Boosting the Lithium-Ion Transport Kinetics of Sn-Based Coordination Polymers through Ligand Aromaticity Manipulation.

Tin-based compounds are promising anode materials for lithium-ion batteries owing to their low charge/discharge voltage and high theoretical capacity but are plagued by both huge volume expansion during cycling and complex synthetic procedures. Constructing a coordination network between Sn and the lithium-active organic matrix can effectively relieve the volume expansion and increase the lithium storage active site utilization. Herein, we report a facile method to prepare two one-dimensional Sn-based coordination polymers [Sn(Hcta)]n (1) and [Sn(Hbtc)]n (2) (H3cta = 1,3,5-cyclohexanetricarboxylic acid, H3btc = 1,3,5-benzenetricarboxylic acid) for lithium storage, which differ only in the aromaticity of the ligand. 2 with an aromatic ligand provided a reversible capacity of 833 mAh g-1 at 200 mA g-1 over 160 cycles, higher than that of 1 without an aromatic ligand due to the quick charge transfer. The reversible lithium storage reactions of metal centers and organic ligands and the volume expansion rate of Sn-based coordination polymers during cycling were studied by detailed characterization and density functional theory (DFT) calculations. This research revealed that the structural factor of ligand aromaticity in these Sn-based coordination polymers boosted the utilization of active sites and rapid charge transfer, offering a coordination chemistry strategy for the design and synthesis of advanced anode materials.

Site-selective superassembly of biomimetic nanorobots enabling deep penetration into tumor with stiff stroma.

Chemotherapy remains as the first-choice treatment option for triple-negative breast cancer (TNBC). However, the limited tumor penetration and low cellular internalization efficiency of current nanocarrier-based systems impede the access of anticancer drugs to TNBC with dense stroma and thereby greatly restricts clinical therapeutic efficacy, especially for TNBC bone metastasis. In this work, biomimetic head/hollow tail nanorobots were designed through a site-selective superassembly strategy. We show that nanorobots enable efficient remodeling of the dense tumor stromal microenvironments (TSM) for deep tumor penetration. Furthermore, the self-movement ability and spiky head markedly promote interfacial cellular uptake efficacy, transvascular extravasation, and intratumoral penetration. These nanorobots, which integrate deep tumor penetration, active cellular internalization, near-infrared (NIR) light-responsive release, and photothermal therapy capacities into a single nanodevice efficiently suppress tumor growth in a bone metastasis female mouse model of TNBC and also demonstrate potent antitumor efficacy in three different subcutaneous tumor models.

Hydrogen-bonded Complex-based Frameworks for Stable Lithium Storage.

Metal-complex-based materials for lithium storage have attracted great interest due to their highly designable structures with multiple active sites and well-defined lithium transport pathways. Their cycling and rate performances, however, are still constrained by structural stability and electrical conductivity. Herein, we present two hydrogen-bonded complex-based frameworks with excellent lithium storage capability. Multiple hydrogen bonds among the mononuclear molecules result in three-dimensional frameworks that are stable in electrolyte. The origin of the remarkable lithium storage performance of this family was revealed through kinetic analysis and DFT calculations.

High-Efficiency Lithium-Ion Transport in a Porous Coordination Chain-Based Hydrogen-Bonded Framework.

Fast and selective Li+ transport in solid plays a key role for the development of high-performance solid-state electrolytes (SSEs) of lithium metal batteries. Porous compounds with tunable Li+ transport pathways are promising SSEs, but the comprehensive performances in terms of Li+ transport kinetics, electrochemical stability window, and interfacial compatibility are difficult to be achieved simultaneously. Herein, we report a porous coordination chain-based hydrogen-bonded framework (NKU-1000) containing arrayed electronegative sites for Li+ transport, exhibiting a superior Li+ conductivity of 1.13 × 10-3 S cm-1, a high Li+ transfer number of 0.87, and a wide electrochemical window of 5.0 V. The assembled solid-state battery with NKU-1000-based SSE shows a high discharge capacity with 94.4% retention after 500 cycles and can work over a wide temperature range without formation of lithium dendrites, which derives from the linear hopping sites that promote a uniformly high-rate Li+ flux and the flexible structure that can buffer the structural variation during Li+ transport.

