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Novel Porous Boron Nitride Nanosheet with Carbon Doping: Potential Metal-Free Photocatalyst for Visible-Light-Driven Overall Water Splitting
摘要: The band gap of hexagonal boron nitride (h-BN) is far too wide for efficiently utilizing visible light, limiting its application in photocatalysis. The present study employs first principles calculations to demonstrate that the band gap energies of porous h-BN (p-BN) can be tuned by carbon doping to levels appropriate for the absorption of visible-light, and that the conduction band and valence band match well with the potentials of both hydrogen and oxygen evolution reactions. Importantly, a strategy of carbon doping to improve the energy level of valence band maximum is also proposed. Moreover, the carbon-doped p-BN exhibits good separation between photogenerated electrons/holes and structural stability at high temperatures. The DFT results help the design of high-performance two-dimensional photocatalysts that avoid the use of metals.
关键词: metal-free catalysts,photocatalyst,porous boron nitride nanosheets,overall water splitting,band structure engineering
更新于2025-09-23 15:22:29
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Polythioethers with Controlled ?±,??a??End Groups Prepared by Visible Light Induced Thiola??Ene Click Polymerization of Dithiol and Divinyl Ether with 4a??( <i>N</i> , <i>N</i> a??diphenylamino)benzaldehyde as Organocatalyst
摘要: This study reports a step-growth click-polymerization of 1,4-benzenedimethane (BDMT) and diethylene glycol divinyl ether (DEGVE) with 4-(N,N-diphenylamino)-benzaldehyde (DPAB) as a photoredox catalyst under irradiation of visible light. DPAB exhibits a strong UV–vis absorption at 350 nm and a strong fluorescence emission at 480 nm in anisole. There is a strong fluorescence quenching between BDMT and DPAB. The molecular weight of the polythiolether can be controlled by reaction time and monomer feed ratios. More importantly, α,ω-dithiol and α,ω-divinyl telechelic polythiolether oligomers are successfully synthesized by simply changing the molar ratios of BDMT to DEGVE. 1H NMR and MALDI-TOF MS spectra demonstrate that the oligomers have high end group fidelity. In addition, strong fluorescence is observed when the α,ω-dithiol terminated polythiolether adds with N-(1-pyrenyl) maleimide, indicating that the as-prepared polythiolether bears reactive thiol end groups. Furthermore, high molecular weight polythiolether are prepared by chain extension with reactive polythiolether oligomers as macro-monomers. For example, α,ω-divinyl oligomer (Mn = 2000 g mol?1) could further react with α,ω-dithiol oligomer (Mn = 2400 g mol?1) to form high molecular weight polythiolether (Mn = 6000 g mol?1).
关键词: metal-free catalysts,thiol–ene click polymerization,photoredox catalysts,telechelic polymers,photopolymerization
更新于2025-09-19 17:13:59
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Triple-Shelled Co-VSex Hollow Nanocages as Superior Bifunctional Electrode Materials for Efficient Pt-Free Dye-Sensitized Solar Cells and Hydrogen Evolution Reactions
摘要: Complex nanostructures with distinct spatial architectures and more active sites hold broad prospects in new energy conversion fields. Herein, a facile strategy was carried out to construct triple-shelled Co-VSex nanocages, starting via an ion-exchange process about Co-based zeolitic imidazolate framework-67 (ZIF-67) nanopolyhedrons and VO3?, followed by the formation of triple-shelled Co-VSex hollow nanocages during the process of rising the solvothermal temperature under the assistance of SeO32?. Meanwhile, triple-shelled Co-VSx and yolk-double shell Co-VOx nanocages were fabricated as references by a similar process. Benefiting from the larger surface areas and more electrolyte adsorption sites, the triple-shelled Co-VSex nanocages exhibited excellent electrocatalytic performances when applied as the electrochemical catalysts for dye-sensitized solar cell (DSSC) and hydrogen evolution reaction (HER). More concretely, the DSSC based on Co-VSex counter electrode (CE) showed outstanding power conversion efficiency of 9.68% when Pt counterpart was 8.46%. Moreover, Co-VSex electrocatalyst exhibited prominent HER performance with a low onset overpotential of 40 mV and a small Tafel slope of 39.1 mV dec?1 in acid solution.
关键词: Dye-sensitized solar cells,Hydrogen evolution reactions,Pt-free catalysts,Triple-shelled nanocages,Co-VSex,Bifunctional electrocatalysts
更新于2025-09-11 14:15:04