Substrate−molecule vibronic coupling enhancement, especially the efficient photoinduced charge transfer (PICT), is pivotal to the performance of nonmetal surface-enhanced Raman scattering (SERS) technology. Here, through developing novel two-dimensional (2D) amorphous TiO 2 nanosheets (a-TiO 2 NSs), we successfully obtained an ultrahigh enhancement factor of 1.86 × 10 6 . Utilizing the Kelvin probe force microscopy (KPFM) technology, we found that these 2D a-TiO 2 NSs possessed more positive surface potential than their 2D crystalline counterpart (c-TiO 2 NSs). First-principles density functional theory (DFT) was used to further reveal that the low coordination number of surface Ti atoms and the large amount of surface oxygen defects endowed the 2D a-TiO 2 with high electrostatic potential, which allowed significant charge transfer from the adsorbed molecule to the 2D a-TiO 2 and facilitated the formation of a stable surface charge-transfer (CT) complex. Significantly, comparing with the 2D c-TiO 2 , the smaller band gap and higher electronic density of states (DOS) of the 2D a-TiO 2 effectively enhanced the vibronic coupling of resonances in the substrate−molecule system. The strong vibronic coupling within the CT complex obviously enhanced the PICT resonance and lead to the remarkable SERS activity of a-TiO 2 NSs. To the best of our knowledge, this is the first report on the remarkable SERS activity of 2D amorphous semiconductor nanomaterials, which may bring the cutting edge of development of stable and highly sensitive nonmetal SERS technology.
Enhancement of the semiconductor-molecule interaction, in particular, promoting the interfacial charge transfer process (ICTP), is key to improving the sensitivity of semiconductor-based surface enhanced Raman scattering (SERS). Herein, by developing amorphous ZnO nanocages (a-ZnO NCs), we successfully obtained an ultrahigh enhancement factor of up to 6.62×10 . This remarkable SERS sensitivity can be attributed to high-efficiency ICTP within a-ZnO NC molecule system, which is caused by metastable electronic states of a-ZnO NCs. First-principles density functional theory (DFT) simulations further confirmed a stronger ICTP in a-ZnO NCs than in their crystalline counterparts. The efficient ICTP can even generate π bonding in Zn-S bonds peculiar to the mercapto molecule adsorbed a-ZnO NCs, which has been verified through the X-ray absorption near-edge structure (XANES) characterization. To the best of our knowledge, this is the first time such remarkable SERS activity has been observed within amorphous semiconductor nanomaterials, which could open a new frontier for developing highly sensitive and stable SERS technology.
A Cu O superstructure is constructed through a recrystallization-induced self-assembly strategy. Single Cu O superstructure particle exhibits an outstanding surface-enhanced Raman spectroscopy performance with the limit of detection as low as 10 mol L and metal comparable enhancement factor (8 × 10 ) due to the synergetic effect of vacancies defect-facilitated charge-transfer process and copper vacancies defect-induced electrostatic adsorption.
A renewable-biomolecule-based full lithium-ion battery is successfully fabricated for the first time. Naturally derivable emodin and humic acid based electrodes are used as cathode and anode, respectively. The as-assembled batteries exhibit superb specific capacity and substantial operating voltage capable of powering a wearable electronic watch, suggesting the great potential for practical applications with the significant merits of sustainability and biocompatibility.
Semiconductor-based surface enhanced Raman scattering (SERS) has attracted great attention due to its excellent spectral reproducibility, high uniformity, and good anti-interference ability. However, its relatively low SERS sensitivity still hinders its further developments in both performance and applications. Since the SERS is a peculiar surface effect, investigating the facet-dependent SERS activity of semiconductor nanostructures is crucial to boost their SERS signals. Although the semiconductor facet-dependent SERS effect is predicted via numerical calculations, convincing experimental evidence is scarce due to complicated and undefined surface conditions. In this work, three facet-defined ({100}, {110}, and {111} facets) Cu O microcrystals (MCs) with clear surface atomic configuration are utilized to investigate the facet-dependent SERS effect. The results from the Kelvin probe force microscopy measurements on single Cu O polyhedron, demonstrate that the facet-dependent work function plays a crucial role in the interfacial charge transfer process. Comparing with the {110} and {111} facets, the {100} facet possesses the lowest electronic work function, which enables more efficient interfacial charge transfer. The simulation results further confirm that the {100}-facets can transfer the most electrons from Cu O MCs to molecules due to its lowest facet work function, resulting in the largest increment of the molecular polarization.
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