Redox-active covalent organic frameworks (COFs) with metal binding sites are increasingly recognized for developing cost-effective, eco-friendly organic electrodes in rechargeable energy storage devices. Here, we report a microwave-assisted synthesis and characterization of a triazine-based polyimide COF that features dual redox-active sites (-C=O from pyromellitic and -C=N- from triazine) and COF@CNT nanocomposites (COF@CNT-X, where X=10, 30, and 50 wt % of NH-MWCNT) formed through covalent linking with amino-functionalized multiwalled carbon nanotubes. These composites are evaluated as cathode materials for the sodium-ion batteries (SIBs).
View Article and Find Full Text PDFHere we study the controlled growth of ultrathin molybdenum dioxide (MoO) flakes, a metallic analogue of the widely studied transition metal dichalcogenide MoS. This study demonstrates the growth of three distinct MoO polymorphs (monoclinic, tetragonal, and a newly identified hexagonal phase) using physical vapor deposition. Comprehensive characterization through atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy confirms their unique structures and validates the newly observed hexagonal polymorph, which is also supported through simulations.
View Article and Find Full Text PDFNanoarchitected materials are at the frontier of metamaterial design and have set the benchmark for mechanical performance in several contemporary applications. However, traditional nanoarchitected designs with conventional topologies exhibit poor stress distributions and induce premature nodal failure. Here, using multi-objective Bayesian optimization and two-photon polymerization, optimized carbon nanolattices with an exceptional specific strength of 2.
View Article and Find Full Text PDFPolymeric membranes with great processability are attractive for the H/CO separation required for hydrogen production from renewable biomass with carbon capture for utilization and sequestration. However, it remains elusive to engineer polymer architectures to obtain desired sub-3.3 Å ultramicropores to efficiently sieve H from CO.
View Article and Find Full Text PDFThe surging demand for electronics is causing detrimental environmental consequences through massive electronic waste production. Urgently shifting toward renewable and eco-friendly materials is crucial for fostering a green circular economy. Herein, we develop a multifunctional bionanocomposite using an algae-derived carbohydrate biopolymer (alginate) and boron nitride nanosheet (BNNS) that can be readily employed as a multifunctional dielectric material.
View Article and Find Full Text PDFHalide perovskite nanocrystals (HPNCs) have emerged as promising materials for various light harvesting applications due to their exceptional optical and electronic properties. However, their inherent instability in water and biological fluids has limited their use as photocatalysts in the aqueous phase. In this study, we present highly water-stable SiO-coated HPNCs as efficient photocatalysts for antimicrobial applications.
View Article and Find Full Text PDFPolymer nanocomposites hold great potential as dielectrics for energy storage devices and flexible electronics. The structural architecture of the nanofillers is expected to play a crucial role in the fundamental mechanisms governing the electrical breakdown and dielectric properties of the nanocomposites. However, the effect of nanofiller structure and dimensionality on these properties has not been studied thoroughly to date.
View Article and Find Full Text PDFCompared to exploratory development of new structure types, pushing the limits of isoreticular synthesis on a high-performance MOF platform may have higher probability of achieving targeted properties. Multi-modular MOF platforms could offer even more opportunities by expanding the scope of isoreticular chemistry. However, navigating isoreticular chemistry towards best properties on a multi-modular platform is challenging due to multiple interconnected pathways.
View Article and Find Full Text PDFGraphene (Gr) is a promising material for addressing microbially induced corrosion (MIC) issues that cause staggering economic losses, estimated at nearly $55 billion annually in the US alone. However, structural defects including edges, grain boundaries, and cracks can compromise its performance in aggressive biological environments. Owing to the technological relevance of nickel (Ni), its key roles in biological mechanisms, and the strong hybridization of d-electrons of Ni with Gr π-orbitals, we explore the effects of the key defects in Gr/Ni exposed to archetype sulfate-reducing bacteria (SRB).
View Article and Find Full Text PDFCovalent organic frameworks (COFs), featuring structural diversity, permanent porosity, and functional versatility, have emerged as promising electrode materials for rechargeable batteries. To date, amorphous polymer, COF, or their composites are mostly explored in lithium-ion batteries (LIBs), while their research in other alkali metal ion batteries is still in infancy. This can be due to the challenges that arise from large volume changes, slow diffusion kinetics, and inefficient active site utilization by the large Na or K ion.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2024
The 2D Ruddlesden-Popper (RP) perovskites CsPbICl (Pb-based, = 1) and CsSnICl (Sn-based, = 1) stand out as unique and rare instances of entirely inorganic constituents within the more expansive category of organic/inorganic 2D perovskites. These materials have recently garnered significant attention for their strong UV-light responsiveness, exceptional thermal stability, and theoretically predicted ultrahigh carrier mobility. In this study, we synthesized Pb and Sn-based = 1 2D RP perovskite films covering millimeter-scale areas for the first time, utilizing a one-step chemical vapor deposition (CVD) method under atmospheric conditions.
