Unraveling nanosprings: morphology control and mechanical characterization.

Nanosprings demonstrate promising mechanical characteristics, positioning them as pivotal components in a diverse array of potential nanoengineering applications. To unlock the full potential of these nanosprings, ongoing research is concentrated on emulating springs at the nanoscale in terms of both morphology and function. This review underscores recent advancements in the field and provides a comprehensive overview of the diverse methods employed for nanospring preparation. Understanding the general mechanism behind nanospring formation lays the groundwork for the informed design of nanosprings. The synthesis section delineates four prominent methods employed for nanospring fabrication: vapor phase synthesis, templating methods, post-treatment techniques, and molecular engineering. Each method is critically analyzed, highlighting its strengths, limitations, and potential for scalability. Mechanical properties of nanosprings are explored in depth, discussing their response to external stimuli and their potential applications in various fields such as sensing, energy storage, and biomedical engineering. The interplay between nanospring morphology and mechanical behavior is elucidated, providing insights into the design principles for tailored functionality. Additionally, we anticipate that the evolution of state-of-the-art characterization tools, such as in situ transmission electron microscopy, 3D electron tomography, and machine learning, will significantly contribute to both the study of nanospring mechanisms and their applications.

Sustainable reprocessing of lithium iron phosphate batteries: A recovery approach using liquid-phase method at reduced temperature.

Lithium iron phosphate batteries, known for their durability, safety, and cost-efficiency, have become essential in new energy applications. However, their widespread use has highlighted the urgency of battery recycling. Inadequate management could lead to resource waste and environmental harm. Traditional recycling methods, like hydrometallurgy and pyrometallurgy, are complex and energy-intensive, resulting in high costs. To address these challenges, this study introduces a novel low-temperature liquid-phase method for regenerating lithium iron phosphate positive electrode materials. By using N2H4·H2O as a reducing agent, missing Li+ ions are replenished, and anti-site defects are reduced through annealing. This process restores nearly all missing Li+ ions at 80 °C/6h. After high-temperature sintering at 700 °C/2h, the regenerated LiFePO4 matches commercial LiFePO4 in terms of anti-site defects and exhibits excellent performance with a 97 % capacity retention rate after 100 cycles at 1C. Compared to high-temperature techniques, this low-temperature liquid-phase method is simpler, safer, and more energy-efficient, offering a blueprint for reclaiming discarded LiFePO4 and similar materials.

Imidazole-Intercalated Cobalt Hydroxide Enabling the Li+ Desolvation/Diffusion Reaction and Flame Retardant Catalytic Dynamics for Lithium Ion Batteries.

Lithium-ion batteries have found extensive applications due to their high energy density and low self-discharge rates, spanning from compact consumer electronics to large-scale energy storage facilities. Despite their widespread use, challenges such as inherent capacity degradation and the potential for thermal runaway hinder sustainable development. In this study, we introduce a unique approach to synthesize anode materials for lithium-ion batteries, specifically imidazole-intercalated cobalt hydroxide. This innovative material significantly enhances the Li+ desolvation/diffusion reaction and flame-retardant dynamics through complexing and catalytic synergetic effects. The lithium-ion batteries incorporating these materials demonstrate exceptional performance, boasting an impressive capacity retention of 997.91 mAh g-1 after 500 cycles. This achievement can be attributed to the optimization of the solid electrolyte interphase (SEI) interface engineering, effectively mitigating anode degradation and minimizing electrolyte consumption. Experimental and theoretical calculations validate these improvements. Importantly, imidazole intercalated Co(OH)2 (MI-Co(OH)2) exhibits a remarkable catalytic effect on electrolyte carbonization and the conversion of CO to CO2. This dual action suppresses smoke and reduces toxicity significantly. The presented work introduces a novel approach to realizing high-performance and safe lithium-ion batteries, addressing key challenges in the pursuit of sustainable energy solutions.

Construction of phase-separated Co/MnO synergistic catalysts and integration onto sponge for rapid removal of multiple contaminants.

