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通过磁性纳米颗粒催化剂与定制的降冰片二烯光开关相结合的分子太阳能热电池

Molecular Solar Thermal Batteries through Combination of Magnetic Nanoparticle Catalysts and Tailored Norbornadiene Photoswitches.

作者信息

Lorenz Patrick, Luchs Tobias, Hirsch Andreas

机构信息

Department of Chemistry and Pharmacy, Institute of Organic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nikolaus-Fiebiger-Strasse 10, 91058, Erlangen, Germany.

出版信息

Chemistry. 2021 Mar 12;27(15):4993-5002. doi: 10.1002/chem.202005427. Epub 2021 Feb 22.

Abstract

Cobalt catalysts are immobilized on the surface of iron oxide nanoparticles for the preparation of highly active quasi-homogeneous catalysts toward an efficient release of photochemically stored energy in norbornadiene-based photoswitches. The facile separation of the iron oxide nanoparticles through exploitation of the intrinsic magnetic properties of this material enables efficient cyclization of energy storage and release. Through the transition from cobalt (II) salphen to cobalt porphyrins, a 22.6-fold increase in the catalytic efficiency of the QC-NBD back-conversion is achieved, with an initial TOF of up to 3.64 s and excellent TON of over 3305. In addition, a series of novel "push-pull" functionalized norbornadiene derivatives is prepared, featuring excellent absorption properties with maxima up to 366 nm, quantum yields around 70 %, high energy storage capacities of up to 98.0 kJ mol , and outstanding thermal stability with t (25 °C) over 100 days. Finally, the energy storage potential of these molecular solar thermal (MOST) systems is harnessed in a heat release experiment. This demonstrates the potential of norbornadiene-based photoswitches in combination with efficient magnetic catalysts for the generation of environmentally benign process heat.

摘要

钴催化剂固定在氧化铁纳米颗粒表面,用于制备高活性的准均相催化剂,以实现基于降冰片二烯的光开关中光化学储存能量的高效释放。利用该材料的固有磁性可轻松分离氧化铁纳米颗粒,从而实现能量存储和释放的高效环化。通过从钴(II)双水杨醛缩邻苯二胺向钴卟啉的转变,QC-NBD反向转化的催化效率提高了22.6倍,初始TOF高达3.64 s,TON超过3305。此外,还制备了一系列新型的“推-拉”功能化降冰片二烯衍生物,其具有优异的吸收性能,最大吸收波长可达366 nm,量子产率约为70%,高储能容量可达98.0 kJ mol,在25℃下的热稳定性超过100天。最后,在放热实验中利用了这些分子太阳能热(MOST)系统的储能潜力。这证明了基于降冰片二烯的光开关与高效磁性催化剂相结合在产生环境友好型过程热方面的潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e4be/7986914/e2961037e624/CHEM-27-4993-g005.jpg

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