Molecular Connectors Boosting the Performance of MoS2 Cathodes in Zinc-Ion Batteries.

Zinc-ion batteries (ZIBs) are promising energy storage systems due to high energy density, low-cost, and abundant availability of zinc as a raw material. However, the greatest challenge in ZIBs research is lack of suitable cathode materials that can reversibly intercalate Zn2+ ions. 2D layered materials, especially MoS2 -based, attract tremendous interest due to large surface area and ability to intercalate/deintercalate ions. Unfortunately, pristine MoS2 obtained by traditional protocols such as chemical exfoliation or hydrothermal/solvothermal methods exhibits limited electronic conductivity and poor chemical stability upon charge/discharge cycling. Here, a novel molecular strategy to boost the electrochemical performance of MoS2 cathode materials for aqueous ZIBs is reported. The use of dithiolated conjugated molecular pillars, that is, 4,4'-biphenyldithiols, enables to heal defects and crosslink the MoS2 nanosheets, yielding covalently bridged networks (MoS2 -SH2) with improved ionic and electronic conductivity and electrochemical performance. In particular, MoS2 -SH2 electrodes display high specific capacity of 271.3 mAh g-1 at 0.1 A g-1 , high energy density of 279 Wh kg-1 , and high power density of 12.3 kW kg-1 . With its outstanding rate capability (capacity of 148.1 mAh g-1 at 10 A g-1 ) and stability (capacity of 179 mAh g-1 after 1000 cycles), MoS2 -SH2 electrodes outperform other MoS2 -based electrodes in ZIBs.

Methane sink of subterranean space in an integrated atmosphere-soil-cave system.

CH4 serves as an important greenhouse gas, yet limited knowledge is available in global and regional CH4 cycling, particularly in widely distributed karst terrain. In this study, we investigated an upland in Puding Karst Ecosystem Research Station, and explored CH4 concentration and/or flux in atmosphere, soil and cave using a closed static chamber method and an eddy covariance system. Meanwhile, we monitored atmospheric temperature, precipitation, temperature and wind velocity in the cave entrance. The results demonstrated that atmospheric CH4 and actual soil CH4 fluxes in the source area of eddy covariance system were -0.19 ± 8.64 nmols-1m-2 and -0.16 nmols-1m-2 respectively. The CH4 concentrations in Shawan Cave exhibited 10 âˆ¼ 100-fold lower than that of the external atmosphere. CH4 oxidation rate dominated by methane-oxidizing bacteria was 1.98 nmols-1m-2 in Shawan Cave when it combined with temperature difference between cave and external atmosphere. Therefore, CH4 sink in global karst subterranean spaces was estimated at 106.2 Tg CH4 yr-1. We supplemented an understanding of CH4 cycling paths and fluxes in karst terrain, as well as CH4 sinks in karst subterranean space. Further works require to establish a karst ecosystem observation network to conduct long-term integrated studies on CH4 fluxes regarding atmosphere, soils, plants and caves.

Supramolecular Engineering of Cathode Materials for Aqueous Zinc-ion Energy Storage Devices: Novel Benzothiadiazole Functionalized Two-Dimensional Olefin-Linked COFs.

Two-dimensional covalent organic frameworks (COFs) have emerged as promising materials for energy storage applications exhibiting enhanced electrochemical performance. While most of the reported organic cathode materials for zinc-ion batteries use carbonyl groups as electrochemically-active sites, their high hydrophilicity in aqueous electrolytes represents a critical drawback. Herein, we report a novel and structurally robust olefin-linked COF-TMT-BT synthesized via the aldol condensation between 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4'-(benzothiadiazole-4,7-diyl)dibenzaldehyde (BT), where benzothiadiazole units are explored as novel electrochemically-active groups. Our COF-TMT-BT exhibits an outstanding Zn2+ storage capability, delivering a state-of-the-art capacity of 283.5 mAh g-1 at 0.1 A g-1 . Computational and experimental analyses reveal that the charge-storage mechanism in COF-TMT-BT electrodes is based on the supramolecularly engineered and reversible Zn2+ coordination by the benzothiadiazole units.