Effect of the incident polarization on in-plane and out-of-plane spin splitting near the critical angle.

To reveal the effect of the incident polarization on the spin splitting of the photonic spin Hall effect (that is, the spatial and angular in-plane and out-of-plane spin splitting), we systematically study the phenomena and characteristics of these four spin splitting generated when the beam with arbitrary linear polarization is reflected from the non-absorbing medium interface and the absorbing medium interface. Several features of the relationship between the incident polarization and the four kinds of spin splitting are found. In addition, It is also found that the in-plane angular and spatial shifts are significantly enhanced near the critical angle, even reaching their theoretical upper limit. However, the out-of-plane shifts are not enhanced. The research in this paper will contribute to a deeper understanding of PSHE. These findings can also provide new ideas and methods for precision metrology, photonic manipulation, and photonic device fabrication.

Selective CO2 electrolysis to CO using isolated antimony alloyed copper.

Renewable electricity-powered CO evolution from CO2 emissions is a promising first step in the sustainable production of commodity chemicals, but performing electrochemical CO2 reduction economically at scale is challenging since only noble metals, for example, gold and silver, have shown high performance for CO2-to-CO. Cu is a potential catalyst to achieve CO2 reduction to CO at the industrial scale, but the C-C coupling process on Cu significantly depletes CO* intermediates, thus limiting the CO evolution rate and producing many hydrocarbon and oxygenate mixtures. Herein, we tune the CO selectivity of Cu by alloying a second metal Sb into Cu, and report an antimony-copper single-atom alloy catalyst (Sb1Cu) of isolated Sb-Cu interfaces that catalyzes the efficient conversion of CO2-to-CO with a Faradaic efficiency over 95%. The partial current density reaches 452 mA cm-2 with approximately 91% CO Faradaic efficiency, and negligible C2+ products are observed. In situ spectroscopic measurements and theoretical simulations reason that the atomic Sb-Cu interface in Cu promotes CO2 adsorption/activation and weakens the binding strength of CO*, which ends up with enhanced CO selectivity and production rates.

One-Step Approach for Constructing High-Density Single-Atom Catalysts toward Overall Water Splitting at Industrial Current Densities.

The construction of highly active, durable, and cost-effective catalysts is urgently needed for green hydrogen production. Herein, catalysts consisting of high-density Pt (24 atoms nm-2 ) and Ir (32 atoms nm-2 ) single atoms anchored on Co(OH)2 were constructed by a facile one-step approach. Remarkably, Pt1 /Co(OH)2 and Ir1 /Co(OH)2 only required 4 and 178 mV at 10 mA cm-2 for hydrogen evolution reaction and oxygen evolution reaction, respectively. Moreover, the assembled Pt1 /Co(OH)2 //Ir1 /Co(OH)2 system showed mass activity of 4.9 A mgnoble metal -1 at 2.0 V in an alkaline water electrolyzer, which is 316.1 times higher than that of Pt/C//IrO2 . Mechanistic studies revealed that reconstructed Ir-O6 single atoms and remodeled Pt triple-atom sites enhanced the occupancy of Ir-O bonding orbitals and improved the occupation of Pt-H antibonding orbital, respectively, contributing to the formation of the O-O bond and the desorption of hydrogen. This one-step approach was also generalized to fabricate other 20 single-atom catalysts.

Insights into the enzymatic degradation of DNA expedited by typical perfluoroalkyl acids.

