Phase is a fundamental structural parameter that distinguishes the atomic arrangement in materials. The recent advancement in phase engineering of nanomaterials (PEN) has witnessed the discovery and intriguing physicochemical properties of a number of unconventional phases in metal nanomaterials, enabling their promising applications in catalysis, optics, and so on. With the aid of advanced characterization techniques and theoretical calculations, phase engineering of metal nanomaterials has made significant progress in terms of precisely controlled synthesis, phase transformation, and phase-dependent property studies. This review summarizes the recent progress of PEN with a focus on metal nanomaterials. First, we introduce various synthetic strategies to prepare unconventional-phase metal nanomaterials, including monometallic and multimetallic nanomaterials. Second, we discuss methods to realize phase transformation of metallic nanomaterials. Then, we demonstrate various phase-dependent properties and applications of metal nanomaterials. Last, current challenges and exciting opportunities in the phase engineering of metal nanomaterials are discussed.
Due to the growing demand on sustainable and environmentally friendly energy storage systems, all-organic batteries (AOBs) are attracting wide attention as promising alternatives to traditional lithium-ion batteries (LIBs). This review comprehensively covers the latest advances in organic materials and technologies in monovalent AOBs based on lithium, sodium, and potassium ions. It explores the numerous benefits of organic electrode materials, addresses several limits including energy density, cycle life, and technological maturity, and presents diverse techniques, such as organic molecule design, polymerization, and symmetrical batteries to mitigate these challenges. Furthermore, this review also investigates the potential of proprietary sodium- and potassium-ion AOBs, which are both resource-abundant and cost-effective, as energy storage systems alongside LIBs. It aims to provide comprehensive guidelines for future AOBs research, with a particular focus on achieving high performance, improving sustainability, and facilitating commercialization.
Atomically dispersed catalysts, i.e., single-atom catalysts (SACs), have attracted considerable interest because of their 100% atom utilization and unique geometric and electronic structures relative to nanoparticles. Atomic manipulation enables the construction of well-defined active sites on an atom-by-atom basis, which is particularly intriguing for electrocatalysis. Bi-atom catalysts (BACs) represent an important branch, where atomic pairs can markedly enhance the efficiency and selectivity of electrocatalysis. Emerging as a new subclass, ordered multiatom catalysts (OMACs) have received significant attention recently. Unlike randomly distributed single atoms, the OMACs possess ordered atomic arrangements, like atomic arrays and ordered single-atom alloys. Geometrically, this order could enhance intrinsic activity and reaction selectivity by making interatomic distance just right or customizing atomic arrangements for the lower activation energy pathway, and simultaneously improve the density of active sites to some extent. Electronically, this order may induce new electronic states and/or strong orbital hybridization between neighboring atoms, thereby enabling unexpected activity. The ensemble effect and/or synergistic effect would become feasible by rational regulation of atomic arrangements and components of OMACs. We herein reviewed the recent advance from single-atom to biatom and ordered multiatom mainly emphasizing OMACs, discussed their synthesis, characterizations, and electrocatalytic applications, and finally proposed some challenges and prospects for better developing single-atom catalysis.
Bioelectrodes in cells can record and monitor monocellular or multicellular signals, contributing to early diagnosis, drug development and public health. To promote the cell analysis platform into integration, miniaturization and intellectualization, development of advanced bioelectrodes has attracted intense attention from both research and industrial communities. Here we present the research progress of bioelectrodes for cell analysis along four lines: materials, fabrications, principles and state-of-the-art applications. Covering from traditional noble metals to frontier conducting polymers, various conductive yet biocompatible materials have been used to develop bioelectrodes. Suitable materials are processed into micro/nano electrodes through electrochemical deposition, sol-gel processes, and self-assembly etc. The prepared bioelectrodes play roles in cellular analysis based on a biochemical process of direct electron transfer, mediator-assisted transfer or biocatalysis, which has been widely used in electrophysiological characterization, chemical analysis, metabolite detection and intercellular communication. To conclude this review, we summarize current challenges remained for cell electrodes in terms of foreign body response, biocompatibility, long-term stability, miniaturization, multifunctional integration, and intelligence, further suggesting possible solutions on performance optimization and material innovation. This review could provide guidance for understanding the working principles of bioelectrodes, designing a feasible cellular analysis platform, and building advanced cell analysis systems.