Chemical Conversion and Locking of the Imine Linkage: Enhancing the Functionality of Covalent Organic Frameworks.

Imine-based covalent organic frameworks (COFs) are a widely studied class of functional, crystalline, and porous nanostructures which combine a relatively facile crystallization with tuneable compositions and porosities. However, the imine linkage constitutes an intrinsic limitation due to its reduced stability in harsh chemical conditions and its unsuitability for in-plane π-conjugation in COFs. Urgent solutions are therefore required in order to exploit the full potential of these materials, thereby enabling their technological application in electronics, sensing, and energy storage devices. In this context, the advent of a new generation of linkages derived from the chemical conversion and locking of the imine bond represents a cornerstone for the synthesis of new COFs. A marked increase in the framework robustness is in fact often combined with the incorporation of novel functionalities including, for some of these reactions, an extension of the in-plane π-conjugation. This Minireview describes the most enlightening examples of one-pot reactions and post-synthetic modifications towards the chemical locking of the imine bond in COFs.

Synthesis of Robust MOFs@COFs Porous Hybrid Materials via an Aza-Diels-Alder Reaction: Towards High-Performance Supercapacitor Materials.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted enormous attention in recent years. Recently, MOF@COF are emerging as hybrid architectures combining the unique features of the individual components to enable the generation of materials displaying novel physicochemical properties. Herein we report an unprecedented use of aza-Diels-Alder cycloaddition reaction as post-synthetic modification of MOF@COF-LZU1, to generate aza-MOFs@COFs hybrid porous materials with extended π-delocalization. A a proof-of-concept, the obtained aza-MOFs@COFs is used as electrode in supercapacitors displaying specific capacitance of 20.35 µF cm-2 and high volumetric energy density of 1.16 F cm-3 . Our approach of post-synthetic modification of MOFs@COFs hybrids implement rational design for the synthesis of functional porous materials and expands the plethora of promising application of MOFs@COFs hybrid porous materials in energy storage applications.

Formation of N-Doped Carbon-Coated ZnO/ZnCo2 O4 /CuCo2 O4 Derived from a Polymetallic Metal-Organic Framework: Toward High-Rate and Long-Cycle-Life Lithium Storage.

Metal-organic frameworks (MOFs) are very promising self-sacrificing templates for the large-scale fabrication of new functional materials owing to their versatile functionalities and tunable porosities. Most conventional metal oxide electrodes derived from MOFs are limited by the low abundance of incorporated metal elements. This study reports a new strategy for the synthesis of multicomponent active metal oxides by the pyrolysis of polymetallic MOF precursors. A hollow N-doped carbon-coated ZnO/ZnCo2 O4 /CuCo2 O4 nanohybrid is prepared by the thermal annealing of a polymetallic MOF with ammonium bicarbonate as a pore-forming agent. This is the first report on the rational design and preparation of a hybrid composed of three active metal oxide components originating from MOF precursors. Interestingly, as a lithium-ion battery anode, the developed electrode delivers a reversible capacity of 1742 mAh g-1 after 500 cycles at a current density of 0.3 mA g-1 . Furthermore, the material shows large storage capacities (1009 and 667 mAh g-1 ), even at high current flow (3 and 10 A g-1 ). The remarkable high-rate capability and outstanding long-life cycling stability of the multidoped metal oxide benefits from the carbon-coated integrated nanostructure with a hollow interior and the three active metal oxide components.

From Metal-Organic Framework to Porous Carbon Polyhedron: Toward Highly Reversible Lithium Storage.

By application of a newly designed T-shaped ligand 5-(4-pyridin-4-yl-benzoylamino)isophthalic acid (H2PBAI) to assemble with Zn(II) ions under solvothermal conditions, a novel porous polyhedral metal-organic framework (Zn-PBAI) with pcu topology has been obtained. When treated as a precursor by annealing of Zn-PBAI at various temperatures, porous carbon polyhedra (PCP) were prepared and tested as an anode material for lithium-ion batteries. The results show that PCP carbonized at 1000 °C (PCP-1000) manifest the highest reversible specific capacity of about 1125 mAh g-1 at a current of 500 mA g-1 after 200 cycles, which is supposed to benefit from the large accessible specific area and high electric conductivity. Moreover, PCP-1000 electrode materials also exhibit superior cyclic stability and good rate capacity.

