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At least 415 records · Page 23

Mechanistic Transformation of CuI Nanoparticles Into Oxidation‐Resistant 2D Copper Nanoplates

Unconventional phase transformations reveal new crystallization mechanisms, yet direct observation of such pathways during nanoscale solution-phase synthesis remains challenging. This study uncovers an atypical growth process in which thermodynamically stable CuI nanoparticles (NPs) transform into high-energy 2D Cu plates. Using a combination of in situ transmission electron microscopy, ex situ structural analysis, and density functional theory calculations shows that the formation of structural defects induced by hexadecylamine and chloride ions facilitates the transformation by promoting surface iodine vacancies. The resulting Cu{111} nanoplates, with ultrathin thicknesses (≈4 nm) and exceptionally high aspect ratios (≈450), display enhanced oxidation resistance and long-term stability under ambient conditions. This resistance is attributed to the close-packed {111} facets, which suppress chemical oxidation even after extended exposure to air over 100 days. These findings provide new insights into non-classical crystallization pathways in metal nanomaterials and suggest a versatile approach for preparing oxidation-resistant, structurally defined Cu nanostructures.

36 MATERIALS SCIENCE↗

Nozzle-Free Printing of CNT Electronics Using Laser-Generated Focused Ultrasound

Printed electronics have made remarkable progress in recent years and inkjet printing (IJP) has emerged as one of the leading methods for fabricating printed electronic devices. However, challenges such as nozzle clogging, and strict ink formulation constraints have limited their widespread use. To address this issue, a novel nozzle-free printing technology is explored, which is enabled by laser-generated focused ultrasound, as a potential alternative printing modality called Shock-wave Jet Printing (SJP). Specifically, the performance of SJP-printed and IJP-printed bottom-gated carbon nanotube (CNT) thin film transistors (TFTs) is compared. While IJP required ten print passes to achieve fully functional devices with channel dimensions ranging from tens to hundreds of micrometers, SJP achieved comparable performance with just a single pass. For optimized devices, SJP demonstrated six times higher maximum mobility than IJP-printed devices. Furthermore, the advantages of nozzle-free printing are evident, as SJP successfully printed stored and unsonicated inks, delivering moderate electrical performance, whereas IJP suffered from nozzle clogging due to CNT agglomeration. Moreover, SJP can print significantly longer CNTs, spanning the entire range of tube lengths of commercially available CNT ink. The findings from this study contribute to the advancement of nanomaterial printing, ink formulation, and the development of cost-effective printable electronics.

47 OTHER INSTRUMENTATION↗

Tuning Interface Electronic Properties via Chiral Two‐Dimensional Metal‐Organic Frameworks

Control over structural symmetries in nanomaterials offers a powerful approach to engineer electronic properties. For instance, breaking of mirror symmetries in two-dimensional (2D) materials with a hexagonal lattice can lead to nontrivial electronic topologies and correlated-electron phenomena. Yet, the impact of structural chirality on the electronic properties of 2D materials and interfaces remains underexplored. Here, how chiral phases of a 2D metal-organic framework (MOF) with a hexagonal lattice—consisting of hexaazatriphenylene molecules coordinated to Cu atoms—scatter, confine, and perturb the Shockley surface state (SS) electrons of an underlying Ag(111) substrate is investigated. Via low-temperature scanning tunneling microscopy and spectroscopy, noncontact atomic force microscopy, and numerical calculations based on an electronic plane-wave expansion method, modifications of the Ag(111) SS band structure are shown and quantified, including gap openings and lifts of band degeneracies, driven exclusively by the structural chirality of the 2D MOF phases. These findings highlight how structural symmetries, in particular chirality, affect electronic states at material interfaces, expanding on the toolkit for designing 2D materials with tailored electronic properties.

