A new three-dimensional barium(II) coordination polymer constructed from N,N'-bis(glycinyl)pyromellitic diimide: microwave-assisted synthesis, structure, Hirshfeld surface analysis and properties.

A new three-dimensional (3D) coordination polymer, namely, poly[diaqua[µ5-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato]barium(II)], [Ba(C14H6N2O8)(H2O)2]n, (I), has been synthesized by the microwave-irradiated reaction of Ba(NO3)2 with N,N'-bis(glycinyl)pyromellitic diimide {BGPD, namely, 2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetatic acid, H2L}. The title compound was structurally characterized by single-crystal X-ray diffraction analysis and powder X-ray diffraction analysis, as well as IR spectroscopy. In the crystal structure of (I), the BaII ion is nine-coordinated by six carboxylate O atoms from five symmetry-related L2- dianions and one imide O atom, as well as two water O atoms. The coordination geometry of the central BaII ion can be described as a spherical capped square antiprism. One carboxylate group of the ligand serves as a µ3-bridge linking the BaII cations into a one-dimensional polynuclear secondary building unit (SBU). Another carboxylate group of the ligand acts as a µ2-bridge connecting the 1D SBUs, thereby forming a two-dimensional (2D) SBU. The resulting 2D SBUs are extended into a 3D framework via the pyromellitic diimide moiety of the ligand as a spacer. The 3D Ba framework can be simplified as a 5-connected hexagonal boron nitride net (bnn) topology. The intermolecular interactions in the 3D framework were further investigated by Hirshfeld surface analysis and the results show that the prominent interactions are H...O (45.1%), Ba...O (11.1%) and C...H (11.1%), as well as H...H (11.1%) contacts. The thermal stability, photoluminescence properties and UV-Vis absorption spectra of (I) were also investigated. The coordination polymer exhibits a fluorescence emission with a quantum yield of 0.071 and high thermal stability.

Pyramid Textured Photonic Films with High-Refractive Index Fillers for Efficient Radiative Cooling.

Sub-ambient cooling technologies relying on passive radiation have garnered escalating research attention owing to the challenges posed by global warming and substantial energy consumption inherent in active cooling systems. However, achieving highly efficient radiative cooling devices capable of effective heat dissipation remains a challenge. Herein, by synergic optimization of the micro-pyramid surface structures and 2D hexagonal boron nitride nanoplates (h-BNNs) scattering fillers, pyramid textured photonic films with remarkable solar reflectivity of 98.5% and a mid-infrared (MIR) emittance of 97.2% are presented. The h-BNNs scattering filler with high thermal conductivity contributed to the enhanced through-plane thermal conductivity up to 0.496 W m-1 K-1 and the in-plane thermal conductivity of 3.175 W m-1 K-1. The photonic films exhibit an optimized effective radiative cooling power of 201.2 W m-2 at 40 °C under a solar irradiance of 900 W m-2 and a daily sub-ambient cooling effect up to 11 °C. Even with simultaneous internal heat generation by a 10 W ceramic heater and external solar irradiance of 500 W m-2, a sub-ambient cooling of 5 °C can be realized. The synergic matching strategy of high thermal conductivity scattering fillers and microstructured photonic surfaces holds promise for scalable sub-ambient radiative cooling technologies.

The Impact of Boron Nitride Additive on Thermal and Thermochromic Properties of Organic Thermochromic Phase Change Materials.

Thermochromic phase change materials (TPCMs) are gaining increasing interest among scientists. These multifunctional materials can store thermal energy but also, at the same time, during the phase transition, they can change colour. Thermal conductivity is also extremely important for this type of material, which is why various additives are used for this purpose. This work aimed to study the properties of thermochromic phase change materials with an inorganic modifier. Stearic acid, behenyl alcohol, and bromocresol purple were used as thermochromic system components, while boron nitride particles were used as an additive. The key tests for such systems are thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), which allow determining the thermal stability of the materials (at around 170 °C) and phase transition parameters (thermal energy storage of 300 J/g in the range of 40-75 °C). The thermochromic properties were tested, and satisfactory results were obtained. In the end, laser flash analysis (LFA) tests indicated that boron nitride improves the thermal conductivity of the organic thermochromic phase change material by almost 30%. The results showed that the tested materials have great potential as thermochromic phase change materials for thermal energy storage.

