A mechanochemical process to capture and separate carbon dioxide from natural gas using boron nitride nanosheets.

Addressing climate change is a critical and pressing matter that requires immediate attention to mitigate its severe repercussions. In order to enhance the capture and separation of carbon dioxide from natural gas and nitrogen gas, it is imperative to develop new capture materials and more efficient storage processes. In this study, we introduce an innovative environmentally friendly storage and separation technique. Through a controlled mechanochemical process, a substantial amount of carbon dioxide (103.6 wt%) was successfully captured within boron nitride. This process also excels at effectively isolating carbon dioxide from a gas mixture containing natural gas (CH4) or nitrogen due to its superior adsorption selectivity for CO2 over the other two gases. The stored carbon dioxide can be released upon heating, and this procedure can be repeated several times (minimum four times), indicating a game changing process in CO2 gas capture and separation technology with the advantages of green, low cost and efficiency.

A Thermoregulatory Flexible Phase Change Nonwoven for All-Season High-Efficiency Wearable Thermal Management.

Phase change materials have a key role for wearable thermal management, but suffer from poor water vapor permeability, low enthalpy value and weak shape stability caused by liquid phase leakage and intrinsic rigidity of solid-liquid phase change materials. Herein, we report for the first time a versatile strategy for designed assembly of high-enthalpy flexible phase change nonwovens (GB-PCN) by wet-spinning hybrid graphene-boron nitride (GB) fiber and subsequent impregnating paraffins (e.g., eicosane, octadecane). As a result, our GB-PCN exhibited an unprecedented enthalpy value of 206.0 J g-1, excellent thermal reliability and anti-leakage capacity, superb thermal cycling ability of 97.6% after 1000 cycles, and ultrahigh water vapor permeability (close to the cotton), outperforming the reported PCM films and fibers to date. Notably, the wearable thermal management systems based on GB-PCN for both clothing and face mask were demonstrated, which can maintain the human body at a comfortable temperature range for a significantly long time. Therefore, our results demonstrate huge potential of GB-PCN for human-wearable passive thermal management in real scenarios.

Hybrid Artificial Solid Electrolyte Interphase with Dendrite-Free Lithium Deposition and High Ion Transport Kinetics.

Interfacial issues and dendritic Li deposition in lithium metal batteries (LMBs) hamper the practical application of liquid or solid-state cells. Here, a hybrid solid electrolyte interphase (SEI), based on hydroxyl-functionalized boron nitride (BN) nanosheets and poly(vinyl alcohol), is designed to solve the unstable nature of the Li anode-electrolyte interface. Rather than acquiring a rich Li halide environment through intense electrolyte decomposition, the hybrid SEI effectively regulates electrolyte decomposition and guarantees uniform Li plating via boosting interfacial Li+ ion transport at the interface. The Li+ ion boosting kinetics were deeply analyzed using simulations and spectroscopic analysis. It is revealed that the hydroxyl-functionalized BN can decrease kinetic energy barriers for Li+ ions and strongly holds TFSI- ions, thereby ensuring faster Li+ ion migration between electrodes and electrolytes. Tailoring the interfacial Li+ ion dynamics with hybrid SEI renders the Li transference number enhancement from 0.391 to 0.562 and 0.178 to 0.327 in liquid and solid-state cells, respectively. Moreover, Li symmetric cells with hybrid SEI exhibit an ultrahigh stability over 3500 h at 2 mA cm-2 with 2 mA h cm-2, along with the improved solid-state LMB performances. Our results suggest increasing Li+ ion transport at the interface is an alternative to resolve Li anode issues.

Nanomaterials enhancing the solid-state storage and decomposition of ammonia.