View Article and Find Full Text PDFIsoreticular chemistry, which enables property optimization by changing compositions without changing topology, is a powerful synthetic strategy. One of the biggest challenges facing isoreticular chemistry is to extend it to ligands with strongly coordinating substituent groups such as unbound -COOH, because competitive interactions between such groups and metal ions can derail isoreticular chemistry. It is even more challenging to have an isoreticular series of carboxyl-functionalized MOFs capable of encompassing chemically disparate metal ions.
View Article and Find Full Text PDFGraphene-based terahertz (THz) devices have emerged as promising platforms for a variety of applications, leveraging graphene's unique optoelectronic properties. This review explores recent advancements in utilizing graphene in THz technology, focusing on two main aspects: THz molecular sensing and THz wave modulation. In molecular sensing, the environment-sensitive THz transmission and emission properties of graphene are utilized for enabling molecular adsorption detection and biomolecular sensing.
View Article and Find Full Text PDFDesigning efficient and cost-effective materials is pivotal to solving the key scientific and technological challenges at the interface of energy, environment, and sustainability for achieving NetZero. Two-dimensional transition metal dichalcogenides (2D TMDs) represent a unique class of materials that have catered to a myriad of energy conversion and storage (ECS) applications. Their uniqueness arises from their ultra-thin nature, high fractions of atoms residing on surfaces, rich chemical compositions featuring diverse metals and chalcogens, and remarkable tunability across multiple length scales.
View Article and Find Full Text PDFHierarchically porous materials containing sub-nm ultramicropores with molecular sieving abilities and microcavities with high gas diffusivity may realize energy-efficient membranes for gas separations. However, rationally designing and constructing such pores into large-area membranes enabling efficient H separations remains challenging. Here, we report the synthesis and utilization of hybrid carbon molecular sieve membranes with well-controlled nano- and micro-pores and single zinc atoms and clusters well-dispersed inside the nanopores via the carbonization of supramolecular mixed matrix materials containing amorphous and crystalline zeolitic imidazolate frameworks.
View Article and Find Full Text PDFXenes, mono-elemental atomic sheets, exhibit Dirac/Dirac-like quantum behavior. When interfaced with other 2D materials such as boron nitride, transition metal dichalcogenides, and metal carbides/nitrides/carbonitrides, it enables them with unique physicochemical properties, including structural stability, desirable bandgap, efficient charge carrier injection, flexibility/breaking stress, thermal conductivity, chemical reactivity, catalytic efficiency, molecular adsorption, and wettability. For example, BN acts as an anti-oxidative shield, MoS injects electrons upon laser excitation, and MXene provides mechanical flexibility.
View Article and Find Full Text PDFSchwarzites are porous (spongy-like) carbon allotropes with negative Gaussian curvatures. They are proposed by Mackay and Terrones inspired by the works of the German mathematician Hermann Schwarz on Triply-Periodic Minimal Surfaces (TPMS). This review presents and discusses the history of schwarzites and their place among curved carbon nanomaterials.
View Article and Find Full Text PDFFluorite mineral holds significant importance because of its optoelectronic properties and wide range of applications. Here, we report the successful exfoliation of bulk fluorite ore (calcium fluoride, CaF) crystals into atomically thin two-dimensional fluoritene (2D CaF) using a highly scalable liquid-phase exfoliation method. The microscopic and spectroscopy characterizations show the formation of (111) plane-oriented 2D CaF sheets with exfoliation-induced material strain due to bond breaking, leading to the changes in lattice parameter.
View Article and Find Full Text PDFTransition metal derivatives exhibit high theoretical capacity, making them promising anode materials for sodium-ion batteries. Sulfides, known for their superior electrical conductivity compared to oxides, enhance charge transfer, leading to improved electrochemical performance. Here, a hierarchical WS micro-flower is synthesized by thermal sulfurization of WO.
View Article and Find Full Text PDF2D materials, given their form-factor, high surface-to-volume ratio, and chemical functionality have immense use in sensor design. Engineering 2D heterostructures can result in robust combinations of desirable properties but sensor design methodologies require careful considerations about material properties and orientation to maximize sensor response. This study introduces a sensor approach that combines the excellent electrical transport and transduction properties of graphite film with chemical reactivity derived from the edge sites of semiconducting molybdenum disulfide (MoS) through a two-step chemical vapour deposition method.
View Article and Find Full Text PDF2D materials exhibit exceptional properties as compared to their macroscopic counterparts, with promising applications in nearly every area of science and technology. To unlock further functionality, the chemical functionalization of 2D structures is a powerful technique that enables tunability and new properties within these materials. Here, the successful effort to chemically functionalize hexagonal boron nitride (hBN), a chemically inert 2D ceramic with weak interlayer forces, using a gas-phase fluorination process is exploited.
View Article and Find Full Text PDFStructural design of 2D conjugated porous organic polymer films (2D CPOPs), by tuning linkage chemistries and pore sizes, provides great adaptability for various applications, including membrane separation. Here, four free-standing 2D CPOP films of imine- or hydrazone-linked polymers (ILP/HLP) in combination with benzene (B-ILP/HLP) and triphenylbenzene (TPB-ILP/HLP) aromatic cores are synthesized. The anisotropic disordered films, composed of polymeric layered structures, can be exfoliated into ultrathin 2D-nanosheets with layer-dependent electrical properties.
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