Perfluoroalkyl acids (PFAAs) are considered forever chemicals, gaining increasing attention for their hazardous impacts. However, the ecological effects of PFAAs remain unclear. Environmental DNA (eDNA), as the environmental gene pool, is often collected for evaluating the ecotoxicological effects of pollutants. In this study, we found that all PFAAs investigated, including perfluorohexanoic acid, perfluorooctanoic acid, perfluorononanoic acid, and perfluorooctane sulfonate, even at low concentrations (0.02 and 0.05 mg/L), expedited the enzymatic degradation of DNA in a nonlinear dose-effect relationship, with DNA degradation fragment sizes being lower than 1,000 bp and 200 bp after 15 and 30 min of degradation, respectively. This phenomenon was attributed to the binding interaction between PFAAs and AT bases in DNA via groove binding. van der Waals force (especially dispersion force) and hydrogen bonding are the main binding forces. DNA binding with PFAAs led to decreased base stacking and right-handed helicity, resulting in loose DNA structure exposing more digestion sites for degrading enzymes, and accelerating the enzymatic degradation of DNA. The global ecological risk evaluation results indicated that PFAA contamination could cause medium and high molecular ecological risk in 497 samples from 11 contamination-hot countries (such as the USA, Canada, and China). The findings of this study show new insights into the influence of PFAAs on the environmental fates of biomacromolecules and reveal the hidden molecular ecological effects of PFAAs in the environment.

Ti3C2(OH)x-assisted LDI-TOF-MS for the rapid analysis of natural small molecules.

The inhomogeneous distribution of co-crystallized analytes and the traditional organic matrices as well as the intensive background interference in the low molecular weight range hinder the application of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) in the analysis of small-molecular compounds. New two-dimensional material MXene (e.g., Ti3C2) exerts better hydrophilicity, homogeneity and repeatability, and higher laser desorption efficiency, as well as less background interference than traditional organic matrices and other nanomaterial matrices such as titanium oxide, graphene, and gold nanostructures. This study was aimed to design Ti3C2 matrix with abundant hydroxyls on its surface, enhance the stability of this hydroxyl-rich Ti3C2 (Ti3C2(OH)x), and evaluate the analytical performances of Ti3C2(OH)x-assisted laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF-MS) for small-molecular natural compounds in complex samples. The developed Ti3C2(OH)x showed the distinct advantages such as minimum background interference, high peak intensity (~105), high salt (0.6 M) and protein (0.5 mg/mL) tolerance, good repeatability (relative standard deviation<20%), and good stability after eight months of storage. Ti3C2(OH)x-assisted LDI-TOF-MS analysis could be used to rapidly identify Artemisia annua (a world-famous traditional Chinese medicine) and quantify the contents of the main chemical ingredients (oxymatrine (OXY) and matrine) of Compound Kushen Injection (CKI). Interestingly, the content of OXY in CKI could be accurately quantified by Ti3C2(OH)x-assisted LDI-TOF-MS, and there was a good linear relationship (R2 -0.9929), a low limit of detection (400 pg), and a low limit of quantification (600 pg) of OXY. Taken together, the rapid and accurate analysis of small-molecular natural compounds in complicated samples could be achieved by the Ti3C2(OH)x-assisted LDI-TOF-MS analysis.

A MOF-derived hierarchical CoP@ZnIn2S4 photocatalyst for visible light-driven hydrogen evolution.

A hierarchical CoP@ZnIn2S4 photocatalyst was prepared via a MOF-templated strategy. Owing to the unique composition and morphology that can facilitate the separation of photoexcited carriers, enhance light absorption and provide high surface area, CoP@ZnIn2S4 exhibited a H2 evolution rate of 0.103 mmol h-1 and remained stable over 24 hours.

Agricultural waste-derived biochars from co-hydrothermal gasification of rice husk and chicken manure and their adsorption performance for dimethoate.

This study aimed to combine energy utilisation of agricultural wastes with the dimethoate (DT) adsorption from agricultural wastewater via hydrogen and biochar production using co-hydrothermal gasification (CHTG). The gasification behaviour after CHTG of five ratios of rice husk (RH) and chicken manure (CM) and the corresponding adsorption performance of biochars on DT were evaluated. The results demonstrated that the feedstock of 3RH+ 1CM achieved the maximum gas yield and hydrogen gasification efficiency (HGE), and the highest adsorption capacity of the derived biochars was 3.57 mg g-1. Surface characterisation and elemental analysis showed that the biochar derived under different C/N ratios varied considerably. The results of the isotherm and kinetic simulation showed that the Langmuir model and pseudo-first-order model best fitted the experimental data. The superior performance of agricultural waste-derived biochars (AWB) over five cycles of regeneration and adsorption indicated that AWB is a green and stable adsorption material for farmland tailwater. In addition, the degradation pathway of DT during hydrothermal gasification (HTG) regeneration of the spent adsorbent was comprehensively discussed. The CHTG treatment enhanced the yield of gaseous products from RH and CM and produced AWBs with high adsorption capacities for DT. This provides a green and efficient technology for resource utilisation of agricultural waste and treatment of agricultural wastewater using pesticide residues.

