Nanoscale最新文献

{"title":"Functionalization with polymer ligands enhances the catalytic activity of surfactant-stabilized gold nanoparticles.","authors":"Sophie Jancke,Christian Rossner","doi":"10.1039/d5nr00910c","DOIUrl":"https://doi.org/10.1039/d5nr00910c","url":null,"abstract":"Plasmonic nanoparticles are increasingly explored as catalytically active entities to affect (photo-)catalytic transformations. Synthesis methods are established for accessing such nanoparticles with defined dimension and shape, thereby controlling their plasmonic behavior, including the possibility of resonance engineering and the control of chiral plasmonic properties of single plasmonic nanoparticles that can be used to drive asymmetric photocatalytic transformations. However, the most productive nanoparticle synthesis procedures employ surfactants that lead to comparably dense surface layers and may limit surface accessibility. In this work, we demonstrate that functionalization of such surfactant-stabilized plasmonic gold nanoparticles with a brush-type polymer-ligand layer results in both significantly increased catalytic activity in the colloidal solution state (by a factor of ∼4) and excellent colloidal stability, enabling several catalytic cycles. Heterogeneous catalysis experiments performed after surface deposition allowed the comparison between polymer ligand-grafted and ligand-free gold nanoparticles, which show comparably weak differences in catalytic rate (a factor of ∼1.8). These results pave the way for efficient (photo-)catalysis driven by well-defined plasmonic nanoparticles in colloidal solution.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"10 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122360","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3D and in situ electron microscopy study of the nucleation and growth processes of cobalt-based nanoparticles synthesized by thermal decomposition on carbon nanotubes","authors":"Mohammed Alae Ait Kerroum, Dris Ihiawakrim, Ovidiu Ersen, Walid Baaziz","doi":"10.1039/d5nr01112d","DOIUrl":"https://doi.org/10.1039/d5nr01112d","url":null,"abstract":"Herein, we investigate the confinement effect of carbon nanotubes (CNTs) on the synthesis of cobalt-based nanoparticles (NPs) by thermal decomposition method. From an ex situ synthesis, the microstructural properties of typical nanoparticles, either confined within or localized on the external surface of CNTs, were first studied using electron tomography (ET) and high-resolution transmission electron microscopy (HR-TEM). The obtained results show that the “inner” NPs display a Co-CoO crystalline structure, homogeneous size (~50 nm) and octahedral morphology. In contrast, NPs anchored to the external surface of CNTs exhibit random morphologies and are made of small particles of ~20 nm with an oxidized layer of Co3O4. The quantitative analysis of the surface faceting of NPs, using a geometrical approach, show that the NPs confined within the CNTs do not adopt regular an octahedral morphology (with eight equal facets) but rather a elongated one, revealing an anisotropic growth along the CNT direction during the synthesis. In the second part of this paper, the nucleation and growth mechanisms of both types of NPs were in situ studied by reproducing the solvothermal reaction for the first time using Environmental-Cell TEM (EC-TEM) approach. Outside the CNT medium, the direct visualization of the NPs formation mechanism as a function of temperature allows to observe that their nucleation does not occur homogeneously in the synthesis medium, as expected, being initiated in the vesicles-like structures that appear in the solvent at the temperature range of the precursor decomposition. The first clusters and the subsequent NPs are formed at the liquid-gas interface in the vesicle “walls”, which are characterized by a higher monomer concentration. Their size grow rapidly until a critical value of 4-5 nm before leaving the walls and form chain-like structures. The NPs close to the CNT were adsorbed at carbon surface due to presence of oxygen functions, and their size increase until ~20 nm by sintering. Inside the confined channel of CNTs, the reaction mixture is incorporated by capillarity at low temperature. Then, a porous micellar aspect of the liquid was observed with an important supply of coalescent precursor from the CNT tip. At higher temperature (~300°C), the structure is densified and form the first separated entities forming the Co-based NPs.