band structure engineering↗

Direct SERDS sensing of molecular biomarkers in plants under field conditions

Molecular biomarkers such as microRNAs (miRNAs) play important roles in regulating various developmental processes in plants. Understanding these pathways will help bioengineer designing organisms for efficient biomass accumulation. Current methods for RNA analysis require sample extraction and multi-step sample analysis, hindering work in field studies. Recent work in the incorporation of nanomaterials for plant bioengineering research is leading the way of an agri-tech revolution. As an example, surface-enhanced Raman scattering (SERS)–based sensors can be used to monitor RNA in vivo. However, the use of SERS in the field has been limited due to issues with observing Raman signal over complex background. To this end, shifted-excitation Raman difference spectroscopy (SERDS) offers an effective solution to extract the SERS signal from high background based on a physical approach. In this manuscript, we report the first application of SERDS on SERS sensors. We investigated this technique on SERS sensor developed for the detection of a microRNA biomarker, miR858. We tested the technique on in vitro samples and validated the technique by detecting the presence of exogenous miR858 in plants directly under ambient light in a growth chamber. The possibility of moving the detection of nucleic acid targets outside the constraints of laboratory setting enables numerous important bioengineering applications. Finally, such applications can revolutionize biofuel production and agri-tech through the use of nanotechnology-based monitoring of plant growth, plant health, and exposure to pollution and pathogens.

09 BIOMASS FUELS↗

Carbon nanospikes have improved sensitivity and antifouling properties for adenosine, hydrogen peroxide, and histamine

Carbon nanospikes (CNSs) are a new nanomaterial that has enhanced surface roughness and surface oxide concentration, increasing the sensitivity for dopamine detection. However, CNS-modified electrodes (CNSMEs) have not been characterized for other neurochemicals, particularly those with higher oxidation potentials. The purpose of this study was to evaluate CNSMEs for the detection of adenosine, hydrogen peroxide (H 2 O 2 ), and histamine. The sensitivity increased with CNSs, and signals at CNSMEs were about 3.3 times higher than CFMEs. Normalizing for surface area differences using background currents, CNSMEs show an increased signal of 4.8 times for adenosine, 1.5 times for H 2 O 2 , and 2 times for histamine. CNSMEs promoted the formation of secondary products for adenosine and histamine, which enables differentiation from other analytes with similar oxidation potentials. Furthermore, CNSs also selectively enhance the sensitivity for adenosine and histamine compared to H 2 O 2 . A scan rate test reveals that adenosine is more adsorption-controlled at CNS electrodes than CFMEs. CNSMEs are antifouling for histamine, with less fouling because the polymers formed after histamine electrooxidation do not adsorb due to an elevated number of edge planes. CNSMEs were useful for detecting each analyte applied in brain slices. Because of the hydrophilic surface compared to CFMEs, CNSMEs also have reduced biofouling when used in tissue. Therefore, CNSMEs are useful for tissue measurements of adenosine, hydrogen peroxide, and histamine with high selectivity and low fouling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermally activated structural transformations in manganese oxide nanoparticles under air and argon atmospheres

The properties of manganese oxide nanomaterials are dictated by the structure and morphology of the particular phases they can adopt. The effects of post-synthesis heat treatments on amorphous monodisperse manganese oxide nanoparticles at ≤1300° under lab. air and argon atmospheres were investigated using X-ray diffraction, thermal analysis and electron microscopy techniques. During heat treatments in air, the nanoparticles undergo three transformations, resulting in: crystallization to cubic Mn 2 O 3 at ~500°, followed by the transformation to tetragonal Mn 3 O 4 at ~1010°, and to cubic Mn 3 O 4 at ~1190°. The first two transformations are irreversible, are associated with oxygen loss, and involve reductions. of the Mn ions. The latter transformation is polymorphic and spontaneously reversible, and so, tetragonal Mn 3 O 4 is observed at ambient temperature in samples heat-treated at >1000°. The samples heat treated in argon firstly crystallize to a mixt. of monoclinic Mn 2 O 3 and tetragonal Mn 3 O 4 at ~475°, followed by complete transformation to tetragonal Mn 3 O 4 at ~820°, and then to mostly cubic MnO at ~1145°; here again, the residual tetragonal Mn 3 O 4 undergoes a reversible polymorphic transformation at ~1180°, whereas the other transformations are irreversible. In both atmospheres, the amorphous material exhibits short-range cryptomelane-type order with a mixture of Mn 3+ and Mn 4+ prior to crystallization. Furthermore, these data indicate that most of the stable manganese oxide phases can be obtained from initially amorphous nanoparticles by heat treatment under appropriate conditions.