Super-Assembled Periodic Mesoporous Organosilica Frameworks for Real-Time Hypoxia-Triggered Drug Release and Monitoring.

Hypoxia, induced by inadequate oxygen supply, is a key indication of various major illnesses, which necessitates the need to develop new nanoprobes capable of sensing hypoxia environments for the targeted system monitoring and drug delivery. Herein, we report a hypoxia-responsive, periodic mesoporous organosilica (PMO) nanocarrier for repairing hypoxia damage. ß-cyclodextrin (ß-CD) capped azobenzene functionalization on the PMO surface could be effectively cleaved by azoreductase under a hypoxia environment. Moreover, the nanosystem is equipped with fluorescence resonance energy transfer (FRET) pair (tetrastyrene derivative (TPE) covalently attached to the PMO framework as the donor and Rhodamine B (RhB) in the mesopores as the receptor) for intracellular visualization and tracking of drug release in real-time. The design of intelligent nanocarriers capable of simultaneous reporting and treating of hypoxia conditions highlights a great potential in the biomedical domain.

Wood-Derived Bimetallic and Heteroatomic Hierarchically Porous Carbon Aerogel for Rechargeable Flow Zn-Air Batteries.

It is necessary to correctly research and synthesize efficient and inexpensive catalysts to achieve reversible oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which is also a prerequisite for zinc-air batteries (ZABs). However, it is still a huge challenge to manufacture electrocatalysts with durable and high electrocatalytic performance from biomass. Here, a convenient method of delignification was used to transform natural balsa wood into a layered porous carbon material, FeCo alloy supported on a N, S-doped wood-based carbon aerogel (FeCo@NS-CA) as the cathode in rechargeable flow ZAB. The obtained FeCo@NS-CA with the porous lamellar architecture exhibits superior bifunctional electrocatalysis, including excellent electrochemical activities and superior stabilities. For ORR, relative to the reversible hydrogen electrode, the onset potential of FeCo@NS-CA is 0.97 V, and the half-wave potential is 0.85 V, which is consistent with the potential of commercial Pt/C. For OER, FeCo@NS-CA obtained an overpotential of 450 mV, which is very similar to the overpotential of the benchmark RuO2. The superior performance could be owing to the alloy carrier interaction between the FeCo alloy and the wood-based carbon aerogel co-doped with N and S. Moreover, the bifunctional air cathode in a flow ZAB assembled with the FeCo@NS-CA catalyst at a current density of 10 mA cm-2; the power density is 140 mW cm-2, and the specific capacitance is 760 mA h gZn-1, with a remarkable long-term stability of 400 h better than ZAB of benchmark Pt/C + RuO2. This research lays the foundation for transforming abundant biomass resources into high environmental protection materials for energy-related applications.

Super-Assembled Hierarchical CoO Nanosheets-Cu Foam Composites as Multi-Level Hosts for High-Performance Lithium Metal Anodes.

Achieving uniform lithium (Li) deposition is the key to tackle uncontrollable dendrite growth, which hinders the application of Li metal anodes. In this study, molten Li is thermally injected into a 3D framework by growing lithiophilic CoO nanosheets on Cu foam (CF). The CoO layer grown on the CF surface physically adsorbs molten Li, which makes it possible to spontaneously wet the framework. The morphology of CoO nanosheets does not change during the Li injection process and formed a multi-level structure with the CF, which is difficult to be achieved previously, as most lithiophilic oxides undergo serious chemical changes due to chemical reaction with Li and cannot provide a stable submicron structure for the subsequent Li stripping/plating process. The super-assembled multi-level structure provides abundant Li nucleation sites and electrolyte/electrode contact areas for rapid charge transfer in the composite anode. Therefore, the prolonged lifespan of symmetrical cells for 300 cycles at 10 and 10 mAh cm-2 with lower polarization is achieved, which further renders the LiFePO4 and Li4 Ti5 O12 based full cells with improved capacity retention up to 87.3% and 80.1% after 500 cycles at 1 C. These results suggest that the composite anode has a great application prospect.

