Advanced Li2 S/Si Full Battery Enabled by TiN Polysulfide Immobilizer.

Lithium sulfide (Li2 S) is a promising cathode material with high capacity, which can be paired with nonlithium metal anodes such as silicon or tin so that the safety issues caused by the Li anode can be effectively avoided. However, the Li2 S full cell suffers from rapid capacity degradation due to the dissolution of intermediate polysulfides. Herein, a Li2 S/Si full cell is designed with a Li2 S cathode incorporated by titanium nitride (TiN) polysulfide immobilizer within parallel hollow carbon (PHC). This full cell delivers a high initial reversible capacity of 702 mAh gLi2S -1 (1007 mAh gsulfur -1 ) at 0.5 C rate and excellent cyclability with only 0.4% capacity fade per cycle over 200 cycles. The long cycle stability is ascribed to the strong polysulfide anchor effect of TiN and highly efficient electron/ion transport within the interconnected web-like architecture of PHC. Theoretical calculations, self-discharge measurements, and anode stability experiments further confirm the strong adsorption of polysulfides on the TiN surface. The present work demonstrates that the flexible Li2 S cathode and paired Si anode can be used to achieve highly efficient Li-S full cells.

The Uncommon Channel-Based Ln-MOFs for Highly Selective Fe3+ Detection and Superior Rhodamine†B Adsorption.

Two new isostructural 3D lanthanide-organic frameworks [H2 N(Me)2 ] [Ln3 (OH)(bpt)3 (H2 O)3 ] (DMF)2 ⋅(H2 O)4 (1-Ln; Ln=Sm and Eu) with a 1D channel (25 Å) have been successfully assembled from the rare trinuclear [Ln3 (OH)(COO)9 ] clusters and biphenyl-3,4',5-tricarboxylic acid (H3 bpt) and exhibit high stability towards water in the pH range 3-10. MOF 1-Eu is a promising luminescent probe for sensing Fe3+ in aqueous solution and is also selective towards rhodamine B (RhB) with a superior adsorption capacity of 735 mg g-1 , which is the highest among the reported Ln-MOFs for RhB removal so far. Periodic DFT calculations further confirmed the selective adsorption of rhodamine B over other dyes.

Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria.

Supported atomic metal sites have discrete molecular orbitals. Precise control over the energies of these sites is key to achieving novel reaction pathways with superior selectivity. Here, we achieve selective oxygen (O2) activation by utilising a framework of cerium (Ce) cations to reduce the energy of 3d orbitals of isolated copper (Cu) sites. Operando X-ray absorption spectroscopy, electron paramagnetic resonance and density-functional theory simulations are used to demonstrate that a [Cu(I)O2]3- site selectively adsorbs molecular O2, forming a rarely reported electrophilic η2-O2 species at 298 K. Assisted by neighbouring Ce(III) cations, η2-O2 is finally reduced to two O2-, that create two Cu-O-Ce oxo-bridges at 453 K. The isolated Cu(I)/(II) sites are ten times more active in CO oxidation than CuO clusters, showing a turnover frequency of 0.028 ± 0.003 s-1 at 373 K and 0.01 bar PCO. The unique electronic structure of [Cu(I)O2]3- site suggests its potential in selective oxidation.

Oxygen-Defective Ultrathin BiVO4 Nanosheets for Enhanced Gas Sensing.

BiVO4 nanomaterials are potentially applicable in gas sensing, but the sensing performance is limited by the less active sites on the BiVO4 surface. In this work, we propose a strategy to improve the gas-sensing performance of BiVO4 by forming ultrathin nanosheets and introducing oxygen vacancies, which increase the surface active sites. Two-dimensional (2D) BiVO4 nanosheets with oxygen vacancies are prepared through a colloidal method with the assistance of nitric acid. Gas sensors based on the oxygen-defective 2D ultrathin BiVO4 nanosheets exhibit an enhanced sensing response, which is 3.4 times higher than those of the sensors based on oxygen-abundant BiVO4 nanosheets. The density functional theory calculation is employed to uncover the promoting effects of oxygen vacancies on enhancing the O2 adsorption capability of BiVO4 nanosheets. This work is not only expected to build a wide range of 2D metal oxide semiconductors with a high gas-sensing performance but also gives an insight into the mechanism of the enhanced response induced by the oxygen vacancies, which will be a guideline for further designing high-performance sensing materials.

