Modularization of Regional Electronic Structure over Defect-Rich CeO2 Rods for Enhancing Photogenerated Charge Transfer and CO2 Activation.

Oxygen vacancy (OV) engineering has been widely applied in different types of metal oxide-based photocatalytic reactions. Our study has shown that the redistributed OVs resulting from voids in CeO2 rods lead to significant differences in the band structure in space. The flat energy band within the highly crystallized bulk region hinders the recombination of photogenerated carrier pairs during the transfer process. The downward curved energy band in the surface region enhances the activation of the absorbents. Therefore, the localization of the band structure through crystal structure regionalization renders V-CeO2 capable of achieving efficient utilization of photogenerated carriers. Practically, the V-CeO2 rod shows a remarkable turnover number of 190.58 µmol g-1 h-1 in CO2 photoreduction, which is ∼9.4 times higher than that of D-CeO2 (20.46 µmol g-1 h-1). The designed modularization structure in our work is expected to provide important inspiration and guidance in coordinating the kinetic behavior of carriers in OV defect-rich photocatalysts.

Does Surface Roughness Necessarily Increase the Fouling Propensity of Polyamide Reverse Osmosis Membranes by Humic Acid?

Surface roughness has crucial influence on the fouling propensity of thin film composite (TFC) polyamide reverse osmosis (RO) membranes. A common wisdom is that rougher membranes tend to experience more severe fouling. In this study, we compared the fouling behaviors of a smooth polyamide membrane (RO-s) and a nanovoid-containing rough polyamide membrane (RO-r). Contrary to the traditional belief, we observed more severe fouling for RO-s, which can be ascribed to its uneven flux distribution caused by the "funnel effect". Additional tracer filtration tests using gold nanoparticles revealed a more patchlike particle deposition pattern, confirming the adverse impact of "funnel effect" on membrane water transport. In contrast, the experimentally observed lower fouling propensity of the nanovoid-containing rough membrane can be explained by: (1) the weakened "funnel effect" thanks to the presence of nanovoids, which can regulate the water transport pathway through the membrane and (2) the decreased average localized flux over the membrane surface due to the increased effective filtration area for the nanovoid-induced roughness features. The current study provides fundamental insights into the critical role of surface roughness in membrane fouling, which may have important implications for the future development of high-performance antifouling membranes.

Porosity Development at Li-Rich Layered Cathodes in All-Solid-State Battery during In Situ Delithiation.

Structural evolutions are crucial for determining the performance of high-voltage lithium, manganese-rich layered cathodes. Moreover, interface between electrode and electrolyte plays a critical role in governing ionic transfer in all-solid-state batteries. Here, we unveil two different types of porous structure in Li1.2Ni0.2Mn0.6O2 cathode with LiPON solid-state electrolyte. Nanopores are found near the cathode/electrolyte interface at pristine state, where cation mixing, phase transformation, oxygen loss, and Mn reduction are also found. In situ Li+ extraction induces the evolution of nanovoids, initially formed near the interface then propagated into the bulk. Despite the development of nanovoids, layered structure is conserved, suggesting the nature of nanopores and nanovoids are different and their impact would be divergent. This work demonstrates the intrinsic interfacial layer, as well as the dynamic scenario of nanovoid formation inside high-capacity layered cathode, which helps to understand the performance fading in cathodes and offers insight into the all-solid-state battery design.

Size-Selective Sub-micrometer-Particle Confinement Utilizing Ionic Entropy-Directed Trapping in Inscribed Nanovoid Patterns.

We have developed a single-step, high-throughput methodology to selectively confine sub-micrometer particles of a specific size into sequentially inscribed nanovoid patterns by utilizing electrostatic and entropic particle-void interactions in an ionic solution. The nanovoid patterns can be rendered positively charged by coating with an aluminum oxide layer, which can then localize negatively charged particles of a specific size into ordered arrays defined by the nanovoid topography. On the basis of the Poisson-Boltzmann model, the size-selective localization of particles in the voids is directed by the interplay between particle-nanovoid geometry, electrostatic interactions, and ionic entropy change induced by charge regulation in the electrical double layer overlapping region. The underlying principle and developed method could potentially be extended to size-selective trapping, separation, and patterning of many other objects including biological structures.

Multi-Purpose Nanovoid Array Plasmonic Sensor Produced by Direct Laser Patterning.

We demonstrate a multi-purpose plasmonic sensor based on a nanovoid array fabricated via inexpensive and highly-reproducible direct femtosecond laser patterning of thin glass-supported Au films. The proposed nanovoid array exhibits near-IR surface plasmon (SP) resonances, which can be excited under normal incidence and optimised for specific applications by tailoring the array periodicity, as well as the nanovoid geometric shape. The fabricated SP sensor offers competitive sensitivity of ≈ 1600 nm/RIU at a figure of merit of 12 in bulk refractive index tests, as well as allows for identification of gases and ultra-thin analyte layers, making the sensor particularly useful for common bioassay experiments. Moreover, isolated nanovoids support strong electromagnetic field enhancement at lattice SP resonance wavelength, allowing for label-free molecular identification via surface-enhanced vibration spectroscopy.

Thermo-Electro-Mechanical Vibrations of Porous Functionally Graded Piezoelectric Nanoshells.

In this work, we aim to study free vibration of functionally graded piezoelectric material (FGPM) cylindrical nanoshells with nano-voids. The present model incorporates the small scale effect and thermo-electro-mechanical loading. Two types of porosity distribution, namely, even and uneven distributions, are considered. Based on Love's shell theory and the nonlocal elasticity theory, governing equations and corresponding boundary conditions are established through Hamilton's principle. Then, natural frequencies of FGPM nanoshells with nano-voids under different boundary conditions are analyzed by employing the Navier method and the Galerkin method. The present results are verified by the comparison with the published ones. Finally, an extensive parametric study is conducted to examine the effects of the external electric potential, the nonlocal parameter, the volume fraction of nano-voids, the temperature rise on the vibration of porous FGPM cylindrical nanoshells.

Toward Mechanically Stable Silicon-Based Anodes Using Si/SiO x@C Hierarchical Structures with Well-Controlled Internal Buffer Voids.

Low conductivity and structural degradation of silicon-based anodes lead to severe capacity fading, which fundamentally hinders their practical application in Li-ion batteries. Here, we report a scalable Si/SiO x@C anode architecture, which is constructed simultaneously by sintering a mixture of SiO/sucrose in argon atmosphere, followed by acid etching. The obtained structure features highly uniform Si nanocrystals embedded in silica matrices with well-controlled internal nanovoids, with all of them embraced by carbon shells. Because of the improvement of the volumetric efficiency for accommodating Si active spices and electrical properties, this hierarchical anode design enables the promising electrochemical performance, including a high initial reversible capacity (1210 mAh g-1), stable cycling performance (90% capacity retention after 100 cycles), and good rate capability (850 mAh g-1 at 2.0 A g-1 rate). More notably, the compact heterostructures derived from micro-SiO allow high active mass loading for practical applications and the facile and scalable fabrication strategy makes this electrode material potentially viable for commercialization in Li-ion batteries.