Interfacial Super-Assembly of T-Mode Janus Porous Heterochannels from Layered Graphene and Aluminum Oxide Array for Smart Oriented Ion Transportation.

Salinity gradient energy existing in seawater and river water is a sustainable and environmentally energy resource that has drawn significant attention of researchers in the background of energy crisis. Nanochannel membrane with a unique nano-confinement effect has been widely applied to harvest the salinity gradient energy. Here, Janus porous heterochannels constructed from 2D graphene oxide modified with polyamide (PA-GO) and oxide array (anodic aluminum oxide, AAO) are prepared through an interfacial super-assembly method, which can achieve oriented ion transportation. Compared with traditional nanochannels, the PA-GO/AAO heterochannels with asymmetric charge distribution and T-mode geometrical nanochannel structure shows directional ionic rectification features and outstanding cation selectivity. The resulting heterochannel membrane can achieve a high-power density of up to 3.73 W m-2 between artificial seawater and river water. Furthermore, high energy conversion efficiency of 30.3% even in high salinity gradient can be obtained. These achievable results indicate that the PA-GO/AAO heterochannels has significant potential application in salinity gradient energy harvesting.

Laser Cladding Induced Spherical Graphitic Phases by Super-Assembly of Graphene-Like Microstructures and the Antifriction Behavior.

Laser cladding coatings with excellent wear resistance behaviors are prepared on a titanium alloy substrate with a new precursor material system comprising nanoscale B4C and Ni60A self-fluxing alloy powder. Structural analysis reveals the existence of micron-size spherical or nearly spherical graphitic phases in the prepared coatings, which are composed of graphene-like microstructures closely associated with other reinforcement phases of high hardness such as TiC and CrB. The formation mechanism of these graphitic phases involves in situ superassembly of uncombined C atoms via repeated growth and reorientation of the graphene-like microstructures and is closely related to the laser processing parameters as well as the precursor compositions. The coexistence of these heterogeneous phases enable the obtained coatings with high wear resistance and low friction coefficient. It was found that the wear resistance of the coating has a remarkable 43.67 times enhancement than that of the titanium alloy while simultaneously showing a low friction coefficient (∼0.35). The understanding of the formation mechanism on the graphene-related novel microstructures with significantly improved mechanical properties is expected to lay the foundation for future developments and applications of graphene and its related carbon materials, such as large-scale production and further incorporation into composite materials with desired local structures.

Implantable and Biodegradable Micro-Supercapacitor Based on a Superassembled Three-Dimensional Network Zn@PPy Hybrid Electrode.

Transient supercapacitors (TSCs), a new type of advanced supercapacitor (SC) that can completely dissolve with environmentally and biologically benign byproducts in vivo after performing their specified function, have broad application prospects in the fields of green electronics, implantable devices, personalized medicine, military security, and other fields. However, research on TSCs is still in its infancy, and there are still many challenges to be solved, such as the complex preparation process and low energy density. Herein, we report a facile superassembly manufacturing method for an implantable and fully biodegradable three-dimensional network Zn@PPy hybrid electrode by screen printing and electrochemical deposition. The produced superassembled interdigital pseudocapacitor exhibits superior electrochemical performances due to the high capacitances and excellent rate performances of the pattern Zn@PPy electrode and NaCl/agarose electrolyte. An optimized biodegradable SC exhibits a maximum energy density of 0.394 mW h cm-2 and can be fully degraded in vivo in 30 days without any adverse effects in the host organism. This work provides a new platform for transient electronic technology for diverse implantable electronic applications.

Electrospinning Superassembled Mesoporous AIEgen-Organosilica Frameworks Featuring Diversified Forms and Superstability for Wearable and Washable Solid-State Fluorescence Smart Sensors.