36 MATERIALS SCIENCE↗

Inkjet printing of epitaxially connected nanocrystal superlattices

Access to a blossoming library of colloidal nanomaterials provides building blocks for complex assembled materials. The journey to bring these prospects to fruition stands to benefit from the application of advanced processing methods. Epitaxially connected nanocrystal (or quantum dot) superlattices present a captivating model system for mesocrystals with intriguing emergent properties. The conventional processing approach to creating these materials involves assembling and attaching the constituent nanocrystals at the interface between two immiscible fluids. Processing small liquid volumes of the colloidal nanocrystal solution involves several complexities arising from the concurrent spreading, evaporation, assembly, and attachment. The ability of inkjet printers to deliver small (typically picoliter) liquid volumes with precise positioning is attractive to advance fundamental insights into the processing science, and thereby potentially enable new routes to incorporate the epitaxially connected superlattices into technology platforms. In this study, we identified the processing window of opportunity, including nanocrystal ink formulation and printing approach to enable delivery of colloidal nanocrystals from an inkjet nozzle onto the surface of a sessile droplet of the immiscible subphase. We demonstrate how inkjet printing can be scaled-down to enable the fabrication of epitaxially connected superlattices on patterned sub-millimeter droplets. Furthermore, we anticipate that insights from this work will spur on future advances to enable more mechanistic insights into the assembly processes and new avenues to create high-fidelity superlattices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Single-atom materials boosting wearable orthogonal uric acid detection

Abstract Uric acid (UA) is a vital biomarker for the diagnosis and management of various health conditions, including cardiovascular diseases, gout, kidney disorders, metabolic syndrome, and wound healing. Despite significant advances in wearable sensor technology, challenges persist in developing wearable sensors that are capable of maintaining high sensitivity, selectivity, and stability. In this study, we present an epidermal sensing platform enhanced with single-atom materials (SAMs) designed for flexible and orthogonal electrochemical detection of UA. We designed and synthesized an SAM with Fe-N 5 active sites to boost the electrochemical sensing signals, integrating it with laser-engraved graphene (LEG) to fabricate a wearable SAM-based UA patch sensor. This design provides superior UA detection performance compared to sensors based on conventional nanomaterials. In addition, we enhanced the detection accuracy and range by using an orthogonal approach that combines direct oxidation through differential pulse voltammetry (DPV) along with parallel biocatalytic amperometric detection. The resulting SAM-based UA orthogonal sensor patch demonstrated exceptional performance in wearable applications through tests measuring sweat UA levels in subjects before and after consuming a purine-rich diet. Graphical Abstract

Ding, Shichao↗

Strong interfaces: the key to high strength in nano metallic laminates

Excellent mechanical properties of nanomaterials are usually attributed to their nanoscale feature size and high-density interfaces. This work explores the effects of intrinsic interface properties on mechanical properties of nano metallic laminates (NMLs). We show that the interface strength significantly affects the mechanical properties of NMLs. Via in situ mechanical testing and characterization, we investigate the deformation behavior and concurrent microstructure evolution in NMLs with four types of dissimilar interfaces. Our results show that the strength and deformation behaviors of NMLs are largely determined by interface strength. Strong interfaces can simultaneously increase the strength, work hardening capability, and deformability of NMLs. In conclusion, this work brings new insight into the design of advanced metallic materials through tuning of interface properties.