Wastewater treatment recycling is critical to ensure safe water supply or to overcome water shortage. Herein, we developed metallic Co integration onto MnO nanorods (MON) resulting in a phase-separated synergetic catalyst by creating more Mn(III) via the Jahn-Teller effect and oxygen vacancies and improving the redox capability of Co nanoparticles mediated by a thin carbon layer. Additionally, the N-doped surface carbon network on MON contributes to polar sites, facilitating the enrichment of contaminants around reactive sites, thereby shortening the migration of reactive oxidative species (ROS) toward contaminants. The optimized MnO@Co/C-600 exhibits superior PMS activation efficiency for bisphenol A degradation (0.463 min-1), displaying nearly a 20-fold enhancement in the rate constant compared to Mn3O4/C-600. Subsequent experiments involving variable modulation and extension were conducted to further elucidate the multiple synergistic effects. The mechanism study further confirms the synergy of ˙SO4-, ˙OH, ˙O2-, and 1O2, along with additional electron transfer pathways. The intermediates generated during degradation pathways and their toxicity to aquatic organisms were identified. Notably, a monolith integrated catalyst was explored by anchoring MnO@Co/C-600 onto a tailored melamine sponge based on Ca ion triggered crosslink tactic for the photothermal degradation of bisphenol A, tetracycline and norfloxacin, endowed with easy recovery and good stability. Furthermore, we demonstrated that the total organic carbon removal of multiple contaminants surpassed that of sole contaminants.

Advancing Lithium-Magnesium Separation: Pioneering Swelling-Embedded Cation Exchange Membranes Based on Sulfonated Poly(ether ether ketone).

With the continuous advancement of electrodialysis (ED) technology, there arises a demand for improved monovalent cation exchange membranes (CEMs). However, limitations in membrane materials and structures have resulted in the low selectivity of monovalent CEMs, posing challenges in the separation of Li+ and Mg2+. In this investigation, a designed CEM with a swelling-embedded structure was created by integrating a polyelectrolyte containing N-oxide Zwitterion into a sulfonated poly(ether ether ketone) (SPEEK) membrane, leveraging the notable solubility characteristic of SPEEK. The membranes were prepared by using N-oxide zwitterionic polyethylenimine (ZPEI) and 1,3,5-benzenetrlcarbonyl trichloride (TMC). The as-prepared membranes underwent systematic characterization and testing, evaluating their structural, physicochemical, electrochemical, and selective ED properties. During ED, the modified membranes demonstrated notable permeability selectivity for Li+ ions in binary (Li+/Mg2+) systems. Notably, at a constant current density of 2.5 mA cm-2, the modified membrane PEI-TMC/SPEEK exhibited significant permeability selectivity (PMg2+Li+=5.63) in the Li+/Mg2+ system, while ZPEI-TMC/SPEEK outperformed, displaying remarkable permeability selectivity (PMg2+Li+=12.43) in the Li+/Mg2+ system, surpassing commercial monovalent cation-selective membrane commercial monovalent cation-selective membrane (CIMS). Furthermore, in the Li+/Mg2+ binary system, Li+ flux reached 9.78 × 10-9 mol cm-2 s-1 for ZPEI-TMC/SPEEK, while its Mg2+ flux only reached 2.7 × 10-9 mol cm-2 s-1, showing potential for lithium-magnesium separation. In addition, ZPEI-TMC/SPEEK was tested for performance and stability at high current densities. This work offers a straightforward preparation process and an innovative structural approach, presenting methodological insights for the advancement of lithium and magnesium separation techniques.

Pioneering Piezoelectric-Driven Atomic Hydrogen for Efficient Dehalogenation of Halogenated Organic Pollutants.

The electrocatalytic hydrodehalogenation (EHDH) process mediated by atomic hydrogen (H*) is recognized as an efficient method for degrading halogenated organic pollutants (HOPs). However, a significant challenge is the excessive energy consumption resulting from the recombination of H* to H2 production in the EHDH process. In this study, a promising strategy was proposed to generate piezo-induced atomic H*, without external energy input or chemical consumption, for the degradation and dehalogenation of HOPs. Specifically, sub-5 nm Ni nanoparticles were subtly dotted on an N-doped carbon layer coating on BaTiO3 cube, and the resulted hybrid nanocomposite (Ni-NC@BTO) can effectively break C-X (X = Cl and F) bonds under ultrasonic vibration or mechanical stirring, demonstrating high piezoelectric driven dehalogenation efficiencies toward various HOPs. Mechanistic studies revealed that the dotted Ni nanoparticles can efficiently capture H* to form Ni-H* (Habs) and drive the dehalogenation process to lower the toxicity of intermediates. COMSOL simulations confirmed a "chimney effect" on the interface of Ni nanoparticle, which facilitated the accumulation of H+ and enhanced electron transfer for H* formation by improving the surface charge of the piezocatalyst and strengthening the interfacial electric field. Our work introduces an environmentally friendly dehalogenation method for HOPs using the piezoelectric process independent of the external energy input and chemical consumption.

