Amorphous Vanadium Oxides with Dual ion Storage Mechanism for High-Performance Aqueous Zinc ion Batteries.

Owing to the extremely limited structural deformation caused by the introduction of guest ions that their rigid structure can sustain, crystalline materials typically fail owing to structural collapse when utilized as electrode materials. Amorphous materials, conversely, are more resistant to volume expansion during dynamic ion transport and can introduce a lot of defects as active sites. Here, The amorphous polyaniline-coated/intercalated V2O5·nH2O (PVOH) nanowires are prepared by in situ chemical oxidation combined with self-assembly strategy, which exhibited impressive electrochemical properties because of its short-range ordered crystal structure, oxygen vacancy/defect-rich, improved electronic channels, and ionic channels. Through in situ techniques, the energy storage mechanism of its Zn2+/H+ co-storage is investigated and elucidated. Additionally, this work provides new insights and perspectives for the investigation and application of amorphous cathodes for aqueous zinc ion batteries.

One-Step Pyrolysis Construction of Bimetallic Atom-Cluster Sites for Boosting Bifunctional Catalytic Activity in Zn-Air Batteries.

Due to their unique advantages, single atoms and clusters of transition metals are expected to achieve a breakthrough in catalytic activity, but large-scale production of active materials remains a challenge. In this work, a simple solvent-free one-step annealing method is developed and applied to construct diatomic and cluster active sites in activated carbon by utilizing the strong anchoring ability of phenanthroline to metal ions, which can be scaled for mass productions. Benefiting from the synergy between the different metals, the obtained sub-nano-bimetallic atom-cluster catalysts (FeNiAC -NC) exhibit high oxygen reduction reactions (ORR) activity (E1/2 = 0.936 V vs. RHE) and a small ORR/oxygen evolution reaction (OER) potential gap of only 0.594 V. An in-house pouch Zn-air battery is assembled using an FeNiAC -NC catalyst, which demonstrates a stability of 1000 h, outperforming previous reports. The existence of clusters and their effects on catalytic activity is analyzed by density functional theory calculations to reveal the chemistry of nano-bimetallic atom-cluster catalysts.

Thickness-Controlled Synthesis of Compact and Uniform MOF Protective Layer for Zinc Anode to Achieve 85% Zinc Utilization.

Zinc anode-based aqueous batteries have attracted considerable interest for large-scale energy storage and wearable devices. Unfortunately, the formation of Zn dendrite, parasitic hydrogen evolution reaction (HER), and irreversible by-products, seriously restrict their practical applications. Herein, a series of compact and uniform metal-organic frameworks (MOFs) films with precisely controlled thickness (150-600 nm) are constructed by a pre-oxide gas deposition (POGD) method on Zn foil. Under the protection of MOF layer with optimum thickness, the corrosion of zinc, the side reaction of hydrogen evolution, and the growth of dendrites on the zinc surface are suppressed. The symmetric cell based on Zn@ZIF-8 anode exhibits exceptional cyclicality for over 1100 h with low voltage hysteresis of≈38 mV at 1 mA cm-2 . Even at current densities of 50 mA cm-2 with an area capacity of 50 mAh cm-2 (85% Zn utilization), the electrode can keep cycling for >100 h. Besides, this Zn@ZIF-8 anode also delivers a high average CE of 99.4% at 1 mA cm-2 . Moreover, a rechargeable Zn ion battery is fabricated based on the Zn@ZIF-8 anode and MnO2 cathode, which presents an exceptionally long lifespan with no capacity attenuation for 1000 cycles.

Critical Role of Phosphorus in Hollow Structures Cobalt-Based Phosphides as Bifunctional Catalysts for Water Splitting.

