Schwarzites and Triply Periodic Minimal Surfaces: From Pure Topology Mathematics to Macroscale Applications.

Schwarzites 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. The main works on schwarzites are summarized and are available in the literature. Their unique structural, electronic, thermal, and mechanical properties are discussed. Although the synthesis of carbon-based schwarzites remains elusive, recent advances in the synthesis of zeolite-templates nanomaterials have brought them closer to reality. Atomic-based models of schwarzites are translated into macroscale ones that are 3D-printed. These 3D-printed models are exploited in many real-world applications, including water remediation and biomedical ones.

3D macroporous solids from chemically cross-linked carbon nanotubes.

Suzuki reaction for covalently interconnected 3D carbon nanotube (CNT) architectures is reported. The synthesis of 3D macroscopic solids made of CNTs covalently connected via Suzuki cross-coupling, a well-known carbon-carbon covalent bond forming reaction in organic chemistry, is scalable. The resulting solid has a highly porous, interconnected structure of chemically cross-linked CNTs. Its use for the removal of oil from contaminated water is demonstrated.

Energy Harvesting Using ZnO Nanosheet-Decorated 3D-Printed Fabrics.

In this work, we decorated piezoresponsive atomically thin ZnO nanosheets on a polymer surface using additive manufacturing (three-dimensional (3D) printing) technology to demonstrate electrical-mechanical coupling phenomena. The output voltage response of the 3D-printed architecture was regulated by varying the external mechanical pressures. Additionally, we have shown energy generation by placing the 3D-printed fabric on the padded shoulder strap of a bag with a load ranging from ∼5 to ∼75 N, taking advantage of the excellent mechanical strength and flexibility of the coated 3D-printed architecture. The ZnO coating layer forms a stable interface between ZnO nanosheets and the fabric, as confirmed by combining density functional theory (DFT) and electrical measurements. This effectively improves the output performance of the 3D-printed fabric by enhancing the charge transfer at the interface. Therefore, the present work can be used to build a new infrastructure for next-generation energy harvesters capable of carrying out several structural and functional responsibilities.

Spontaneous hydrogen production using gadolinium telluride.

Developing materials for controlled hydrogen production through water splitting is one of the most promising ways to meet current energy demand. Here, we demonstrate spontaneous and green production of hydrogen at high evolution rate using gadolinium telluride (GdTe) under ambient conditions. The spent materials can be reused after melting, which regain the original activity of the pristine sample. The phase formation and reusability are supported by the thermodynamics calculations. The theoretical calculation reveals ultralow activation energy for hydrogen production using GdTe caused by charge transfer from Te to Gd. Production of highly pure and instantaneous hydrogen by GdTe could accelerate green and sustainable energy conversion technologies.

Energy Harvesting Using Cotton Fabric Embedded with 2D Hexagonal Boron Nitride.

Continuous health monitoring through sensitive physiological signals (using a wearable device) is crucial for the early detection of heart diseases and breathing problems. Here, we have developed a flexible hBN/cotton hybrid device that can detect minor signals such as heartbeat and breathed-out air pressure. Systematic observation of the real-time motion sensing showed a peak-to-peak voltage output of ∼1.5 V for each heart rate pulse. The as-fabricated device showed a high voltage output of up to ∼10 V upon applying a pressure of ∼3 MPa. The FTIR results and DFT calculation suggested a chemical interaction between hBN and cellulose, giving rise to flat band characteristics and partially filled σ-bonding (sp2) hybridization. The atomic-scale chemical interface between atomically thin hBN and surface functional groups present on cotton resulted in charge localization and enhanced output voltage. An hBN/cotton hybrid device can bring new insights and opportunities to develop a self-charging and health-monitoring energy-harvesting cloth.

Pseudocapacitive TiNb2O7/reduced graphene oxide nanocomposite for high-rate lithium ion hybrid capacitors.