Low Dielectric Medium for Hyperbolic Phonon Polariton Waveguide in van der Waals Heterostructures.

Polar van der Waals (vdW) crystals, composed of atomic layers held together by vdW forces, can host phonon polaritons-quasiparticles arising from the interaction between photons in free-space light and lattice vibrations in polar materials. These crystals offer advantages such as easy fabrication, low Ohmic loss, and optical confinement. Recently, hexagonal boron nitride (hBN), known for having hyperbolicity in the mid-infrared range, has been used to explore multiple modes with high optical confinement. This opens possibilities for practical polaritonic nanodevices with subdiffractional resolution. However, polariton waves still face exposure to the surrounding environment, leading to significant energy losses. In this work, we propose a simple approach to inducing a hyperbolic phonon polariton (HPhP) waveguide in hBN by incorporating a low dielectric medium, ZrS2. The low dielectric medium serves a dual purpose-it acts as a pathway for polariton propagation, while inducing high optical confinement. We establish the criteria for the HPhP waveguide in vdW heterostructures with various thicknesses of ZrS2 through scattering-type scanning near-field optical microscopy (s-SNOM) and by conducting numerical electromagnetic simulations. Our work presents a feasible and straightforward method for developing practical nanophotonic devices with low optical loss and high confinement, with potential applications such as energy transfer, nano-optical integrated circuits, light trapping, etc.

Hexagonal Boron Nitride Quantum Simulator: Prelude to Spin and Photonic Qubits.

The quest for qubit operation at room temperature is accelerating the field of quantum information science and technology. Solid state quantum defects with spin-optical properties are promising spin- and photonic qubit candidates for room temperature operations. In this regard, a single boron vacancy within hexagonal boron nitride (h-BN) lattice such as VB- defect has coherent quantum interfaces for spin and photonic qubits owing to the large band gap of h-BN (6 eV) that can shield a computational subspace from environmental noise. However, for a VB- defect in h-BN to be a potential quantum simulator, the design and characterization of the Hamiltonian involving mutual interactions of the defect and other degrees of freedom are needed to fully understand the effect of defects on the computational subspace. Here, we studied the key coupling tensors such as zero-field splitting, Zeeman effect, and hyperfine splitting in order to build the Hamiltonian of the VB- defect. These eigenstates are spin triplet states that form a computational subspace. To study the phonon-assisted single photon emission in the VB- defect, the Hamiltonian is characterized by electron-phonon interaction with Jahn-Teller distortions. A theoretical demonstration of how the VB- Hamiltonian is utilized to relate these quantum properties to spin- and photonic-quantum information processing. For selecting promising host 2D materials for spin and photonic qubits, we present a data-mining perspective based on the proposed Hamiltonian engineering of the VB- defect in which h-BN is one of four materials chosen to be room temperature qubit candidates.

Atomic and Electronic Structure of Defects in hBN: Enhancing Single-Defect Functionalities.

Defect centers in insulators play a critical role in creating important functionalities in materials: prototype qubits, single-photon sources, magnetic field probes, and pressure sensors. These functionalities are highly dependent on their midgap electronic structure and orbital/spin wave function contributions. However, in most cases, these fundamental properties remain unknown or speculative due to the defects being deeply embedded beneath the surface of highly resistive host crystals, thus impeding access through surface probes. Here, we directly inspected the atomic and electronic structures of defects in thin carbon-doped hexagonal boron nitride (hBN:C) by using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Such investigation adds direct information about the electronic midgap states to the well-established photoluminescence response (including single-photon emission) of intentionally created carbon defects in the most commonly investigated van der Waals insulator. Our joint atomic-scale experimental and theoretical investigations reveal two main categories of defects: (1) single-site defects manifesting as donor-like states with atomically resolved structures observable via STM and (2) multisite defect complexes exhibiting a ladder of empty and occupied midgap states characterized by distinct spatial geometries. Combining direct probing of midgap states through tunneling spectroscopy with the inspection of the optical response of insulators hosting specific defect structures holds promise for creating and enhancing functionalities realized with individual defects in the quantum limit. These findings underscore not only the versatility of hBN:C as a platform for quantum defect engineering but also its potential to drive advancements in atomic-scale optoelectronics.