The transition to renewable energy systems has intensified the need for sustainable, large-scale energy storage solutions, and redox flow batteries (RFBs) have emerged as a promising technology due to their scalability, safety, and long cycle life. However, conventional RFBs that rely on metal-based electrolytes face significant challenges, including high cost, resource scarcity, and environmental toxicity. Bio-derived electrolytes offer a sustainable alternative that combines renewable sources with tunable electrochemical properties. This review comprehensively summarizes the latest progress of RFB bio-derived electrolytes and discusses the electrochemical performances of plant-derived quinones, lignin derivatives, and fungal metabolites. The limitations in the systems, such as lower solubility limits, crossover issues, and long-term stability are evaluated, with suggested future research directions. The work provides valuable insights for the development of next-generation green RFB systems, which align with global sustainability goals.
The global urgency to achieve carbon neutrality and peak carbon emissions (“dual carbon” strategy) has spurred remarkable progress in catalytic technologies, such as photocatalysis, electrocatalysis, and photothermal catalysis, aiming at addressing environmental and energy challenges. This review systematically examines the latest breakthroughs in catalyst design [e.g., metal-organic frameworks (MOFs), covalent organic frameworks (COFs), black semiconductors, and p-block metal chalcogenides] and mechanism innovations (e.g., electron spin control, defect engineering, and heterojunction construction), which enhance solar-to-chemical conversion efficiency and product selectivity. Advanced characterization techniques, including operando spectroscopy and machine learning, are emphasized for unraveling dynamic catalytic processes and guiding material optimization. Applications range from CO2 reduction to high-value fuels (e.g., CO, CH4, C2+ products), green hydrogen production, and pollutant degradation, showcasing the transformative potential of these technologies in energy storage, environmental remediation, and sustainable synthesis. Challenges related to scalability, stability, and economic feasibility are critically analyzed, providing insights into future research directions for industrial implementation.
The porous transport layer (PTL) and the catalyst layer are two critical components in the proton exchange membrane water electrolyzer (PEMWE). The gas/liquid two-phase transport and electron/heat transfer between the two layers have a significant impact on the performance of the whole device. Catalyst layers and PTLs prepared by different methods or structures have unique effects. The coordination between the PTL and catalyst layer can greatly impact the catalyst and PEMWE performance, which is induced by the interface between the two. However, this coupled effect has not been well studied and the optimized interface mechanism is still unclear. In this work, three types of PTLs, including carbon paper, Ti felt and sintered Ti particles, were adopted, and their interfacial relationships between catalyst layers were investigated. We found that the interface between PTL and catalyst layer can be regulated by PTL structure, surface property, and catalyst layer thickness. The surface coating improves the electron transport at the interface and in the PTL itself, thereby increasing the local current density and weakening the influence of Schottky basis and pinch-off effects, and thus improving the PEMWE performance. The catalyst layer thickness could affect the in-plane electrical conductivity, which adjusts the active site distribution and enhances the local current density uniformity. This work reveals the coupled effects of PTL and catalyst layer on the interface and PEMWE performance, which provides the optimization strategy for the interface in PEMWE.
Promoting the photocatalytic proton-coupled electron transfer (PCET) kinetics in the two-electron oxygen reduction reaction (2e− ORR) is crucial for the photocatalytic hydrogen peroxide (H2O2) production. Herein, four kinds of covalent organic frameworks (COFs) were successfully prepared via a sub-stoichiometric strategy through a one-step solvothermal method. Among them, B1.5T1-COF with polar aldehyde groups displays a high photocatalytic H2O2 generation rate of 1081.8 µmol·g−1·h−1, which is 3 times higher than that of B1T1.5-COF and 2 times higher than that of B1T1-COF. Through the corresponding experiments and density functional theory (DFT) calculation, the photocatalytic mechanism is revealed that B1.5T1-COF with free aldehyde groups can raise the PCET kinetics for 2e− ORR with the aid of a stable transfer channel for e− and a favorable hydrogen donation for H+. This work might provide some insights for design and preparation of COFs with functional groups through a sub-stoichiometric strategy to modulate their photocatalytic activities.