Annual ecosystem respiration variability of alpine peatland on the eastern Qinghai-Tibet Plateau and its controlling factors.

Peatlands are widely developed in the eastern Qinghai-Tibet Plateau, but little is known about carbon budgets for these alpine peatland ecosystems. In this study, we used an automatic chamber system to measure ecosystem respiration in the Hongyuan peatland, which is located in the eastern Qinghai-Tibet Plateau. Annual ecosystem respiration measurements showed a typical seasonal pattern, with the peak appearing in June. The highest respiration was 10.43 µmol CO2/m(2)/s, and the lowest was 0.20 µmol CO2/m(2)/s. The annual average ecosystem respiration was 2.06 µmol CO2/m(2)/s. The total annual respiration was 599.98 g C/m(2), and respiration during the growing season (from May to September) accounted for 78 % of the annual sum. Nonlinear regression revealed that ecosystem respiration has a significant exponential correlation with soil temperature at 10-cm depth (R (2) = 0.98). The Q 10 value was 3.90, which is far higher than the average Q 10 value of terrestrial ecosystems. Ecosystem respiration had an apparent diurnal variation pattern in growing season, with peaks and valleys appearing at approximately 14:00 and 10:00, respectively, which could be explained by soil temperature and soil water content variation at 10-cm depth.

MOF (UiO-66-NH2)@COF (TFP-TABQ) hybrids via on-surface condensation reactions for sustainable energy storage.

Core-shell MOF@COF hybrids were synthesized via subsequent modification of MOF UiO-66-NH2 with 1,3,5-triformylphloroglucinol (TFP) and 2,3,5,6-tetraaminobenzoquinone (TABQ). The hybrids exhibited significant surface area (236 m2 g-1) and outstanding electrochemical performance (103 F g-1 at 0.5 A g-1), surpassing both COFs and MOFs, thereby showcasing the potential of on-surface condensation reactions for developing high-performance energy storage devices.

Effects of Misalignment of c-axis on the Properties of Hydrogenation-Disproportionation-Desorption-Recombination Particles.

Hydrogenation-Disproportionation-Desorption-Recombination (HDDR) Nd2Fe14B particles have excellent magnetic properties, but the magnetic properties of powder are not uniform across different particle sizes. The remanence and maximum magnetic energy products of samples with a particle size of 120 µm are 14.0 kGs and 41.35 MGOe, while the products of samples with a particle size of 60 µm are only 13.3 kGs and 36.31 MGOe. The macroscopic morphology of HDDR Nd2Fe14B particles and the gradient distribution of microstructures in different micro-regions were observed. By modifying the macroscopic morphology of the particles, the poorly oriented clusters on the surface of the particles were precisely eliminated, and the remanence and maximum magnetic energy products of the particles increased to 14.5 kGs and 45 MGOe, respectively. Compared with the original particles, the samples after mechanical grinding had better grain arrangement. The effects of the nanocrystalline c-axis and field misalignment angle θ on the magnetic properties of HDDR Nd2Fe14B particles were investigated through micromagnetic simulation. The targeted removal of macroscopic defects on the particle surface contributed to a 3.6% increase in remanence and an 8.8% increase in the maximum magnetic energy product, offering a promising approach to enhance the microstructure of high-performance HDDR Nd2Fe14B particles.

A novel prognostic model related to oxidative stress for treatment prediction in lung adenocarcinoma.

