2D Honeycomb Research Articles

Pair-Density-Wave Superconductivity: A Microscopic Model on the 2D Honeycomb Lattice

Pair-Density-Wave Superconductivity: A Microscopic Model on the 2D Honeycomb Lattice

HKUST-1 in-situ loaded ultrastable covalently crosslinked agarose aerogel with solvothermal for highly efficient removal of methylene blue.

A new HKUST-1@covalently crosslinked agarose aerogel (HKUST-1@CCAGA) was synthesized for the highly effective elimination of Methylene Blue (MB). Firstly, the covalently crosslinked agarose aerogel (CCAGA) was obtained by hydrothermal crosslinking reaction with epichlorohydrin (ECH) as crosslinker, which remained stabilized under hydrothermal and solvothermal conditions. Then, HKUST-1 was made to bind to CCAGA by in situ solvothermal assays, and the HKUST-1 loading rate reached 47.4 % based on thermogravimetric data and calculated using the cross over method. Meanwhile, the SEM exhibited the complete 3D honeycomb structure of CCAGA, and HKUST-1 particles uniformly distributed on its layers. Additionally, the specific surface area of HKUST-1@CCAGA can reached 648.59 m2·g-1. The HKUST-1@CCAGA composite was utilized for MB removal, achieving a high adsorption capacity of 424.30 mg·g-1 at pH 8. The adsorption of MB was also maintained at 80 % after 5 cycles of the experiment. The composite aerogel exhibits good recyclability and has excellent adsorption capacity.

Unraveling the enhanced sodium-storage mechanism in a strongly bonded 2D honeycomb borophene/boron phosphide heterostructure

The growing modern demand for battery capacity is driving the development of high-capacity metal-ion battery anodes for future energy storage. Two-dimensional (2D) material-based heterostructures have shown advantages as alternative anodes due to their enhanced adsorption capacity. The lightweight nature of honeycomb borophene (HB) is beneficial for serving as a high-capacity anode but is constrained by structural instability arising from electron deficiency. In this study, using first-principles calculations, we propose a HB/boron phosphide (BP) heterostructure as an anode for both lithium-ion batteries and sodium-ion batteries (SIBs). The heterostructure engineering not only stabilizes the HB structure but also leads to a bonding heterostructure instead of common van der Walls type. The HB/BP demonstrates robust structural stability and reversibility when multiple ions are stored. In addition, the HB/BP offers stable storage sites and low diffusion barriers for lithium (0.31 eV) and sodium (0.28 eV), indicating rapid charging–discharging performance. Notably, the predicted maximum sodium storage capacity reaches 2402 mAh/g, surpassing that of the constituent monolayers and most 2D heterostructures. The underlying mechanism for high storage capacity is elucidated through detailed charge image model analysis, offering atomistic-scale insights for constructing high-capacity anodes. All results suggest that the presented HB/BP is a promising anode candidate for SIBs and opens an avenue for stabilizing HB in energy storage.

Carbon-intercalated halloysite-based aerogel efficiently encapsulating phase change materials with excellent photothermal conversion and energy storage

Latent heat storage systems based on organic phase change materials (PCMs) are considered to be an efficient solar energy utilization strategy, but leakage vulnerability and insensitivity to sunlight of PCMs limit their further application in energy storage. In this work, a new hierarchical porous aerogel was constructed with the carbon intercalated halloysite nanotubes (CHNTs) as the assembly units for PCMs encapsulation to improve the load weight, stability and sunlight absorption. The CHNTs were first successfully synthesized through intercalation and carbonization, with the aim of increasing their specific surface area and sunlight absorption.Subsequently, the CHNTs/polyvinyl alcohol (PVA) aerogels with 3D honeycomb structure were prepared by self-assembly using a freeze-drying method, which can significantly promote the encapsulation ratio of lauric acid (LA) in the pores of both aerogels and CHNTs. The CHNTs can not only improve compressive strength of the aerogels and shape stability of the composite PCMs, but also enhance light absorption ability of the composites compared to pristine HNTs. As a support material, CHNTs aerogel (CHNP) loaded more than 92 wt% PCM (LA@CHNP) and exhibited an extremely high latent heat capacity (170.9 J/g). The LA@CHNP had good structural and thermal stability in 300 cycles without visible leakage. Besides, solar energy absorption increased from 43 % to 98 %, and the solar-to-thermal energy conversion efficiency increased to 95.88 %, which could be attributed to 3D porousness and carbon nanolayers of the CHNTs. We have successfully synthesized an eco-friendly and facile composite LA@CHNP, which will contribute to the design of advanced composites with excellent solar energy storage properties, and provide a new direction for the application of carbonized materials.