Cobalt phosphides electrocatalysts have great potential for water splitting, but the unclear active sides hinder the further development of cobalt phosphides. Wherein, three different cobalt phosphides with the same hollow structure morphology (CoP-HS, CoP2 -HS, CoP3 -HS) based on the same sacrificial template of ZIF-67 are prepared. Surprisingly, these cobalt phosphides exhibit similar OER performances but quite different HER performances. The identical OER performance of these CoPx -HS in alkaline solution is attributed to the similar surface reconstruction to CoOOH. CoP-HS exhibits the best catalytic activity for HER among these CoPx -HS in both acidic and alkaline media, originating from the adjusted electronic density of phosphorus to affect absorption-desorption process on H. Moreover, the calculated ΔGH* based on P-sites of CoP-HS follows a quite similar trend with the normalized overpotential and Tafel slope, indicating the important role of P-sites for the HER process. Moreover, CoP-HS displays good performance (cell voltage of 1.67 V at a current density of 50 mA cm-2 ) and high stability in 1 M KOH. For the first time, this work detailly presents the critical role of phosphorus in cobalt-based phosphides for water splitting, which provides the guidance for future investigations on transition metal phosphides from material design to mechanism understanding.

Recent Advances of Pore Structure in Disordered Carbons for Sodium Storage: A Mini Review.

Disordered carbons as the most promising anode materials for sodium ion batteries (SIBs) have attracted much attention, due to the widely-distributed sources and potentially high output voltage when applied in full cells owing to the almost lowest voltage plateau. The complex microstructure makes the sodium storage mechanism of disordered carbons controversial. Recently, many studies show that the plateau region of disordered carbons are closely related to the embedment of sodium ion/semimetal in nanopores. In this regard, the classification, characterization and construction of nanopores are exhaustively discussed in this review. In addition, perspectives about the controllable construction of nanopores are presented in the last section, aiming to catch out more valuable studies include not only the construction of closed pores to enhance capacity but also the design of carbon materials to understand Na storage mechanism.

Cathodic Electrodeposition of MOF Films Using Hydrogen Peroxide.

Metal-organic framework (MOF) films can be made by cathodic electrodeposition, where a Brønsted base is formed electrochemically which deprotonates the MOF linkers that are present in solution as undissociated/partially dissociated weak acids. However, the co-deposition of metal and the narrow range of possible metal nodes limit the scope of this method. In this work, we propose the use of hydrogen peroxide (hydrogen peroxide assisted cathodic deposition or HPACD), to overcome these limitations. Electrochemical measurements indicate that in DMF, hydrogen peroxide is reduced to superoxide anions that deprotonate the carboxylic ligands. This single-electron reduction happens at much higher potentials than all previous reported methods. This prevents the co-deposition of metal and extends the range of possible metal nodes. Various pure MOF films (HKUST-1, MIL-53(Fe) and MOF-5) were prepared via this approach. HPACD was also used for the preparation of patterned MOF films and of flexible Cu-BTC coated paper membranes which reject 99.1 % of Rose Bengal from water with a permeance of 8.4 L m-2 h-1 bar-1 .

Metal organic framework MIL-53(Fe) as an efficient artificial oxidase for colorimetric detection of cellular biothiols.

Biothiols play critical roles in many biological processes and their aberrant is related to a variety of syndromes. A simple and reliable colorimetric method is developed in this work for biothiols detection based on an oxidase mimic, a metal organic framework (MOF) MIL-53(Fe), and a peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB). In this design, MIL-53(Fe) is utilized to catalyze the conversion of TMB to a blue colored 3,3',5,5'-tetramethylbenzidine diimine, which can be read on a spectrophotometer at 652 nm. The oxidation-induced blue color generation can be efficiently inhibited by biothiols, thus a colorimetric analytical method is proposed for biothiols detection based on the above system. Under optimal conditions, a linear relationship in a range from 1 to 100 µM and a limit of detection (LOD) at 120 nM are achieved with Cys as a model target. The developed platform is further applied to evaluate cellular biothiols in normal (RWPE-1) and cancer (LNCap) cell lines, revealing that the overall biothiols level in LNCap is much higher than that in RWPE-1. This work renders a powerful tool for identifying cancer cells in a simple manner for biomedical diagnosis associated with biothiols.