Controllable synthesis of porous boron nitride fibers modified by cobalt and nickel oxides for efficient ceftriaxone sodium adsorption from aqueous solution.

Antibiotics can easily enter the water environment through direct or indirect approach, causing environmental pollution and endangering the health of organisms. Therefore, development of highly efficient adsorbent materials to adsorb and remove antibiotics is necessary. Here, cobalt oxide and nickel oxide are uniformly and tightly bonded on the surface of porous boron nitride fibers (PBNFs-NiCo), significantly increasing the number of functional groups (B-O and N-H) and hydrogen bond receptors within PBNFs. The total pore volume and specific surface area of resulting PBNFs-NiCo can reach up to 0.48 cm3/g and 720.3 m2/g, respectively. Encouraged by the unique micromorphology and chemical composition mentioned above, PBNFs-NiCo exhibits excellent ceftriaxone sodium (CS) adsorption ability, showing the adsorption capacity and removal efficiency up to 410.9 mg/g and 96.5%, respectively. Chemical adsorption plays an important role in their adsorption behavior, abiding by Langmuir adsorption theory and pseudo-second-order kinetic equation. Importantly, PBNFs-NiCo exhibits fascinating adsorption effects in surroundings with pH ranging from 4 to 6, 25 °C and varying salt concentrations. This work would establish a practical and feasible foundation for the practical application of PBNFs-NiCo for CS adsorption in aqueous solution.

Highly Anisotropic Thermally Conductive Dielectric Polymer/Boron Nitride Nanotube Composites for Directional Heat Dissipation.

An ideal dielectric material for microelectronic devices requires a combination of high anisotropic thermal conductivity and low dielectric constant (ɛ') and loss (tan δ). Polymer composites of boron nitride nanotubes (BNNTs), which offer excellent thermal and dielectric properties, show promise for developing these dielectric polymer composites. Herein, a simple method for fabricating polymer/BNNT composites with high directional thermal conductivity and excellent dielectric properties is presented. The nanocomposites with directionally aligned BNNTs are fabricated through melt-compounding and in situ fibrillation, followed by sintering the fibrous nanocomposites. The fabricated nanocomposites show a significant enhancement in thermal properties, with an in-plane thermal conductivity (K‖) of 1.8 Wm-1K-1-a 450% increase-yielding a high anisotropy ratio (K‖/K⊥) of 36, a 1700% improvement over isotropic samples containing only 7.2 vol% BNNT. These samples exhibit a 120% faster in-plane heat dissipation compared to the through-plane within 2 s. Additionally, they display low ɛ' of ≈3.2 and extremely low tan δ of ≈0.014 at 1 kHz. These results indicate that this method provides a new avenue for designing and creating polymer composites with enhanced directional heat dissipation properties along with high K‖, suitable for thermal management applications in electronic packaging, thermal interface materials, and passive cooling systems.

Polymeric Nanocomposites of Boron Nitride Nanosheets for Enhanced Directional or Isotropic Thermal Transport Performance.

Polymeric composites with boron nitride nanosheets (BNNs), which are thermally conductive yet electrically insulating, have been pursued for a variety of technological applications, especially those for thermal management in electronic devices and systems. Highlighted in this review are recent advances in the effort to improve in-plane thermal transport performance in polymer/BNNs composites and also the growing research activities aimed at composites of enhanced cross-plane or isotropic thermal conductivity, for which various filler alignment strategies during composite fabrication have been explored. Also highlighted and discussed are some significant challenges and major opportunities for further advances in the development of thermally conductive composite materials and their mechanistic understandings.

Separation performance of boron nitride nanotube stainless-steel filter.