Revealing microscopic dynamics: in situ liquid-phase TEM for live observations of soft materials and quantitative analysis via deep learning.

In various domains spanning materials synthesis, chemical catalysis, life sciences, and energy materials, in situ transmission electron microscopy (TEM) methods exert a profound influence. These methodologies enable the real-time observation and manipulation of gas-phase and liquid-phase reactions at the nanoscale, facilitating the exploration of pivotal reaction mechanisms. Fundamental research areas like crystal nucleation, growth, etching, and self-assembly have greatly benefited from these techniques. Additionally, their applications extend across diverse fields such as catalysis, batteries, bioimaging, and drug delivery kinetics. However, the intricate nature of 'soft matter' presents a challenge due to the unique molecular properties and dynamic behavior of these substances that remain insufficiently understood. Investigating soft matter within in situ liquid-phase TEM settings demands further exploration and advancement compared to other research domains. This research harnesses the potential of in situ liquid-phase TEM technology while integrating deep learning methodologies to comprehensively analyze the quantitative aspects of soft matter dynamics. This study centers on diverse phenomena, encompassing surfactant molecule nucleation, block copolymer behavior, confinement-driven self-assembly, and drying processes. Furthermore, deep learning techniques are employed to precisely analyze Ostwald ripening and digestive ripening dynamics. The outcomes of this study not only deepen the understanding of soft matter at its fundamental level but also serve as a pivotal foundation for developing innovative functional materials and cutting-edge devices.

Recent Advancements of Graphene-Based Materials for Zinc-Based Batteries: Beyond Lithium-Ion Batteries.

Graphene-based materials (GBMs) possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries. This review highlights recent advancements and development of a variety of graphene derivative-based materials and its composites, with a focus on their potential applications in rechargeable batteries such as LIBs, zinc-air batteries (ZABs), zinc-ion batteries (ZIBs), and zinc-iodine batteries (Zn-I2 Bs). Finally, there is an outlook on the challenges and future directions of this great potential research field.

Enhancing reductive C-N coupling of nitrocompounds through interfacial engineering of MoO2 in thin carbon layers.

In this study, we developed an approach by coating silica nanospheres with polydopamine and metal precursor, followed by carbonization to create interfacial engineered MoO2. The presence of numerous crystal interfaces and metal-carbon interactions resulted in a remarkable enhancement of C-N coupling activity and stability of catalyst compared to one obtained by air calcination.

Optimizing oxygen vacancies through grain boundary engineering to enhance electrocatalytic nitrogen reduction.

Electrocatalytic nitrogen reduction is a challenging process that requires achieving high ammonia yield rate and reasonable faradaic efficiency. To address this issue, this study developed a catalyst by in situ anchoring interfacial intergrown ultrafine MoO2 nanograins on N-doped carbon fibers. By optimizing the thermal treatment conditions, an abundant number of grain boundaries were generated between MoO2 nanograins, which led to an increased fraction of oxygen vacancies. This, in turn, improved the transfer of electrons, resulting in the creation of highly active reactive sites and efficient nitrogen trapping. The resulting optimal catalyst, MoO2/C700, outperformed commercial MoO2 and state-of-the-art N2 reduction catalysts, with NH3 yield and Faradic efficiency of 173.7 µg h-1 mg-1cat and 27.6%, respectively, under - 0.7 V vs. RHE in 1 M KOH electrolyte. In situ X-ray photoelectron spectroscopy characterization and density functional theory calculation validated the electronic structure effect and advantage of N2 adsorption over oxygen vacancy, revealing the dominant interplay of N2 and oxygen vacancy and generating electronic transfer between nitrogen and Mo(IV). The study also unveiled the origin of improved activity by correlating with the interfacial effect, demonstrating the big potential for practical N2 reduction applications as the obtained optimal catalyst exhibited appreciable catalytic stability during 60 h of continuous electrolysis. This work demonstrates the feasibility of enhancing electrocatalytic nitrogen reduction by engineering grain boundaries to promote oxygen vacancies, offering a promising avenue for efficient and sustainable ammonia production.