36 MATERIALS SCIENCE↗

Impact of hydrogen bonding pendant groups in polymer grafted nanoparticles on interlayer adhesion and mechanical properties in material extrusion printing

The addition of nanoparticles or copolymer grafted nanoparticles (CPGNPs) to polymeric matrices greatly improves thermomechanical properties of the resulting nanocomposite, but corresponding studies of nanocomposite systems created by 3D printing are few, especially in the realm of functional polymeric materials. Here we describe how silica nanoparticle-grafted, random copolymers of poly(methyl methacrylate-random-2-uriedo-[1H]-pyrimidinone methacrylate) (P(MMA-r-UPyMA) dramatically increases the mechanical properties of poly(methyl methacrylate) (PMMA) based nanocomposite specimens created by melt extrusion printing. Most notably, when these novel CPGNPs are combined with PMMA matrix chains via a solution-based process, printed specimens containing only 0.5 wt% additive show significant increases in Young’s modulus (90%), storage modulus (93%), tensile modulus (148%) and ultimate tensile strength (110%). These improvements are ascribed to strengthening of adhesion across interfaces due to multi-point hydrogen bonding between UPyMA groups, the reinforcement effect of the P(MMA-r-UPyMA)-grafted silica nanoparticles, as well as hydrogen bonding interactions and entanglements between graft and matrix chains. Imaging of fracture surfaces after tensile testing reveals that in comparison to nanocomposites created by simple mechanical mixing of solids, the solution-casting process improves the dispersion of nanoparticles and reduces the void spaces between printed roads. These studies demonstrate that introducing functionality into polymer grafts, such as hydrogen bonding interactions, and intimate mixing of polymer-modified nanomaterials can greatly improve interlayer adhesion and mechanical properties, thereby advancing this method of polymer additive manufacturing

36 MATERIALS SCIENCE↗

Catalytic Activity and Water Stability of the MgO(111) Surface for 2-Pentanone Condensation

Nanomaterials derived from earth-abundant metal oxides have gained tremendous interest as catalysts; although, water stability remains a challenge. This study examines MgO(111) surfaces for 2-pentanone condensation and their evolution during D2O hydration. Catalyst screening confirmed the high activity of fresh MgO(111) for 2-pentanone condensation relative to conventionally prepared MgO(100). Computational modeling suggests that the (111) surface is readily hydroxylated, and that surface hydroxyls help stabilize the surface and reduce the barrier for 2-pentanone condensation. Vapor-phase D2O hydration after 3 min increased MgO(111) hydroxyls and retained surface area and activity; however, after 1 h, deuteroxide formation reduced the surface area and activity by >30 %. After 24 h, deuteroxide growth slowed down, and surface area and activity remained stable. This suggests MgO(111)-derived hydroxide may be the dominant surface responsible for 2-pentanone condensation following water exposure. Thermal regeneration of the 24-h sample restored 86 % of the surface area and 94 % of the activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A review of radiation-induced damage to quantum dots

Quantum dots (QDs) are versatile nano structures that have applications in many fields of research and production, including biosensor technology, computing, photovoltaics, and optoelectronics. QDs have gained interest in the field of radiation detection because of their relative ease of production, tunable photoluminescence, and sensitivity to ionizing radiation. The photoluminescent properties of QDs diminish proportionally to prolonged ionizing radiation interactions, leading many groups to seek out these materials as potential candidates for the next generation of inexpensive, easily manufactured dosimetry and sensors. To use QDs in these applications, the mechanisms of radiation damage to the nanomaterial must be clearly understood and characterized. Herein, we review the study of ionizing radiation damage to QDs. First, the synthesis and properties of QDs are briefly discussed. Next, the radiation damage to QDs due to heavy charged particles, fast electrons, high energy photons, and neutrons are detailed. After this, experimental methods and modelling of QDs in radiation environments are examined. Lastly, future research directions are provided. The goal of this review is to aid in understanding the ionizing radiation effects on QD-based devices.