Background: The prognostic model based on oxidative stress for lung adenocarcinoma (LUAD) remains unclear. Methods: The information of LUAD patients were acquired from TCGA dataset. We also collected two external datasets from GEO for verification. Oxidative stress-related genes (ORGs) were extracted from Genecards. We performed machine learning algorithms, including Univariate Cox regression, Random Survival Forest, and Least Absolute Shrinkage and Selection Operator (Lasso) analyses on the ORGs to build the OS-score and OS-signature. We drew the Kaplan-Meier and time-dependent receiver operating characteristic curve (ROC) to evaluate the efficacy of the OS-signature in predicting the prognosis of LUAD. We used GISTIC 2.0 and maftool algorithms to explore Genomic mutation of OS-signature. To analyze characteristic of tumor infiltrating immune cells, ESTIMATE, TIMER2.0, MCPcounter and ssGSEA algorithms were applied, thus evaluating the immunotherapeutic strategies. Chemotherapeutics sensitivity analysis was based on pRRophetic package. Finally, PCR assays was also used to detect the expression values of related genes in the OS-signature in cell lines. Results: Ten ORGs with prognostic value and the OS-signature containing three prognostic ORGs were identified. The significantly better prognosis of LUAD patients was observed in LUAD patients. The efficiency and accuracy of OS-signature in predicting prognosis for LUAD patients was confirmed by survival ROC curves and two external validation data sets. It was clearly observed that patients with high OS-scores had lower immunomodulators levels (with a few exceptions), stromal score, immune score, ESTIMATE score and infiltrating immune cell populations. On the contrary, patients with higher OS-scores were more likely to have higher tumor purity. PCR assays showed that, MRPL44 and CYCS were significantly higher expressed in LUAD cell lines, while CAT was significantly lower expressed. Conclusion: The novel oxidative stress-related model we identified could be used for prognosis and treatment prediction in lung adenocarcinoma.

Anthropogenic activity and millennial climate variability affect Holocene mercury deposition of an alpine wetland near the largest mercury mine in China.

Mercury (Hg) is a potentially toxic element that can be transported globally through the atmosphere, once deposited in the environment, has strong bioaccumulation and extreme toxicity in food webs, especially in wetland ecosystems. Anthropogenic Hg emissions have enhanced Hg deposition by 3-5 times since the industrial revolution, and the mining and smelting of Hg ore are important emission sources. However, the dynamics in Hg deposition around the largest Hg mine in China before the industrial revolution and their driving forces remain poorly explored. Here we reconstruct the atmospheric Hg depositional fluxes (named here Hg influx (Hginflux)) during the Holocene using a 450-cm alpine wetland sediment core taken from the Jiulongchi wetland, which is only 65 km to the Wanshan Mercury Mine. Our record shows an abrupt rapid increase in Hg concentration since 2500 cal yr BP, suggesting that Hg mining in southwest China may have started before the establishment of the Qin dynasty. Two major Hginflux peaks were found during the periods 10,000-6000 and 6000 - 3800 cal yr BP, with an increase in Hg deposition by a factor of 4-8. These two peaks are also found in other terrestrial archives from several sites across the Northern Hemisphere. We speculate that critical millennial-scale climate changes, i.e., the Holocene Climatic Optimum (HCO) and the Mid-Holocene Transition (MHT), were the potential triggers of these two Hginflux peaks. This study highlights the importance of climatic variability and local Hg mining in controlling atmospheric Hg deposition during the Holocene.

A Preprogrammable Continuum Robot Inspired by Elephant Trunk for Dexterous Manipulation.

Cable-driven continuum robots with hyper-redundant deformable backbones show great promise in applications, such as inspection in unstructured environments, where traditional rigid robots with discrete links and joints fail to operate. However, the motion of existing continuum robots is still constrained by their homogeneous backbones, and limited to environments with modest geometrical complexity. In this study, inspired by highly deformable elephant trunks, we presented a modular tensegrity structure with preprogrammable stiffness for continuum robots. Then we derived a mechanical model based on a positional formulation finite element method for predicting the configuration of the structure in different deformation scenarios. Theoretical predictions revealed that the curvature of each segment could be regulated by preprogramming their spring stiffness. Hence, our customizable design could offer an effective route for efficient robotic interactions. We further fabricated a continuum robot consisting of 12 modules, and showcased its deformation patterns under multiple scenarios. By regulating the distribution of spring stiffness, our robot could move through channels with varying curvatures, exhibiting its potential for applications where varying curvature, and conformal and efficient interactions are needed. Leveraging the inherent intelligence, this robotic system could simplify the complexity of the required actuation and control systems.

