Photochemistry using inexhaustible solar energy is an eco‐friendly way to produce fine chemicals outside the typical laboratory or chemical plant environment. However, variations in solar irradiation conditions and the need for an external energy source to power electronic components limits the accessibility of this approach. In this work, a chemical solar‐driven “mini‐plant” centred around a scaled‐up luminescent solar concentrator photomicroreactor (LSC‐PM) was built. To account for the variations in solar irradiance at ground level and passing clouds, a responsive control system was designed that rapidly adapts the flow rate of the reagents to the light received by the reaction channels. Supplying the plant with solar panels, integrated into the module by placing it behind the LSC to utilize the transmitted fraction of the solar irradiation, allowed this setup to be self‐sufficient and fully operational off‐grid. Such a system can shine in isolated environments and in a distributed manufacturing world, allowing to decentralize the production of fine chemicals.
Sunlight strikes our planet every day with more energy than we consume in an entire year. Therefore, many researchers have explored ways to efficiently harvest and use sunlight energy for the activation of organic molecules. However, implementation of this energy source in the large-scale production of fine chemicals has been mostly neglected. The use of solar energy for chemical transformations suffers from potential drawbacks including scattering, reflections, cloud shading and poor matches between the solar emission and absorption characteristics of the photochemical reaction. In this account, we provide an overview of our efforts to overcome these issues through the development of Luminescent Solar Concentrator-based PhotoMicroreactors (LSC-PM). Such reactors can efficiently convert solar energy with a broad spectral distribution to concentrated and wavelength-shifted irradiation which matches the absorption maximum of the photocatalyst. Hence, the use of these conceptually new photomicroreactors provides an increased solar light harvesting capacity, enabling efficient solar-powered photochemistry.
Graphical abstract
Despite their abundance in organic molecules, considerable limitations still exist in synthetic methods that target the direct C−H functionalization at sp3‐hybridized carbon atoms. This is even more the case for light alkanes, which bear some of the strongest C−H bonds known in Nature, requiring extreme activation conditions that are not tolerant to most organic molecules. To bypass these issues, synthetic chemists rely on prefunctionalized alkyl halides or organometallic coupling partners. However, new synthetic methods that target regioselectively C−H bonds in a variety of different organic scaffolds would be of great added value, not only for the late‐stage functionalization of biologically active molecules but also for the catalytic upgrading of cheap and abundant hydrocarbon feedstocks. Here, we describe a general, mild and scalable protocol which enables the direct C(sp3)−H carbonylation of saturated hydrocarbons, including natural products and light alkanes, using photocatalytic hydrogen atom transfer (HAT) and gaseous carbon monoxide (CO). Flow technology was deemed crucial to enable high gas‐liquid mass transfer rates and fast reaction kinetics, needed to outpace deleterious reaction pathways, but also to leverage a scalable and safe process.
The sun is the most sustainable source of photons on
the earth
but is rarely used in photochemical transformations due its relatively
low and variable intensity, broad wavelength range, and lack of focus.
Luminescent solar concentrator-based photomicroreactors (LSC-PMs)
can be an answer to all these issues, but widespread adoption is plagued
by challenges associated with their complicated manufacturing. Herein,
we developed a new strategy to accelerate and ease the production
of LSC-PMs by depositing a thin luminescent film on commercially and
widely available silicon-based microreactors. The protocol is fast
and operationally simple, and the luminescent coating can be easily
removed and replaced. This enables rapid tuning of the luminescent
coating to fit the requirements of the photocatalytic system and to
increase the photon flux inside the microreactor channels.
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