Li-CO2 batteries have garnered considerable attention due to their high energy density and their ability to utilize CO2 resources. However, the generation of insulating discharge product Li2CO3 severely weakens its cyclability, which places high demands on the cathode catalyst in Li-CO2 batteries. This study focuses on the development of Ru nanoparticles modified Mo2CTx as the cathode for Li-CO2 batteries, which is integrated with a high surface area, abundant active sites, and enhanced conductivity. As a result, the Ru@Mo2CTx cathode achieves a remarkable discharge capacity of 20995 mA·h·g−1 and a long cycle life of 1750 h. Additionally, density functional theory calculations provide further insights into the enhancement in absorptivity with Ru introduced onto Mo2CTx. This research paves the way for manipulating the catalytic activity of Mo2CTx and reducing the amount of usage of Ru in Li-CO2 batteries.
Non-metallic phosphors with high thermal stability and low thermal quenching (TQ) are expected to achieve the development and application of environmentally friendly and low-cost efficient light-emitting diodes (LEDs). Herein, a novel non-metallic hydrogen-bonded organic framework (TCBPE-HOF) phosphor with aggregation-induced emission (AIE) characteristic is synthesized by the assembly of 1,1,2,2-tetra(4-carboxy biphenyl)ethylene (TCBPE) under a simple solvothermal method for efficient LEDs with low TQ. The TCBPE-HOF shows a rare example of a 4-fold interpenetrated network based on an 8-connected hex net. It can maintain 71% of its initial emission intensity after being heated to 150 °C, outperforming several commercial inorganic phosphors. The fabrication of cyan LED devices enables it to be a viable alternative to currently available commercial phosphors.
With the increasing global concern over carbon dioxide emissions, the electrocatalytic carbon dioxide reduction reaction (CO2RR) has gained significant attention. Copper (Cu)-containing materials have shown potential for multielectron transfer reduction products. This study employs density functional theory (DFT) calculations to investigate the effect of axial ligands (O, F, Cl) on the CO2RR performance of Cu-porphyrin with N-coordinated metal centers. Our study have designed an axial coordinated Cu-porphyrin structure with several ligands. The adsorption energy and Gibbs free energy change were calculated to evaluate the catalytic performance. The results show that the introduction of axial ligands significantly affects the electron density distribution and the catalytic activity. The Cu-porphyrin-O (CuPO) catalyst exhibits stronger adsorption of CO2 and lower energy barriers for the initial step of CO2RR process compared to the other catalysts, while the other two catalysts Cu-porphyrin-F (CuPF) and Cu-porphyrin-Cl (CuPCl) greatly promote the potential-determining step (PDS), respectively. The d-band center theory further explains the enhanced adsorption strength of intermediates on these catalysts. Our research provides insights into the design of high-performance CO2RR single-atom catalysts.
Pd-based catalysts have been widely used in CO2 hydrogenation to formic acid/formate and their catalytic performance is strongly related to the metal-support interaction, which determines the geometric and electronic structure of Pd sites. Herein, the interaction of Pd species with ZrO2 support is effectively regulated by altering the synthesis method. Pd0.4/ZrOx(SG) prepared by the sol-gel (SG) method shows higher catalytic activity than Pd0.4/ZrOx(IM) prepared by the impregnation method (IM) in CO2 hydrogenation to formate. This is due to the strong metal-support interaction that hinders the agglomeration of Pd species at high temperatures, thus, exposing more active sites. However, further improvement of the interaction of Pd with the support by decreasing Pd loading on ZrOx(SG) leads to a considerable decrease of both formate formation rate and TON. This is because of the suppression of the reduction of PdOx species that decreases H2 dissociation and subsequent hydrogenation activity.
In this study, we optimized a previously reported method for preparing bicyclic iminosugars from D-ribose tosylate. Through systematic screening and optimization of the reaction conditions, bicyclic iminosugars containing O-, S-, and N-glycosides were successfully prepared with yields of up to 99% and excellent stereoselectivity. Based on the formation of compound I-2-1, we hypothesize that the reaction proceeds via imine cation intermediates. Key improvenments over prior studies include the substitution of toluene with CH2Cl2 as the solvent and the incorporation of Et3N as an acid-binding agent, both of which significantly enhanced the reaction yield and stereoselectivity. Furthermore, we successfully modified two of the products with a butyryl group, demonstrating the potential for further modification and subsequent biological activity studies.