F-Doping effects on carbon-coated Li3V2(PO4)3 as a cathode for high performance lithium rechargeable batteries: combined experimental and DFT studies.

F-Doping effects on polyaniline-derived carbon coated Li3V2(PO4)3 (Li3V2(PO4)3-xFx@C) as a cathode for high performance Li rechargeable batteries are systematically investigated with a combined experimental and DFT theoretical calculation approach. The results clearly indicate that the doping amount has a significant impact on the rate capability and long cycle life. The optimal material (Li3V2(PO4)2.88F0.12@C) delivers 123.16 mA h g-1@2C, which is close to the theoretical value (133 mA h g-1), while showing a greatly improved cycle stability. Rietveld refinements show that the F- doping does not obey Vegard's Law, which may be attributed to the generated lower valence of V ions. AC impedance spectroscopy shows that the F-doping can achieve faster interfacial charge transfer for higher reaction reversibility. DFT calculations confirm that the lower V2+ (t2g↑)3 does exist in Li3V2(PO4)2.88F0.12, and the mean nearest neighbor Li-O bond length also increases for faster electrochemical kinetics, and further reveal that there is a tendency for a transition from the insulator to the n-type semiconductor due to the F dopant. The combined experimental and calculated results suggest that F-doping indeed greatly facilitates the charge transfer rate of the Li+ insertion/de-insertion process for better reversibility and enhances the Li+ diffusion rate to access the reaction sites, thus resulting in high rate capacity and cycling stability. This work not only offers a facile and effective approach to synthesize high performance Li-ion battery material for very promising practical applications, but also discloses scientific insights on element coating and doping to guide the electrode material design for fast electrode kinetics in energy storage devices.

Nanosized Metal Phosphides Embedded in Nitrogen-Doped Porous Carbon Nanofibers for Enhanced Hydrogen Evolution at All pH Values.

Transition-metal phosphides (TMPs) have emerged as promising catalyst candidates for the hydrogen evolution reaction (HER). Although numerous methods have been investigated to obtain TMPs, most rely on traditional synthetic methods that produce materials that are inherently deficient with respect to electrical conductivity. An electrospinning-based reduction approach is presented, which generates nickel phosphide nanoparticles in N-doped porous carbon nanofibers (Ni2 P@NPCNFs) in situ. Ni2 P nanoparticles are protected from irreversible fusion and aggregation in subsequent high-temperature pyrolysis. The resistivity of Ni2 P@NPCNFs (5.34â€…Ω cm) is greatly decreased by 104 times compared to Ni2 P (>104 â€…Ω cm) because N-doped carbon NFs are incorporated. As an electrocatalyst for HER, Ni2 P@NPCNFs reveal remarkable performance compared to other previously reported catalysts in acidic media. Additionally, it offers excellent catalytic ability and durability in both neutral and basic media. Encouraged by the excellent electrocatalytic performance of Ni2 P@NPCNFs, a series of pea-like Mx P@NPCNFs, including Fe2 P@NPCNFs, Co2 P@NPCNFs, and Cu3 P@NPCNFs, were synthesized by the same method. Detailed characterization suggests that the newly developed method could render combinations of ultrafine metal phosphides with porous carbon accessible; thereby, extending opportunities in electrocatalytic applications.

Uniform implantation of CNTs on total activated carbon surfaces: a smart engineering protocol for commercial supercapacitor applications.