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"59 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Production of synthetic natural gas: a study of nickel catalysts obtained by solid-state combustion of nickel complexes with ethylenediamine.","authors":"Olga V Netskina,Kirill A Dmitruk,Ignat A Podolyako,Svetlana A Mukha,Arkadiy V Ishchenko,Igor P Prosvirin,Olga A Bulavchenko,Vladimir A Rogov,Alexey P Suknev,Oxana V Komova","doi":"10.1039/d5nr00186b","DOIUrl":"https://doi.org/10.1039/d5nr00186b","url":null,"abstract":"Bulk nickel and nickel-alumina catalysts were prepared by solid-state combustion (SSC) from energy-rich complexes that are formed by adding liquid ethylenediamine to solid nickel nitrate at molar ratios of 1 : 2 and 1 : 3. It was noted that the fast gasification of a complex mixed with alumina minimized their interaction; therefore, the main condensed combustion product was nickel oxide, as with the combustion of individual complexes. A study of the obtained nickel-containing catalysts for CO2 methanation showed that a catalytically active phase was formed at temperatures ranging from 250 to 350 °C, even in a reaction medium in the presence of CO2. It was found that after activation, the nickel-alumina catalyst more effectively catalyzed the methanation of CO2 compared to the synthesized bulk catalyst and the industrial NIAP-07-01 catalyst containing ∼2 times more nickel. Indeed, the amount of CO2 converted into methane on the synthesized nickel-alumina catalyst was 1.5, 3, 8 and 9 times higher than on NIAP-07-01 at 350, 300, 250 and 200 °C, respectively. Furthermore, the catalyst synthesized by the SSC method is capable of methanating CO2 even at 150 °C. Its activity does not decrease over time, and it steadily converts about 55% of CO2 into methane at 350 °C for 10 hours.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"75 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Controlling the Formation of Fast-Growing Silver Nanocubes in Non-Polar Solvents","authors":"Maximilian Joschko, Moritz Schattmann, Deniz Grollmusz, Christina Maria Graf","doi":"10.1039/d5nr01350j","DOIUrl":"https://doi.org/10.1039/d5nr01350j","url":null,"abstract":"The key to the most efficient nanostructures is a deep understanding and control of all factors influencing the reaction mechanism. To realize the full potential of a synthesis of Ag nanocubes in a non-polar solvent mixture, the factors that determine the results are thoroughly investigated. In this hot-injection approach, an Ag precursor reacts with a Cl precursor to form AgCl and multiply twinned (MT) Ag nanoparticles. The AgCl is then reduced to single crystalline Ag nanoparticles while the MT nanoparticles are oxidized. As a result, the single crystals grow into nanocubes. Previously unidentified factors like the catalytic influence of Fe(III) ions and the in situ formation of HCl, which leads to an undefined chloride content, are revealed. A high reproducibility is achieved by controlling the amount of Fe(III) ions and adding a stable Cl source. Thoroughly investigating and combining the effects of chloride concentration with temperature and oxidative etching allows for adjusting the edge length of the nanocubes in the range of 40 to 100 nm and improving their uniformity. These findings lead to a robust protocol for producing non-polar silver nanocubes with sharp edges, low polydispersity, tunable size, and thus tunable optical properties in a short reaction time.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"18 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113450","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational modelling of nanoparticle catalysis","authors":"Sam M McIntyre, Anna L. Garden","doi":"10.1039/d4nr04364b","DOIUrl":"https://doi.org/10.1039/d4nr04364b","url":null,"abstract":"In recent years computational methods have complemented a range of experimental techniques to enrich our understanding of chemical systems. This is particularly true in catalysis, as it is possible to gain atomic level insight into the active sites, adsorbate interactions, and the potential mechanisms occurring. Nanoparticles or nanoscale materials have become increasingly popular as catalysts in recent years, requiring additional computational considerations. In this review we present an overview of existing and emerging computational methods in nanocatalysis and the unique catalytic behaviour that is revealed by these methods. We first discuss numerical tools used to calculate structures, energies and rates of catalytic reactions as well as different approaches to representing active sites of nanoparticle catalysts. We then focus on alloy and supported nanoparticle catalysts and explore how computational methods can reveal the more complex behaviours of these catalytic systems. Finally, we highlight some of the additional challenges in moving towards realistic systems, such as the dynamic nature of catalysts, the role of solvent, ensemble effects, the distribution of active sites and influence of defects, which also have the potential to change the observed catalytic properties. We also present a discussion on emerging machine learning approaches as applied to nanocatalysis. Overall, this article aims to highlight the various methods available to model nanocatalysis and the catalytic insights that can be gained from a computational approach, using a range of examples from recent literature.