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Heterogeneous carbon nitrides have numerous advantages as photocatalysts, including strong light absorption, tunable band edges, and scalability, but their performance and continued development are limited by fast charge recombination and an under-developed mechanistic understanding of photodriven interfacial electron transfer. These shortcomings are a result of complex photophysics, leading to rate asynchrony between oxidation and reduction, as well as redox processes driven out of electronic trap states rather than excited states. We show that a well-defined triplet excited state in cyanamide-modified carbon nitride is realized with appropriately sized particles. The utility of this long-lived excited state is demonstrated by its ability to drive a hydroamidation photoredox cycle. By the tuning of the particle size of CNx, the oxidation-reduction photochemistry of carbon nitride may be balanced to achieve a redox-neutral closed photocatalytic cycle. These results uncover a triplet excited state chemistry for appropriately sized CNx particles that preludes a rich energy and electron transfer photochemistry for these materials.

Nickel-catalysed aryl amination and etherification are driven with sunlight using a surface-modified carbon nitride to extend the absorption of the photocatalyst into a wide range of the visible region. In contrast to traditional homogeneous photochemical methodologies, the lower cost and higher recyclability of the metal-free photocatalyst, along with the use of readily available sunlight, provides an efficient and sustainable approach to promote nickel-catalysed cross-couplings., Nickel-catalysed aryl amination and etherification are driven with sunlight using a surface-modified carbon nitride to extend the absorption of the photocatalyst such that they may be driven with solar light.

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

Carbon quantum dots (CQDs) are new-generation light absorbers for photocatalytic H2 evolution in aqueous solution, but the performance of CQD-molecular catalyst systems is currently limited by the decomposition of the molecular component. Clean oxidation of the electron donor by donor recycling prevents the formation of destructive radical species and non-innocent oxidation products. This approach allowed a CQD-molecular nickel bis(diphosphine) photocatalyst system to reach a benchmark lifetime of more than 5 days and a record turnover number of 1094±61 molH2 (molNi )(-1) for a defined synthetic molecular nickel catalyst in purely aqueous solution under AM1.5G solar irradiation.

We gratefully acknowledge the following funding sources: The Marshall Aid Commemoration Commission (CMC), the Advanced Institute for Materials Research-­‐Cambridge Joint Research Centre (KLO), the Ernest Oppenheimer Fund, Cambridge (BCMM), and the EPSRC (EP/H00338X/2; ER).

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.

The novel synthesis of formic acid has been achieved in a room temperature ionic liquid via the reaction of electro-activated carbon dioxide and protons on pre-anodised platinum. Only mild reaction conditions of room temperature and 1 atm CO(2) were used. This work highlights the effect of pre-anodisation on Pt surfaces.

Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride ((NCN)CNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The (NCN)CNx-NiP system showed an activity of 763 μmol (g CNx)(-1) h(-1) toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h(-1), and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of (NCN)CNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited (NCN)CNx in the presence of an organic substrate can accumulate ultralong-lived "trapped electrons", which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel.