Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

Oxygen functionalization-assisted anionic exchange toward unique construction of flower-like transition metal chalcogenide embedded carbon fabric for ultra-long life flexible energy storage and conversion

The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storage and conversion application.The NiCCZ was then oxygen functionalized,facilitating the next step of stoichiometric sulfur anion diffusion during hydrothermal sulfurization,generating a flower-like metal hydroxysulfide structure(NiCCZOS)with strong partial implantation inside CC.Thus obtained NiCCZOS shows an excellent capacity when tested as a supercapacitor electrode in a three-electrode configuration.Moreover,when paired with the biomass-derived nitrogen-rich activated carbon,the asymmetric supercapacitor device shows almost 100%capacity retention even after 45,000 charge–discharge cycles with remarkable energy density(59.4 Wh kg^(-1)/263.8μWh cm^(–2))owing to a uniquely designed cathode.Furthermore,the same electrode performed as an excellent bifunctional water-splitting electrocatalyst with an overpotential of 271 mV for oxygen evolution reaction(OER)and 168.4 mV for hydrogen evolution reaction(HER)at 10 mA cm−2 current density along with 30 h of unhinged chronopotentiometric stability performance for both HER and OER.Hence,a unique metal chalcogenide composite electrode/substrate configuration has been proposed as a highly stable electrode material for flexible energy storage and conversion applications.

Regulating zinc ion transport behavior and solvated structure towards stable aqueous Zn metal batteries

Aqueous Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metallic Zn anode and the incompatibility between electrode and electrolytes lead to the deterioration of electrochemical performance of AZMBs during the cycling.The critical point to achieve the stable cycling of AZMBs is to properly regulate the zinc ion solvated structure and transfer behavior between metallic Zn anode and electrolyte.In recent years,numerous achievements have been made to resolve the formation of Zn dendrite and interface incompatible issues faced by AZMBs via optimizing the sheath structure and transport capability of zinc ions at electrode-electrolyte interface.In this review,the challenges for metallic Zn anode and electrode-electrolyte interface in AZMBs including dendrite formation and interface characteristics are presented.Following the influences of different strategies involving designing advanced electrode structu re,artificial solid electrolyte interphase(SEI)on Zn anode and electrolyte engineering to regulate zinc ion solvated sheath structure and transport behavior are summarized and discussed.Finally,the perspectives for the future development of design strategies for dendrite-free Zn metal anode and long lifespan AZMBs are also given.

From Liquid to Solid‑State Lithium Metal Batteries:Fundamental Issues and Recent Developments

The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.

From Topological Nodal-Line Semimetals to Quantum Spin Hall Insulators in Tetragonal SnX Monolayers(X=F,Cl,Br,I)

Two-dimensional(2D)topological materials have recently garnered significant interest due to their profound physical properties and promising applications for future quantum nanoelectronics.Achieving various topological states within one type of materials is,however,seldom reported.Based on first-principles calculations and tightbinding models,we investigate topological electronic states in a novel family of 2D halogenated tetragonal stanene(T-SnX,X=F,Cl,Br,I).All the four monolayers are found to be unusual topological nodal-line semimetals(NLSs),protected by a glide mirror symmetry.When spin-orbit coupling(SOC)is turned on,T-SnF and TSnCl are still ascertained as topological NLSs due to the remaining band inversion,primarily composed of Sn pxy orbitals,while T-Sn Br and T-SnI become quantum spin Hall insulators.The phase transition is ascribed to moving up in energy of Sn s orbitals and increasing of SOC strengths.The topology origin in the materials is uniformly rationalized through elementary band representations.The robust and diverse topological states found in the 2D T-SnX monolayers position them as an excellent material platform for development of innovative topological electronics.

Towards advanced zinc anodes by interfacial modification strategies for efficient aqueous zinc metal batteries

Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.

Evaluation of Four Anthropogenic Activity Impacts on Heavy Metal Quality of the Kumba River in the South West Region of Cameroon

