鑽石舞台｜痞客邦

光催化CO2轉化獲得高價值化學品是緩解全球變暖、促進可持續碳循環、實現碳中和目標的理想途徑之一。致力於實現高活性、高選擇性CO2轉化的光催化材料研發因而成為能源環境領域的重要研究方向。金屬有機骨架材料（metal-organic framework, MOF）作為一類新興的多孔晶體材料已成為多領域的研究熱點。近年來，一些MOF被報道具有類半導體性質和良好的可見光吸收，有望成為潛在的新型光催化材料。特別是MOF的特定基團和孔道結構可進一步負載功能組分從而豐富其應用功能。單原子催化（Single-atom catalysis, SAC）即通過構建單一金屬催化位點顯著提升催化效率甚至獲得意外產物選擇性，因而在催化領域備受關注。而MOF的特定基團，如：金屬氧團簇或有機配體等恰能為單原子提供配位原子，實現構型精確且局域微環境可控的單原子位點構建，有望進一步提升MOF基光催化劑的光催化CO2轉化活性及選擇性。

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Sep 18 Sun 2022 03:30
MOFs在線 - MOFs@Top J：2022.09.11-2022.09.17

Organo-macrocycle-containing hierarchical metal–organic frameworks and cages: design, structures, and applications

Chemical Society Reviews，Pub Date:2022-09-16,

DOI:10.1039/d2cs00232aYu Liang, Errui Li, Kunyu Wang, Zong-Jie Guan, Hui-hui He, Liangliang Zhang, Hong-Cai Zhou, Feihe Huang, Yu Fang

Developing hierarchical ordered systems is challenging. Using organo-macrocycles to construct metal–organic frameworks (MOFs) and porous coordination cages (PCCs) provides an efficient way to obtain hierarchical assemblies. Macrocycles, such as crown ethers, cyclodextrins, calixarenes, cucurbiturils, and pillararenes, can be incorporated within MOFs/PCCs and they also endow the resultant composites with enhanced properties and functionalities. This review summarizes recent developments of organo-macrocycle-containing hierarchical MOFs/PCCs, emphasizing applications and structure–property relationships of these hierarchically porous materials. This review provides insights for future research on hierarchical self-assembly using macrocycles as building blocks and functional ligands to extend the applications of the composites.

https://pubs.rsc.org/en/content/articlelanding/2022/cs/d2cs00232a

A Covalent Organic Framework for Cooperative Water Oxidation

Journal of the American Chemical Society，Pub Date:2022-09-15, DOI:10.1021/jacs.2c07282Suvendu Karak, Vladimir Stepanenko, Matthew A. Addicoat, Philipp Keßler, Simon Moser, Florian Beuerle, Frank Würthner

The future of water-derived hydrogen as the 「sustainable energy source」 straightaway bets on the success of the sluggish oxygen-generating half-reaction. The endeavor to emulate the natural photosystem II for efficient water oxidation has been extended across the spectrum of organic and inorganic combinations. However, the achievement has so far been restricted to homogeneous catalysts rather than their pristine heterogeneous forms. The poor structural understanding and control over the mechanistic pathway often impede the overall development. Herein, we have synthesized a highly crystalline covalent organic framework (COF) for chemical and photochemical water oxidation. The interpenetrated structure assures the catalyst stability, as the catalyst’s performance remains unaltered after several cycles. This COF exhibits the highest ever accomplished catalytic activity for such an organometallic crystalline solid-state material where the rate of oxygen evolution is as high as ∼26,000 μmol L–1s–1(second-order rate constantk≈ 1650 μmol L s–1g–2). The catalyst also proves its exceptional activity (k≈ 1600 μmol L s–1g–2) during light-driven water oxidation under very dilute conditions. The cooperative interaction between metal centers in the crystalline network offers 20–30-fold superior activity during chemical as well as photocatalytic water oxidation as compared to its amorphous polymeric counterpart.

https://pubs.acs.org/doi/full/10.1021/jacs.2c07282

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