The chemical inertness of the defect-free basal plane confers environmental stability to MoS single layers, but it also limits their chemical versatility and catalytic activity. The stability of pristine MoS basal plane against oxidation under ambient conditions is a widely accepted assumption however, here we report single-atom-level structural investigations that reveal that oxygen atoms spontaneously incorporate into the basal plane of MoS single layers during ambient exposure. The use of scanning tunnelling microscopy reveals a slow oxygen-substitution reaction, during which individual sulfur atoms are replaced one by one by oxygen, giving rise to solid-solution-type 2D MoSO crystals. Oxygen substitution sites present all over the basal plane act as single-atom reaction centres, substantially increasing the catalytic activity of the entire MoS basal plane for the electrochemical H evolution reaction.
Construction of cellular architectures has been expected to enhance materials' mechanical tolerance and to stimulate and broaden their efficient utilizations in many potential fields. However, hitherto, there have been rather scarce developments in boron nitride (BN)-type cellular architectures because of well-known difficulties in the syntheses of BN-based structures. Herein, cellular-network multifunctional foams made of interconnective nanotubular hexagonal BN (h-BN) architectures are developed using carbothermal reduction-assisted in situ chemical vapor deposition conversion from N-doped tubular graphitic cellular foams. These ultralight, chemically inert, thermally stable, and robust-integrity (supporting about 25,000 times of their own weight) three-dimensional-BN foams exhibit a 98.5% porosity, remarkable shape recovery (even after cycling compressions with 90% deformations), excellent resistance to water intrusion, thermal diffusion stability, and high strength and stiffness. They remarkably reduce the coefficient of thermal expansion and dielectric constant of polymeric poly(methyl methacrylate) composites, greatly contribute to their thermal conductivity improvement, and effectively limit polymeric composite softening at elevated temperatures. The foams also demonstrate high-capacity adsorption-separation and removal ability for a wide range of oils and organic chemicals in oil/water systems and reliable recovery under their cycling usage as organic adsorbers. These created multifunctional foams should be valuable in many high-end practical applications.
The importance for
the global carbon cycle, the P–T phase diagram of CaCO3 has
been under extensive investigation since the invention of the high-pressure
techniques. However, this study is far from being completed. In the
present work, we show the existence of two new high-pressure polymorphs
of CaCO3. The crystal structure prediction performed here
reveals a new polymorph corresponding to distorted aragonite structure
and named aragonite-II. In situ diamond anvil cell experiments confirm
the presence of aragonite-II at 35 GPa and allow identification of
another high-pressure polymorph at 50 GPa, named CaCO3-VII.
CaCO3-VII is a structural analogue of CaCO3-P21/c-l, predicted theoretically
earlier. The P–T phase diagram
obtained based on a quasi-harmonic approximation shows the stability
field of CaCO3-VII and aragonite-II at 30–50 GPa
and 0–1200 K. Synthesized earlier in experiments on cold compression
of calcite, CaCO3-VI was found to be metastable in the
whole pressure–temperature range.
Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on NiN nanostructure (NiN@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The NiN@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that NiN and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior NiN from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.
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