Rational Design and Functionalization of a Zinc Metal-Organic Framework for Highly Selective Detection of 2,4,6-Trinitrophenol.

To develop potential metal-organic frameworks (MOFs) for 2,4,6-trinitrophenol (TNP) detection, an amino-functionalized Zn-MOF, [NH2(CH3)2][Zn4O(bpt)2(bdc-NH2)0.5]·5DMF (where H3bpt = biphenyl-3,4',5-tricarboxylate, H2bdc-NH2 = 2-aminoterephthalic acid, and DMF = N,N-dimethylformamide), has been designed theoretically and synthesized experimentally. Its structure is composed of Zn4O(CO2)7 secondary building units linked by mixed ligands, exhibiting a three-dimensional framework. Fluorescence exploration revealed that the amino-functionalized Zn-MOF shows high selectivity and sensitivity for TNP, which agrees well with the predictions of theoretical simulations. This work provides a suitable means to develop new potential MOFs for TNP detection performance with a combination of experimental and theoretical perspectives.

Mesoporous Silica Nanoparticles Coated by Layer-by-Layer Self-assembly Using Cucurbit[7]uril for in Vitro and in Vivo Anticancer Drug Release.

Mesoporous silica nanoparticles (MSNs) are promising solid supports for controlled anticancer drug delivery. Herein, we report biocompatible layer-by-layer (LbL) coated MSNs (LbL-MSNs) that are designed and crafted to release encapsulated anticancer drugs, e.g., doxorubicin hydrochloride (DOX), by changing the pH or by adding competitive agents. The LbL coating process comprises bis-aminated poly(glycerol methacrylate)s (BA-PGOHMAs) and cucurbit[7]uril (CB[7]), where CB[7] serves as a molecular bridge holding two different bis-aminated polymeric layers together by means of host-guest interactions. This integrated nanosystem is tuned to respond under specific acidic conditions or by adding adamantaneamine hydrochloride (AH), attributed to the competitive binding of hydronium ions or AH to CB[7] with BA-PGOHMAs. These LbL-MSN hybrids possess excellent biostability, negligible premature drug leakage at pH 7.4, and exceptional stimuli-responsive drug release performance. The pore sizes of the MSNs and bis-aminated compounds (different carbon numbers) of BA-PGOHMAs have been optimized to provide effective integrated nanosystems for the loading and release of DOX. Significantly, the operating pH for the controlled release of DOX matches the acidifying endosomal compartments of HeLa cancer cells, suggesting that these hybrid nanosystems are good candidates for autonomous anticancer drug nanocarriers actuated by intracellular pH changes without any invasive external stimuli. The successful cellular uptake and release of cargo, e.g., propidium iodide (PI), in human breast cancer cell line MDA-231 from PI-loaded LbL-MSNs have been confirmed by confocal laser scanning microscopy (CLSM), while the cytotoxicities of DOX-loaded LbL-MSNs have been quantified by the Cell Counting Kit-8 (CCK-8) viability assay against HeLa cell lines and fibroblast L929 cell lines. The uptake of DOX-loaded LbL-MSNs by macrophages can be efficiently reduced by adding biocompatible hydrophilic poly(ethylene glycol) or CB[7] without destroying the capping. In vivo tumor-growth inhibition experiments with BALB/c nude mice demonstrated a highly efficient tumor-growth inhibition rate of DOX-loaded LbL-MSNs, suggesting that the novel type of LbL-MSN materials hold great potentials in anticancer drug delivery.