Advantageous Interfacial Effects of AgPd/g-C3N4 for Photocatalytic Hydrogen Evolution: Electronic Structure and H2O Dissociation

Bimetallic AgPd nanoparticles have been synthesized before, but the interfacial electronic effects of AgPd on the photocatalytic performance have been investigated less. In this work, the results of hydrogen evolution suggest that the bimetallic AgPd/g-C₃N₄ sample has superior activity to Ag/g-C₃N₄ and Pd/g-C₃N₄ photocatalysts. The UV/Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, CO adsorption diffuse reflectance FTIR spectroscopy, and FTIR results demonstrate that in the AgPd/g-C₃N₄, the surface electronic structures of Pd and Ag are changed, which is beneficial for faster photogenerated electron transfer and greater H₂O molecule adsorption. In situ ESR spectra suggest that, under visible light irradiation, there is more H₂O dissociation to radical species on the AgPd/g-C₃N₄ photocatalyst. Furthermore, DFT calculations confirm the interfacial electronic effects of AgPd/g-C₃N₄, that is, Pd^δ−⋅⋅⋅Ag^δ+, and the activation energy of H₂O molecule dissociation on AgPd/g-C₃N₄ is the lowest, which is the main contributor to the enhanced photocatalytic H₂ evolution.     

Extended phase diagram of La1-xCaxMnO3 by interfacial engineering

The interfacial enhanced ferromagnetism in maganite/ruthenate system is regarded as a promising path to broaden the potential of oxide-based electronic device applications. Here, we systematically studied the physical properties of LaLa_1-xCa_xMnO₃/SrRuO₃ superlattices and compared them with the LaLa_1-xCa_xMnO₃ thin films and bulk compounds. The LaLa_1-xCa_xMnO₃/SrRuO₃ superlattices exhibit significant enhancement of Curie temperature (T_C) beyond the corresponding thin films and bulks. Based on these results, we constructed an extended phase diagram of LaLa_1-xCa_xMnO₃ under interfacial engineering. We considered the interfacial charge transfer and structural proximity effects as the origin of the interface-induced high T_C. The structural characterizations revealed a pronounced increase of B-O-B bond angle, which could be the main driving force for the high T_C in the superlattices. Our work inspires a deeper understanding of the collective effects of interfacial charge transfer and structural proximity on the physical properties of oxide heterostructures.     

One-pot two step synthesis of unsymmetrically substituted indenes from 3,4-diarylbutadiene sulfones

A new one-pot two step synthesis of unsymmetrically substituted indenes from available 3,4-diarylbutadiene sulfones involves SO₂ thermal extrusion followed by acid- catalyzed cyclization of the diene formed, the cyclization proceeding selectively at the more electron-rich aryl rings. The procedure is efficient for substrates bearing donor, acceptor, as well as bulky substituents.     

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.     

GaN单晶衬底上同质外延界面杂质的研究

氮化镓单晶衬底上的同质外延具有显著的优势,但是二次生长界面上的杂质聚集一直是困扰同质外延广泛应用的难题,特别是对电子器件会带来沟道效应,对激光器应用会影响谐振腔中的光场分布。本文通过金属有机化合物化学气相沉积(MOCVD)生长的原位处理,实现了界面杂质聚集的有效抑制。研究发现,界面上的主要杂质是C、H、O和Si,其中C、H、O可以通过原位热清洗去除;界面Si聚集的问题主要是由衬底外延片保存过程中暴露空气带来的,其次是氮化镓衬底中Si背底浓度,在外延过程中,生长载气对氮化镓单晶衬底不稳定的N面造成刻蚀,释放的杂质元素会对二次生长界面产生影响,本文较系统地阐明了界面杂质的形成机制,并提出了解决方案。     

SAPO-34提升铁钒基催化剂抗碱性能研究

采用浸渍法制备Fe-VO_x/SAPO-34和Fe-VO_x/TiO₂脱硝催化剂,探究SAPO-34分子筛与TiO₂两种载体负载铁钒基氧化物催化活性及抗碱性能的差异。借助X射线衍射(XRD)、X射线光电子能谱(XPS)、氨气程序升温脱附(NH₃-TPD)、氢气程序升温还原(H₂-TPR)、原位红外漫反射(in-situ DRIFTs)等表征手段对催化剂的骨架结构、表面物化性质、氧化还原能力以及对反应气体的吸脱附情况进行分析。结果表明:SAPO-34分子筛内部特定的孔道结构和稳定的骨架,有利于活性组分在载体上均匀分散,降低碱金属对表面活性中心的物理覆盖作用;同时其表面丰富的酸位点能够作为碱金属捕获位,保护催化剂表面的活性中心,保证催化剂的吸附-反应过程能够正常进行,从而使Fe-VO_x/SAPO-34表现出良好的抗碱金属能力。     

Hole/Electron Transporting Materials for Nonfullerene Organic Solar Cells

Nonfullerene acceptor based organic solar cells (NF-OSCs) have witnessed rapid progress over the past few years owing to the intensive research efforts on novel electron donor and nonfullerene acceptor (NFA) materials, interfacial engineering, and device processing techniques. Interfacial layers including electron transporting layers (ETL) and hole transporting layers (HTLs) are crucially important in the OSCs for facilitating electron and hole extraction from the photoactive blend to the respective electrodes. In this review, the lates progress in both ETLs and HTLs for the currently prevailing NF-OSCs are discussed, in which the ETLs are summarized from the categories of metal oxides, metal chelates, non-conjugated electrolytes and conjugated electrolytes, and the HTLs are summarized from the categories of inorganic and organic materials. In addition, some bifunctional interlayer materials served as both ETLs and HTLs are also introduced. Finally, the prospects of ETL/HTL materials for NF-OSCs are provided.     

Enzyme-catalyzed asymmetric domino aza-Michael/aldol reaction for the synthesis of 1,2-dihydroquinolines using pepsin from porcine gastric mucosa

An unprecedented enzyme-catalyzed asymmetric domino aza-Michael/aldol reaction of 2-aminobenzaldehyde and a,b-unsaturated aldehydes is achieved. Pepsin from porcine gastric mucosa provided mild and efficient access to diverse substituted 1,2-dihydroquinolines in yields of 38%–97% with 6%–24%enantiomeric excess(ee). This work not only provides a novel method for the synthesis of dihydroquinoline derivatives, but also promotes the development of enzyme catalytic promiscuity.     

Anchoring Mechanism of ZnO Nanoparticles on Graphitic Carbon Nanofiber Surfaces through a Modified Co‐Precipitation Method to Improve Interfacial Contact and Photocatalytic Performance

A facile three‐step co‐precipitation method is developed to synthesize graphitic carbon nanofibers (CNFs) decorated with ZnO nanoparticles (NPs). By interchanging intermediate steps of the reaction processes, two kinds of nanohybrids are fabricated with stark morphological and physicochemical differences. The morphologies differ because of the different chemical environments of the NP/nanocluster formation. The hybrid with larger and non‐uniform ZnO nanocluster size is formed in liquid phase and resulted in considerable interfacial defects that deteriorate the charge‐transfer properties. The hybrid with smaller and uniform ZnO NPs was formed in a dry solid phase and produced near‐defect‐free interfaces, leading to efficient charge transfer for superior photocatalytic performance. The results broaden the understanding of the anchoring/bonding mechanism in ZnO/CNF hybrid formation and may facilitate further development of more effective exfoliation strategies for the preparation of high‐performance composites/hybrids.