A comprehensive investigation is conducted in the present study to analyze the non-covalent interactions displayed by the methyl salicylate complex when exposed to various solvents. The density functional theory (DFT) method is utilized to explore the impact of cation-π interaction on the strength and characteristics of the intramolecular hydrogen bond (IMHB). The findings display an augmentation in the strength of cation-π interaction within the gas phase compared to the solution. The analyses of atoms in molecules (AIM) and the natural bond orbital (NBO) are employed to provide further information on the nature of the studied interactions. According to the findings, the HB present in the considered complex falls into the medium HBs category. In addition, our investigation indicates that the cation-π interaction reinforces the IMHB in diverse solvents, but the reverse is true for the gas phase. Finally, an evaluation of the electronic properties, stability, and reactivity of the complex is performed by investigating frontier molecular orbitals, such as energy gap, chemical hardness, and electronic chemical potential. The results of this study that are ubiquitous in biological systems may be useful for the design and synthesis of a variety of supramolecular complexes with the desired properties.
A silicate inorganic phosphor matrix, CJU-1-Eu (K3EuSi6O15), based on rice husk-derived biomass silicon, was synthesized via a hydrothermal method. The material was doped with Tb3+ ions, and the effect of Tb3+ concentration was investigated, resulting in a series of tunable white-light inorganic phosphors (CJU-1-Eu:xTb3+) ranging from warm white to cool white. The CJU-1-Eu:0.04Tb3+ inorganic white-light phosphor was combined with a UV chip to produce the white-light-emitting diode (WLED) device. The device exhibited CIE coordinates of (0.332, 0.327) and the color rendering index (CRI) of 86.5 at 100 mA current. This white-light phosphor achieves both the recycling and high-value utilization of rice husk ash.
The sensitive and selective detection of ppb-level (ppb: parts per billion) H2S using miniaturized and portable gas sensor is of great significance in environmental monitoring, medical diagnosis and many other fields. MXenes, with high electrical conductivity, large surface area, and abundant active sites, hold great promise for room temperature gas sensing applications. In this work, a room temperature H2S sensor was constructed utilizing Mo2CTx MXene sensitive material, synthesized by a typical LiF/HCl etching method. The H2S sensing characteristics of Mo2CTx sensor were further improved by controlling ultrasonic time and optimizing heat-treated temperature. The M-50 sensor utilizing optimized Mo2CTx sensing material exhibited good selectivity, the highest response value (−39.92%) to 1 ppm (ppm: parts per million) H2S, and the lowest detection limit of 30 ppb (theoretically 0.35 ppb). The enhanced H2S sensing properties are largely attributed to the fragmented nanosheet structure and surface defects caused by prolonging ultrasonic time and adjusting treatment temperature. Additionally, density functional theory (DFT) calculations demonstrated that surface Mo atom vacancy and edge of Mo2CTx could significantly improve the adsorption ability of H2S. The present work contributes to advancing exploration of Mo2CTx material in sensing applications.
A tungsten-doping strategy was developed to enhance the photocatalytic dye degradation and corrosion resistance of graphitic carbon nitride (CN). Using WCl6 as a tungsten source, tungsten-doped CN (W-CN) was synthesized through a straightforward copolymerization process. Comprehensive characterization confirmed that tungsten ion incorporation modified the electronic band structure and disrupted local electron distribution, leading to extended visible light adsorption and improved separation and migration of photoexcited charge carriers. The resulting W-CN photocatalyst achieved a 5.14-fold increase in atrazine (ATZ) degradation rate. Additionally, the corrosion resistance of W-CN within waterborne polyurethane (WPU) coatings on metal substrates was evaluated. Enhanced hydrophobicity and a stronger physical barrier effect enabled the W-CN@WPU composite coating to significantly improve the corrosion resistance of Q235 carbon steel. This study demonstrates that tungsten doping not only boosts the photocatalytic degradation efficiency of organic pollutants by CN but also enhances the corrosion resistance of WPU coatings.
