ABSTRACT
Nanoporous carbons are very attractive for various applications including energy storage. Templating methods with assembled amphiphilic molecules or porous inorganic templates are typically used for the synthesis. Amongst the different members of this family, CMK-5-like structures that are constructed to consist of sub-10 nm amorphous carbon nanotubes and ultrahigh specific surface area due to their thin pore walls, have the best properties in various respects. However, the fabrication of such hollow-structured mesoporous carbons entails elaborately tailoring the surface properties of the template pore walls and selecting specific carbon precursors. Thus, very limited cases are successful. Herein, a versatile and general silanol-assisted surface-casting method to create hollow-structured mesoporous carbons and heteroatom-doped derivatives with numerous organic molecules (e.g., furfuryl alcohol, resol, 2-thiophene methanol, dopamine, tyrosine) and different structural templates is reported. These carbon materials exhibit ultrahigh surface area (2400 m2 g-1 ), large pore volume (4.0 cm3 g-1 ), as well as satisfactory lithium-storage capacity (1460 mAh g-1 at 0.1 A g-1 ), excellent rate capability (320 mAh g-1 at 5 A g-1 ), and very outstanding cycling performance (2000 cycles at 5 A g-1 ).
ABSTRACT
Sodium-ion batteries stand a chance of enabling fast charging ability and long lifespan while operating at low temperature (low-T). However, sluggish kinetics and aggravated dendrites present two major challenges for anodes to achieve the goal at low-T. Herein, we propose an interlayer confined strategy for tailoring nitrogen terminals on Ti3C2 MXene (Ti3C2-Nfunct) to address these issues. The introduction of nitrogen terminals endows Ti3C2-Nfunct with large interlayer space and charge redistribution, improved conductivity and sufficient adsorption sites for Na+, which improves the possibility of Ti3C2 for accommodating more Na atoms, further enhancing the Na+ storage capability of Ti3C2. As revealed, Ti3C2-Nfunct not only possesses a lower Na-ion diffusion energy barrier and charge transfer activation energy, but also exhibits Na+-solvent co-intercalation behavior to circumvent a high de-solvation energy barrier at low-T. Besides, the solid electrolyte interface dominated by inorganic compounds is more beneficial for the Na+ transfer at the electrode/electrolyte interface. Compared with of the unmodified sample, Ti3C2-Nfunct exhibits a twofold capacity (201 mAh g-1), fast-charging ability (18 min at 80% capacity retention), and great superiority in cycle life (80.9%@5000 cycles) at - 25 °C. When coupling with Na3V2(PO4)2F3 cathode, the Ti3C2-Nfunct//NVPF exhibits high energy density and cycle stability at - 25 °C.
ABSTRACT
The 1,3-conjugated diynes are an important class of chemical intermediates, and the selective crosscoupling of terminal alkynes is an efficient chemical process for manufacturing asymmetrical 1,3-conjugated diynes. However, it often occurs in homogenous conditions and costs a lot for reaction treatment. Herein, a copper catalyzed strategy is used to synthesize highly ordered mesoporous nitrogen-doped carbon material (OMNC), and the copper species is in situ transformed into the copper single-atom site with four nitrogen coordination (CuN4 ). These features make the CuN4 /OMNC catalyst efficient for selective oxidative crosscoupling of terminal alkynes, and a wide range of asymmetrical and symmetrical 1,3-diynes (26 examples) under mild conditions (40 °C) and low substrates ratio (1.3). Density functional theory (DFT) calculations reveal that the aryl-alkyl crosscoupling has the lowest energy barrier on the CuN4 site, which can explain the high selectivity. In addition, the catalyst can be separated and reused by simply centrifugation or filtration. This work can open a facile avenue for constructing single-atom loaded mesoporous materials to bridge homogeneous and heterogeneous catalysis.
