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Performing quantitative in situ spectroscopic analysis on minuscule sample volumes is a common difficulty in photochemistry. To address this challenge, we use a hollow-core photonic crystal fiber (HC-PCF) that guides light at the center of a microscale liquid channel and acts as an optofluidic microreactor with a reaction volume of less than 35 nL. The system was used to demonstrate in situ optical detection of photoreduction processes that are key components of many photocatalytic reaction schemes. The photoreduction of viologens (XV2+) to the radical XV•+ in a homogeneous mixture with carbon nanodot (CND) light absorbers is studied for a range of different carbon dots and viologens. Time-resolved absorption spectra, measured over several UV irradiation cycles, are interpreted with a quantitative kinetic model to determine photoreduction and photobleaching rate constants. The powerful combination of time-resolved, low-volume absorption spectroscopy and kinetic modeling highlights the potential of optofluidic microreactors as a highly sensitive, quantitative, and rapid screening platform for novel photocatalysts and flow chemistry in general.

Artificial photosynthesis is the mimicry of the natural process of solar energy conversion into chemical energy carriers. Photocatalytic systems that combine light-harvesting materials and catalysts in solution or suspension provide a promising route towards this goal. A key requirement for a sustainable solar fuel production system is a low-cost, stable and non-toxic light harvester. Photoluminescent carbon nanoparticles, carbon dots (CDs), are promising emerging light-harvesters for photocatalytic fuel production systems. CDs possess many desirable properties for this purpose, such as inexpensive, scalable synthetic routes, low-toxicity and tuneable surface chemistry. In this tutorial review, the integration of CDs in photocatalytic fuel generation systems with metallic, molecular and enzymatic catalysts is discussed. An overview of CD types, synthesis and properties is given along with a discussion of tuneable CD properties that can be optimised for applications in photocatalysis. Current understanding of the photophysical electron transfer processes present in CD photocatalytic systems is outlined and various avenues for their further development are highlighted., Christian Doppler Research Association, OMV Group, Poynton PhD scholarship, Oppenheimer PhD scholarship

CuGa2In3S8 (CGIS) nanoparticles were synthesised by a hot-injection method and rendered water dispersible by modification with the hydrophilic ligand 3-mercaptopropionic acid (MPA). The CGIS nanoparticles were characterised by X-ray diffraction, transmission electron microscopy, X-ray photoelectron, diffuse reflectance and infrared spectroscopy as well as inductively coupled plasma optical emission spectroscopy. Photocatalytic H2 production using the MPA modified CGIS nanoparticles and a nickel salt under visible light irradiation was achieved from acidic solution (pH 2.6) with ascorbic acid as a sacrificial electron donor. Previously, CGIS required the presence of a precious metal co-catalyst and sulfide ions as a sacrificial reagent in alkaline solution to display photocatalytic activity for H2 generation. In the reported system, visible light irradiation of the MPA modified CGIS nanoparticles with a Ni salt displayed even superior sacrificial H2 evolution activity than when employing the precious metals Pt, Rh and Ru. An external quantum efficiency of more than 12% was achieved at λ = 540 nm, which is almost twice that previously reported for CGIS nanoparticles in the presence of a noble metal co-catalyst and sulfide ions as an electron donor.

Single-source precursor syntheses have been devised for the preparation of structurally similar graphitic carbon dots (CDs), with (g-N-CD) and without (g-CD) core nitrogen doping for artificial photosynthesis. An order of magnitude improvement has been realized in the rate of solar (AM1.5G) H$_{2}$ evolution using g-N-CD (7950 μmolH2 (gCD)$^{−1}$ h$^{−1}$ ) compared to undoped CDs. All graphitized CDs show significantly enhanced light absorption compared to amorphous CDs (a-CD) yet undoped g-CD display limited photosensitizer ability due to low extraction of photogenerated charges. Transient absorption spectroscopy showed that nitrogen doping in g-N-CD increases the efficiency of hole scavenging by the electron donor and thereby significantly extends the lifetime of the photogenerated electrons. Thus, nitrogen doping allows the high absorption coefficient of graphitic CDs to be translated into high charge extraction for efficient photocatalysis.

Light-driven enzymatic catalysis is enabled by the productive coupling of a protein to a photosensitizer. Photosensitizers used in such hybrid systems are typically costly, toxic, and/or fragile, with limited chemical versatility. Carbon dots (CDs) are low-cost, nanosized light-harvesters that are attractive photosensitizers for biological systems as they are water-soluble, photostable, nontoxic, and their surface chemistry can be easily modified. We demonstrate here that CDs act as excellent light-absorbers in two semibiological photosynthetic systems utilizing either a fumarate reductase (FccA) for the solar-driven hydrogenation of fumarate to succinate or a hydrogenase (H

Carbon quantum dots (CQDs) are established as excellent photosensitizers in combination with a molecular catalyst for solar light driven hydrogen production in aqueous solution. The inexpensive CQDs can be prepared by straightforward thermolysis of citric acid in a simple one-pot, multigram synthesis and are therefore scalable. The CQDs produced reducing equivalents under solar irradiation in a homogeneous photocatalytic system with a Ni-bis(diphosphine) catalyst, giving an activity of 398 μmolH2 (gCQD)(-1) h(-1) and a "per Ni catalyst" turnover frequency of 41 h(-1). The CQDs displayed activity in the visible region beyond λ455 nm and maintained their full photocatalytic activity for at least 1 day under full solar spectrum irradiation. A high quantum efficiency of 1.4% was recorded for the noble- and toxic-metal free photocatalytic system. Thus, CQDs are shown to be a highly sustainable light-absorbing material for photocatalytic schemes, which are not limited by cost, toxicity, or lack of scalability. The photocatalytic hybrid system was limited by the lifetime of the molecular catalyst, and intriguingly, no photocatalytic activity was observed using the CQDs and 3d transition metal salts or platinum precursors. This observation highlights the advantage of using a molecular catalyst over commonly used heterogeneous catalysts in this photocatalytic system.