University of Crete, Department of Chemistry, Laboratory of Bioinorganic Chemistry, Voutes Campus, Heraklion, Crete, Greece.
Departamento de Química en Ciencias Farmacéuticas, Universidad Complutense de Madrid, 28040 Madrid, Spain.
Chem Soc Rev. 2022 Aug 15;51(16):6965-7045. doi: 10.1039/d2cs00183g.
The increasing energy demand and environmental issues caused by the over-exploitation of fossil fuels render the need for renewable, clean, and environmentally benign energy sources unquestionably urgent. The zero-emission energy carrier, H is an ideal alternative to carbon-based fuels especially when it is generated photocatalytically from water. Additionally, the photocatalytic conversion of CO into chemical fuels can reduce the CO emissions and have a positive environmental and economic impact. Inspired by natural photosynthesis, plenty of artificial photocatalytic schemes based on porphyrinoids have been investigated. This review covers the recent advances in photocatalytic H production and CO reduction systems containing porphyrin or phthalocyanine derivatives. The unique properties of porphyrinoids enable their utilization both as chromophores and as catalysts. The homogeneous photocatalytic systems are initially described, presenting the various approaches for the improvement of photosensitizing activity and the enhancement of catalytic performance at the molecular level. On the other hand, for the development of the heterogeneous systems, numerous methods were employed such as self-assembled supramolecular porphyrinoid nanostructures, construction of organic frameworks, combination with 2D materials and adsorption onto semiconductors. The dye sensitization on semiconductors opened the way for molecular-based dye-sensitized photoelectrochemical cells (DSPECs) devices based on porphyrins and phthalocyanines. The research in photocatalytic systems as discussed herein remains challenging since there are still many limitations making them unfeasible to be used at a large scale application before finding a large-scale application.
由于化石燃料的过度开采导致能源需求不断增加和环境问题日益严重，因此对可再生、清洁和环境友好型能源的需求变得非常迫切。零排放能源载体 H 是碳基燃料的理想替代品，特别是当它通过光催化从水中产生时。此外，通过光催化将 CO 转化为化学燃料可以减少 CO 排放，对环境和经济具有积极影响。受自然光合作用的启发，人们研究了大量基于卟啉类的人工光催化方案。本综述涵盖了包含卟啉或酞菁衍生物的光催化 H 生产和 CO 还原系统的最新进展。卟啉类化合物的独特性质使其既可用作发色团，也可用作催化剂。最初描述了均相光催化系统，介绍了提高光敏化活性和在分子水平上增强催化性能的各种方法。另一方面，为了开发非均相系统，采用了许多方法，例如自组装超分子卟啉类纳米结构、构建有机框架、与二维材料结合以及吸附到半导体上。半导体上的染料敏化为基于卟啉和酞菁的分子基染料敏化光电化学电池 (DSPEC) 器件开辟了道路。正如本文所讨论的那样，光催化系统的研究仍然具有挑战性，因为仍然存在许多限制，使得它们在找到大规模应用之前无法在大规模应用中使用。