Anthropogenic activities have contributed to pollution of water bodies through deposition of diverse pollutants amongst which are heavy metals. These pollutants, which at times are above the maximum concentration levels recommended, are detrimental to the quality of the water, soil and crops (plant) with subsequent human health risks. The objective of the work was to evaluate the impacts of human-based activities on the heavy metal properties of surface water with focus on the Kumba River basin. Field observations, interviews, field measurements and laboratory analyses of different water samples enabled us to collect the different data. The results show four main human-based activities within the river basin (agriculture, livestock production, domestic waste disposal and carwash activities) that pollute surface water. Approximately 20.61 tons of nitrogen and phosphorus from agricultural activities, 156.48 tons of animal wastes, 2517.5 tons of domestic wastes and 1.52 tons of detergent from carwash activities were deposited into the river each year. A highly significant difference at 1% was observed between the upstream and downstream heavy metal loads in four of the five heavy metals tested except for copper that was not significant. Lead concentrations were highest in all the activities with an average of 2.4 mg∙L−1 representing 57.81%, followed by zinc with 1.596 mg∙L−1 (38.45%) and manganese with 0.155 mg∙L−1 (3.74%) for the different anthropogenic activities thus indicating that these activities highly lead to pollution of the Kumba River water. The level of zinc and manganese was significantly influenced at ρ 005 by anthropogenic activities though generally the variations were in the order: carwash (3.196 mg∙L−1) < domestic waste disposal (3.347 mg∙L−1) < agriculture (4.172 mg∙L−1) < livestock (4.886 mg∙L−1) respectively and leading to a total of 14.04 tons of heavy metal pollutants deposited each day.

A Review on Engineering Transition Metal Compound Catalysts to Accelerate the Redox Kinetics of Sulfur Cathodes for Lithium–Sulfur Batteries

Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.

Distinct vibrational signatures and complex phase behavior in metallic oxygen

Evidence for metallization in dense oxygen has been reported for over 30 years[Desgreniers et al.,J.Phys.Chem.94,1117(1990)]at a now routinely accessible 95 GPa[Shimizu et al.,Nature 393,767(1998)].However,despite the longevity of this result and the technological advances since,the nature of the metallic phase remains poorly constrained[Akahama et al.,Phys.Rev.Lett.74,4690(1995);Goncharov et al.,Phys.Rev.B 68,224108(2003);Ma,Phys.Rev.B 76,064101(2007);and Weck et al.,Phys.Rev.Lett.102,255503(2009)].In this work,through Raman spectroscopy,we report the distinct vibrational characteristics of metallicζ-O_(2) from 85 to 225 GPa.In comparison with numerical simulations,wefind reasonable agreement with the candidate structure up to about 150 GPa.At higher pressures,the C2/mstructure is found to be unstable and incompatible with experimental observations.Alternative candidate structures,and Ci,with C2/m C2/conly two molecules in the primitive unit cell,are found to be stable and more compatible with measurements above 175 GPa,indicative of the dissociation of(O_(2))4 units.Further,we report and discuss a strong hysteresis and metastability with the precursory phaseϵ-O_(2).Thesefindings will reinvigorate experimental and theoretical work into the dense oxygen system,which will have importance for oxygen-bearing chemistry,prevalent in the deep Earth,as well as fundamental physics.

Analysis and Assessment on the Heavy Metals in a Severely Degraded Subtropical Red Soil Region

5 different forests of Pinus massoniana, Schima superba, Liquidambar formosana, P. massoniana × S. superba, P. massoniana × L. formosana as the research object were set up to study the Cr, Cu and Zn content of degraded red soil region in subtropics. The soil heavy metal pollution degree was evaluated by national environmental quality standard (II class). The results showed that three soil metals of P. massoniana × S. superba were the highest, and the soil metals enrichment ability was strong. The order of single factor pollution index of metal elements was Cu (1.38) > Cr (0.81) > Zn (0.42), and moderately pollution, pollution warning and no pollution, respectively. There was no significant correlation between three soil heavy metals and soil total carbon (TC), total nitrogen (TN) and total phosphorus (TP). These results suggested that the accumulation of heavy metal elements was not derived from the parent material of soil. There was a significant positive correlation between the three metal elements which indicated that the sources of the three elements were similar. The structural equation model showed that the direct and indirect effects among the influencing factors ultimately affected the activity of heavy metals by cascade effects.

On the thermodynamics of plasticity during quasi-isentropic compression of metallic glass

Entropy production in quasi-isentropic compression (QIC) is critically important for understanding the properties of materials under extremeconditions. However, the origin and accurate quantification of entropy in this situation remain long-standing challenges. In this work, a framework is established for the quantification of entropy production and partition, and their relation to microstructural change in QIC. Cu50Zr50is taken as a model material, and its compression is simulated by molecular dynamics. On the basis of atomistic simulation-informed physicalproperties and free energy, the thermodynamic path is recovered, and the entropy production and its relation to microstructural change aresuccessfully quantified by the proposed framework. Contrary to intuition, entropy production during QIC of metallic glasses is relativelyinsensitive to the strain rate ˙γ when ˙γ ranges from 7.5 × 10^(8) to 2 × 10^(9)/s, which are values reachable in QIC experiments, with a magnitudeof the order of 10^(−2)kB/atom per GPa. However, when ˙γ is extremely high (>2 × 10^(9)/s), a notable increase in entropy production rate with˙γ is observed. The Taylor–Quinney factor is found to vary with strain but not with strain rate in the simulated regime. It is demonstrated thatentropy production is dominated by the configurational part, compared with the vibrational part. In the rate-insensitive regime, the increase inconfigurational entropy exhibits a linear relation to the Shannon-entropic quantification of microstructural change, and a stretched exponential relation to the Taylor–Quinney factor. The quantification of entropy is expected to provide thermodynamic insights into the fundamentalrelation between microstructure evolution and plastic dissipation.

