Electronic Spin Alignment within Homologous NiS2/NiSe2 Heterostructures to Promote Sulfur Redox Kinetics in Lithium-Sulfur Batteries.

The catalytic activation of the Li-S reaction is fundamental to maximize the capacity and stability of Li-S batteries (LSBs). Current research on Li-S catalysts mainly focuses on optimizing the energy levels to promote adsorption and catalytic conversion, while frequently overlooking the electronic spin state influence on charge transfer and orbital interactions. Here, hollow NiS2/NiSe2 heterostructures encapsulated in a nitrogen-doped carbon matrix (NiS2/NiSe2@NC) are synthesized and used as a catalytic additive in sulfur cathodes. The NiS2/NiSe2 heterostructure promotes the spin splitting of the 3d orbital, driving the Ni3+ transformation from low to high spin. This high spin configuration raises the electronic energy level and activates the electronic state. This accelerates the charge transfer and optimizes the adsorption energy, lowering the reaction energy barrier of the polysulfides conversion. Benefiting from these characteristics, LSBs based on NiS2/NiSe2@NC/S cathodes exhibit high initial capacity (1458 mAh·g⁻1 at 0.1C), excellent rate capability (572 mAh·g⁻1 at 5C), and stable cycling with an average capacity decay rate of only 0.025% per cycle at 1C during 500 cycles. Even at high sulfur loadings (6.2 mg·cm⁻2), high initial capacities of 1173 mAh·g⁻1 (7.27 mAh·cm⁻2) are measured at 0.1C, and 1058 mAh·g⁻1 is retained after 300 cycles.

Enhanced Electrochemical Hydrogenation of Benzaldehyde to Benzyl Alcohol on Pd@Ni-MOF by Modifying the Adsorption Configuration.

Electrocatalytic hydrogenation (ECH) approaches under ambient temperature and pressure offer significant potential advantages over thermal hydrogenation processes but require highly active and efficient hydrogenation electrocatalysts. The performance of such hydrogenation electrocatalysts strongly depends not only on the active phase but also on the architecture and surface chemistry of the support material. Herein, Pd nanoparticles supported on a nickel metal-organic framework (MOF), Ni-MOF-74, are prepared, and their activity toward the ECH of benzaldehyde (BZH) in a 3 M acetate (pH 5.2) aqueous electrolyte is explored. An outstanding ECH rate up to 283 µmol cm-2 h-1 with a Faradaic efficiency (FE) of 76% is reached. Besides, higher FEs of up to 96% are achieved using a step-function voltage. Materials Studio and density functional theory calculations show these outstanding performances to be associated with the Ni-MOF support that promotes H-bond formation, facilitates water desorption, and induces favorable tilted BZH adsorption on the surface of the Pd nanoparticles. In this configuration, BZH is bonded to the Pd surface by the carbonyl group rather than through the aromatic ring, thus reducing the energy barriers of the elemental reaction steps and increasing the overall reaction efficiency.

Identifying the Role of the Cationic Geometric Configuration in Spinel Catalysts for Polysulfide Conversion in Sodium-Sulfur Batteries.

An AB2X4 spinel structure, with tetrahedral A and octahedral B sites, is a paradigmatic class of catalysts with several possible geometric configurations and numerous applications, including polysulfide conversion in metal-sulfur batteries. Nonetheless, the influence of the geometric configuration and composition on the mechanisms of catalysis and the precise manner in which spinel catalysts facilitate the conversion of polysulfides remain unknown. To enable controlled exposure of single active configurations, herein, Cotd2+ and Cooh3+ in Co3O4 catalysts for sodium polysulfide conversion are in large part replaced by Fetd2+ and Feoh3+, respectively, generating FeCo2O4 and CoFe2O4. Through an examination of electrochemical activation energies, the characterization of symmetric cells, and theoretical calculations, we determine that Cooh3+ serves as the active site for the breaking of S-S bonds, while Cotd2+ functions as the active site for the formation of S-Na bonds. The current study underlines the subtle relationship between activity and geometric configurations of spinel catalysts, providing unique insights for the rational development of improved catalysts by optimizing their atomic geometric configuration.

Spin Effect to Promote Reaction Kinetics and Overall Performance of Lithium-Sulfur Batteries under External Magnetic Field.