Lithium ion hybrid capacitors (LIHCs) have a capacitor-type cathode and a battery-type anode and are a prospective energy storage device that delivers high energy/power density. However, the kinetic imbalance between the cathode and the anode is a key obstacle to their further development and application. Herein, we prepared TiNb2O7 nanoparticles through a facile solvothermal method and annealing treatment. Then a homogeneous three-dimensional (3D) self-supported reduced graphene oxide (rGO)-coated TiNb2O7 (TiNb2O7/rGO) nanocomposite was constructed by freeze-drying, followed by a high-temperature reduction, which demonstrates an enhanced pseudocapacitive lithium ions storage performance. Benefiting from the improved electrical conductivity, ultrashort ions diffusion paths, and 3D architecture, the TiNb2O7/rGO nanocomposite exhibits a high specific capacity of 285.0 mA h g-1, excellent rate capability (73.6% capacity retention at 8 A g-1), and superior cycling stability. More importantly, quantitative kinetics analysis reflects that the capacity of TiNb2O7/rGO is mainly dominated by capacitive behavior, making it perfectly match with the capacitor-type activated carbon (AC) cathode. By using pre-lithiated TiNb2O7/rGO as anode material and AC as cathode material, a high-rate TiNb2O7/rGO//AC LIHC device can be fabricated, which delivers an ultrahigh energy density of 127 Wh kg-1 at the power density of 200 W kg-1, a maximum power density of 10 kW kg-1 at the energy density of 56.4 Wh kg-1, and durable service life.

Two-dimensional cobalt telluride as a piezo-tribogenerator.

Two-dimensional (2D) materials have been shown to be efficient in energy harvesting. Here, we report the use of waste heat to generate electricity via the combined piezoelectric and triboelectric properties of 2D cobalt telluride (CoTe2). The piezo-triboelectric nanogenerator (PTNG) produced an open-circuit voltage of ∼5 V under 1 N force and the effect of temperature in the range of 305-363 K shows a four-fold energy conversion efficiency improvement. The 2D piezo-tribogenerator shows excellent characteristics with a maximum voltage of ∼10 V, fast response time, and high responsivity. Density functional theory was used to gain further insights and validation of the experimental results. Our results could lead to energy harvesting approaches using 2D materials from various thermal sources and dissipating waste heat from electronic devices.

Reversible temperature-dependent photoluminescence in semiconductor quantum dots for the development of a smartphone-based optical thermometer.

Photoluminescence (PL) intensity-based non-contact optical temperature sensors are in great demand due to their non-contact nature, rapid response, sensitivity, as well as thermal and chemical stability at different environmental conditions. However, herein, reversible temperature dependent PL emission quenching properties of chemically synthesized Mn2+-doped ZnS QDs (MZQDs) have been advantageously utilized for achieving the development of a smartphone-based optical thermometer. The temperature dependent variations of PL have been studied by taking MZQDs in various forms, such as in aqueous dispersion, powder form, and a polymer-encapsulated thin film. The origin of the PL quenching of MZQD in the polymer film has been cross-verified through temperature-dependent electrical conductivity measurement and the movement of charge carriers has also been confirmed by the first-principles DFT simulation. Through thermal cycling experiments on QD-encapsulated polymer film and by utilizing an indigenously-developed Android App based on color coordinates, a novel smartphone-based colorimetric imaging method for the measurement of temperature has been demonstrated in this work. The synthesized smart QDs might be suitable candidates for temperature sensing and the colorimetric thermometer probe may be utilized in various photonics applications as a smart optical sensor for daily life applications.

2D Hexagonal Boron Nitride-Coated Cotton Fabric with Self-Extinguishing Property.

Here, we report on the fabrication of flame retardant hydrophobic cotton fabrics based on the coating with two-dimensional hexagonal boron nitride (2D hBN) nanosheets. A simple one-step solution dipping process was used to coat the fabrics by taking advantage of the strong bonding between diethylenetriamine and hBN on the cotton surface. Exposure to direct flame confirmed the improvement of the flame retardant properties of the coated cotton fabrics. In turn, removal of the flame source revealed self-extinguishing properties. Molecular dynamics simulations indicate that hBN hinders combustion by reducing the rate at which oxygen molecules reach the cotton surface. This time-saving and one-step approach for the fabrication of flame-retardant cotton fabrics offers significant advantages over other, less efficient production methods.

Graphene Supported MoS2 Structures with High Defect Density for an Efficient HER Electrocatalysts.

The development of novel efficient and robust electrocatalysts with sufficient active sites is one of the key parameters for hydrogen evolution reactions (HER) catalysis, which plays a key role in hydrogen production for clean energy harvesting. Recently, two-dimensional (2D) materials, especially those based upon transition metal dichalcogenides such as molybdenum disulfide (MoS2), have gained attention for the catalysis of hydrogen production because of their exceptional properties. Innovative strategies have been developed to engineer these material systems for improvements in their catalytic activity. Toward this aim, the facile growth of MoS2 clusters by sulfurization of molybdenum dioxide (MoO2) particles supported on reduced graphene oxide (rGO) foams using the chemical vapor deposition (CVD) method is reported. This approach created various morphologies of MoS2 with large edges and defect densities on the basal plane of rGO supported MoS2 structures, which are considered as active sites for HER catalysis. In addition, MoS2 nanostructures on the surface of the porous rGO network show robust physical interactions, such as van der Waals and π-π interactions between MoS2 and rGO. These features result in an improved process to yield a suitable HER catalyst. In order to gain a better understanding of the improvement of this MoS2-based HER catalyst, fully atomistic molecular dynamics (MD) simulations of different defect geometries were also performed.