Preparation and characterization of pH-responsive metal-polyphenol structure coated nanoparticles

In this paper,tannic acid(TA)and Fe~(3+)were added to form a layer of metal-polyphenol network structure on the surface of the nanoparticles which were fabricated by zein and carbon quantum dots(CQDs)encapsulating phlorotannins(PTN).pH-Responsive nanoparticles were prepared successfully(zein-PTN-CQDs-Fe-~Ⅲ).Further,the formation of composite nanoparticles was confirmed by a series of characterization methods.The zeta-potential and Fourier transform infrared spectroscopy data proved that electrostatic interaction and hydrogen bonding are dominant forces to form nanoparticles.The encapsulation efficiency(EE)revealed that metal-polyphenol network structure could improve the EE of PTN.Thermogravimetric analysis and differential scanning calorimetry experiment indicated the thermal stability of zein-PTN-CQDs-Fe~Ⅲnanoparticles increased because of metal-polyphenol network structure.The pH-responsive nanoparticles greatly increased the release rate of active substances and achieved targeted release.

Loosely coordinating diluted highly concentrated electrolyte toward -60℃ Li metal batteries

Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferior lithium metal anode(LMA) compatibility and sluggish Li^(+) desolvation.Here,we demonstrate that cyclopentylmethyl ether(CPME) based diluted high-concentration electrolyte(DHCE)enables-60℃ LMBs operation.By leveraging the loose coordination between Li^(+) and CPME,such developed electrolyte boosts the formation of ion clusters to derive anion-dominant interfacial chemistry for enhancing LMA compatibility and greatly accelerates Li^(+) desolvation kinetics.The resulting electrolyte demonstrates high Coulombic efficiencies(CE),providing over 99.5%,99.1%,98.5% and 95% at 25,-20,-40,and-60℃respectively.The assembled Li-S battery exhibits remarkable cyclic stability in-20,and-40℃ at 0.2 C charging and 0.5 C discharging.Even at-60℃,Li-S cell with this designed electrolyte retains> 70% of the initial capacity over 170 cycles.Besides,lithium metal coin cell and pouch cell with10 mg cm^(-2) high S cathode loading exhibit cycling stability at-20℃.This work offers an opportunity for rational designing electrolytes toward low temperature LMBs.

Arbitrary skin metallization by pencil-writing inspired solid-ink rubbing for advanced energy storage and harvesting

The development of a durable metallic coating on diverse substrates is both intriguing and challenging,particularly in the research of metal-conductive materials for applications such as batteries,soft electronics,and beyond.Herein,by learning from the pencil-writing process,a facile solid-ink rubbing technology(SIR-tech)is invented to address the above challenge.The solid-ink is exampled by rational combination of liquid metal and graphite particles.By harnessing the synergistic effects between rubbing and adhesion,controllable metallic skin is successfully formed onto metals,woods,ceramics,and plastics without limitation in size and shape.Moreover,outperforming pure liquid-metal coating,the composite metallic skin by SIR-tech is very robust due to the self-lamination of graphite nanoplate exfoliated by liquid-metal rubbing.The critical factors controlling the structures-properties of the composite metallic skin have been systematically investigated as well.For applications,the SIR-tech is demonstrated to fabricate high-performance composite current collectors for next-generation batteries without traditional metal foils.Meanwhile,advanced skin-electrodes are further demonstrated for stable triboelectricity generation even under temperature fluctuation from-196 to 120℃.This facile and highly-flexible SIR-tech may work as a powerful platform for the studies on functional coatings by liquid metals and beyond.

Surface Metallization of Glass Fiber(GF)/Polyetheretherketone(PEEK) Composite with Cu Coatings Deposited by Magnetron Sputtering and Electroplating

Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.

