The femtosecond time-resolved multiplex coherent anti-Stokes Raman scattering (CARS) technique has been performed to investigate intramolecular vibrational redistribution (IVR) through vibrational couplings in 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) molecules. In the multiplex CARS experiment, the supercontinuum (SC) was used as broad-band Stokes light to coherently and collectively excite multiple vibrational modes, and quantum beats arising from vibrational couplings among these modes were observed. The IVR of RDX is visualized by a topological graph of these vibrational couplings, and with analysis of the topological graph, two vibrational modes, both of which are assigned to ring bending, are confirmed to have coupling interactions with most of the other vibrational modes and are considered to have a tendency of energy transfer with these vibrational modes. We suggest that the mode at 466 cm is a portal of energy transfer from outside to inside of the RDX molecule and the mode at 672 cm is an important transit point of energy transfer in the IVR.

Establishing a heterojunction for two kinds of semiconductor catalysts is a promising way to enhance photocatalytic activity. In this study, nanodiamond (ND) and CuFe-layered double hydroxide (LDH) were hybridized by a simple coprecipitation method as a novel heterojunction to photoactivate H2O2. The ND/LDH possessed a hydrotalcite-like structure, large specific surface area (SBET = 99.16 m2/g), strong absorption of visible-light and low band gap (Eg = 0.94 eV). Under the conditions of ND/LDH dosage 0.0667 g/L, H2O2 concentration 19.6 mmol/L, and without initial pH adjustment, 93.5% of 10 mg/L methylene blue (MB) was degraded within 120 minutes, while only 78.3% of MB was degraded in the presence of LDH instead of ND/LDH. The ND/LDH exhibited excellent stability and maintained relatively high activity, sufficient to photoactivate H2O2 even after five recycles. The mechanism study revealed that in the heterojunction of ND/LDH, the photoelectrons transferred from the valence band of LDH (Cu/Fe 3d t2g) to the conduction band of LDH (Cu/Fe 3d eg) could spontaneously migrate onto the conduction band of ND, promoting the separation of photo-induced charges. Thus, the photoelectrons had sufficient time to accelerate the redox cycles of Cu3+/Cu2+ and Fe3+/Fe2+ to photoactivate H2O2 to produce hydroxyl radicals, resulting in excellent photo-Fenton efficiency on MB degradation.

Using a facile top-down etching approach, a subwavelength-sized diamond pit structure infilled with semi-ellipsoidal gold nanoparticles was fabricated. The three-dimensional finite-difference time-domain simulations reveal strong localized surface plasmon resonance (LSPR) scattering and enhanced electric field exhibited by this hybrid nanoassembled metal-diamond-pit. Experimentally, with excitation at 633 and 830 nm close to the calculated LSPR wavelength, the photoluminescence (PL) intensities of the peak at 738 nm originating from the single photon source of silicon-vacancy centers in diamond were significantly enhanced by factors of ~100 and ~50, respectively, with respect to that from normal Si-doped diamond without the hybrid structure. By means of time-resolved PL measurements, the decay kinetic mechanisms of the plasmon-related PL enhancement were investigated and are discussed.

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