Tailoring of structural and photoluminescence emissions by Mn and Cu co-doping in 2D nanostructures of ZnS for the visualization of latent fingerprints and generation of white light.

There has been a recent demand for the development of luminescent materials for visualizations of latent fingerprints (LFPs) for achieving enhanced security. Also recently, there has been a new research trend in the development of 2D materials from non-layered semiconductors with strong luminescence properties in the visible region. The conventional growth process of luminescent materials limits their capacity of tuning the structure and light emission efficiency. However, multi-atom doping provides an additional degree of freedom to tune the basic morphologies and optical properties of luminescent semiconductors by controlling the defect levels. Here, by using a simple chemical technique, multi-atom (Cu and Mn) doped rarely reported 2D nanosheets of zinc sulphide (ZnS) have been grown. Thus, a stable high fluorescence efficiency of ∼62% in the visible region has been realized for the visualization of LFPs. Furthermore, near-white light emission has been demonstrated by coating the synthesized materials with a suitable doping concentration on a commercially available UV-LED chip. The proposed technique may be utilized further to build up other 2D nanostructured materials for multifunctional applications in solid state lighting, LFPs and forensic science.

Hybrid MoS2/h-BN Nanofillers As Synergic Heat Dissipation and Reinforcement Additives in Epoxy Nanocomposites.

Two-dimensional (2D) nanomaterials as molybdenum disulfide (MoS2), hexagonal boron nitride (h-BN), and their hybrid (MoS2/h-BN) were employed as fillers to improve the physical properties of epoxy composites. Nanocomposites were produced in different concentrations and studied in their microstructure, mechanical and thermal properties. The hybrid 2D mixture imparted efficient reinforcement to the epoxy leading to increases of up to 95% in tensile strength, 60% in ultimate strain, and 58% in Young's modulus. Moreover, an enhancement of 203% in thermal conductivity was achieved for the hybrid composite as compared to the pure polymer. The incorporation of MoS2/h-BN mixture nanofillers in epoxy resulted in nanocomposites with multifunctional characteristics for applications that require high mechanical and thermal performance.

Atomically thin gallium layers from solid-melt exfoliation.

Among the large number of promising two-dimensional (2D) atomic layer crystals, true metallic layers are rare. Using combined theoretical and experimental approaches, we report on the stability and successful exfoliation of atomically thin "gallenene" sheets on a silicon substrate, which has two distinct atomic arrangements along crystallographic twin directions of the parent α-gallium. With a weak interface between solid and molten phases of gallium, a solid-melt interface exfoliation technique is developed to extract these layers. Phonon dispersion calculations show that gallenene can be stabilized with bulk gallium lattice parameters. The electronic band structure of gallenene shows a combination of partially filled Dirac cone and the nonlinear dispersive band near the Fermi level, suggesting that gallenene should behave as a metallic layer. Furthermore, it is observed that the strong interaction of gallenene with other 2D semiconductors induces semiconducting to metallic phase transitions in the latter, paving the way for using gallenene as promising metallic contacts in 2D devices.

Bacteria as Bio-Template for 3D Carbon Nanotube Architectures.

It is one of the most important needs to develop renewable, scalable and multifunctional methods for the fabrication of 3D carbon architectures. Even though a lot of methods have been developed to create porous and mechanically stable 3D scaffolds, the fabrication and control over the synthesis of such architectures still remain a challenge. Here, we used Magnetospirillum magneticum (AMB-1) bacteria as a bio-template to fabricate light-weight 3D solid structure of carbon nanotubes (CNTs) with interconnected porosity. The resulting porous scaffold showed good mechanical stability and large surface area because of the excellent pore interconnection and high porosity. Steered molecular dynamics simulations were used to quantify the interactions between nanotubes and AMB-1 via the cell surface protein MSP-1 and flagellin. The 3D CNTs-AMB1 nanocomposite scaffold is further demonstrated as a potential substrate for electrodes in supercapacitor applications.