The main obstacles to building better supercapacitors are still trade-offs between energy and power parameters. To promote commercial supercapacitor behaviors, proper optimization toward electrode configurations/architectures may be a feasible and effective way. We herein propose a smart and reliable electrode engineering protocol, by in situ implantation of carbon nanotubes (CNTs) on total activated carbon (AC) surfaces via a mild chemical vapor deposition process at ∼550 °C, using nickel nitrate hydroxide (NNH) thin films and waste ethanol solvents as the catalyst and carbon sources, respectively. The direct and conformal growth of NNH layers onto carbonaceous scaffold guarantees the later uniform implantation of long and high-quality CNTs on total AC outer surfaces. Such fluffy and entangled CNTs preserve ionic diffusion channels, well connect neighboring ACs and function as superhighways for electrons transfer, endowing electrodes with outstanding capacitive behaviors including large output capacitances of ∼230 F g-1 in 1 M Na2SO4 neutral solution and ∼502.5 F g-1 in 6 M KOH using Ni valence state variation, and very negligible capacity decay in long-term cycles. Furthermore, a full symmetric supercapacitor device of CNTs@ACs//CNTs@ACs has been constructed, capable of delivering both high specific energy and power densities (maximum values reaching up to ∼97.2 Wh kg-1 and ∼10.84 kW kg-1), which holds great potential in competing with current mainstream supercapacitors.

Electrospun graphene-wrapped Na6.24Fe4.88(P2O7)4 nanofibers as a high-performance cathode for sodium-ion batteries.

Na6.24Fe4.88(P2O7)4 is one of the intensively investigated polyanionic compounds and has shown high rate discharge capacity, but its relatively low electronic conductivity hampers the high performance of the batteries. Herein for the first time we report new graphene wrapped Na6.24Fe4.88(P2O7)4 composite nanofibers (NFPO@C@rGO) made from electrospinning for cathodes of SIBs to achieve an even higher performance with a highly stable discharge capacity of ∼99 mA h g-1 at a current density of 40 mA g-1 after 320 cycles, which is 1.6 times higher than that of the pristine Na6.24Fe4.88(P2O7)4 (NFPO@C) composite. In particular, the NFPO@C@rGO composite cathode exhibits an even higher discharge rate capacity of ∼53.9 mA h g-1 at a current density of 1280 mA g-1 (11C) than that of ∼40 mA h g-1 at a current density of 1100 mA g-1 (9.4C) for the reported best high discharge rate performance of NFPO. The superior cycling and high rate capability are attributed to the unique spinning vein fiber based porous structure offering a good intimate contact between NFPO@C and graphene for great electronic conductivity, fast ionic transport, a large reaction surface and a strong solid structure preventing collapse during cycling, thus achieving a high rate discharge performance and high cycling stability.

Carbon nanotubes implanted manganese-based MOFs for simultaneous detection of biomolecules in body fluids.

Metal-organic frameworks (MOFs) have recently attracted much interest in electrochemical fields due to their controlled porosity, large internal surface area, and countless structural topologies. However, the direct application of single component MOFs is limited since they also exhibit poor electronic conductivity, low mechanical stability, and inferior electrocatalytic ability. To overcome these problems, we implanted multi-walled carbon nanotubes (MWCNTs) into manganese-based metal-organic frameworks (Mn-BDC) using a one-step solvothermal method and found that the introduction of MWCNTs can initiate the splitting of bulky Mn-BDC into thin layers. This splitting is highly significant in that it enhances the electronic conductivity and electrocatalytic ability of Mn-BDC. The constructed Mn-BDC@MWCNT composites were utilized as an electrode modifying material in the fabrication of an electrochemical sensor and then were used successfully for the determination of biomolecules in human body fluid. The sensor displayed successful detection performance with wide linear detection ranges (0.1-1150, 0.01-500, and 0.02-1100 µM for AA, DA and UA, respectively) and low limits of detection (0.01, 0.002, and 0.005 µM for AA, DA and UA, respectively); thus, this preliminary study presents an electrochemical biosensor constructed with a novel electrode modifying material that exhibits superior potential for the practical detection of AA, DA and UA in urine samples.

Three-dimensional nanotubes composed of carbon-anchored ultrathin MoS2 nanosheets with enhanced lithium storage.