Light-element and purely charge-based topological materials

We examine a class of Hamiltonians characterized by interatomic, interorbital even-odd parity hybridization as a model for a family of topological insulators without the need for spin-orbit coupling. Non-trivial properties of these materials are exemplified by studying the topologically-protected edge states ofs-phybridized alkali and alkaline earth atoms in one and two-dimensional lattices. In 1D the topological features are analogous to the canonical Su-Schrieffer-Heeger model but, remarkably, occur in the absence of dimerization. Alkaline earth chains, with Be standing out due to its gap size and near particle-hole symmetry, are of particular experimental interest since their Fermi energy without doping lies directly at the level of topological edge states. Similar physics is demonstrated to occur in a 2D honeycomb lattice system ofs-pbonded atoms, where dispersive edge states emerge. Lighter elements are predicted using this model to host topological states in contrast to spin-orbit coupling-induced band inversion favoring heavier atoms.

Hazardous CO, NO, NH3 gases over boron and beryllium doped α-CN monolayers: A first principles study for sensing and removal applications

The exploration of two-dimensional (2D) honeycomb layered structure (HLS) has garnered significant attention due to their multifunctional properties, with diverse applications emerging in various fields. Motivated by the challenges posed by hazardous gases such as CO, NO, NH3 and inspired by the unique properties of 2D HLS this first principles study digs into the structural, electronic, and sensing properties of Boron and Beryllium doped α-CN monolayers. Rendering the structural and electronic variations induced by B and Be doping, our analysis reveals distinct functionalities for α-CN monolayers. Boron doping at the C-site exhibits promise for NO and NH3 sensing (with 73 % and 77 % increment in adsorption energies), while B-doping at the N-site enhances suitability for gas removal applications. Similarly, Be doping demonstrates effectiveness in gas removal across both C and N sites. Notably, the ultra-fast response (2.31 × 10−8 s) observed for NO adsorption over B-doped α-CN highlights its potential as a rapid sensor. Additionally, work function analysis suggests the suitability of B-doped α-CN for φ-type sensing in NH3 adsorption. These findings underscore the applicability of doped α-CN monolayers in gas sensing mechanisms.

Realization of Honeycomb Tellurene with Topological Edge States.

The two-dimensional (2D) honeycomb lattice has attracted intensive research interest due to the appearance of Dirac-type band structures as the consequence of two sublattices in the honeycomb structure. Introducing strong spin-orbit coupling (SOC) leads to a gap opening at the Dirac point, transforming the honeycomb lattice into a 2D topological insulator as a platform for the quantum spin Hall effect (QSHE). In this work, we realize a 2D honeycomb-structured film with tellurium, the heaviest nonradioactive element in Group VI, namely, tellurene, via molecular beam epitaxy. We revealed the gap opening of 160 meV at the Dirac point due to the strong SOC in the honeycomb-structured tellurene by angle-resolved photoemission spectroscopy. The topological edge states of tellurene are detected via scanning tunneling microscopy/spectroscopy. These results demonstrate that tellurene is a novel 2D honeycomb lattice with strong SOC, and they unambiguously prove that tellurene is a promising candidate for a room-temperature QSHE system.