Mg2+ and Cu2+ Charging Agents Improving Electrophoretic Deposition Efficiency and Coating Adhesion of Nano-TbF3 on Sintered Nd-Fe-B Magnets.

In order to prepare nano-TbF3 coating with high quality on the surface of Nd-Fe-B magnets by electrophoretic deposition (EPD) more efficiently, Mg2+ and Cu2+ charging agents are introduced into the electrophoretic suspension and the influence on the electrophoretic deposition is systematically investigated. The results show that the addition of Mg2+ and Cu2+ charging agents can improve the electrophoretic deposition efficiency and coating adhesion of nano-TbF3 powders on sintered Nd-Fe-B magnets. The EPD efficiency increases by 116% with a relative content of Mg2+ as 3%, while it increases by 109% with a relative content of Cu2+ as 5%. Combining the Hamaker equation and diffusion electric double layer theory, the addition of Mg2+ and Cu2+ can change the zeta potential of charged particles, resulting in the improvement of EPD efficiency. The relative content of Mg2+ below 3% and Cu2+ below 5% can increase the thickness of the diffusion electric double layer, the excessive addition of a charging agent will compress the diffusion electric double layer, and thicker diffusion layer represents higher zeta potential. Furthermore, the addition of Mg2+ and Cu2+ charging agents greatly improves the coating adhesion, and the critical load for the cracking of the coating increases to 146.4 mN and 40.2 mN from 17.9 mN, respectively.

Mercury deposition and redox transformation processes in peatland constrained by mercury stable isotopes.

Peatland vegetation takes up mercury (Hg) from the atmosphere, typically contributing to net production and export of neurotoxic methyl-Hg to downstream ecosystems. Chemical reduction processes can slow down methyl-Hg production by releasing Hg from peat back to the atmosphere. The extent of these processes remains, however, unclear. Here we present results from a comprehensive study covering concentrations and isotopic signatures of Hg in an open boreal peatland system to identify post-depositional Hg redox transformation processes. Isotope mass balances suggest photoreduction of HgII is the predominant process by which 30% of annually deposited Hg is emitted back to the atmosphere. Isotopic analyses indicate that above the water table, dark abiotic oxidation decreases peat soil gaseous Hg0 concentrations. Below the water table, supersaturation of gaseous Hg is likely created more by direct photoreduction of rainfall rather than by reduction and release of Hg from the peat soil. Identification and quantification of these light-driven and dark redox processes advance our understanding of the fate of Hg in peatlands, including the potential for mobilization and methylation of HgII.

Novel thiophene-based donor-acceptor scaffolds as cathodes for rechargeable aqueous zinc-ion hybrid supercapacitors.

Well-defined π-conjugated thiophene donor-acceptor molecules play an important role in different fields ranging from synthetic chemistry to materials science. Their chemical structure provides specific electronic and physicochemical properties, which can be further tuned by the introduction of functional groups. Herein, we design and synthesize two novel thiophene-based π-conjugated donor-acceptor molecules TDA-1 and TDA-2 through Aldol and Knoevenagel condensations. In our proof-of-concept study we report for the first time on the use of small organic molecules employed in aqueous zinc-ion hybrid supercapacitors (Zn-HSCs),which exhibit capacitance as high as 206.7 and 235.2 F g-1 for TDA-1, and TDA-2, respectively.

A Physics-Guided Coordinated Distributed MPC Method for Shape Control of an Antenna Reflector.

Active shape control for an antenna reflector is a significant procedure used to compensate for the impacts of a complicated space environment. In this article, a physics-guided distributed model predictive control (DMPC) framework for reflector shape control with input saturation is proposed. First, guided by the actual physical characteristics, an overall structural system is decomposed into multilevel subsystems with the help of a so-called substructuring technique. For each subsystem, a prediction model with information interaction is discretized by an explicit Newmark- ß method. Then, to improve the system-wide control performance, a coordinator among all the subsystems is designed in an iterative fashion. The input saturation constraints are addressed by transforming the original problem into a linear complementarity problem (LCP). Finally, by solving the LCP, the input trajectory can be obtained. The performance of the proposed DMPC algorithm is validated through an experiment on the shape control of an antenna reflector structure.

