In Situ Enzyme Immobilization by Covalent Organic Frameworks

Enzyme immobilization is a widely reported method to favor the applicability of enzymes by enhancing their stability and re-usability. Among the various existing solid supports and immobilization strategies, the in situ encapsulation of enzymes within crystalline porous matrices is a powerful tool to design biohybrids with a stable and protected catalytic activity. However, to date, only a few metal–organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) have been reported. Excitingly, for the first time, Y. Chen and co-workers expanded the in situ bio-encapsulation to a new class of crystalline porous materials, namely covalent organic frameworks (COFs). The enzyme@COF materials not only exhibited high enzyme loading with minimal leaching, high catalytic activity and selectivity, chemical and long-term stability and recyclability but could also be scaled up to a few grams. Undoubtedly, this work opens new striking opportunities for enzymatic immobilization and will stimulate new research on COF-based matrices.     

Single Crystalline,Non-stoichiometric Cocrystals of Hydrogen-Bonded Organic Frameworks

Porous frameworks composed of non-stoichiometrically mixed multicomponent molecules attract much attention from a functional viewpoint. However, their designed preparation and precise structural characterization remain challenging. Herein, we demonstrate that cocrystallization of tetrakis(4-carboxyphenyl)hexahydropyrene and pyrene derivatives ( CP-Hp and CP-Py , respectively) yields non-stoichiometric mixed frameworks through networking via hydrogen bonding. The composition ratio of CP-Hp and CP-Py in the framework was determined by single crystalline X-ray crystallographic analysis, indicating that the mixed frameworks were formed over a wide range of composition ratios. Furthermore, microscopic Raman spectroscopy on the single crystal indicates that the components are not uniformly distributed such as ideal solid solution, but are done gradationally or inhomogeneously.     

环境响应性微胶囊及其在农业领域中应用的研究进展

在传统农业中,如何高效率地使用农药,提高其利用率,一直是一大难题。环境响应性微胶囊是一类在外界环境的刺激下,可以相适应地改变其表面结构的物质。这一类微胶囊具有智能、可控、精准、高效等特点。目前,这一项技术已经被广泛地应用于农业生产中。本文主要综述了环境中pH、温度、光以及磁场四大因素对响应性微胶囊的影响,并且简要介绍了该类微胶囊的制备技术、形成机理、主要材料以及在农业领域的应用。     

Mobility of Li+, Na+, and Cs+ cations in Nafion membrane,as studied by NMR techniques

The local mobility and diffusion of Li⁺, Na⁺, and Cs⁺ cations in Nafion 117 membrane were explored by ⁷Li, ²³Na, and ¹³³Cs spin relaxation and pulsed field gradient NMR techniques. It was shown that the macroscopic mass transfer of cations is controlled by ion motion near sulfonate groups. Lithium and sodium cations, whose hydrated energy is higher than the water hydrogen bond energy, are moving together with water molecules, but cesium cations possessing a low hydrated energy are jumping directly between the neighboring sulfonate groups.     

卤化物固态电解质研究进展

全固态电池因其高能量密度和高安全性而成为具有发展前景的下一代储能技术。开发具有高室温离子电导率、优异化学/电化学稳定性、良好正/负极兼容性的固态电解质是实现全固态电池实用化的关键。卤化物固态电解质因其优异的电化学窗口、高正极稳定性、可接受的室温锂离子电导率等优势,受到了广泛的关注。本文通过对近年来卤化物电解质的相关研究进行总结,综述了该类电解质的组成、结构、离子传导路径及制备方法,并分析了金属卤化物电解质的电导率、稳定性特点,归纳了近年来该电解质在全固态电池中具有代表性的应用,并基于以上总结和分析,指出了卤化物固态电解质的研究难点及发展方向。     

Dredging the Charge-Carrier Transfer Pathway for Efficient Low-Dimensional Ruddlesden-Popper Perovskite Solar Cells

Low-dimensional Ruddlesden-Popper (LDRP) perovskites still suffer from inferior carrier transport properties. Here, we demonstrate that efficient exciton dissociation and charge transfer can be achieved in LDRP perovskite by introducing γ-aminobutyric acid (GABA) as a spacer. The hydrogen bonding links adjacent spacing sheets in (GABA)₂MA₃Pb₄I₁₃ (MA=CH₃NH₃⁺), leading to the charges localized in the van der Waals gap, thereby constructing “charged-bridge” for charge transfer through the spacing region. Additionally, the polarized GABA weakens dielectric confinement, decreasing the (GABA)₂MA₃Pb₄I₁₃ exciton binding energy as low as ≈73 meV. Benefiting from these merits, the resultant GABA-based solar cell yields a champion power conversion efficiency (PCE) of 18.73 % with enhanced carrier transport properties. Furthermore, the unencapsulated device maintains 92.8 % of its initial PCE under continuous illumination after 1000 h and only lost 3 % of its initial PCE under 65 °C for 500 h.     