Understanding ZIF particle chemical etching dynamics and morphology manipulation: in situ liquid phase electron microscopy and 3D electron tomography application.

In situ liquid phase transmission electron microscopy (TEM) and three-dimensional electron tomography are powerful tools for investigating the growth mechanism of MOFs and understanding the factors that influence their particle morphology. However, their combined application to the study of MOF etching dynamics is limited due to the challenges of the technique such as sample preparation, limited field of view, low electron density, and data analysis complexity. In this research, we present a study employing in situ liquid phase TEM to investigate the etching mechanism of colloidal zeolitic imidazolate framework (ZIF) nanoparticles. The etching process involves two distinct stages, resulting in the development of porous structures as well as partially and fully hollow morphologies. The etching process is induced by exposure to an acid solution, and both in situ and ex situ experiments demonstrate that the outer layer etches faster leading to overall volume shrinking (stage I) while the inner layer etches faster giving a hollow morphology (stage II), although both the outer layer and inner layer have been etched in the whole process. 3D electron tomography was used to quantify the properties of the hollow structures which show that the ZIF-67 crystal etching rate is larger than that of the ZIF-8 crystal at the same pH value. This study provides valuable insights into MOF particle morphology control and can lead to the development of novel MOF-based materials with tailored properties for various applications.

Pearl-Structure-Enhanced NASICON Cathode toward Ultrastable Sodium-Ion Batteries.

Based on the favorable ionic conductivity and structural stability, sodium superionic conductor (NASICON) materials especially utilizing multivalent redox reaction of vanadium are one of the most promising cathodes in sodium-ion batteries (SIBs). To further boost their application in large-scale energy storage production, a rational strategy is to tailor vanadium with earth-abundant and cheap elements (such as Fe, Mn), reducing the cost and toxicity of vanadium-based NASICON materials. Here, the Na3.05 V1.03 Fe0.97 (PO4 )3 (NVFP) is synthesized with highly conductive Ketjen Black (KB) by ball-milling assisted sol-gel method. The pearl-like KB branch chains encircle the NVFP (p-NVFP), the segregated particles possess promoted overall conductivity, balanced charge, and modulated crystal structure during electrochemical progress. The p-NVFP obtains significantly enhanced ion diffusion ability and low volume change (2.99%). Meanwhile, it delivers a durable cycling performance (87.7% capacity retention over 5000 cycles at 5 C) in half cells. Surprisingly, the full cells of p-NVFP reveal a remarkable capability of 84.9 mAh g-1 at 20 C with good cycling performance (capacity decay rate is 0.016% per cycle at 2 C). The structure modulation of the p-NVFP provides a rational design on the superiority of others to be put into practice.

Imaging the Surface/Interface Morphologies Evolution of Silicon Anodes Using in Situ/Operando Electron Microscopy.

Si-based rechargeable lithium-ion batteries (LIBs) have generated interest as silicon has remarkably high theoretical specific capacity. It is projected that LIBs will meet the increasing need for extensive energy storage systems, electric vehicles, and portable electronics with high energy densities. However, the Si-based LIB has a substantial problem due to the volume cycle variations brought on by Si, which result in severe capacity loss. Making Si-based anodes-enabled high-performance LIBs that are easy to utilize requires an understanding of the fading mechanism. Due to its distinct advantage in morphological changes from microscale to nanoscale, even approaching atomic resolution, electron microscopy is one of the most popular methods. Based on operando electron microscopy characterization, the general comprehension of the fading mechanism and the morphology evolution of Si-based LIBs are debated in this review. The current advancements in compositional and structural interpretation for Si-based LIBs using advanced electron microscopy characterization methods are outlined. The future development trends in pertinent silicon materials characterization methods are also highlighted, along with numerous potential research avenues for Si-based LIBs design and characterization.

Sustainable Production of Molybdenum Carbide (MXene) from Fruit Wastes for Improved Solar Evaporation.

Invited for the cover of this issue is the group of Edison Huixiang Ang at the National Institute of Education, an institute of Nanyang Technological University, Singapore. The image depicts the sustainable fabrication of two-dimensional MXene sheets from the upcycling of fruit waste for solar desalination. Read the full text of the article at 10.1002/chem.202203184.