In this study, boron nitride nanotubes (BNNTs) were utilized as covering and reinforcing materials owing to their extraordinary insulation and extremely high hydrophobicity. The gas-liquid-solid annealing process was used to manufacture the BNNT stainless-steel filter, with a 120 mesh stainless steel filter serving as the substrate and B2O3 as the raw material. Scanning electron microscopy showed that the average diameter of the nanotubes was 0.40 µm. The BNNTs were bamboo shaped, and the BNNT stainless-steel filter was superhydrophobic, with a water contact angle was 150.49°. The materials demonstrated good separation performance, as indicated by the separation results obtained under four different test conditions (0 and 0.3 MPa, 3 and 10 mL/min). The solid-liquid separation effect of the BNNT stainless-steel filter was better than that of the Teflon filter. In oil-water separation experiments with varying water contents (1.2 and 5.8 wt%), the BNNT stainless-steel filter was more hydrophobic. Based on the results, the role of the hydrodynamic method in the separation of two superhydrophobic materials is discussed. The method introduced in this study can serve as a reference for the application of other filtration separation technologies. Furthermore, the superior separation performance of the superhydrophobic BNNT stainless-steel filter may enable the quick, effective, and continuous collection of water contaminated with oil, giving it a wide range of potential applications.

Highly Sustainable h-BN Encapsulated MoS2 Hydrogen Evolution Catalysts.

Despite the importance of the stability of the 2D catalysts in harsh electrolyte solutions, most studies have focused on improving the catalytic performance of molybdenum disulfide (MoS2) catalysts rather than the sustainability of hydrogen evolution. In previous studies, the vulnerability of MoS2 crystals is reported that the moisture and oxygen molecules can cause the oxidation of MoS2 crystals, accelerating the degradation of crystal structure. Therefore, optimization of catalytic stability is crucial for approaching practical applications in 2D catalysts. Here, it is proposed that monolayered MoS2 catalysts passivated with an atomically thin hexagonal boron nitride (h-BN) layer can effectively sustain hydrogen evolution reaction (HER) and demonstrate the ultra-high current density (500 mA cm⁻2 over 11 h) and super stable (64 h at 150 mA cm⁻2) catalytic performance. It is further confirmed with density functional theory (DFT) calculations that the atomically thin h-BN layer effectively prevents direct adsorption of water/acid molecules while allowing the protons to be adsorbed/penetrated. The selective penetration of protons and prevention of crystal structure degradation lead to maintained catalytic activity and maximized catalytic stability in the h-BN covered MoS2 catalysts. These findings propose a promising opportunity for approaching the practical application of 2D MoS2 catalysts having long-term stability at high-current operation.

Dual regulation of thermal conductivity and mechanical performance of nano cellulose-based composite via mimicking plant cell wall structure.

Combining thermal conductive fillers and flexible polymers is an agile approach to fabricating composites with heat-conducting performance. However, the thermal conductivity of the composites is hard to reach an equal level to the functional fillers. The mainspring is that the thermally conductive pathways within the composite could not be well-constructed due to the air-induced interface thermal resistance. Herein, inspired by the plant cell wall structure, polyvinyl alcohol (PVA) with abundant hydroxyl groups was adopted as a binder for boosting the thermally conductive pathways construction between cellulose nanofiber (CNF) and alkalized hexagonal boron nitride (BN-OH), also for strengthening the mechanical performance of the composite. The results showed that the tensile strength and through-plane thermal conductivity of the composite were high up to 91.0 MPa and 2.2 W m-1 K-1 at 40 wt% PVA content, exhibiting 121 % and 450 % enhancements compared to pure CNF film (41.2 MPa and 0.4 W m-1 K-1). Moreover, the composite also presented high thermal stability (decomposition temperature of onset was 218 °C) and good hydrophobicity properties. Overall, this study innovatively proposes an idea for enhancing the thermal conductivity and improving the mechanical properties of the composite, which is indispensable for developing thermal management materials for next-generation electronics.

Preparation of poly(allylamine hydrochloride) grafted porous boron nitride fibers for efficient Cr(VI) adsorption from aqueous solution.

