RESUMEN
Efficient methane photooxidation to formic acid (HCOOH) has emerged as a sustainable approach to simultaneously generate value-added chemicals and harness renewable energy. However, the persistent challenge lies in achieving a high yield and selectivity for HCOOH formation, primarily due to the complexities associated with modulating intermediate conversion and desorption after methane activation. In this study, we employ first-principles calculations as a comprehensive guiding tool and discover that by precisely controlling the O2 activation process on noble metal cocatalysts and the adsorption strength of carbon-containing intermediates on metal oxide supports, one can finely tune the selectivity of methane photooxidation products. Specifically, a bifunctional catalyst comprising Pd nanoparticles and monoclinic WO3 (Pd/WO3) would possess optimal O2 activation kinetics and an intermediate oxidation/desorption barrier, thereby promoting HCOOH formation. As evidenced by experiments, the Pd/WO3 catalyst achieves an exceptional HCOOH yield of 4.67 mmol gcat-1 h-1 with a high selectivity of 62% under full-spectrum light irradiation at room temperature using molecular O2. Notably, these results significantly outperform the state-of-the-art photocatalytic systems operated under identical condition.
RESUMEN
Ultracompact chiral plasmonic nanostructures with unique chiral light-matter interactions are vital for future photonic technologies. However, previous studies are limited to reporting their steady-state performance, presenting a fundamental obstacle to the development of high-speed optical devices with polarization sensitivity. Here, a comprehensive analysis of ultrafast chiroptical response of chiral gold nano-oligomers using time-resolved polarimetric measurements is provided. Significant differences are observed in terms of the absorption intensity, thus hot electron generation, and hot carrier decay time upon polarized photopumping, which are explained by a phenomenological model of the helicity-resolved optical transitions. Moreover, the chiroptical signal is switchable by reversing the direction of the pump pulse, demonstrating the versatile modulation of polarization selection in a single device. The results offer fundamental insights into the helicity-resolved optical transitions in photoexcited chiral plasmonics and can facilitate the development of high-speed polarization-sensitive flat optics with potential applications in nanophotonics and quantum optics.
RESUMEN
Artificial chiral nanostructures have been subjected to extensive research for their unique chiroptical activities. Planarized chiral films of ultrathin thicknesses are in particular demand for easy on-chip integration and improved energy efficiency as polarization-sensitive metadevices. Recently, controlled twisted stacking of two or more layers of nanomaterials, such as 2D van der Waals materials, ultrathin films, or traditional metasurfaces, at an angle has emerged as a general strategy to introduce optical chirality into achiral solid-state systems. This method endows new degrees of freedom, e.g., the interlayer twist angle, to flexibly engineer and tune the chiroptical responses without having to change the material or the design, thus greatly facilitating the development of multifunctional metamaterials. In this review, recent exciting progress in planar chiral metasurfaces are summarized and discussed from the viewpoints of building blocks, fabrication methods, as well as circular dichroism and modulation thereof in twisted stacked nanostructures. The review further highlights the ever-growing portfolio of applications of these chiral metasurfaces, including polarization conversion, information encryption, chiral sensing, and as an engineering platform for hybrid metadevices. Finally, forward-looking prospects are provided.