Advanced Covalent Organic Frameworks for Multi-Valent Metal Ion Batteries.

Covalent organic frameworks (COFs) have received increased interest in recent years as an advanced class of materials. By virtue of the available monomers, multiple conformations and various linkages, COFs offer a wide range of opportunities for complex structural design and specific functional development of materials, which has facilitated the widespread application in many fields, including multi-valent metal ion batteries (MVMIBs), described as the attractive candidate replacing lithium-ion batteries (LIBs). With their robust skeletons, diverse pores, flexible structures and abundant functional groups, COFs are expected to help realize a high performance MVMIBs. In this review, we present an overview of COFs, describe advances in topology design and synthetic reactions, and study the application of COFs in MVMIBs, as well as discuss challenges and solutions in the preparation of COFs electrodes, in the hope of providing constructive insights into the future direction of COFs.

Membranes prepared from graphene-based nanomaterials for water purification: a mini-review.

Graphene-based nanomaterials (GBnMs) are currently regarded as a critical building block for the fabrication of membranes for water purification due to their advantageous properties such as easy surface modification of functional groups, adjustable interlayer pore channels for solvent transportation, robust mechanical properties, and superior photothermal capabilities. By combining graphene derivatives with other emerging materials, heteroatom doping and rational design of a three-dimensional network can enhance water transportation and evaporation rates through channels of GBnM laminates and such layered structures have been applied in various water purification technologies. Herein, this mini-review summarizes recent progress in the synthesis of GBnMs and their applications in water treatment technologies, specifically, nanofiltration (NF) and solar desalination (SD). Finally, personal perspectives on the challenges and future directions of this promising nanomaterial are also provided.

High-Resolution Electron Tomography of Ultrathin Boerdijk-Coxeter-Bernal Nanowire Enabled by Superthin Metal Surface Coating.

The rapid advancement of transmission electron microscopy has resulted in revolutions in a variety of fields, including physics, chemistry, and materials science. With single-atom resolution, 3D information of each atom in nanoparticles is revealed, while 4D electron tomography is shown to capture the atomic structural kinetics in metal nanoparticles after phase transformation. Quantitative measurements of physical and chemical properties such as chemical coordination, defects, dislocation, and local strain have been made. However, due to the incompatibility of high dose rate with other ultrathin morphologies, such as nanowires, atomic electron tomography has been primarily limited to quasi-spherical nanoparticles. Herein, the 3D atomic structure of a complex core-shell nanowire composed of an ultrathin Boerdijk-Coxeter-Bernal (BCB) core nanowire and a noble metal thin layer shell deposited on the BCB nanowire surface is discovered. Furthermore, it is demonstrated that a new superthin noble metal layer deposition on an ultrathin BCB nanowire could mitigate electron beam damage using an in situ transmission electron microscope and atomic resolution electron tomography. The colloidal coating method developed for electron tomography can be broadly applied to protect the ultrathin nanomaterials from electron beam damage, benefiting both the advanced material characterizations and enabling fundamental in situ mechanistic studies.

Ultrafast Universal Fabrication of Metal-Organic Complex Nanosheets by Joule Heating Engineering.

Two-dimensional metal-organic complex (MOC) nanosheets are of great interest in various areas. Current strategies applied to synthesize MOC nanosheets are suffering from low yield, usage of large amounts of environmentally unfriendly organic solvent, are time and energy consuming, and cumbersome steps for 2D nanostructures. In this work, a novel joule heating mechanism is proposed to fabricate MOC nanosheets about 5 nm in thickness with tunable metal compositions (i.e. M = Co, CoNi, and CoFe) within 60 s. Small amount of water is used as the only solvent. Under the intense irradiation of the microwave, fast heating via ionic conduction loss is realized, and urea is catalytically condensed into the long-chain organic ligands rich in N atoms that are capable of coordinating with metal ions to form the stubborn MOC framework, which is simultaneously puffed into an ultrathin nanosheet structure by the intensive release of gas. As a proof of concept, the as-synthesized Co-MOC nanosheet exhibits a superior lithium storage performance of 360 and 330 mA h g-1 after 1200 and 2300 cycles at a current density of 500 and 1000 mA g-1 , respectively.