Robust motion trajectory optimization of overhead cranes based on polynomial chaos expansion.

In this paper, we present a polynomial chaos-based framework for the trajectory optimization of an overhead crane system under uncertainty. The main research described in this paper is as follows. First, the deterministic trajectory optimization problem formulation of a two-dimensional overhead crane model is constructed. Based on this basic mathematical formulation, the uncertainty trajectory optimization problem is formed considering the uncertainty of initial state and system parameter. Then, to solve the uncertainty trajectory optimization problem efficiently, a robust trajectory optimization problem formulation is proposed. However, it is difficult to solve the robust trajectory optimization problem directly because it contains stochastic function terms, such as stochastic dynamic equations, constraint functions and objective functions. We consider both the system state and control input as functions of uncertainty and use polynomial chaos expansion to quantify these stochastic functions. An augmented deterministic trajectory optimization problem which can be solved directly is finally obtained. Based on the proposed robust trajectory optimization formation, the motion trajectory optimization of an overhead crane system under two different uncertainty types of is solved. All simulation results are compared with traditional sampling-based Monte Carlo simulations to demonstrate the feasibility and effectiveness of the proposed method.

Emulsion-Guided Controllable Construction of Anisotropic Particles: Droplet Size Determines Particle Structure.

Anisotropic particles have attracted significant attention due to their alluring features that distinguish them from isotropic particles. One of the most appealing strategies for the synthesis of anisotropic particles is the emulsion-guided method. However, morphological control and the understanding of formation mechanisms have remained a major challenge. Based on a novel mechanism, here, a facile one-pot emulsion-templating method for the tunable construction of anisotropic polymeric particles (APPs) with different defined structures is reported. Three types of monocomponent APPs with new morphologies and sizes in the range of 240-650 nm, including Janus mushroom-like mesoporous poly(m-phenylenediamine) (PmPD) particles, wheel-shaped particles, and acorn-like PmPD particles, are obtained by controlling the average size of the oil droplets in the emulsion. Furthermore, the APPs demonstrate the ability for conversion to nitrogen-doped anisotropic carbon particles (ACPs) by pyrolysis at 800 °C under a N2 atmosphere, thereby inheriting their structures. These novel ACPs show appreciable potential as metal-free electrocatalysts for use in oxygen reduction reactions. Compared to their isotropic counterpart, these ACPs exhibit remarkable advantages such as enhanced specific surface area and pore volume, reduced stacking density, and easy fabrication of continuous and uniform membrane electrodes.

Quantum Capacitance through Molecular Infiltration of 7,7,8,8-Tetracyanoquinodimethane in Metal-Organic Framework/Covalent Organic Framework Hybrids.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been extensively investigated during the last two decades. More recently, a family of hybrid materials (i.e., MOF@COF) has emerged as particularly appealing for gas separation and storage, catalysis, sensing, and drug delivery. MOF@COF hybrids combine the unique characteristics of both MOF and COF components and exhibit peculiar properties including high porosity and large surface area. In this work, we show that the infiltration of redox-active 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecules into the pores of MOF@COF greatly improves the characteristics of the latter, thereby attaining high-performance energy storage devices. Density functional theory (DFT) calculations were employed to guide the design of a MOF@COF-TCNQ hybrid with the TCNQ functional units incorporated in the pores of MOF@COF. To demonstrate potential application of our hybrids, the as-synthesized MOF@COF-TCNQ hybrid has been employed as an active material in supercapacitors. Electrochemical energy storage analysis revealed outstanding supercapacitor performance, as evidenced by a specific areal capacitance of 78.36 mF cm-2 and a high stack volumetric energy density of 4.46 F cm-3, with a capacitance retention of 86.4% after 2000 cycles completed at 0.2 A cm-2. DFT calculation results strongly indicate that the high capacitance of MOF@COF-TCNQ has a quantum capacitance origin. Our liquid-phase infiltration protocol of MOF@COF hybrids with redox-active molecules represents a efficacious approach to design functional porous hybrids.