Cover Picture: Exfoliatable Layered 2D Honeycomb Crystals of Host‐guest Complexes Networked by CH‐π Hydrogen Bonds (Angew. Chem. Int. Ed. 34/2024)

Cover Picture: Exfoliatable Layered 2D Honeycomb Crystals of Host‐guest Complexes Networked by CH‐π Hydrogen Bonds (Angew. Chem. Int. Ed. 34/2024)

Titelbild: Exfoliatable Layered 2D Honeycomb Crystals of Host‐guest Complexes Networked by CH‐π Hydrogen Bonds (Angew. Chem. 34/2024)

Titelbild: Exfoliatable Layered 2D Honeycomb Crystals of Host‐guest Complexes Networked by CH‐π Hydrogen Bonds (Angew. Chem. 34/2024)

Exfoliatable Layered 2D Honeycomb Crystals of Host‐guest Complexes Networked by CH‐π Hydrogen Bonds

AbstractStudies of graphene show that robust chemical bonds such as covalent bonds with trigonal‐planar atoms afford layered atomic 2D crystals possessing unique properties. Although layered molecular crystals are of interest to diversify elements and structures of 2D materials, the structural diversity of molecules as well as weak intermolecular interactions inevitably makes the design to be one‐off and individual. We herein report a versatile method to assemble layered molecular crystals. By developing a D3‐symmetry host at vertices to form a honeycomb layer, a diverse range of layered 2D host–guest crystals were obtained. Substituents on the host, elements/structures of the guest, the stereochemistry of the host and types of intercalants were diversified, which should allow for 6×32×3×2 combinations for structural diversification.

Exfoliatable Layered 2D Honeycomb Crystals of Host-guest Complexes Networked by CH-π Hydrogen Bonds.

Studies of graphene show that robust chemical bonds such as covalent bonds with trigonal-planar atoms afford layered atomic 2D crystals possessing unique properties. Although layered molecular crystals are of interest to diversify elements and structures of 2D materials, the structural diversity of molecules as well as weak intermolecular interactions inevitably makes the design to be one-off and individual. We herein report a versatile method to assemble layered molecular crystals. By developing a D3-symmetry host at vertices to form a honeycomb layer, a diverse range of layered 2D host-guest crystals were obtained. Substituents on the host, elements/structures of the guest, the stereochemistry of the host and types of intercalants were diversified, which should allow for 6×32×3×2 combinations for structural diversification.

Equilibrium Moisture Mediated Esterification Reaction to Achieve Over 100% Lignocellulosic Nanofibrils Yield.

Lignocellulosic nanofibrils (LCNFs) isolation is recognized as an efficient strategy for maximizing biomass utilization. Nevertheless, achieving a 100% yield presents a formidable challenge. Here, an esterification strategy mediated by the equilibrium moisture in biomass is proposed for LCNFs preparation without the use of catalysts, resulting in a yield exceeding 100%. Different from anhydrous chemical thermomechanical pulp (CTMP0%), the presence of moisture (moisture content of 7wt%, denoted as CTMP7%) introduces a notably distinct process for the pretreatment of CTMP, comprising the initial disintegration and the post-esterification steps. The maleic acid, generated through maleic anhydride (MA) hydrolysis, degrades the recalcitrant lignin-carbohydrate complex (LCC) structures, resulting in esterified CTMP7% (E-CTMP7%). The highly grafted esters compensate for the mass loss resulting from the partial removal of hydrolyzed lignin and hemicellulose, ensuring a high yield. Following microfluidization, favorable LCNF7% with a high yield (114.4 ± 3.0%) and a high charge content (1.74 ± 0.09mmolg-1) can be easily produced, surpassing most previous records for LCNFs. Additionally, LCNF7% presented highly processability for filaments, films, and 3D honeycomb structures preparation. These findings provide valuable insights and guidance for achieving a high yield in the isolation of LCNFs from biomass through the mediation of equilibrium moisture.

