Proceedings of MATSUS23 & Sustainable Technology Forum València (STECH23) (MATSUS23)
Publication date: 22nd December 2022
With the massive use of solid fuels as the unique source of energy to power our civilization during the last century, the troubles caused by the speed-up of climate change have been exacerbated. As a consequence, only the propel toward new clean and renewable energy sources could mitigate these effects. On this matter, the harnessing of solar irradiation has emerged as one of the most promising alternatives for providing a cheap and abundant energy source, meanwhile, the technologies for harvesting and storing it are swiftly progressing. In this context, the photocatalytic processes that involve the absorption of sunlight to efficiently drive chemical reactions have been used for the production of solar fuels (such as H2, CO, and methanol) or the synthesis of valuable organic compounds.[1] Traditionally, the most used photocatalyst for the synthesis of organic molecules has been dominated by the employment of expensive and harsh to prepare noble-metal complexes. However, despite their good efficiency and selectivity, these homogeneous photocatalysts have hampered the use of sunlight as green and sustainable energy at the industrial scale owing to the difficulties in terms of product separation, recyclability of the photoactive species, and the elevated production costs. Thus, the development of low-cost, easy-to-produce, recyclable and efficient photocatalysts remains an important challenge. In this sense, the recent rediscovery of semiconductor lead halide perovskites (LHPs) as exceptional candidates for solar energy capture and lighting applications, due to their interesting optoelectronic properties and low-cost manufacture, has brought LHPs to the spotlight of a new generation of photocatalysts. The features that make LHPs suitable to mediate photocatalytic reactions are their strong absorption in the whole UV-visible range, long excited-state lifetimes, effective charge separation and transport, and ultrafast interfacial charge transfer.[2] Here, we demonstrate the potential of CsPbBr3 nanocrystals (NCs) as photocatalysts to transfer the photogenerated charges and conduct redox reactions with electron acceptors and donors. In particular, we study the potential of LHP NCs in demanding homo- and cross-coupling reactions of different p-substituted benzyl bromides at room temperature, using visible light and an electron donor without requiring the presence of a co-catalyst. Turnover numbers (TONs) of up to 17500 are attained, the products can be straightforwardly separated and the LHPS NCs recycled. Furthermore, we claim the importance of the organic capping ligands to pre-concentrate organic substrates close to the NCs highlighting the synergy between the NC surface and the ligands shell to achieve good photocatalytic efficiencies.[3] These results shed light on the exploitation of LHPs NCs as an active photosensitizer in light-induced photocatalytic organic transformations.
We thank MCIN (PID2020-115710GB-I00), I.R.P. FPU17/05564 grant, and Generalitat Valenciana funds (PROMETEO/2019/080; IDIFEDER/2018/064).