Dopant-free NiOx Nanocrystals: A Low-cost and Stable Hole Transport Material for Commercializing Perovskite Optoelectronics

Advancing inverted (p-i-n) perovskite solar cells (PSCs) is critical for commercial applications given their compatibility with different bottom cells for tandem photovoltaics, low-temperature processability (≤100 °C), and promising operational stability. Although inverted PSCs have achieved an efficiency of over 25 % using doped or expensive organic hole transport materials (HTMs), their synthesis cost and stability still cannot meet the requirements for their commercialization. Recently, dopant-free and low-cost non-stoichiometric nickel oxide nanocrystals (NiO_x NCs) have been extensively studied as a low-cost and effective HTM in perovskite optoelectronics. In this minireview, we summarize the synthesis and surface-functionalization methods of NiO_x NCs. Then, the applications of NiO_x NCs in other perovskite optoelectronics beyond photovoltaics are discussed. Finally, we provide a perspective for the future development of NiO_x NCs for the commercialization of perovskite optoelectronics.     

Low Bandgap 2D Perovskite Single Crystal with Anomalous-large Charges/ions Collection Ratio for Ultra-sensitive and Stable X-ray Detectors

The low-dimensional halide perovskites have attracted increasing attention due to their improved moisture stability, reduced defects, and suppressed ions migration in many optoelectronic devices such as solar cells, light-emitting diodes, X-ray detectors, and so on. However, they are still limited by their large band gap and short charge carriers’ diffusion length. Here, we demonstrate that the introduction of metal ions into organic interlayers of two-dimensional (2D) perovskite by cross-linking the copper paddle-wheel cluster-based lead bromide ([Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄) perovskite single crystals with coordination bonds can not only significantly reduce the perovskite band gap to 0.96 eV to boost the X-ray induced charge carriers, but can also selectively improve the charge carriers’ transport along the out-of-plane direction and blocking the ions motion paths. The [Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄ single-crystal device can reach a record charges/ions collection ratio of 1.69×10¹⁸±4.7 % μGy_air⁻¹ s, and exhibit a large sensitivity of 1.14×10⁵±7% μC Gy_air⁻¹ cm⁻² with the lowest detectable dose rate of 56 nGy_air s⁻¹ under 120 keV X-rays irradiation. In addition, [Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄ single-crystal detector exposed to the air without any encapsulation shows excellent X-ray imaging capability with long-term operational stability without any attenuation of 120 days.     

Reversible Li Plating on Graphite Anodes through Electrolyte Engineering for Fast-Charging Batteries

The difficulties to identify the rate-limiting step cause the lithium (Li) plating hard to be completely avoided on graphite anodes during fast charging. Therefore, Li plating regulation and morphology control are proposed to address this issue. Specifically, a Li plating-reversible graphite anode is achieved via a localized high-concentration electrolyte (LHCE) to successfully regulate the Li plating with high reversibility over high-rate cycling. The evolution of solid electrolyte interphase (SEI) before and after Li plating is deeply investigated to explore the interaction between the lithiation behavior and electrochemical interface polarization. Under the fact that Li plating contributes 40 % of total lithiation capacity, the stable LiF-rich SEI renders the anode a higher average Coulombic efficiency (99.9 %) throughout 240 cycles and a 99.95 % reversibility of Li plating. Consequently, a self-made 1.2-Ah LiNi_0.5Mn_0.3Co_0.2O₂ | graphite pouch cell delivers a competitive retention of 84.4 % even at 7.2 A (6 C) after 150 cycles. This work creates an ingenious bridge between the graphite anode and Li plating, for realizing the high-performance fast-charging batteries.     

Solid Interhalogen Compounds with Effective Br0 Fixing for Stable High-energy Zinc Batteries

Though massive efforts have been devoted to exploring Br-based batteries, the highly soluble Br₂/Br₃⁻ species causing rigorous “shuttle effect”, leads to severe self-discharge and low Coulombic efficiency. Conventionally, quaternary ammonium salts such as methyl ethyl morpholinium bromide (MEMBr) and tetrapropylammonium bromide (TPABr) are used to fix Br₂ and Br₃⁻, but they occupy the mass and volume of battery without capacity contribution. Here, we report an all-active solid interhalogen compound, IBr, as a cathode to address the above challenges, in which the oxidized Br⁰ is fixed by iodine (I), thoroughly eliminating cross-diffusing Br₂/Br₃⁻ species during the whole charging and discharging process. The Zn||IBr battery delivers remarkably high energy density of 385.8 Wh kg⁻¹, which is higher than those of I₂, MEMBr₃, and TPABr₃ cathodes. Our work provides new approaches to achieve active solid interhalogen chemistry for high-energy electrochemical energy storage devices.