Redox-active “Structural Pillar” molecular doping strategy towards High-Performance polyaniline-based flexible supercapacitors

To coordinate flexibility to electrodes without sacrificing their electrochemical properties is critical for the development of wearable supercapacitors (SCs). Polyaniline (PANI) is well-known pseudocapacitive electrode material due to its high conductivity and different oxidation states upon switchable structures. However, its rigid conjugated backbone and structural instability caused by repeated doping/de-doping during cycling severely impede its utilization in flexible SCs. Herein, we deploy a directional freezing and redox-active “structural pillar” molecular doping strategy to boost PANI-based flexible SCs with high performance. The directional freezing strategy constructs an interconnected 3D honeycomb hydrogel structure with PANI nanofibers, which guarantees fast ion diffusion and electron transport and meanwhile exposes abundant active sites. The large-sized dopant 2-amino-4-bromoanthraquinone-2-sulfonic acid sodium (AQNS) is used as the structural pillar to alleviate the structural instability of PANI during cycling and provides additional pseudocapacitance arising from its redox active quinone groups. Moreover, the negatively charged −SO3− on AQNS can further interact with H+ in the electrolyte to act as an internal proton reservoir, assisting the protonation of –NH- and −N = in PANI to facilitate its charge storage process. Consequently, the PANI-AQNS electrode achieves a high specific capacitance of 578 F g−1 at 1 A g−1 and its symmetric SCs exhibit a specific capacitance of 199 F g−1 at 0.5 A g−1 with an energy density of 13.61 W h kg−1 at a power density of 175 W kg−1. Upon 2000 cycles of dynamic deformations, the SCs can still maintain above 90 % of the initial capacitance, verifying their excellent flexibility-relevant property.

Nano-silicon embedded in 3D honeycomb carbon frameworks as a high-performance lithium-ion-battery anode

The fabrication of three-dimensional (3D) honeycomb carbon frameworks, incorporating embedded silicon (Si) nanoparticles (NPs), is successfully achieved through a facile method involving mixing, carbonization, and acid pickling. The as-prepared Si@PVPC composites exhibit excellent electrochemical performances due to reasons as follows. (1) Honeycomb channels supply enough space to accommodate the expansion of Si NPs and so structural integrity of 3D honeycomb carbon frameworks are maintained during lithiation/delithiation processes. (2) Honeycomb channels offers fast transfer paths for Li-ion diffusion. (3) 3D carbon frameworks afford reliable and stable electric contact points. As a result, Si@PVPC electrodes show a capacity of 1294.3 mAh g−1 at 2 A g−1 after 1400 cycles with a capacity retention of 85.5 %. Even at an ultrahigh current of 16 A g−1, Si@PVPC electrodes still show a capacity of 619.6 mAh g−1.

An Exploration of the Phonon Frequency Spectrum and Born–von Karman Periodic Boundary Conditions in 1D and 2D Lattice Systems Using a Computational Approach

Periodic boundary conditions (PBCs) are a pivotal concept in the treatment of ideal lattices of infinite extent as a finite lattice. Most undergraduate texts that delve into the analytical treatment of lattice dynamics solve the problem in the reciprocal space with an implicit assumption of PBCs. While the traditional approach centered in the reciprocal or [Formula: see text]-space is elegant for simple one-dimensional lattice structures, the method becomes mathematically cumbersome for more complex lattices with real-world applications, such as a honeycomb lattice involving a [Formula: see text] secular determinant. In this work, we have explored the solution of lattice dynamics in direct space numerically, by constructing unit cells through an explicit implementation of Born–von Karman PBCs and solving the lattice dynamical equations in the displacement–time domain using the fourth-order Runge–Kutta algorithm. The Fast Fourier Transform technique is then used to obtain the phonon frequency spectrum corresponding to the computed instantaneous displacements. The fidelity of the model is validated by the agreement of the computational results obtained for the phonon spectrum at high symmetry points in the Brillouin zone with the analytical values for the given problem. Initially, the dynamics and the phonon spectrum are explored for monatomic and diatomic linear lattices which serve to act as introductory cases for the approach before investigating the 2D monatomic square and honeycomb lattices using the nearest and next-nearest neighbor approximations. A short-range force constant model employing the central forces and angular forces is used for the monatomic square lattice to account for the interatomic interactions. Our computational approach is expected to be physically more intuitive for a student for visualizing the periodicity of a given lattice and understanding its related dynamics. The approach demonstrates the usage of Born–von Karman PBCs in constructing a unit cell that effectively captures the dynamics of a lattice system, complementing the traditional secular determinant formalism. The work also illustrates an instance of how the computer programming can be used as a tool to empower the students to explore abstract concepts in physics. A honing of programming and computational skills of students enables them to interact with dynamic models in physics and gain deeper insight into the real-world applications of physics principles. Target group of this work is the students and educators at undergraduate level who seek a thorough and didactic comprehension of lattice dynamics.

