This paper presents a p–n heterojunction photoanode based on a p-type porphyrin metal–organic framework (MOF) thin film and an n-type rutile titanium dioxide nanorod array for photoelectrochemical water splitting. The TiO₂@MOF core–shell nanorod array is formed by coating an 8 nm thick MOF layer on a vertically aligned TiO₂ nanorod array scaffold via a layer-by-layer self-assembly method. This vertically aligned core–shell nanorod array enables a long optical path length but a short path length for extraction of photogenerated minority charge carriers (holes) from TiO₂ to the electrolyte. A p–n junction is formed between TiO₂ and MOF, which improves the extraction of photogenerated electrons and holes out of the TiO₂ nanorods. In addition, the MOF coating significantly improves the efficiency of charge injection at the photoanode/electrolyte interface. Introduction of Co(Ⅲ) into the MOF layer further enhances the charge extraction in the photoanode and improves the charge injection efficiency. As a result, the photoelectrochemical cell with the TiO₂@Co-MOF nanorod array photoanode exhibits a photocurrent density of 2.93 mA/cm² at 1.23 V (vs. RHE), which is ~ 2.7 times the photocurrent achieved with bare TiO₂ nanorod array under irradiation of an unfiltered 300 W Xe lamp with an output power density of 100 mW/cm².

A facile synthetic approach has been developed to prepare uniform and size-tunable spiky Au@Ag core-shell nanoparticles (NPs) to tailor the localized surface plasmon resonance (LSPR) properties. The gradual assembly of small Au nanocrystals allows the size of spiky Au NPs to be modulated from tens to several hundreds of nanometers by tuning the concentration of initial Au seeds and Au source; and the thickness of the Ag shell can be adjusted with stepwise reduction of Ag(Ⅰ) ions. The LSPR bands of such spiky Au@Ag core-shell NPs resemble those of pure spiky Au NP cores of similar sizes in near-infrared region, and increasing the Ag shell thickness results in a blue shift and broadening of the LSPR band in the near-infrared region. Additionally, the spiky Au@Ag core-shell NPs exhibit improved surface-enhanced Raman scattering (SERS) activity as compared to the bare spiky Au NPs and spherical Ag@Au NPs. This work has offered a facile route to synthesize plasmonic metal NPs with LSPR band in 650 to 800 nm that show strong enhancement of localized electromagnetic field, which provides an effective SERS substrate for SERS imaging and detection in biological fluids and tissues.

Inexpensive copper nanoparticles are generally thought to possess weak and broad localized surface plasmon resonance (LSPR). The present experimental and theoretical studies show that tailoring the Cu nanoparticle to a cubic shape results in a single intense, narrow, and asymmetric LSPR line shape, which is even superior to round-shaped gold nanoparticles. In this study, the dielectric function of copper is decomposed into an interband transition component and a free-electron component. This allows interband transition-induced plasmon damping to be visualized both spectrally and by surface polarization charges. The results reveal that the LSPR of Cu nanocubes originates from the corner mode as it is spectrally separated from the interband transitions. In addition, the interband transitions lead to severe damping of the local electromagnetic field but the cubic corner LSPR mode survives. Cu nanocubes display an extinction coefficient comparable to the dipole mode of a gold nanosphere with the same volume and show a larger local electromagnetic field enhancement. These results will guide development of inexpensive plasmonic copper-based nanomaterials.

Approximately 15 nm thick nitrogen-doped lanthanum titanate (La₂Ti₂O₇) nanosheets with a single-crystalline perovskite structure have been prepared by hydrothermal processing and subsequent heat treatment in NH₃ at 600 ℃. Doping nitrogen into the La₂Ti₂O₇ nanosheets results in the narrowing of the band gap, extending the light absorption into the visible light region (~495 nm). The nitrogen-doped La₂Ti₂O₇ nanosheets not only show significant visible light photocatalytic activity toward the decomposition of methyl orange but also exhibit enhanced the ultraviolet light photocatalytic activity. The enhancement of photocatalytic activity originates from the narrowing of the band gap of La₂Ti₂O₇ nanosheets. The results obtained show that the desirable route to extend the photocatalytic activity of a semiconductor from the ultraviolet to the visible light region is to narrow the band gap rather than to create localized mid-gap states.