Lithium-sulfur batteries (LSBs) are still limited by the shuttle of lithium polysulfides (LiPS) and the slow Li-S reaction. Herein, we demonstrate that when using cobalt sulfide as a catalytic additive, an external magnetic field generated by a permanent magnet can significantly improve the LiPS adsorption ability and the Li-S reaction kinetics. More specifically, the results show both experimentally and theoretically how an electron spin polarization of Co ions reduces electron repulsion and enhances the degree of orbital hybridization, thus resulting in LSBs with unprecedented performance and stability. Under an external magnetic field, LSBs with 0.0084 % per cycle decay rate at 2 C during 8150 cycles are produced. Overall, this work not only demonstrates an effective strategy to promote LiPS adsorption and electrochemical conversion in LSBs at no additional energy cost but also enriches the application of the spin effect in the electrocatalysis fields.

Metal Ion Cutting-Assisted Synthesis of Defect-Rich MoS2 Nanosheets for High-Rate and Ultrastable Li2S Catalytic Deposition.

Active metal ions often show a strong cutting effect on the chemical bonds during high-temperature thermal processes. Herein, a one-pot metal ion cutting-assisted method was adopted to design defect-rich MoS2-x nanosheet (NS)/ZnS nanoparticle (NP) heterojunction composites on carbon nanofiber skeletons (CNF@MoS2-x/ZnS) via a simple Ar-ambience annealing. Results show that Zn2+ ions capture S2- ions from MoS2 and form into ZnS NPs, and the MoS2 NSs lose S2- ions and become MoS2-x ones. As sulfur hosts for lithium-sulfur batteries (LSBs), the CNF@MoS2-x/ZnS-S cathodes deliver a high reversible capacity of 1233 mA h g-1 at 0.1 C and keep 944 mA h g-1 at 3 C. Moreover, the cathodes also show an extremely low decay rate of 0.012% for 900 cycles at 2 C. Series of analysis indicate that the MoS2-x NSs significantly improve the chemisorption and catalyze the kinetic process of redox reactions of lithium polysulfides, and the heterojunctions between MoS2-x NSs and ZnS NPs further accelerate the transport of electrons and the diffusion of Li+ ions. Besides, the CNF@MoS2-x/ZnS-S LSBs also show an ultralow self-discharge rate of 1.1% in voltage. This research would give some new insights for the design of defect-rich electrode materials for high-performance energy storage devices.

Construction of all-carbon micro/nanoscale interconnected sulfur host for high-rate and ultra-stable lithium-sulfur batteries: Role of oxygen-containing functional groups.

Carbon nanotubes (CNTs) are often used to settle down the sluggish reaction kinetics in lithium-sulfur batteries (LSBs). However, the self-aggregation of CNTs often makes them fail to effectively inhibit the shuttling effect of soluble lithium polysulfide (LiPS) intermediates. Herein, a type of ultra-stable carbon micro/nano-scale interconnected "carbon cages" has been designed by incorporating polar acid-treated carbon fibers (ACF) into three-dimensional (3D) CNT frameworks during vacuum filtration processes. Results show that the ACF-CNT composite frameworks possess a reinforced-concrete-like structure, in which the ACFs can well work as the main mechanical supporting frames for the composite electrodes, and the oxygen-containing functional groups (OFGs) formed on them as cross linker between ACFs and CNTs. Benefitted from this design, the ACF-CNT/S cathodes deliver an excellent rate capability (retain 72.6% at 4C). More impressively, the ACF-CNT/S cathodes also show an ultrahigh cycling stability (capacity decay rate of 0.001% per cycle over 350 cycles at 2C). And further optimization suggests that the suitable treatment on CFs could balance the chemical adsorption (OFGs) and physical confinement (carbon cages), leading to fast and durable electrochemical reaction dynamics. In addition, the assembled soft-pack LSBs further show a high dynamic bending stability.

Dissymmetric interface design of SnO2/TiO2 side-by-side bi-component nanofibers as photoanodes for dye sensitized solar cells: Facilitated electron transport and enhanced carrier separation.

