Anodic Electrochromism for Energy‐Efficient Windows: Cation/Anion‐Based Surface Processes and Effects of Crystal Facets in Nickel Oxide Thin Films

Anodic electrochromic (EC) oxides are of major interest as counter electrodes for smart window applications owing to their unique optical properties upon charge insertion and extraction. However, performance optimization of such oxides has been hampered by limited understanding of their EC mechanism, particularly in Li⁺‐conducting electrolytes. This paper reports on NiO_x films with 1.16 ≤ x ≤ 1.32, prepared by sputter deposition. These films are immersed in an electrolyte of lithium perchlorate in propylene carbonate, and EC properties are studied by cyclic voltammetry and in situ optical transmittance measurements. The electrochromism is significantly enhanced at large values of x. It has been found that charge exchange in Ni oxide is mainly due to surface processes and involves both cations and anions from the electrolyte, which is different from the case of cathodic EC materials such as WO₃. Whereas previous studies of Ni oxide have focused on cation intercalation, the cation/anion‐based mechanism presented here offers a new paradigm for designing and developing EC devices such as smart windows for energy efficient buildings.     

Two‐Dimensional Nanostructured Materials for Gas Sensing

Two‐dimensional (2D) nanostructures are highly attractive for fabricating nanodevices due to their high surface‐to‐volume ratio and good compatibility with device design. In recent years 2D nanostructures of various materials including metal oxides, graphene, metal dichalcogenides, phosphorene, BN and MXenes, have demonstrated significant potential for gas sensors. This review aims to provide the most recent advancements in utilization of various 2D nanomaterials for gas sensing. The common methods for the preparation of 2D nanostructures are briefly summarized first. The focus is then placed on the sensing performances provided by devices integrating 2D nanostructures. Strategies for optimizing the sensing features are also discussed. By combining both the experimental results and the theoretical studies available, structure‐properties correlations are discussed. The conclusion gives some perspectives on the open challenges and future prospects for engineering advanced 2D nanostructures for high‐performance gas sensors devices.     

蒸汽加氧吹洗新技术的研究与应用

本文着重介绍了蒸汽加氧吹洗新技术的原理及应用情况。该方法具有创造性、新颖性和实用性。解决了基建炉过热器、再热器的酸洗难题，并能在金属表面形成致密的保护膜，是提高我国吹管技术管理水平，提高水汽品质的一种有效方法。能确保机组在投产后安全、经济地运行，延长锅炉的使用寿命。如在全国范围内大力推广应用，其社会经济效益显著。     

Colossal Barocaloric Effect by Large Latent Heat Produced by First-Order Intersite-Charge-Transfer Transition

Materials which show novel thermal properties can be used to make highly efficient and environmentally friendly energy systems for thermal energy storage and refrigeration through caloric effects. An A-site-ordered quadruple perovskite-structure oxide, NdCu₃Fe₄O₁₂, is found to release significant latent heat, 25.5 kJ kg⁻¹ (157 J cc⁻¹), at the intersite-charge-transfer transition temperature near room temperature. The transition is first-order and accompanied by an unusual magnetic ordering and a large negative-thermal-expansion-like volume change, and thus, it causes a large entropy change (84.2 J K⁻¹ kg⁻¹). The observed entropy change is comparable to the largest changes reported in inorganic solid materials, and more importantly, it is utilized through a colossal barocaloric effect. The adiabatic temperature change by applying 5.1 kbar pressure is estimated to reach 13.7 K, which means efficient refrigeration can be realized through this effect.     

Structural and vibrational properties of high-dielectric oxides, HfO2 and TiO2: A comparative study

Within the framework of density functional theory, we have computed structural and vibrational properties of high-κ dielectric oxides, HfO₂ and TiO₂. We have considered different polytypes of these oxides and computed the corresponding static dielectric constants in order to investigate what are the more promising materials suitable for technological application. We found the flourite phase of hafnium dioxide, that is a promising candidate as gate oxide in ultra-scaled complementary metal-oxide-semiconductor (CMOS) technology, is structurally unstable due to the presence of soft phonon modes that have wave-vectors in the region of the Brillouin zone containing the K- and X-points. According to our results, the fluorite TiO₂ is structurally unstable as well but, contrary to HfO₂, the soft phonon modes have wave-vectors in the whole Brilouin zone. Calculations of the thermodynamical properties of the baddeleyite HfO₂, the stable phase at ambient condition, complete the work.     