MoS2 nanotubes (denoted as MoS2 NTs) assembled from well-aligned amorphous carbon-modified ultrathin MoS2 nanosheets (denoted as MoS2 NT@C) were successfully fabricated via a facile solvothermal method combined with subsequent annealing treatment. With the assistance of octylamine as a solvent and carbon source, interconnected MoS2 nanosheets (denoted as MoS2 NSs) can assemble into hierarchical MoS2 NTs. Such a hybrid nanostructure can effectively facilitate charge transport and accommodate volume variation upon prolonged charge/discharge cycling for reversible lithium storage. As a result, the MoS2 NT@C composite manifests a very stable high reversible capacity of around 1351 mA h g(-1) at a current density of 100 mA g(-1); even after 150 cycles, the electrode reaches a capacity of 1106 mA h g(-1) and it retains a reversible capacity of 650 mA h g(-1) after the 10th cycle at a current density of 3 A g(-1), all of which indicate that the MoS2 NT@C nanocomposite is a promising negative electrode material for high-energy lithium ion batteries.

pH-controllable synthesis of unique nanostructured tungsten oxide aerogel and its sensitive glucose biosensor.

This work presents a controllable synthesis of nanowire-networked tungsten oxide aerogels, which was performed by varying the pH in a polyethyleneimine (PEI)-assisted hydrothermal process. An enzyme-tungsten oxide aerogel co-modified electrode shows high activity and selectivity toward glucose oxidation, thus holding great promise for applications in bioelectronics.

Achieving highly stable sodium metal batteries with self-adapting and high-ionic-mobility ceramic fiber membranes.

Tough issues like sodium (Na) dendrite growth and poor anode reversibility hinder the practical application of sodium metal batteries (SMBs) with moderate liquid electrolytes. To settle these problems, using a smart self-adapting Al2SiO5 ceramic fiber (CF) membrane is demonstrated to enable homogeneous Na depositions and inhibit the dendritic growth. This inorganic membrane itself has superb thermal stability, high ionic mobility (Na+ transference number: 0.65) and electrolyte wettability over traditional glass fiber (GF) or polymeric ones, guaranteeing the low voltage polarization (14 mV) and long-cyclic lifetime (over 600 h) in symmetric cells testing. Notably, aluminous components in CF membranes would interact with F-based molecules in the electrolyte phase, thereby releasing some Al3+ species that can be electrochemically deposited onto the anodic interface. The packed (+)Na3V2(PO4)3|CF|Na(-) full SMBs exhibit far superior cyclic stability (capacity retention over 78.7 % after 600 cycles at 1C) than other counterparts. The in-situ detection/postmortem analysis reveal that Al/F-based inorganics formed in as-built SEI layers play a vital role in Na metal anode protection. This work may provide a viable strategy to overcome the constraints of high-energy SMBs in practical applications.

Superhydrophobic stereocomplex-type polylactide/ultra-fine glass fibers aerogel for passive daytime radiative cooling.

Passive daytime radiative cooling (PDRC) technology offers a green and sustainable strategy for cooling, eliminating the need for external energy sources through its exceptional efficiency in heat radiation and sunlight reflection. Despite its benefits, the widespread usage of non-biodegradable PDRC materials has unfortunately caused environmental pollution and resource wastage. Furthermore, the effectiveness of outdoor PDRC materials can be significantly diminished by rainfall. In this work, a superhydrophobic composite aerogel composed of stereocomplex-type polylactide and ultra-fine glass fiber has been successfully developed through simple physical blending and freeze-drying, which exhibits low thermal conductivity (36.26 mW m-1 K-1) and superhydrophobicity (water contact angle up to 150°). Additionally, its high solar reflectance (91.68 %) and strong infrared emissivity (93.95 %) enable it to effectively lower surface temperatures during daytime, resulting in a cooling effect of approximately 3.8 °C below the ambient temperature during the midday heat of summer, with a cooling power of 68 W/m2. This aerogel offers an environmentally friendly and sustainable approach for the utilization of radiative refrigeration materials, paving the way for environmental protection and sustainable development.

Structural regulation of asphalt-based hard carbon microcrystals based on liquid-phase crosslinking to enhance sodium storage.