Snow, Jesse [University of Utah, Salt Lake City, U↗

Investigation on the AgPt and AgPd hybrid alloy nanoparticles (HANPs) for the hybrid MoS 2 /ZnO/HANP UV photodetector application

We report hybrid photodetectors made of two or more nanomaterial components can offer the high potential for advanced photodetection applications with enhanced light absorption, improved efficiency and structural tunability. A hybrid UV photodetector (PD) configuration incorporating the plasmonic hybrid alloy nanoparticles (HANP), ZnO quantum dots (QDs) and MoS 2 nanoflakes, namely MoS2/ZnO/HANP PD, is demonstrated. The optimized MoS 2 /ZnO/HANP PD exhibits a high photocurrent of 5.66 mA at 0.34 mW/mm 2 under 385 nm illumination with two orders of improvement from the bare ZnO, which is one of the highest photocurrents by the ZnO-based PDs. It also demonstrates high figure-of-merits with the responsivity of 14,523 mA/W, detectivity of 8.13 x 10 11 jones, and external quantum efficiency (EQE) of 4,680 %, outperforming most of the ZnO-based hybrid architectures. The enhanced photoresponse is primarily attributed to the significantly enhanced hot electron generation by the AgPd HANPs and photocarrier collection through the ZnO QD layer. MoS 2 nanoflakes also provide additional photon absorption sites and boost the photo-carrier transfer process. HANPs are grown by adapting a dual-step solid-state dewetting process (SSD) approach and the superiority of AgPd HANPs is confirmed by systematic investigation, FDTD simulation and comparison of AgPt and AgPd HANPs.

MoS2↗

One-dimensional heterocyclic carbene–Au metal–organic frameworks bridging ultra-high vacuum models and scalable liquid-phase growth

The controlled design of molecule–metal interfaces is central to the development of functional nanomaterials for catalysis, sensing, and molecular electronics. Here we show that the adsorption of a Janus-type diimidazolium precursor on gold yields one-dimensional (1D) N-heterocyclic carbene (NHC)–Au–NHC metal organic frameworks (MOFs) featuring positively charged gold nodes. Using synchrotron X-ray photoemission spectroscopy (XPS), near edge X-ray adsorption fine structure (NEXAFS) spectroscopy and scanning tunnelling microscopy (STM), we demonstrate that thermal activation promotes counterion removal and drives the formation of extended 1D arrays, characterized by ∼1.0 nm Au–Au spacing and adatom densities up to 0.6 atom nm −2 (∼4% of surface atoms). Importantly, we translate this ultra-high vacuum (UHV) benchmark into a scalable solution-phase protocol in ethanol, enabling 1D-MOF growth under mild, base-free, open-air conditions. The resulting films retain structural and electronic signatures of UHV-grown systems, bridging model studies and practical synthesis. This approach establishes NHC–metal frameworks as accessible, tunable platforms for catalysis and materials design.

Gold adatoms↗

Nano-FET-enabled biosensors: Materials perspective and recent advances in North America

Field-effect transistor (FET) is a very promising platform for biosensor applications due to its magnificent properties, including label-free detection, high sensitivity, fast response, real-time measurement capability, low running power, and the feasibility to miniaturize to a portable device. 1D (e.g. carbon nanotubes, Si nanowires, conductive polymer nanowires, 1D metal oxides, and others) and 2D (e.g. graphene materials, transition metal dichalcogenides, black phosphorus, and 2D metal oxides) materials, with their unique structural and electronic properties that are unavailable in bulk materials, have helped improve the sensitivity of FET biosensors and enabled detection down to single molecule. In this article, we give insights into the rapidly evolving field of 1D and 2D materials-based FET biosensors, with an emphasis on structure and electronic properties, synthesis, and biofunctionalization approaches of these nanomaterials. In addition, the progress in the 1D/2D-FET biosensors in North America, in the last decade, is summarized in tables. Moreover, challenges and future perspectives of 1D/2D-FET biosensors are covered.