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"57 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insights into the copolymerization of metal–organic nanotubes from ligand mixtures using small angle neutron scattering†","authors":"Md Ashraful Haque, Jacob A. Barrett, Xian B. Carroll, David M. Jenkins and Mark D. Dadmun","doi":"10.1039/D4NR04820B","DOIUrl":"10.1039/D4NR04820B","url":null,"abstract":"<p >Metal–organic nanotubes (MONTs) are porous, tunable 1D nanomaterials akin to metal–organic frameworks (MOFs). MONTs are synthesized <em>via</em> metal salts and coordinating ligands akin to MOFs, but crucially they are anisotropic, unlike most MOFs. Recently, MONTs have been shown to form statistically random copolymers; however, their mechanism of growth remains largely unexplored. Full realization of the potential of MONTs necessitates a thorough understanding of the mechanism of MONT growth. Herein, small-angle neutron scattering (SANS) was employed to investigate the copolymerization mechanism of two 1,2,4-ditriazole ligands and to quantify the inclusion of a solvent within the MONT pores. The results show parallelepiped-shaped structures are initially formed, which then aggregate to form larger lamellar structures. Additional experimentation with a deuterated ligand showed that the reactivities of all ligands are approximately equal, causing random ligand distribution within the resulting MONT. Finally, the results quantify the amount of solvent incorporated within the nanostructure pores at different stages of the formation process. These results show that early in the reaction the MONTs contain <em>ca.</em> 45% solvent, and they contain <em>ca.</em> 55% solvent late in the reaction when the MONTs are nearly fully formed.</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":" 22","pages":" 13905-13914"},"PeriodicalIF":5.8,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Facile Synthesis of Magnetic Core-Shell Structures for Tunable Microwave Absorption","authors":"Jiao Liu, Xukang Han, Wenjuan Ren, Longqiang Liang, Xiyao Wang, Di Lan, Mingliang Ma, Shengtao Gao","doi":"10.1039/d5nr01174d","DOIUrl":"https://doi.org/10.1039/d5nr01174d","url":null,"abstract":"The rapid development of electronic communication and radar technologies in the 5G era has exacerbated electromagnetic pollution, thereby driving the urgent need for cutting-edge microwave absorption materials. In this study, a novel SnCo/C@MoS2 composite was proposed, and the core-shell structure was synthesized via electrospinning and hydrothermal methods. This composite uniquely integrated the high conductivity and magnetic properties of Sn and Co while capitalizing on the superior dielectric performance of MoS2 nanosheets, which are uniformly grown on carbon nanofibers. This design capitalized on the synergistic effects of a one-dimensional (1D) carbon fibers (CF) framework and two-dimensional (2D) MoS2 nanostructures, enhancing interfacial polarization and multi-loss mechanisms. The SnCo/C@MoS2 exhibited remarkable microwave absorption properties, achieving a minimum reflection loss (RLmin) of -64.27 dB at a thickness of 1.52 mm and an effective absorption bandwidth (EAB) of 5.20 GHz. Moreover, computer simulation technology (CST) demonstrated that SnCo/CNF@MoS2 simulated radar cross-section (RCS) values felled below -20 dB m2. These results demonstrated a substantial improvement in absorption performance compared to the individual SnCo/CNF and MoS2 components. This work underscored the effectiveness of combining 1D and 2D materials to obtain core-shell structures for superior electromagnetic wave (EMW) attenuation.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"136 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Asymmetric thiol-modified hybrid polyoxometalates: building blocks for hierarchical nanostructured redox materials","authors":"Graham Newton, Elizabeth Hampson, Alexander Kibler, Jamie Cameron, Julie A Watts, Abigail Bellamy-Carter, Alex Saywell, Lee Johnson, Darren Walsh","doi":"10.1039/d5nr00544b","DOIUrl":"https://doi.org/10.1039/d5nr00544b","url":null,"abstract":"The development of hierarchical, redox-active nanostructures can drive new advances in fields ranging from energy storage to sensors and memristors. The self assembly of redox-active molecular building blocks into redox-active structures is especially promsing, offering synthetic chemists the prospects of introducing unique