Air-oxidation is an effective strategy to obtain promising carbon materials from asphalt for sodium-ion batteries. However, this method would generate a vast amount of gaseous pollutant, which pose challenges for recycling. Herein, a simple, cost-effective and environmentally friendly liquid-phase oxidation method is proposed. The oxygen-containing functional groups (-NO2) are introduced into asphalt, which effectively prevents the melting of asphalt and rearrangement of carbon layers during subsequent carbonization process. As a result, a carbon material with notable disorder degree, large interlayer spacing and abundant closed pores, is prepared. The as-prepared product demonstrates an impressive initial Coulombic efficiency of 88.3 % and an enhanced specific capacity of 317.0 mA h g-1, which is 2.6 times that of the pristine product. Moreover, when assembled with a Na3.32Fe2.34(P2O7)2 cathode, the full-cell delivers a high reversible capacity of 271.7 mA h g-1 at 30 mA g-1 with superb cycle life. This study offers a novel oxidation strategy and provides a solution for producing highly disordered carbon anodes from soft carbon precursors.

ZnO Additive Boosts Charging Speed and Cycling Stability of Electrolytic Zn-Mn Batteries.

Electrolytic aqueous zinc-manganese (Zn-Mn) batteries have the advantage of high discharge voltage and high capacity due to two-electron reactions. However, the pitfall of electrolytic Zn-Mn batteries is the sluggish deposition reaction kinetics of manganese oxide during the charge process and short cycle life. We show that, incorporating ZnO electrolyte additive can form a neutral and highly viscous gel-like electrolyte and render a new form of electrolytic Zn-Mn batteries with significantly improved charging capabilities. Specifically, the ZnO gel-like electrolyte activates the zinc sulfate hydroxide hydrate assisted Mn2+ deposition reaction and induces phase and structure change of the deposited manganese oxide (Zn2Mn3O8·H2O nanorods array), resulting in a significant enhancement of the charge capability and discharge efficiency. The charge capacity increases to 2.5 mAh cm-2 after 1 h constant-voltage charging at 2.0 V vs. Zn/Zn2+, and the capacity can retain for up to 2000 cycles with negligible attenuation. This research lays the foundation for the advancement of electrolytic Zn-Mn batteries with enhanced charging capability.

Sb-Doped Biphasic P2/O3-Type Mn-Rich Layered Oxide Cathode Material for High-Performance Sodium-Ion Batteries.

Mn-rich P2-type layered oxide cathode materials suffer from severe capacity loss caused by detrimental phase transition and transition metal dissolution, making their implementation difficult in large-scale sodium-ion battery applications. Herein, we introduced a high-valent Sb5+ substitution, leading to a biphasic P2/O3 cathode that suppresses the P2-O2 phase transformation in the high-voltage condition attributed to the stronger Sb-O covalency that introduces extra electrons to the O atom, reducing oxygen loss from the lattices and improving structural stability, as confirmed by first-principle calculations. Besides, the enhanced Na+ diffusion kinetics and thermodynamics in the modified sample are associated with the enlarged lattice parameters. As a result, the proposed cathode delivers a discharge capacity of 142.6 mAh g-1 at 0.1C between 1.5 and 4.3 V and excellent performance at a high mass loading of 8 mg cm3 with a specific capacity of 131 mAh g-1 at 0.2C. Furthermore, it also possesses remarkable rate capability (90.3 mAh g-1 at 5C), specifying its practicality in high-energy-density sodium-ion batteries. Hence, this work provides insights into incorporating high-valent dopants for high-performance Mn-rich cathodes.

A green and facile route for constructing flower-shaped TiO2 nanocrystals assembled on graphene oxide sheets for enhanced photocatalytic activity.

We have demonstrated an environmentally friendly in situ assembly method for the preparation of novel three-dimensional TiO2/graphene oxide (TiO2/GO) nanostructures with favorable flower-shaped architectures. Very little information on such a morphology of TiO2/GO nanostructures is available in the literature. The as-synthesized sample was characterized by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption measurements and Raman spectroscopy. Also the TiO2/GO composites exhibited enhanced photocatalytic properties.