Robust high capacity in-plane elastic wave transport in 2D chiral metastructures

Novel 2D tri-chiral metastructures with mass inclusion are proposed in this work. Compared to conventional 2D honeycomb metastructures, these superior metastructures have a wide in-plane low-frequency bandgap (BG) and single Dirac cone (DC) simultaneously. Ligament width and inclusion density are both key factors for tuning the DC and low-frequency BGs. Due to the superior dispersion properties, metamolecules analog of quantum spin Hall effects (QSHEs) are built by the band folding method, and topological phase transition is obtained by shrinking/expanding distance between the mass inclusion and metamolecule center. Topological interface states (TISs) are observed between the two domains with distinct topological properties. To further enhance energy capacity of in-plane elastic wave transport, a 2D heterostructure is constructed by doping waveguiding layer at the topological interface. As expected, robust high capacity in-plane elastic wave transport is realized, named as topological waveguide states (TWSs). While TWS velocity remains unaffected, an increasing number of waveguiding layers additionally leads to a reduced bandgap width and transition from TWSs to conventional edge states (CESs). Average transmitted energy is also observed to increase almost linearly with the thickness of waveguide layer. By virtue of the robust high-capacity wave transport, two potential applications for energy focusing and beam splitting are clearly demonstrated. Besides, the temperature field is introduced into the 2D topological heterostructure to widen the operating frequency of TWSs. Fortunately, TWSs can be tuned to the lower frequency range by increasing temperature, and retain gapless and high-capacity characteristics. Last but not least, we demonstrate that temperature can be used as a switch for in-plane topological wave transport. The proposed 2D chiral metastructures have great potentials to serve as building blocks for multifunctional topological devices.

Investigation of bending behavior of two and three-dimensional honeycomb and auxetic sandwich beams

The bending behavior of two (2D) and three-dimensional (3D) sandwich beams that have a negative Poisson’s ratio (auxetic) and conventional honeycomb was investigated for different geometries, sheet thicknesses, and cell thicknesses. The re-entrant and solid specimens were produced with a stereolithographic (SLA) 3D printer and subjected to a three-point bending test under the conditions specified in the ASTM C393 standard. The data obtained from the tests were used to verify finite element analysis (FEA) results. The radius of curvatures was calculated for each specimen depending on the load step. In addition, Poisson’s ratio was calculated for each auxetic sample. As a result, the 3D arrowhead beam, with a cell thickness of 1 mm and a sheet thickness of 2 mm, exhibits peak force values that are 497.340% and 461.500% higher than re-entrant and missing rib beams, respectively. Besides, the maximum strain energy values of same 3D arrowhead specimens (596.120 mJ) are higher than re-entrant (101.032 mJ) and missing rib (108.201 mJ) specimens. It was determined that the arrowhead is the most durable structure compared to other auxetic structure geometries. Therefore, when arrowhead and honeycomb 3D beams are compared, it was observed that the maximum strain energy of arrowhead specimens was higher in both horizontal (84.310%) and perpendicular (131.910%) positioned specimens. Comparing the arrowhead and honeycomb 2D beams with the highest maximum strain energy, it can be concluded that the arrowhead beam absorbs 20.000% more energy.