Cr(VI) pollution poses great harm to the cyclic utilization of groundwater and surface water resources. Efficient adsorbent materials have great potential to change this situation and assist in the restoration of ecosystems. This work chooses porous boron nitride fibers (pBN) with stable physical and chemical properties as the matrix, 3-aminopropyltriethoxysilane (APTES) as the coupling agent, and uses a one-step crosslinking method to graft poly(allylamine hydrochloride) (PAH) onto pBN, forming pBN-AS@PAH with fascinating Cr(VI) adsorption capacity. PAH is uniformly covered and modified on the surface of pBN, and the composite with high specific surface area (383.33 m2/g), large pore volume (0.37 cm3/g), and abundant amino groups. Its equilibrium adsorption capacity for Cr(VI) can reach up to 123.32 mg/g, and the adsorption behavior follows the quasi second-order kinetic model and Langmuir model, indicating the chemical adsorption process of monolayer. The adsorption style belongs to a spontaneous exothermic process and has the optimal adsorption effect at a pH of ~ 2. Additionally, after cycling for 5 times, the decrease rate of adsorption capacity is less than 10%, showing an excellent reusability.

Hexagonal Boron Nitride Based Photonic Quantum Technologies.

Hexagonal boron nitride is rapidly gaining interest as a platform for photonic quantum technologies, due to its two-dimensional nature and its ability to host defects deep within its large band gap that may act as room-temperature single-photon emitters. In this review paper we provide an overview of (1) the structure, properties, growth and transfer of hexagonal boron nitride; (2) the creationof colour centres in hexagonal boron nitride and assignment of defects by comparison with ab initio calculations for applications in photonic quantum technologies; and (3) heterostructure devices for the electrical tuning and charge control of colour centres that form the basis for photonic quantum technology devices. The aim of this review is to provide readers a summary of progress in both defect engineering and device fabrication in hexagonal boron nitride based photonic quantum technologies.

Constructing the Snail Shell-Like Framework in Thermal Interface Materials for Enhanced Through-Plane Thermal Conductivity.

Melioration of the through-plane thermal conductivity (TC) of thermal interface materials (TIMs) is a sore need for efficient heat dissipation to handle an overheating concern of high-power-density electronics. Herein, we constructed a snail shell-like thermal conductive framework to facilitate vertical heat conduction in TIMs. With inspiration from spirally growing calcium carbonate platelets of snail shells, a facile double-microrod-assisted curliness method was developed to spirally coil boron nitride nanosheet (BNNS)/aramid nanofiber (ANF) laminates where interconnected BNNSs lie along the horizontal plane. Thus, vertical alignment of BNNSs in the resultant TIM was achieved, exhibiting a through-plane TC enhancement of ∼100% compared to the counterpart with randomly distributed BNNSs at the same BNNS addition (50 wt %). The Foygel's nonlinear model revealed that this unique snail shell-like BNNS framework reduced interfacial thermal resistance by 4 orders of magnitude. Our TIM showed superior interfacial thermal dissipation efficiency, leading to a temperature reduction of 42.6 °C for the LED chip compared to the aforementioned counterpart. Our work paves a valuable way for fabricating high-performance TIMs to ensure reliable operation of electrical devices.

Horizontal Lithium Electrodeposition on Atomically Polarized Monolayer Hexagonal Boron Nitride.

Both uncontrolled Li dendrite growth and corrosion are major obstacles to the practical application of Li-metal batteries. Despite numerous attempts to address these challenges, effective solutions for dendrite-free reversible Li electrodeposition have remained elusive. Here, we demonstrate the horizontal Li electrodeposition on top of atomically polarized monolayer hexagonal boron nitride (hBN). Theoretical investigations revealed that the hexagonal lattice configuration and polarity of the monolayer hBN, devoid of dangling bonds, reduced the energy barrier for the surface diffusion of Li, thus facilitating reversible in-plane Li growth. Moreover, the single-atom-thick hBN deposited on a Cu current collector (monolayer hBN/Cu) facilitated the formation of an inorganic-rich, homogeneous solid electrolyte interphase layer, which enabled the uniform Li+ flux and suppressed Li corrosion. Consequently, Li-metal and anode-free full cells containing the monolayer hBN/Cu exhibited improved rate performance and cycle life. This study suggests that the monolayer hBN is a promising class of underlying seed layers to enable dendrite- and corrosion-free, horizontal Li electrodeposition for sustainable Li-metal anodes in next-generation batteries.