1D materials↗

Flash graphene from rubber waste

Most conventional production processes for graphene are time-consuming, solvent-intensive, and energetically demanding. To circumvent these limitations for mass production, flash Joule heating (FJH) has been shown to be an effective method to synthesize graphene. Here, methods for optimizing production of graphene from rubber waste feedstocks are shown. Through careful control of system parameters, such as pulse voltage and pulse time, turbostratic flash graphene (tFG) can be produced from rubber waste. It is characterized by Raman spectroscopy, X-ray diffraction and thermogravimetric analysis. Here, the resulting tFG can be easily exfoliated and dispersed into various solvents because of its turbostratic arrangement. Addition of tFG into Portland cement results in a significant increase in the compressive strength of the composite. From a materials perspective, FJH offers a facile and inexpensive method for producing high quality tFG from rubber waste materials, which would otherwise be disposed of in landfills or burned for fuel. FJH allows for upcycling of low-value rubber waste into high-value carbon nanomaterials for use as reinforcing additives.

54 ENVIRONMENTAL SCIENCES↗

Waste plastic- and coke-derived flash graphene as lubricant additives

Lubricants play an essential role in reducing wear in mechanical systems. Carbon nanomaterial additives, such as graphene, have been found to significantly improve tribological performance when used as lubricant additives. Here, in this study, post-consumer plastic and metallurgical coke are converted into turbostratic flash graphene (FG) through flash Joule heating (FJH). The FG is then added to either poly(alpha olefin) 6 or 9 (PAO 6 or PAO 9). Adding waste plastic-derived FG (WPFG) and metallurgical coke-derived FG (MCFG) to lubricants resulted in a significant decrease in the coefficient of friction (CoF), wear scar diameter (WSD), and roughness during four-ball testing. WPFG and MCFG decrease the CoF in PAO 9 by 6% and 9% at 0.1 mg mL -1 , respectively, and in PAO 6 by 23% and 6% at 0.5 mg mL -1 , respectively. WPFG and MCFG decrease the WSD of steel balls in PAO 9 by 14% and 8% at 0.5 mg mL -1 , respectively, and in PAO 6 by 12% and 14% at 0.5 mg mL -1 , respectively, by forming a coating-like layer between the metal surfaces. Roughness decreased by 38% and 32% for WPFG and MCFG in PAO 6, respectively, and by 35% and 29% for WPFG and MCFG in PAO 9, respectively. Finally, preliminary life cycle analyses demonstrate that production of FG produces up to 99% less greenhouse gas emissions, requires 98% less energy, and consumes 99.9% less water when compared to conventional production techniques of graphene. Hence, metallurgical coke and waste plastic are shown to be ready feedstocks for high-quality FG lubricant additives.

36 MATERIALS SCIENCE↗

Disorder and hydrogenation in graphene nanopowder revealed by complementary X-ray and neutron scattering

Functionalization of graphene's two-dimensional sheets can be used to modify the physical properties of graphene, such as changing its conductivity or inducing ferromagnetism, which is of broad interest for a myriad of applications. However, functionalized graphene can possess significant structural disorder that is often overlooked and is difficult to characterize quantitatively. Here we investigate hydrogenated graphene nanopowder (H-Gr) produced by Birch reduction of graphene oxide. By combining complementary x-ray and neutron diffraction, we show how to quantitatively characterize the H-Gr nanostructure, including the hydrogen content. Further, we show that the majority of the H-Gr consists of highly disordered molecular-scale carbon while a small portion of the sample contains few-layered graphene having an expanded interlayer spacing. Modeling the coherent diffuse scattering for both x-ray and neutron diffraction, and comparing it with the incoherent neutron scattering, the hydrogen to carbon ratio was measured and it was determined that most of the hydrogen resides within the disordered carbon rather than in the graphene. Evidence is presented for hydrogen clustering as well as for hydrogen bonded perpendicular to the plane of molecular-carbon bonds. Our quantitative approach to characterizing carbon nanopowders has broad relevance to understanding disorder and bonding of hydrogen in graphitic carbons and other nanomaterials.

36 MATERIALS SCIENCE↗