Precise modification of the C-terminus of proteins is crucial for investigating protein-protein interaction and enhancing protein functionalities. While traditional methods face challenges due to multiple reactive sites, recent advancements have introduced cysteine protease domain (CPD) tag for efficient C-terminal modifications. CPD, when fused with proteins of interest (POI), can facilitate concurrent hydrolysis and amidation under Inositol hexakisphosphate (InsP6) activation. Herein, we explored the influence of substituting the Ala residue following Leu in the CPD cleavage motif (VDALADGK) with each of the 19 other amino acids. By creating a series of green fluorescent protein (GFP)-CPD fusion constructs, we evaluated their hydrolysis and amidation efficiencies. Our results revealed that mutations to Ser and Asn significantly enhanced C-terminal modification, while Pro substitution completely hindered hydrolysis activity. Additionally, we demonstrated the successful labeling of a Ser mutant with a fluorescent probe, establishing its potential for Förster resonance energy transfer (FRET) applications. Structural analyses using AlphaFold2 indicated that the observed variations in activity could be attributed to the differences in molecular interactions and the flexibility of the substituted amino acids. Overall, this research highlights the utility of strategically designed mutations in enhancing C-terminal modifications, offering valuable insights for future protein engineering endeavors.
The Co-MOF-5 catalyst was synthesized by substituting Zn2+ ions with Co2+ ions within the Zn4O metal clusters of MOF-5, achieved via direct agitation at room temperature. The removal of solvent molecules that exhibit additional coordination with Co2+ can be accomplished through high-temperature treatment, thereby enabling the catalyst to function effectively in ethylene dimerization reactions. At 10 atm (1 atm=101325 Pa) and 25 °C, with Et2AlCl as a cocatalyst, it showed significant activity and 1-C4 selectivity. At a Co/(Co+Zn) molar ratio of 20%, the oligomerization activity of ethylene was observed to be 5.38×105 g·mol−1·h−1. Additionally, the selectivity for C4 products was recorded at 97.11%, with 1-butene constituting 88.06% of the resultant product. Density functional theory (DFT) calculations corroborated that the ethylene oligomerization process catalyzed by Co-MOF-5 adheres to the Cossee-Arlman mechanism. Co-MOF-5 not only facilitates the dimerization process effectively but also directs the reaction pathway to preferentially yield 1-C4. Consequently, Co-MOF-5 presents significant potential for applications in industrial catalysis and organic synthesis, particularly in processes that necessitate highly selective products. By further optimizing and modifying the structure and reaction conditions of Co-MOF-5, it is anticipated that its catalytic performance can be enhanced, thereby advancing the development and application of ethylene dimerization reaction technologies.
Developing green and efficient way for producing biofuel and high-value chemical from lignocellulosic biomass is of great significance for promoting green chemistry and sustainable development. Present work intended to explore a novel recyclable MnFe2O4 catalytic pre-treatment means to strengthen the synthesis of bioethanol and biofuel. The MnFe2O4 catalytic pre-treatment raised saccharification of lignocellulosic biomass, which was beneficial for the formation of ethanol intermediate and the production of biofuel. After MnFe2O4 catalytic pre-treatment, ethanol yield reached 34.2%. High ethanol conversion (93.8%) and good jet fuel selectivity (63.3%) were achieved in synthesizing biofuel process. According to catalyst’s characterization, lignocellulose’s characterization as well as radical’s detection, probable function/mechanism of MnFe2O4 catalytic pre-treatment was proposed. The MnFe2O4 catalyst facilitated the formation of hydroxyl radicals, thereby enhancing the depolymerization of lignocellulose and subsequent fuel synthesis. Considering that MnFe2O4 catalytic pre-treatment can be conducted by utilizing recyclable MnFe2O4 catalyst under gentle condition, this technology may provide an environmental-friendly pre-treatment means for facilitating the transformation of lignocellulose into biofuel.