SnO2/TiO2 type II heterojunctions are often introduced to enhance the separation efficiency of photogenerated carriers in photoelectrochemical electrodes, while most of these heterojunctions are of core-shell structure, which often limits the synergistic effect from the two components. In this work, dissymmetric SnO2/TiO2 side-by-side bi-component nanofibers (SBNFs) with tunable composition ratios have been prepared by a novel needleless electrospinning technique with two V-shape connected conductive channels (V-channel electrospinning). Results show that this V-channel electrospinning technique is more stable, controllable and tunable for the large-scale preparation of SBNF materials compared to the traditional electrospinning using two side-by-side metal needles. And these SnO2/TiO2 SBNFs are dissymmetric and comprised of a tiny SnO2 NF (tunable diameter within 20-80 nm) and a Sn-doped TiO2 NF (diameter of ~ 250 nm) with a side-by-side structure. Moreover, the dye-sensitized solar cells (DSSCs) based these dissymmetric SnO2/TiO2 SBNFs show the maximum power conversion efficiency (PCE) of 8.3%, which is 2.59 times that of the ones based on the TiO2 NFs. Series of analyses indicate that the enhancements in PCE could mainly be due to the improved electron transport via SnO2 NFs and the enhanced carrier separation via dissymmetric SnO2/TiO2 heterojunction interface. This research will give some new insight in the preparation of SBNFs for high-performance photoelectrochemical devices.

Role of nickel dopant on gas response and selectivity of electrospun indium oxide nanotubes.

It has been demonstrated that the incorporation of Ni into metal oxide-based gas sensors often enhances the sensing performance by increasing the catalytic and heterojunction effects. However, it remains unclear how these two effects work either individually or synergistically in gas sensing. Herein, a series of Ni-doped In2O3 nanotubes (NIO NTs) with different doping concentrations were synthesized through a traditional electrospinning technique. The as-prepared NIO NTs were uniform, with length of micron scale, an average diameter of approximately 70 nm, and a tube wall thickness of approximately 10 nm. Following their incorporation into gas sensors, the NIO NTs often showed improved sensing properties (including excellent response and selectivity) for ethanol vapor compared to the pristine In2O3 NTs. Specifically, at 100 ppm ethanol and 220 °C, the response of NIO-7 NTs (7 mol% Ni) was approximately four-fold higher than that of pristine In2O3 NTs (49.74 vs. 13.39). The gas sensing test results indicated that the improved sensing performance was due to the formation of a heterojunction between In2O3 and NiO, as well as to the catalysis effects of Ni3+ ions. Additionally, simulation results indicated that the improved gas selectivity could be due to the Ni doping-induced change in surface adsorption energies of the tested gases.

Energy storage mechanism in aqueous fiber-shaped Li-ion capacitors based on aligned hydrogenated-Li4Ti5O12 nanowires.

It is reported that Li ions can contribute a lot to the capacitance of aqueous Li-ion capacitors (LICs), which might be due to the intercalation/de-intercalation processes of Li+ ions that also occur at the anodes. However the energy storage mechanism in the aqueous LIC system still requires further proof. In this work, a type of aqueous fiber-shaped LIC has been designed and developed using hydrogenated Li4Ti5O12 (H-LTO) anodes, active carbon (AC) cathodes, and LiCl/PVA gel electrolytes with a double-helical structure. The obtained single LTO wire electrode exhibits a high specific capacitance in volume (34.1 F cm-3) and superior cycling stabilities (∼100% over 100 000 cycles), both of which are due to the formed amorphous layers at the surface of the electrodes. Moreover, it is found via sweep voltammetry analysis that most of the energy stored in an aqueous fiber-shaped capacitor electrode is attributed to the Li ions' intercalation, whose content exceeds 85% at a low scan rate and gradually decreases with increasing scan rate; while the energy stored by the double electric layers remains almost unchanged with different scan rates. Furthermore, the well-matched wearable fiber-shaped LICs show high capacitive behaviors (18.44 µW h cm-2) and superior static/dynamic cycling stabilities. This research would provide some insight into the charge storage mechanism in electrodes in the aqueous system, and give more suggestions to develop high-energy-density fiber-shaped energy storage devices.

Amide proton transfer magnetic resonance imaging of Alzheimer's disease at 3.0 Tesla: a preliminary study.

