Heptazine‐based polymeric carbon nitrides (PCN) are promising photocatalysts for light‐driven redox transformations. However, their activity is hampered by low surface area resulting in low concentration of accessible active sites. Herein, we report a bottom‐up preparation of PCN nanoparticles with a narrow size distribution (ca. 10±3 nm), which are fully soluble in water showing no gelation or precipitation over several months. They allow photocatalysis to be carried out under quasi‐homogeneous conditions. The superior performance of water‐soluble PCN, compared to conventional solid PCN, is shown in photocatalytic H2O2 production via reduction of oxygen accompanied by highly selective photooxidation of 4‐methoxybenzyl alcohol and benzyl alcohol or lignocellulose‐derived feedstock (ethanol, glycerol, glucose). The dissolved photocatalyst can be easily recovered and re‐dissolved by simple modulation of the ionic strength of the medium, without any loss of activity and selectivity.

Chemical vapor deposition (CVD) allows growing transition metal dichalcogenides (TMDs) over large surface areas on inexpensive substrates. In this work, we correlate the structural quality of CVD grown MoS 2 monolayers (MLs) on SiO 2 /Si wafers studied by high-resolution transmission electron microscopy (HRTEM) with high optical quality revealed in optical emission and absorption from cryogenic to ambient temperatures. We determine a defect concentration of the order of 10 13 cm −2 for our samples with HRTEM. To have access to the intrinsic optical quality of the MLs, we remove the MLs from the SiO 2 growth substrate and encapsulate them in hBN flakes with low defect density, to reduce the detrimental impact of dielectric disorder. We show optical transition linewidth of 5 meV at low temperature (T=4 K) for the free excitons in emission and absorption. This is comparable to the best ML samples obtained by mechanical exfoliation of bulk material. The CVD grown MoS 2 ML photoluminescence is dominated by free excitons and not defects even at low temperature. High optical quality of the samples is further confirmed by the observation of excited exciton states of the Rydberg series. We optically generate valley coherence and valley polarization in our CVD grown MoS 2 layers, showing the possibility for studying spin and valley physics in CVD samples of large surface area. arXiv:1907.03342v1 [cond-mat.mes-hall]

Controlling the flow rate of precursors is essential for the growth of high quality monolayer single crystals of transition metal dichalcogenides (TMDs) by chemical vapor deposition. Thus, introduction of an excess amount of the precursors affects reproducibility of the growth process and results in the formation of TMD multilayers and other unwanted deposits. Here we present a simple method for controlling the precursor flow rates using the Knudsen-type effusion cells. This method results in a highly reproducible growth of large area and high density TMD monolayers. The size of the grown crystals can be adjusted between 10 and 200 μm. We characterized the grown MoS 2 and WS 2 monolayers by optical, atomic force and transmission electron microscopies as well as by x-ray photoelectron, Raman and photoluminescence spectroscopies, and by electrical transport measurements showing their high optical and electronic quality based on the single crystalline nature.

We experimentally investigate coupling of the photoluminescence (PL) from monolayers of MoS2 to Mie-resonant metasurfaces consisting of silicon nanocylinders. By a systematic variation of the nanocylinder diameter, we sweep the metasurface resonances over the excitonic emission band of monolayer MoS2. We observe strong enhancement, as well as spectral and directional reshaping of the emission. By a comprehensive optical characterization, we unveil the different physical factors, including electronic, photonic, and mechanical influences, responsible for the observed PL changes. Importantly, we show that by geometrical tuning of the nanocylinder resonances, the emission can be tailored from occurring under very large angles to being directed out of the substrate plane. Our results highlight the need and potential of controlling not only the photonic, but also electronic and mechanical environmental factors for tailoring PL from TMD monolayers by integrating them in nanophotonic architectures.

Defect-free graphene is impermeable to gases and liquids [1][2][3][4] but highly permeable to thermal protons [5][6][7][8] . Atomic-scale defects such as vacancies, grain boundaries and Stone-Wales defects are predicted [9][10][11] to enhance graphene's proton permeability and may even allow small ions through, whereas larger species such as gas molecules should remain blocked. These expectations have so far remained untested in experiment. Here we show that atomically thin carbon films with a high density of atomic-scale defects continue blocking all molecular transport, but their proton permeability becomes ~1,000 times higher than that of defect-free graphene. Lithium ions can also permeate through such disordered graphene. The enhanced proton and ion permeability is attributed to a high density of 8-carbon-atom rings. The latter pose approximately twice lower energy barriers for incoming protons compared to the 6-atom rings of graphene and a relatively low barrier of ~0.6 eV for Li ions. Our findings suggest that disordered graphene could be of interest as membranes and protective barriers in various Li-ion and hydrogen technologies.Despite being a one-atom-thick material, no more than a few gas atoms per hour can permeate through micrometer-sized defect-free graphene membranes, as proven experimentally 3 . Even the smallest ions are blocked by the crystal 4 . These phenomena arise because the dense electron clouds of graphene's crystal lattice impose energy barriers of several eV to incoming molecular and ionic species [9][10][11] , which forbids their permeation under ambient conditions. In contrast, it has been shown experimentally that protons, nuclei of hydrogen atoms, can transport through defect-free graphene relatively easily, overcoming an energy barrier of only ≲1 eV (refs 3-6 ). In this context, theory predicts