chemical functionality into redox materials. In this contribution, we present an asymmetrically-functionalised organic-inorganic hybrid Wells-Dawson polyoxometalate bearing a chelating metal-binding group and a thiol-terminated aliphatic chain unit. The thiol-bearing group facilitates the solvent-dependent self-assembly of the cluster into soft nanostructures and grafting of the cluster onto Au surfaces and nanoparticles. We demonstrate how the redox properties of the molecular units are translated across the different classes of materials .","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"15 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Physicochemical Characterization of a New Porous 2D Semiconductor Carbon Allotrope, C16: An Investigation via Density Functional Theory and Machine Learning-based Molecular Dynamics","authors":"Kleuton Antunes Lopes Lima, Rodrigo Alves, Elie A. Moujaes, Alexandre Cavalheiro Dias, D. S. Galvao, Marcelo Lopes Pereira Júnior, Luiz Antonio Ribeiro, Jr.","doi":"10.1039/d5nr01282a","DOIUrl":"https://doi.org/10.1039/d5nr01282a","url":null,"abstract":"This study comprehensively characterizes, with suggested applications, a novel two-dimensional carbon allotrope, C<small>₁₆</small>, using Density Functional Theory and machine learning-based molecular dynamics. This nanomaterial is derived from naphthalene and bicyclopropylidene molecules, forming a planar configuration with sp<small>²</small> hybridization and featuring 3-, 4-, 6-, 8-, and 10-membered rings. The cohesive energy of -7.1 eV/atom, the absence of imaginary frequencies in the phonon spectrum, and the retention of the system's topology after ab initio molecular dynamics simulations confirm the structural stability of C$_{16}$. The nanomaterial exhibits a semiconducting behavior with a direct band gap of 0.59 eV and anisotropic optical absorption in the $y$ direction. Assuming a complete absorption of incident light, it registers a power conversion efficiency of 13 %, demonstrating relatively good potential for applications in solar energy conversion. Excluding the vacuum effect along the non-periodic $z$ direction, the planar lattice thermal conductivity $kappa_L$ reaches ultralow values of 1.90$times$ 10$^{-2}$ W/(m.K), 0.90$times$ 10$^{-2}$, and 0.59$times$ 10$^{-2}$ for T=300K, 600K, and 1000K, respectively along both x and y directions. Very close to the Fermi level, the thermoelectric figure of merit (zT) can reach a maximum value of 0.93 at room temperatures along both planar directions, indicating an excellent ability to convert a temperature gradient into electrical power. Additionally, C<small>₁₆</small> demonstrates high mechanical strength, with Young's modulus values of 500 GPa and 630 GPa in the x and y directions, respectively. Insights into the electronic, optical, thermoelectric, and mechanical properties of C<small>₁₆</small> reveal its promising capability for energy conversion applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"31 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Titanium Diboride-Derived Nanosheets Enhance the Mechanical Properties of Polyurethane: Experiments and Simulation","authors":"Bhagyashri Gaykwad, Sree Harsha Bharadwaj H, Archit Bahirat, Raghavan Ranganathan, Kabeer Jasuja","doi":"10.1039/d5nr01185j","DOIUrl":"https://doi.org/10.1039/d5nr01185j","url":null,"abstract":"AlB2-type metal diborides have garnered significant attention in recent years owing to their ability to yield quasi-2D nanostructures. Titanium diboride (TiB2), a key member of the metal diboride family, is well known for its extraordinary mechanical properties. However, the candidacy of TiB2-based nanosheets to reinforce a polymer matrix has largely remained unexplored. In this work, we compare three kinds of TiB2 reinforcements – bulk form, pristine nanosheets, and functionalized nanosheets, for their prospects in the mechanical reinforcement of polyurethane (PU). We find that while all fillers lead to an improvement in the mechanical properties of PU, the composite comprising pristine nanosheets exhibits the most significant enhancement. A 2 wt.% loading of pristine nanosheets results in ~80% increase in ultimate tensile strength and toughness. Detailed molecular dynamics simulations reveal that the TiB2 nanosheets are not only able to distribute load effectively, but they also promote isotropic mechanical behaviour, which makes the composite stiff and strong. These insights are supplemented by inferences from the hydrogen bonding index (HBI) and degree of phase separation (DPS). This study exemplifies the rich prospects offered by the metal diboride-derived nanosheets for reinforcing polymer matrices.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"7 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}