Synthesis,Characterization, and Application of Mesoporous Silica Functionalized with Alkyl‐Hydroperoxides

A variety of alkyl hydroperoxides such as tert‐butyl‐, tert‐octyl‐, 1‐cyclopentyl‐, 1‐cyclohexyl‐, 3,4‐disubstituted‐1‐cyclohexyl‐, n‐propyl, and n‐undecyl‐hydroperoxides have been functionalized onto ordered mesoporous silica, SBA‐15, from the corresponding covalently anchored synthons. All the tert‐hydroperoxides are prepared by autoxidation using molecular O₂ and an initiator, whereas other hydroperoxides are obtained by reaction with H₂O₂. For autoxidation, the use of a combination of an azoinitiator (AIBN) and N‐hydroxyphthalimide increased the hydroperoxide yield compared with using the azoinitiator alone. Synthons containing two or more tert‐ and sec‐hydrogens lead to higher peroxide yield compared to synthons with a single reactive site. Oxidation of Si–OH (silanol groups) with acidic H₂O₂ at low temperature produces Si–OOH. Reusability of these alkyl hydroperoxides is carried out by oxidation of alcohols obtained from the corresponding alkyl hydroperoxides using H₂O₂. Both the covalently anchored synthons and the resulting hydroperoxides are thoroughly characterized by powder X‐ray diffraction, ¹³C cross‐polarized magic angle spinning NMR, TG/DTA, Fourier transform IR spectroscopy, sorption, and surface area measurements. The quantification of the amount of alkyl hydroperoxide was carried out by iodometric titration using a thio solution. The hydroperoxides exhibit high activity for the epoxidation of styrene to styrene oxide and exhibit reasonably high efficiency for oxygen transfer.     

Dissolution Behaviors and Applications of Silicon Oxides and Nitrides in Transient Electronics

Silicon oxides and nitrides are key materials for dielectrics and encapsulation layers in a class of silicon‐based high performance electronics that has ability to completely dissolve in a controlled fashion with programmable rates, when submerged in bio‐fluids and/or relevant solutions. This type of technology, referred to as “transient electronics”, has potential applications in biomedical implants, environmental sensors, and other envisioned areas. The results presented here provide comprehensive studies of transient behaviors of thin films of silicon oxides and nitrides in diverse aqueous solutions at different pH scales and temperatures. The kinetics of hydrolysis of these materials depends not only on pH levels/ion concentrations of solutions and temperatures, but also on the morphology and chemistry of the films, as determined by the deposition methods and conditions. Encapsulation strategies with a combination of layers demonstrate enhancement of the lifetime of transient electronic devices, by reducing water/vapor permeation through the defects.     

Polar Perturbations in Functional Oxide Heterostructures

Growth and characterization of metal-oxide thin films foster successful development of oxide-material-integrated thin-film devices represented by metal-oxide-semiconductor field-effect transistors (MOSFET), drawing enormous technological and scientific interest for several decades. In recent years, functional oxide heterostructures have demonstrated remarkable achievements in modern technologies and provided deeper insights into condensed-matter physics and materials science owing to their versatile tunability and selective amplification of the functionalities. One of the most critical aspects of their physical properties is the polar perturbation stemming from the ionic framework of an oxide. By engineering and exploiting the structural, electrical, magnetic, and optical characteristics through various routes, numerous perceptive studies have clearly shown how polar perturbations advance functionalities or drive exotic physical phenomena in complex oxide heterostructures. In this review, both intrinsic (engraved by thin-film heteroepitaxy) and extrinsic (reversibly controllable defect-mediated disorder and polar adsorbates) elements of polar perturbations, highlighting their abilities for the development of highly tunable functional properties are summarized. Scientifically, the recent approaches of polar perturbations render one to consolidate a prospect of atomic-level manipulation of polar order in epitaxial oxide thin films. Technologically, this review also offers useful guidelines for rational design to heterogeneously integrated oxide-based multi-functional devices with high performances.     

Local Electronic Structure Modulation Enables Fast-Charging Capability for Li-Rich Mn-Based Oxides Cathodes With Reversible Anionic Redox Activity

Anionic and cationic redox chemistries boost ultrahigh specific capacities of Li-rich Mn-based oxides cathodes (LRMO). However, irreversible oxygen evolution and sluggish kinetics result in continuous capacity decay and poor rate performance, restricting the commercial fast-charging cathodes application for lithium ion batteries. Herein, the local electronic structure of LRMO is appropriately modulated to alleviate oxygen release, enhance anionic redox reversibility, and facilitate Li⁺ diffusion via facile surface defect engineering. Concretely, oxygen vacancies integrated on the surface of LRMO reduce the density of states of O 2p band and trigger much delocalized electrons to distribute around the transition metal, resulting in less oxygen release, enhancing reversible anionic redox and the MnO₆ octahedral distortion. Besides, partially reduced Mn and lattice vacancies synchronously stimulate the electrochemical activity and boost the electronic conductivity, Li⁺ diffusion rate, and fast charge transfer. Therefore, the modified LRMO exhibits enhanced cyclic stability and fast-charging capability: a high discharging capacity of 212.6 mAh·g⁻¹ with 86.98% capacity retention after 100 cycles at 1 C is obtained and to charge to its 80%, SOC is shortened to 9.4 min at 5 C charging rate. This work will draw attention to boosting the fast-charging capability of LRMO via the local electronic structure modulation.