Flexible optical sensors are widely studied and applied in many fields. However, developing highly stable and washable wearable sensors in optics is still facing significant challenges. Here, we demonstrate an AIEgen-organosilica framework (TPEPMO) hybrid nanostructure-based flexible optical sensor, which is prepared by a two-step co-condensation and electrospinning superassembly process. Organosilica precursors with aggregation-induced emission (AIE) features are covalently linked into periodic mesoporous organosilica (PMO) frameworks with high fluorescent efficiency due to the restriction of intramolecular motion. The three-dimensional space of ordered porous materials provides abundant reaction sites, allowing rapid and sensitive monitoring of analytes. TPEPMOs exhibit good properties as acidic pH fluorescent sensors with a pKa of 4.3. A flexible film is obtained by dispersing TPEPMO nanospheres in a poly(lactic-co-glycolic acid) (PLGA) and polyacrylonitrile (PAN) hybrid fibrous matrix (TPEPMO-CFs) using the electrospinning superassembly technique and is successfully served as an efficient fluorescent probe for the naked eye detection of ammonia gas and HCl vapor by emission changes. The fluorescence of TPEPMO-CFs can be reversed in the presence of volatile acidic/alkaline gas for more than five cycles, exhibiting excellent recyclability. In addition, TPEPMO-CF sensors show excellent washability and long-term photostability (fluorescence was maintained above 94% after washing 10 times). These stimuli-responsive AIEgen-organosilica frameworks featuring diversified forms and superstability for wearable and washable solid-state fluorescence exhibit great potential for smart gas sensors, wearable devices, and solid-state lighting applications.

Formation and inhibition of polycyclic aromatic hydrocarbons from the gasification of cyanobacterial biomass in supercritical water.

Polycyclic aromatic hydrocarbons (PAHs) formation and inhibition from supercritical water gasification (SCWG) of cyanobacterial biomass were investigated. High reaction temperature, long residence time, and low feedstock concentration favoured higher molecular weight (HMW) PAH formation. The total PAH yield reached 34.80 µg g-1 at 500 °C, 22.5 MPa, and 10 min. The main PAHs formed in the liquid phase and the solid residue were 3-ring and 4-ring PAHs, which were generated from the cycloaddition reaction of lower molecular weight (LMW) PAHs. In addition, 2-ring PAHs were produced from the Diels-Alder reaction of phenols and unsaturated hydrocarbons. The possible control methods for PAH formation during the SCWG of cyanobacterial biomass were proposed. H2O2 addition effectively inhibited the reaction pathways underlying PAH formation, and the addition at more than 1.0% concentration suppressed H2 production. The work revealed that the inhibition of PAHs was achieved in terms of improving the oxidisation condition during the SCWG process for converting wet biomass or organic wastes to energy sources.

Interfacial Superassembly of Grape-Like MnO-Ni@C Frameworks for Superior Lithium Storage.

Despite the excellent electrochemical performance of MnO-based electrodes, a large capacity increase cannot be avoided during long-life cycling, which makes it difficult to seek out appropriate cathode materials to match for commercial applications. In this work, a grape-like MnO-Ni@C framework from interfacial superassembly with remarkable electrochemical properties was fabricated as anode materials for lithium-ion batteries. Electrochemical analysis indicates that the introduction of Ni not only contributes to the excellent rate capability and high specific capacity but also prevents further oxidation of MnO to the higher valence states for ultrastable long-life cycling performance. Furthermore, thermodynamic calculation proves that the ultrastable long cycling life of the Ni-Mn-O system originated from a buffer composition region to stabilize the MnO structure. Because of the unique grape-like structure and performance of the Ni-Mn-O system, the MnO-Ni@C electrode displayed an invertible specific capacity of 706 mA h g-1 after 200 cycles at a current density of 0.1 A g-1 and excellent cycling stability maintained a capacity of 476.8 mA h g-1 after 2100 cycles at 1.0 A g-1 without obvious capacity change. This new nanocomposite material could offer a novel fabrication strategy and insight for MnO-based materials and other metal oxides as anodes for improved electrochemical performance.