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 λ > 455 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.
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.
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 evolution using g-N-CD (7950 μmol (g ) h ) 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 (Hase) for reduction of protons to H. The tunable surface chemistry of the CDs was exploited to synthesize positively charged ammonium-terminated CDs (CD-NHMe), which were capable of transferring photoexcited electrons directly to the negatively charged enzymes with high efficiency and stability. Enzyme-based turnover numbers of 6000 mol succinate (mol FccA) and 43,000 mol H (mol Hase) were reached after 24 h. Negatively charged carboxylate-terminated CDs (CD-CO) displayed little or no activity, and the electrostatic interactions at the CD-enzyme interface were determined to be essential to the high photocatalytic activity observed with CD-NHMe. The modular surface chemistry of CDs together with their photostability and aqueous solubility make CDs versatile photosensitizers for redox enzymes with great scope for their utilization in photobiocatalysis.
The unique properties exhibited by nanoscale materials, coupled with the multitude of chemical surface derivatisation possibilities, enable the rational design of multifunctional nanoscopic devices. Such functional devices offer exciting new opportunities in medical research and much effort is currently invested in the area of "nanomedicine", including: multimodal imaging diagnostic tools, platforms for drug delivery and vectorisation, polyvalent, multicomponent vaccines, and composite devices for "theranostics". Here we will review the surface derivatisation of nanoparticulate oxides of iron and iron@iron-oxide core-shells. They are attractive candidates for MRI-active therapeutic platforms, being potentially less toxic than lanthanide-based materials, and amenable to functionalisation with ligands. However successful grafting of groups onto the surface of iron-based nanoparticles, thus adding functionality whilst preserving their inherent properties, is one of the most difficult challenges for creating truly useful nanodevices from them. Functionalised catechol-derived ligands have enjoyed success as agents for the masking of superparamagnetic iron-oxide particles, often so as to render them biocompatible with medium to long-term colloidal stability in the complex chemical environments of biological milieux. In this perspective, the opportunities and limitations of functionalising the surfaces of iron-oxide nanoparticles, using coatings containing a catechol-derived anchor, are analysed and discussed, including recent advances using dopamine-terminated stabilising ligands. If light-driven ligand to metal charge transfer (LMCT) processes, and pH-dependent ligand desorption, leading to nanoparticle degradation under physiologically relevant conditions can be suppressed, colloidal stability of samples can be maintained and toxicity ascribed to degradation products avoided. Modulation of the redox behaviour of iron catecholate systems through the introduction of an electron-withdrawing substituent to the aromatic π-system of the catechol is a promising approach towards achieving these goals.
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.A no rder of magnitude improvement has been realized in the rate of solar (AM1.5G) H 2 evolution using g-N-CD (7950 mmol H2 (g CD ) À1 h À1 )c ompared to undoped CDs.All graphitized CDs show significantly enhanced light absorption compared to amorphous CDs (a-CD) yet undoped g-CD displaylimited photosensitizer ability due to lowe xtraction of photogenerated charges.T ransient absorption spectroscopys howed 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.T hus,n itrogen doping allows the high absorption coefficient of graphitic CDs to be translated into high charge extraction for efficient photocatalysis.
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 (XV 2+ ) 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.
Visible light irradiation of CGIS nanoparticles with a Ni salt displayed superior sacrificial H2 evolution activity than when employing the precious metals Pt, Rh and Ru.
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