Le Zhou

MoS2/TiO2 heterostructures as nonmetal plasmonic photocatalysts for highly efficient hydrogen evolution

In this study, we report nonmetal plasmonic MoS2@TiO2 heterostructures for highly efficient photocatalytic H2 generation. Large area laminated MoS2 in conjunction with TiO2 nanocavity arrays is achieved via carefully controlled anodization, physical vapor deposition, and chemical vapor deposition processes. The broad spectral response ranging from ultraviolet-visible (UV-vis) to near-infrared (NIR) wavelengths and finite element frequency-domain simulations suggest that this MoS2@TiO2 heterostructure enhances photocatalytic activity for H+ reduction. A high H2 yield rate of 181 μmol h−1 cm−2 (equal to 580 mmol h−1 g−1 based on the loading mass of MoS2) is achieved using a low catalyst loading mass. The spatially uniform heterostructure, correlated with plasmon-resonance through the conformal MoS2 coating that effectively regulates charge transfer pathways, is proven to be vitally important for the unique solar energy harvesting and photocatalytic H2 production. As an innovative exploration, our study demonstrates that the photocatalytic activities of nonmetal, earth-abundant materials can be enhanced with plasmonic effects, which may serve as an excellent catalytic agent for solar energy conversion to chemical fuels.

Enhanced Photoelectrocatalytic Reduction of Oxygen Using Au@TiO2 Plasmonic Film

Novel Au@TiO2 plasmonic films were fabricated by individually placing Au nanoparticles into TiO2 nanocavity arrays through a sputtering and dewetting process. These discrete Au nanoparticles in TiO2 nanocavities showed strong visible-light absorption due to the plasmonic resonance. Photoelectrochemical studies demonstrated that the developed Au@TiO2 plasmonic films exhibited significantly enhanced catalytic activities toward oxygen reduction reactions with an onset potential of 0.92 V (vs reversible hydrogen electrode), electron transfer number of 3.94, and limiting current density of 5.2 mA cm-2. A superior ORR activity of 310 mA mg-1 is achieved using low Au loading mass. The isolated Au nanoparticle size remarkably affected the catalytic activities of Au@TiO2, and TiO2 coated with 5 nm Au (Au5@TiO2) exhibited the best catalytic function to reduce oxygen. The plasmon-enhanced reductive activity is attributed to the surface plasmonic resonance of isolated Au nanoparticles in TiO2 nanocavities and suppressed electron recombination. This work provides comprehensive understanding of a novel plasmonic system using isolated noble metals into nanostructured semiconductor films as a potential alternative catalyst for oxygen reduction reaction.

Periodically Patterned Au-TiO2 Heterostructures for Photoelectrochemical Sensor

Periodically patterned Au nanorods in TiO2 nanocavities (Au NRs@TiO2) were fabricated via magnetron sputtering followed by a thermal dewetting process. This innovative Au NRs@TiO2 heterostructure was used as a plasmonic sensing platform for photoelectrochemical detection of glucose and lactose. This Au NRs@TiO2 patterned heterostructure possesses superior sensing properties to other Au nanoparticle-based sensors because (i) localized surface plasmon resonance (LSPR) generated at Au/TiO2 interfaces enhanced sensitivity of glucose (lactose) amperometric detection; (ii) periodic Au nanocrystals in TiO2 nanocavities accelerated charge separation and transfer rate, especially under monochromatic blue light irradiation; (iii) discrete planar architectures comprising Au NRs immobilized on TiO2 substrates significantly improved stability and reusability of the sensors. A low detection limit of 1 μM (10 μM) and a high sensitivity of 812 μA mM-1 cm-2 (270 μA mM-1 cm-2) were achieved on the Au NRs@TiO2 heterostructures for glucose (lactose) detection without the addition of enzymes. Good selectivity and superb stability over more than 8 weeks was also demonstrated using these Au NRs@TiO2 heterostructures for glucose (lactose) detection. Additionally, this cost-efficient technique can be easily extended to other photoelectrochemical sensing systems when considering the combination of sensing and visible or infrared light source enhancement.

Freestanding NiFe Oxyfluoride Holey Film with Ultrahigh Volumetric Capacitance for Flexible Asymmetric Supercapacitors

In this work, a freestanding NiFe oxyfluoride (NiFeOF) holey film is prepared by electrochemical deposition and anodic treatments. With the combination of good electrical conductivity and holey structure, the NiFeOF holey film offers superior electrochemical performance with maximum specific capacitance of 670 F cm-3 (134 mF cm-2 ), due to the following reasons: (i) The residual metal alloy framework can be used as the current collector to improve electrode conductivity. Moreover, the as-prepared freestanding NiFeOF holey film can be used as a supercapacitor electrode without reliance on binders and other additives. The residual metal alloy framework and binder-free electrode effectively reduce electrode resistance, thus improving electron transport. (ii) The highly interconnected holey structure and hierarchical pore distribution provide a high specific surface area to improve electron transport, enhancing rapid ion transport, and mitigating diffusion limitations throughout the holey film. (iii) The excellent mechanical characteristics facilitate flexibility and cyclability related performance. Additionally, the NiFeOF holey film presents exceptional electrochemical performance, showing that it is a promising alternative for small/microsize electronic devices.