Promoting Photon-to-Chemical Conversion through a Dielectric Antenna-Hybrid Bilayered Reactor Configuration.

The application of scattered light via an antenna-reactor configuration is promising for converting thermocatalysts into photocatalysts. However, the efficiency of dielectric antennas in photon-to-chemical conversion remains suboptimal. Herein, we present an effective approach to promote light utilization efficiency by designing dielectric antenna-hybrid bilayered reactors. Experimental studies and finite-difference time-domain simulations demonstrate that the engineered SiO2-carbon/metal dielectric antenna-hybrid bilayered reactors exhibit a synergy of absorption superposition and electric field confinement between carbon and metals, leading to the improved absorption of scattered light, upgraded charge carriers density, and ultimately promoted photoactivity in hydrogenating chlorobenzene with an average benzene formation rate of 18 258 µmol g-1 h-1, outperforming the reported results. Notably, the carbon interlayer proves to be more effective than the commonly explored dielectric TiO2 interlayer in boosting the benzene formation rate by over 3 times. This research paves the way for promoting near-field scattered photon-to-chemical conversion through a dielectric antenna-hybrid reactor configuration.

Engineering the Metal/Dielectric Interface to Unlock the Potential of Scattered Light for Boosted Photoredox Catalysis.

The recycling of scattered light by metals has been emerging as a promising light-manipulation-capture strategy, but how to bring its potential into better play remains to be explored. Herein, we present that constructing dual metal/high-refractive-index dielectric interfaces within the SiO2 core@TiO2 shell-Pd satellite@TiO2 shell effectively strengthens both the scattering efficiency of the dielectric SiO2 support and electric field confinement. Consequently, the absorption of Pd toward near-field scattered light and the interfacial charge carrier separation are both enhanced. The synergy of these effects leads to boosted photoactivity toward the aerobic oxidation of cyclohexanol to cyclohexanone and the anaerobic reduction of proton for hydrogen evolution under visible-light irradiation as compared to the counterparts with a single metal/dielectric interface and dual metal/dielectric interfaces consisting of low-refractive-index dielectric component. Notably, the similar enhancements in both optical absorption and photoactivity can be achieved through the present dual metal/high-refractive-index dielectric interfaces engineering strategy for other metals, such as Pt nanoparticles. This work presents an instructive avenue to upgrade the optical response of metals and thus the photocatalytic performance by engineering metal/dielectric interfaces.

A study on the role of plasmonic Ti3C2Tx MXene in enhancing photoredox catalysis.

Engineering the spatial separation and transfer of photogenerated charge carriers has been one of the most enduring research topics in the field of photocatalysis due to its crucial role in determining the performances of photocatalysts. Herein, as a proof-of-concept, Ti3C2Tx MXene is coupled with a typical heterojunction of TiO2@CdS through a co-assembly strategy to boost electron pumping towards improving the photocatalytic efficiency. In addition to the band alignment-mediated electron transfer in TiO2@CdS-Ti3C2Tx heterojunctions, the plasmon-induced electric field enhancement of Ti3C2Tx is found to cooperate with the electron-reservoir role of Ti3C2Tx to extract photoinduced electrons. The synergistic dual functions of Ti3C2Tx promote multichannel electron transfer in TiO2@CdS-Ti3C2Tx hybrids to improve the photocatalytic efficiency. These results intuitively show that there is a wide scope to manipulate the spatial separation and transfer of photoinduced electrons by cultivating the fertile ground of Ti3C2Tx toward boosting the efficiency of solar-to-chemical conversion.

Achieving High-Performance 3D K+ -Pre-intercalated Ti3 C2 Tx MXene for Potassium-Ion Hybrid Capacitors via Regulating Electrolyte Solvation Structure.

The development of high-performance anode materials for potassium-based energy storage devices with long-term cyclability requires combined innovations from rational material design to electrolyte optimization. A three-dimensional K+ -pre-intercalated Ti3 C2 Tx MXene with enlarged interlayer distance was constructed for efficient electrochemical potassium-ion storage. We found that the optimized solvation structure of the concentrated ether-based electrolyte leads to the formation of a thin and inorganic-rich solid electrolyte interphase (SEI) on the K+ -pre-intercalated Ti3 C2 Tx electrode, which is beneficial for interfacial stability and reaction kinetics. As a proof of concept, 3D K+ -Ti3 C2 Tx //activated carbon (AC) potassium-ion hybrid capacitors (PIHCs) were assembled, which exhibited promising electrochemical performances. These results highlight the significant roles of both rational structure design and electrolyte optimization for highly reactive MXene-based anode materials in energy storage devices.

Fingerprinting of Nitroaromatic Explosives Realized by Aphen-functionalized Titanium Dioxide.

Developing sensing materials for military explosives and improvised explosive precursors is of great significance to maintaining homeland security. 5-Nitro-1,10-phenanthroline (Aphen)-modified TiO2 nanospheres are prepared though coordination interactions, which broaden the absorption band edge of TiO2 and shift it to the visible region. A sensor array based on an individual TiO2/Aphen sensor is constructed by regulating the excitation wavelength (365 nm, 450 nm, 550 nm). TiO2/Aphen shows significant response to nitroaromatic explosives since the Aphen capped on the surface of TiO2 can chemically recognize and absorb nitroaromatic explosives by the formation of the corresponding Meisenheimer complex. The photocatalytic mechanism is proved to be the primary sensing mechanism after anchoring nitroaromatic explosives to TiO2. The fingerprint patterns obtained by combining kinetics and thermodynamics validated that the single TiO2/Aphen sensor can identify at least six nitroaromatic explosives and improvised explosives within 8 s and the biggest response reaches 80%. Furthermore, the TiO2/Aphen may allow the contactless detection of various explosives, which is of great significance to maintaining homeland security.

A Sensor Array Realized by a Single Flexible TiO2/POMs Film to Contactless Detection of Triacetone Triperoxide.

The homemade explosive, triacetone triperoxide (TATP), is easy to synthesize, sensitive to detonation but hard to detect directly. Vapor sensor arrays composed of a few sensor materials have the potential to discriminate TATP, but the stability of the sensor array is always a tricky problem since each sensor may encounter a device fault. Thus, a sensor array based on a single optoelectronic TiO2/PW11 sensor was first constructed by regulating the excitation wavelength to discriminate TATP from other explosives. By in situ doping of Na3PW12O40, a Keggin structure of PW11 formed on the TiO2 to promote the photoinduced electron-hole separation, thus obviously improving the detection sensitivity of the sensor film and shortening the response time. The response of the TiO2/PW11 sensor film to TATP under 365, 450 and 550 nm illumination is 81%, 42%, and 37%, respectively. The TiO2/PW11 sensor features selectivity to TATP and is able to detect less than 50 ppb. The flexibility and stability of the flexible sensor film is also demonstrated with the extent of bending. Furthermore, the sensing response cannot be affected by ambient air below 60% relative humidity.