Optimizing the photocatalytic properties of macroporous geopolymer foam: Influence of SILAR-technique synthesis conditions

Macroporous cross-linked materials such as 3D honeycomb foams are used as substrates for heterogeneous photocatalysis. They offer a number of interesting properties. They are highly open-porosity substrates, guaranteeing optimum mass and radiation transfer, making them ideal for photo-conversion applications such as photo-oxidation or photo-reduction, which take place in photo-reactors for pollutant degradation or solar fuel production. Many cross-linked supports such as polymeric and metallic foams studied in the literature have revealed photocatalytic capacities similar to those obtained for the catalyst nanoparticle suspensions used as a reference. To reduce the production costs of this type of material, geopolymers, widely used in civil engineering, offer a wide range of properties suitable for shaping cellular foams. In addition to their low cost and mechanical properties, it is also possible to impart porous properties and modulate their characteristics according to the synthesis operating conditions so as to elaborate macroporous cellular foams. In this study, we propose to investigate the photocatalytic properties of honeycomb geopolymer foams coated with a catalyst: ZnO. To achieve ZnO deposition, the SILAR technique was applied by modifying the key synthesis operating conditions, i.e. precursor concentration and the number of quenching cycles applied. The results obtained make it possible to define the optimum operating conditions (pH, temperature) and, above all, the number of cycles and precursor concentration required to obtain the best photocatalytic efficiency. These innovative and promising materials, little studied in the literature, are prime candidates for solar photo-conversion applications.

Tailoring 3D Star-Shaped Auxetic Structures for Enhanced Mechanical Performance

Auxetic lattice structures are three-dimensionally designed intricately repeating units with multifunctionality in three-dimensional space, especially with the emergence of additive manufacturing (AM) technologies. In aerospace applications, these structures have potential for use in high-performance lightweight components, contributing to enhanced efficiency. This paper investigates the design, numerical simulation, manufacturing, and testing of three-dimensional (3D) star-shaped lattice structures with tailored mechanical properties. Finite element analysis (FEA) was employed to examine the effect of a lattice unit’s vertex angle and strut diameter on the lattice structure’s Poisson’s ratio and effective elastic modulus. The strut diameter was altered from 0.2 to 1 mm, while the star-shaped vertex angle was adjusted from 15 to 90 degrees. Laser powder bed fusion (LPBF), an AM technique, was employed to experimentally fabricate 3D star-shaped honeycomb structures made of Ti6Al4V alloy, which were then subjected to compression testing to verify the modelling results. The effective elastic modulus was shown to decrease when increasing the vertex angle or decreasing the strut diameter, while the Poisson’s ratio had a complex behaviour depending on the geometrical characteristics of the structure. By tailoring the unit vertex angle and strut diameter, the printed structures exhibited negative, zero, and positive Poisson’s ratios, making them applicable across a wide range of aerospace components such as impact absorption systems, aircraft wings, fuselage sections, landing gear, and engine mounts. This optimization will support the growing demand for lightweight structures across the aerospace sector.

A comparative analysis of 3D woven honeycomb-based aircrew helmet liners against Nomex and Aluminum alternatives

This study investigates the energy dissipation efficiency of an aircrew helmet liner developed using 3D woven honeycomb structural composites compared to different commercially available honeycomb liner materials such as Nomex, and Aluminium. In contrast to liners with discrete density differences, the use of a honeycomb-based liner reduces the concern about delamination, back face deformation and fracture propagation. The research involves comparing several parameters related to crashworthiness, such as specific energy absorption (SEA), crush force efficiency (CFE), and margin of safety, which are crucial for head protection and ensuring helmet injury tolerance. These parameters play a vital role in assessing the ability of different configurations of the honeycomb liner during impacts. Flatwise compression and dynamic impact tests were conducted to evaluate the helmet liner’s performance while maintaining consistency in the helmet shell component. Finite element analysis (FEA) and 3D x-ray Tomography techniques were utilized to analyse the back face deformation (BFD) at high-velocity impact and the internal damage resulting from impacts on the helmet liners, respectively. The results revealed that the 3D woven honeycomb liner configuration performs optimally in terms of energy absorption by demonstrating sufficient and balanced competency across these three critical factors. Additionally, the simulation result revealed that the 3D woven honeycomb liner exhibits wave propagation. This phenomenon enhances its energy absorption capacity and reduces back-face deformation attributed to its crushing behaviour. This research offers valuable insights for improving the performance of aircrew helmet liners, with a particular focus on utilizing 3D woven honeycomb liners featuring 3D woven solid structure to maintain exceptional structural integrity.