酯。因此，在开发用于工业上可行的氢化催化剂的新型基于POP的非均相催化剂方面，这项工作具有重要意义。

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A phenanthroline-based porous organic polymer for the iridium-catalyzed hydrogenation of carbon dioxide to formate†

The phenanthroline unit represents one of the most significant ligand frameworks in coordination chemistry. Constructing phenanthroline-based porous organic polymers with nonreactive functional groups in the polymer skeleton is a very challenging goal in the field of heterogeneous catalysis, because it would offer a novel platform for doping molecular catalytic modules and generating single-site, stable, and porous heterogeneous catalytic entities for a wide range of catalytic applications. In this regard, a unique strategy to construct phenanthroline-based porous organic polymer (phen-POP) without other reactive/coordinating functional groups in the polymer skeleton has been designed for the first time, and synthesized via a solvent knitting Friedel–Crafts polymerization method with a high BET surface area of 560 m² g⁻¹. The well-defined and isolated phen sites of the phen-POP can serve as a platform for immobilizing transition metal catalysts through N–N coordination bonds. The post-synthetic metalation of phen-POP with iridium(III) chloride afforded the most active (initial turnover frequency of 40 000 h⁻¹), simple and selective heterogeneous Ir catalyst for the hydrogenation of CO₂ to formate. Thus, the work is significant in constructing novel POP-based heterogeneous catalysts for the development of industrially viable hydrogenation catalysts.

更新日期：2019-05-14

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