Evidence for an Interface of Hybrid Cocatalysts Favoring Photocatalytic Hydrogen Evolution Kinetics.

Hybrid cocatalysts have great application potential for improving the photocatalytic hydrogen evolution performance of semiconductors. The interfaces between components of hybrid cocatalysts make a great contribution to the improvement, but the associated mechanisms remain unclear. Herein, we prepared and tested three comparative CdS-based photocatalysts with NiS, NiS/Ni9S8, and Ni9S8 as the cocatalysts separately. The emphasis is placed on investigating the effect of the NiS/Ni9S8 interfaces on the photocatalytic hydrogen evolution performance of CdS. NiS/Ni9S8 exhibits a higher ability than NiS and Ni9S8 in making CdS a more active photocatalyst for water splitting. It shows that NiS, NiS/Ni9S8, and Ni9S8 perform similarly in terms of promoting the charge transfer and separation of CdS based on steady-state and time-resolved photoluminescence studies. At the same time, the linear sweep voltammetry and electrochemical impedance spectroscopy tests combined with the density functional theory calculations reveal that the component interfaces of NiS/Ni9S8 enable us to lower the water splitting activation energy, the charge-transfer resistance from the cocatalyst to sacrificial agent, and hydrogen adsorption Gibbs free energy. It is evidenced from this work that component interfaces of hybrid cocatalysts play a vital role in accelerating the dynamics of hydrogen evolution reactions.

Upconversion nanoparticles@single-walled carbon nanotubes composites as efficient self-monitored photo-thermal agents.

Conventional photothermal therapy (PTT) usually relies on a macroscopic heat source to raise the temperature of tissues to 41-45 °C, which not only kills the pathological cells but causes severe side effects on nearby normal tissues, thus reducing the accuracy of PTT. Here we successfully fabricated nanocomposites of NaYF4:Yb3+,Tm3+@NaYF4:Yb3+@SiO2-SWCNTs, in which the upconversion nanoparticles (UCNPs) serve as real-time temperature-feedback moiety and the single-walled carbon nanotubes (SWCNTs) serve as efficient nano-heaters. The sample displays an excellent photothermal conversion capacity, i.e., the temperature of the aqueous dispersion increases from 23.3 °C up to 60.1 °C under 980 nm excitation due to the intense absorption and highly efficient heat generation of SWCNTs. Meanwhile, the temperature of the nanocomposites is monitored in real time based on the fluorescent intensity ratio of UCNPs. The in-vitro experiments demonstrate that the temperature of the nanocomposites at tissue injection of 1 mm can reach PTT temperature of 42.2 °C with a facile surrounding temperature of 36.2 °C under moderate laser power (980 nm, 2.0 W cm-2). These results provide a novel design for multifunctional nanocomposites that enable safe and controlled PTT.

Efficient fabrication of single-wall carbon nanotube nanoreactors by defect-induced cutting.

Single-wall carbon nanotubes (SWCNTs) with ultra-thin channels are considered promising nanoreactors for confined catalysis, chemical reactions, and drug delivery. The fabrication of SWCNT nanoreactors by cutting usually suffers from low efficiency and poor controllability. Here we develop a defect-induced gas etching method to efficiently cut SWCNTs and to obtain nanoreactors with ultrasmall confined space. H2 plasma treatment was performed to generate defects in the walls of SWCNTs, then H2O vapor was used as a "knife" to cut SWCNTs at the defect sites, and short cut-SWCNTs with an average length of 175 nm were controllably obtained with a high yield of 75% under optimized conditions. WO3@SWCNT derivatives with different morphologies were synthesized using short cut-SWCNTs as nanoreactors. The radiation resistance of WO3@SWCNT hybrids improved obviously, thus providing a platform for the synthesis of novel SWCNT-based derivatives with fascinating properties.