A sandwich-type photoelectrochemical biosensor based on anthocyanin-sensitized ZnO/P5FIn heterojunction for the sensitive detection of CYFRA21-1.

. A sandwich-type photoelectrochemical (PEC) immunosensor based on a ZnO/poly(5-formylindole) (P5FIn)/anthocyanin heterostructure was developed to achieve sensitive background-free detection of the tumor marker CYFRA21-1. ZnO with good photovoltaic properties is combined with narrow bandgap P5FIn to form a p-n type heterojunction. This structure reduces the electron-hole pair recombination, thereby enhancing the photocurrent response of the composite. Anthocyanidins are environmentally friendly natural compounds with excellent antioxidant, redox properties, and remarkable electrochemical activity. After sensitization by anthocyanins, the absorption and utilization of visible light in the composites are enhanced, further improving the PEC luminescence efficiency of the materials. Additionally, boron nitride quantum dots (BN QDs) are combined with Ab2 via polydopamine (PDA) as a secondary antibody marker, enhancing its sensitivity. The biosensor exhibited a linear detection range of 0.001-100 ng mL-1 with a limit of detection (LOD) of 0.00033 ng mL-1. Furthermore, this biosensor demonstrates excellent selectivity, reproducibility, and stability, as well as successful results in analyzing actual human serum samples. This approach provides a feasible method for tumor marker detection.

Nonlinear Chiral Metasurfaces Based on Structured van der Waals Materials.

Nonlinear chiral photonics explores the nonlinear response of chiral structures, and it offers a pathway to novel optical functionalities not accessible through linear or achiral systems. Here we present the first application of nanostructured van der Waals materials to nonlinear chiral photonics. We demonstrate the 3 orders of magnitude enhancement of the third-harmonic generation from hBN metasurfaces driven by quasi-bound states in the continuum and accompanied by strong nonlinear circular dichroism at the resonances. This novel platform for chiral metaphotonics can be employed for achieving large circular dichroism combined with high-efficiency harmonic generation in a broad frequency range.

Stretching Aligned Hydrogen Bonding Network to Evoke Mechanically Robust and High-Energy-Density P(VDF-HFP) Dielectric Film Capacitors.

Polymer-based dielectric film capacitors are essential energy storage components in electronic and power systems due to their ultrahigh power density and ultra-fast charge storage/release capability. Nonetheless, their relatively low energy density does not fully meet the requirements of power electronics and pulsed power systems. Herein, a scalable composite dielectric film based on a ferroelectric polymer with edge hydroxylated boron nitride nanosheets (BNNS-OH) is fabricated via the construction of a hydrogen bonding network and stretching orientation strategy. The presence of hydroxyl groups on boron nitride aids in forming a robust hydrogen bonding network within the ferroelectric polymer, leading to a significant increase in Young's modulus and superior dielectric performance. Furthermore, the stretching process aligns the BNNS-OH and the hydrogen bonding network along the drawing direction via covalent and hydrogen bonding interaction, resulting in a remarkable tensile strength (109 MPa), breakdown strength (688 MV m-1), and energy density (28.2 J cm-3), outperforming mostrepresentative polymer-based dielectric films. In combining the advantages of a simple preparation process, extraordinary energy storage performance, and low-cost raw materials, this strategy is viable for large-scale production of polymer-based dielectric films with high mechanical and dielectric performance and opens a new path for the development of next-generation energy storage applications.

Modification Strategies of Hexagonal Boron Nitride Nanomaterials for Photocatalysis.

Although hexagonal boron nitride (h-BN) was initially considered a less promising photocatalyst due to its large band gap and apparent chemical inertness, its unique two-dimensional lamellar structure coupled with high stability and environmental friendliness, as the second largest van der Waals material after graphene, provides a unique platform for photocatalytic innovation. This review not only highlights the intrinsic qualities of h-BN with photocatalytic potentials, such as high stability, environmental compatibility, and tunable bandgap through various modification strategies but also provides a comprehensive overview of the recent advances in h-BN-based nanomaterials for environmental and energy applications, as well as an in-depth description of the modification methods and fundamental properties for these applications. In addition, we discuss the challenges and prospects of h-BN-based nanomaterials for future photocatalysis.