Unlock the full potential of carbon cloth-based scaffolds towards magnesium metal storage via regulation on magnesiophilicity and surface geometric structure

The development of rechargeable magnesium(Mg) batteries is of practical significance to upgrade the electric energy storage devices due to exceptional capacity and abundant resources of Mg-metal anode.However,the reversible Mg electrochemistry suffers from unsatisfied rate capability and lifespan,mainly caused by non-uniform distribution of electrodeposits.In this work,a fresh design concept of threedimensional carbon cloths scaffolds is proposed to overcome the uncontrollable Mg growth via homogenizing electric field and improving magnesiophilicity.A microscopic smooth and nitrogen-containing defective carbonaceous layer is constructed through a facile pyrolysis of ZIF8 on carbon cloths.As revealed by finite element simulation and DFT calculation results,the smooth surface endows with uniform electric field distribution and simultaneously the nitrogen-doping species enable good magnesiophilicity of scaffolds.The fine and uniform Mg nucleus as well as the inner electrodeposit behavior are also disclosed.As a result,an exceptional cycle life of 500 cycles at 4.0 mA cm^(-2) and 4.0 mA h cm^(-2) is firstly realized to our best knowledge.Besides,the functional scaffolds can be cycled for over 2200 h at 2.0 mA cm^(-2) under a normalized capacity of 5.0 mA h cm^(-2),far exceeding previous results.This work offers an effective approach to enable the full potential of carbon cloths-based scaffolds towards metal storage for next generation battery applications.

Pyrometallurgical recycling of end-of-life lithium-ion batteries

The global importance of lithium-ion batteries(LIBs)has been increasingly underscored with the advancement of high-performance energy storage technologies.However,the end-of-life of these batteries poses significant challenges from environmental,economic,and resource management perspectives.This review paper focuses on the pyrometallurgy-based recycling process of lithium-ion batteries,exploring the fundamental understanding of this process and the importance of its optimization.Centering on the high energy consumption and emission gas issues of the pyrometallurgical recycling process,we systematically analyzed the capital-intensive nature of this process and the resulting technological characteristics.Furthermore,we conducted an in-depth discussion on the future research directions to overcome the existing technological barriers and limitations.This review will provide valuable insights for researchers and industry stakeholders in the battery recycling field.

Synthesis and Physico-Chemical Characterizations of Novel Hydrazone Ligands and Their Metal Complexes against Hormone-Dependent and Independent Cancers

This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.

Naturally Crosslinked Biocompatible Carbonaceous Liquid Metal Aqueous Ink Printing Wearable Electronics for Multi-Sensing and Energy Harvesting

Achieving flexible electronics with comfort and durability comparable to traditional textiles is one of the ultimate pursuits of smart wearables.Ink printing is desirable for e-textile development using a simple and inexpensive process.However,fabricating high-performance atop textiles with good dispersity,stability,biocompatibility,and wearability for high-resolution,large-scale manufacturing,and practical applications has remained challenging.Here,waterbased multi-walled carbon nanotubes(MWCNTs)-decorated liquid metal(LM)inks are proposed with carbonaceous gallium–indium micro-nanostructure.With the assistance of biopolymers,the sodium alginate-encapsulated LM droplets contain high carboxyl groups which non-covalently crosslink with silk sericin-mediated MWCNTs.E-textile can be prepared subsequently via printing technique and natural waterproof triboelectric coating,enabling good flexibility,hydrophilicity,breathability,wearability,biocompatibility,conductivity,stability,and excellent versatility,without any artificial chemicals.The obtained e-textile can be used in various applications with designable patterns and circuits.Multi-sensing applications of recognizing complex human motions,breathing,phonation,and pressure distribution are demonstrated with repeatable and reliable signals.Self-powered and energy-harvesting capabilities are also presented by driving electronic devices and lighting LEDs.As proof of concept,this work provides new opportunities in a scalable and sustainable way to develop novel wearable electronics and smart clothing for future commercial applications.

Heavy metal pollution of river water and eco-friendly remediation using potent microalgal species

Pollution of rivers is mainly caused by anthropogenic activities such as discharge of effluent from industrial facilities,maintenance of sewage/effluent treatment plants,and dumping of solid waste on river banks.This study dealt with the pollution issues of the Cooum River in the well-known city of Chennai in South India.Water samples from 27 locations were collected and analyzed for 12 elements,including Ba,B,and Al,as well as heavy metals such as Pb,Cr,Mn,Fe,Co,Ni,Cu,Zn,and Cd.The samples showed levels of these elements that exceeded World Health Organization recommendations.Pearson correlation analysis revealed the inter-dependency among elements,and the contribution of each element based on factor loadings showed its percentage contribution compared to others.Water samples from six significant locations were chosen for remediation with three algae:Chlorella vulgaris,Scenedesmus dimorphus,and Phormedium sp.The uptake of pollutants led to the continuous growth of algae during the incubation period of 15 d,effectively removing heavy metals from the river water.The increasing levels of algal counts and the chlorophyll a content confirmed the algal growth during the incubation period,followed by a declining stage after the incubation period.The scanning electron microscopic images of algae before and after the remediation showed no remarkable modification of morphological patterns.This study showed that the uptake of heavy metals using algae is an effective water pollution remediation measure,making the process practicable in the field on a large scale in the near future.