RESUMO
Liquid methanol has the potential to be the hydrogen energy carrier and storage medium for the future green economy. However, there are still many challenges before zero-emission, affordable molecular H2 can be extracted from methanol with high performance. Here, we present noble-metal-free Cu-WC/W plasmonic nanohybrids which exhibit unsurpassed solar H2 extraction efficiency from pure methanol of 2,176.7 µmol g-1 h-1 at room temperature and normal pressure. Macro-to-micro experiments and simulations unveil that local reaction microenvironments are generated by the coperturbation of WC/W's lattice strain and infrared-plasmonic electric field. It enables spontaneous but selective zero-emission reaction pathways. Such microenvironments are found to be highly cooperative with solar-broadband-plasmon-excited charge carriers flowing from Cu to WC surfaces for efficient stable CH3OH plasmonic reforming with C3-dominated liquid products and 100% selective gaseous H2. Such high efficiency, without any COx emission, can be sustained for over a thousand-hour operation without obvious degradation.
RESUMO
Black phosphorene quantum dots (BPQDs) are most commonly derived from high-cost black phosphorus, while previous syntheses from the low-cost red phosphorus (Pred ) allotrope are highly oxidised. Herein, we present an intrinsically scalable method to produce high quality BPQDs, by first ball-milling Pred to create nanocrystalline Pblack and subsequent reductive etching using lithium electride solvated in liquid ammonia. The resultant ~25â nm BPQDs are crystalline with low oxygen content, and spontaneously soluble as individualized monolayers in tertiary amide solvents, as directly imaged by liquid-phase transmission electron microscopy. This new method presents a scalable route to producing quantities of high quality BPQDs for academic and industrial applications.
RESUMO
Defect sites present on the surface of catalysts serve a crucial role in different catalytic processes. Herein, we have investigated defect engineering within a hybrid system composed of "soft" polymer catalysts and "hard" metal nanoparticles, employing the disparity in their thermal expansions. Electron paramagnetic resonance, X-ray photoelectron spectroscopy, and mechanistic studies together reveal the formation of new abundant defects and their synergistic integrability with plasmonic enhancement within the hybrid catalyst. These active defects, co-localized with plasmonic Ag nanoparticles, promote the utilization efficiency of hot electrons generated by local plasmons, thereby enhancing the CO2 photoreduction activity while maintaining the high catalytic selectivity.