BACKGROUND: Amide proton transfer (APT) imaging has recently emerged as an important contrast mechanism for magnetic resonance imaging (MRI) in the field of molecular and cellular imaging. The aim of this study was to evaluate the feasibility of APT imaging to detect cerebral abnormality in patients with Alzheimer's disease (AD) at 3.0 Tesla. METHODS: Twenty AD patients (9 men and 11 women; age range, 67-83 years) and 20 age-matched normal controls (11 men and 9 women; age range, 63-82 years) underwent APT and traditional MRI examination on a 3.0 Tesla MRI system. The magnetic resonance ratio asymmetry (MTR asym ) values at 3.5 ppm of bilateral hippocampi (Hc), temporal white matter regions, occipital white matter regions, and cerebral peduncles were measured on oblique axial APT images. MTR asym (3.5 ppm) values of the cerebral structures between AD patients and control subjects were compared with independent samples t-test. Controlling for age, partial correlation analysis was used to investigate the associations between mini-mental state examination (MMSE) and the various MRI measures among AD patients. RESULTS: Compared with normal controls, MTR asym (3.5 ppm) values of bilateral Hc were significantly increased in AD patients (right 1.24% ± 0.21% vs. 0.83% ± 0.19%, left 1.18% ± 0.18% vs. 0.80%± 0.17%, t = 3.039, 3.328, P = 0.004, 0.002, respectively). MTR asym (3.5 ppm) values of bilateral Hc were significantly negatively correlated with MMSE (right r = -0.559, P = 0.013; left r = -0.461, P = 0.047). CONCLUSIONS: Increased MTR asym (3.5 ppm) values of bilateral Hc in AD patients and its strong correlations with MMSE suggest that APT imaging could potentially provide imaging biomarkers for the noninvasive molecular diagnosis of AD.

Analysis of the risk factors of postoperative respiratory dysfunction of type A aortic dissection and lung protection.

AIM: Retrospectively to analyze the risk factors of postoperative respiratory dysfunction (RD) in 196 patients with type A dissection operated on with cerebral perfusion and a lower body hypothermia circulatory arrest (HCA) and to investigate the method of the lung protection. METHODS: From January 2005 to April 2008, 196 patients with type A dissection underwent surgical repair with cerebral perfusion and HCA. There were 142 male patients and 54 female patients, with ages from 17 to 78 years. Antegrade selective cerebral perfusion (SCP) through the axillary artery was performed for 168 patients and retrograde cerebral perfusion (RCP) from the superior vena cava for 28 patients. All the factors underwent univariate and multivariate analysis. RESULTS: Mean cardiopulmonary bypass (CPB) duration was (186+/-56) minutes and mean cerebral perfusion time was (35+/-15) minutes; mean HCA time was (39+/-14) minutes. Postoperative RD was detected in 26 patients (13.3%). Multivariate analysis showed that the longer duration of circulatory arrest (CA), P=0.008, OR=1.048, and the higher temperature in the bladder during CA, P=0.002, OR=1.614, were independent risk factors of postoperative RD. There was a higher mortality (23.1%, P=0.025) in patients with postoperative RD when compared with the other patients. CONCLUSION: The longer duration of CA and the higher temperature in the bladder during CA were found to be the independent risk factors of postoperative RD after type A aortic dissection surgery. Attention should be paid to lung protection for these patients and the adjunct of continuing descending aortic perfusion and cerebral perfusion should be a safe and feasible procedure and it would be valuable to perform a prospective trial.

SiC Nanorods Grown on Electrospun Nanofibers Using Tb as Catalyst: Fabrication, Characterization, and Photoluminescence Properties.

Well-crystallizedß-SiC nanorods grown on electrospun nanofibers were synthesized by carbothermal reduction of Tb doped SiO2(SiO2:Tb) nanofibers at 1,250 °C. The as-synthesized SiC nanorods were 100-300 nm in diameter and 2-3 µm in length. Scanning electron microscopy (SEM) results suggested that the growth of the SiC nanorods should be governed by vapor-liquid-solid (VLS) mechanism with Tb metal as catalyst. Tb(NO3)3particles on the surface of the electrospun nanofibers were decomposed at 500 °C and later reduced to the formation of Tb nanoclusters at 1,200 °C, and finally the formation of a Si-C-Tb ally droplet will stimulate the VLS growth at 1,250 °C. Microstructure of the nanorod was further investigated by transmission electron microscopy (TEM). It was found that SiC <111> is the preferred initial growth direction. The liquid droplet was identified to be Si86Tb14, which acted as effective catalyst. Strong green emissions were observed from the SiC nanorod samples. Four characteristic photoluminescence (PL) peaks of Tb ions were also identified.