Elasticity of biodegradable fibrous scaffolds is one of essential requirements for soft tissue regeneration, and sufficient compliance of small-diameter vascular grafts is necessary. In this work, electrospun fibrous membranes with high resilience are prepared through blend electrospinning of poly(ε-caprolactone) (PCL)/methacrylated poly(glycerol sebacate) (PGS) and in situ photo-crosslinking with poly(ethylene glycol) diacrylate. The obtained PCL/PGS electrospun membranes have minor hemolysis, low platelet adherence, and favorable cytocompatibility. In the wet state, the PCL/PGS electrospun membranes in 5/5 or 4/6 mass ratio exhibit lowered modulus and reversible deformation with improved compliance in comparison with PCL, which can be comparable to the human saphenous vein. This study provides a feasible way to prepare electrospun fibrous scaffolds with high elasticity, that can be suitable for applications in vascular regeneration and relative soft tissue repair.
Analyzing organic, metallic, and anionic components in PM2.5 (particulate matter less than 2.5 µm in size) is critical for understanding its formation, evaluating health risks, and tracing pollution sources. Conventional methods require a combination of multiple offline extraction and detection techniques, leading to high sample consumption, long analysis time, and high costs. To address these challenges, we developed an electrochemistry mass spectrometry (EC-MS) technique that sequentially analyzes organic, metallic, and anionic components in PM2.5. Water and methanol were used to extract water-soluble and fat-soluble components, while EDTA-2Na extracted insoluble metals. Electrochemistry was employed to dissociate oxidizable and reducible species. The extracted components were then ionized and detected online: electrospray for polar organics and anions, Ag+ complexation for polycyclic aromatic hydrocarbons, and EDTA complexation for metal ions. The ionized components were detected by mass spectrometry in alternating positive and negative ion modes. This method offers a comprehensive analysis of PM2.5 components with minimal sample consumption and simplified pretreatment. It covers three forms of metals (water-soluble, insoluble, and oxidizable/reducible), multiple anions (NO3−, Cl−, CH3COO−, HCOO−, NO2−, BO2−), water-soluble dicarboxylic acids, and methanol-soluble organics (fatty acids, aromatic acids, and polycyclic aromatic hydrocarbons). This approach provides an efficient and integrated solution for multi-component detection in PM2.5 analysis.
Chiral nanostructured Ag films (CNAFs) with lattice distorted nanoflakes were fabricated utilizing phenylalanine (Phe) as the symmetry-breaking agent and AgNO3 as a silver source through an electrodeposition method. With prolonged electrodeposition duration or reduced applied potentials, the nanoflakes gradually thickened and enlarged, ultimately transforming into nanoblock architectures in CNAFs. The morphology of CNAFs underwent a progressive transition from nanoblocks to nanoflakes as the Phe and AgNO3 concentrations increased. The CNAFs stacked with vertically aligned Ag nanoflakes exhibited plasmon resonance absorption-based and scattering-based optical activities in the range of 200–800 nm. It is speculated that the carboxyl and amine groups of Phe could interact with silver ions through electrostatic and coordination interactions, while the π-π stacking of Phe would facilitate the formation of chiral assemblies to achieve chirality transfer.
Poly(lactic-co-glycolic acid) (PLGA)-based nanomedicines exhibit significant potential for biomedical applications. Despite the approval and clinical use of PLGA microparticle products, no PLGA nanomedicine is currently available due to challenges including scaling up production. Nanoprecipitation is a one-step method with simplicity and efficiency that is capable of scaling up. However, studies on the preparation of PLGA nanoparticles (NPs) via nanoprecipitation exhibit significant variability in synthesis conditions, leading to inconsistencies in NP properties. Herein, we systematically evaluated the factors influencing the preparation of PLGA NPs through nanoprecipitation. Our results indicate that a rapid bolus injection of PLGA into aqueous solution with vigorous stirring yields smaller NPs (e.g., 125 nm with bolus versus 190 nm with 0.05 mL/min dropwise, 75 nm at 1500 r/min versus 106 nm at 100 r/min). Besides, low-concentration PLGA solutions, low ion concentrations, alkaline pH aqueous solutions, water-miscible solvents capable of dissolving PLGA, and carboxyl-terminated low molecular weight PLGA are beneficial for synthesizing NPs with smaller sizes. Importantly, this method was successfully scaled up to 1 L while maintaining consistent NP properties. The consistency, reproducibility, and scalability of this optimized method provide valuable guidance for the design and preparation of PLGA NPs, potentially facilitating their industrial production and clinical translation.