Hydrogen is ideal for producing carbon-free and clean-green energy with which to save the world from climate change. Proton exchange membrane fuel cells use to hydrogen to produce 100% clean energy, with water the only by-product. Apart from generating electricity, hydrogen plays a crucial role in hydrogen-powered vehicles. Unfortunately, the practical uses of hydrogen energy face many technical and safety barriers. Research into hydrogen generation and storage and reversibility transportation are still in its very early stages. Ammonia (NH3) has several attractive attributes, with a high gravimetric hydrogen density of 17.8 wt% and theoretical hydrogen conversion efficiency of 89.3%. Ammonia storage and transport are well-established technologies, making the decomposition of ammonia to hydrogen the safest and most carbon-free option for using hydrogen in various real-time applications. However, several key challenges must be addressed to ensure its feasibility. Current ammonia decomposition technologies require high temperatures, pressures and non-recyclable catalysts, and a sustainable decomposition mechanism is urgently needed. This review article comprehensively summarises current knowledge about and challenges facing solid-state storage of ammonia and decomposition. It provides potential strategic solutions for developing a scalable process with which to produce clean hydrogen by eliminating possible economic and technical barriers.

Boron Nitride Nanosheet Dispersion at High Concentrations.

There is an increasing demand for boron nitride nanosheets (BNNSs) for a range of applications such as advanced composite materials, ion/gas selective membranes, and energy storage. These applications require stable, high-concentration BNNS dispersions as a precursor, which is a challenge because BNNSs do not disperse easily. We report a simple, yet efficient, mechanochemical exfoliation technique to prepare functionalized BNNSs with excellent dispersibility in water and organic solvents. The resultant amino-modified BNNSs (BNNS-NH2) are stable in ethanol for 3 months at an unprecedented high concentration of 46 ± 2 mg/mL. We provide insights into the dispersibility mechanism for amino- and hydroxyl-functionalized BNNSs. High-concentration BNNS dispersions enable a facile painting method that can coat a uniform, insulating, and antioxidant BNNS layer on arbitrary surfaces. In addition, different functional groups enhance the selectivity of different ions of the functionalized BNNS membranes for water purification and other ion separation applications. These stable, high-concentration BNNS dispersions make many exciting applications possible.

Mechanochemistry: A force in disguise and conditional effects towards chemical reactions.

Mechanochemistry refers to unusual chemical reactions induced by mechanical energy at room temperatures. It has attracted increased attention because of advantages, such as being a solution-free, energy saving, high-productivity and low-temperature process. However, there is limited understanding of the mechanochemical process because mechanochemistry is often conducted using closed milling devices, which are often regarded as a black box. This feature article shows that mechanochemical reactions can be controlled by varying milling parameters, such as the mechanical force, milling intensity, time and atmosphere. New nanomaterials with doped and functionalized structures can be produced under controlled conditions, which provide a critical insight for understanding mechanochemistry. A fundamental mechanism investigation using force microscopy is discussed.

An Ultra-Long-Life Flexible Lithium-Sulfur Battery with Lithium Cloth Anode and Polysulfone-Functionalized Separator.

Flexible and high-performance batteries are urgently required for powering flexible/wearable electronics. Lithium-sulfur batteries with a very high energy density are a promising candidate for high-energy-density flexible power source. Here, we report flexible lithium-sulfur full cells consisting of ultrastable lithium cloth anodes, polysulfone-functionalized separators, and free-standing sulfur/graphene/boron nitride nanosheet cathodes. The carbon cloth decorated with lithiophilic three-dimensional MnO2 nanosheets not only provides the lithium anodes with an excellent flexibility but also limits the growth of the lithium dendrites during cycling, as revealed by theoretical calculations. Commercial separators are functionalized with polysulfone (PSU) via a phase inversion strategy, resulting in an improved thermal stability and smaller pore size. Due to the synergistic effect of the PSU-functionalized separators and boron nitride-graphene interlayers, the shuttle of the polysulfides is significantly inhibited. Because of successful control of the shuttle effect and dendrite formation, the flexible lithium-sulfur full cells exhibit excellent mechanical flexibility and outstanding electrochemical performance, which shows a superlong lifetime of 800 cycles in the folded state and a high areal capacity of 5.13 mAh cm-2. We envision that the flexible strategy presented herein holds promise as a versatile and scalable platform for large-scale development of high-performance flexible batteries.

In situ production of a two-dimensional molybdenum disulfide/graphene hybrid nanosheet anode for lithium-ion batteries.

A solvent-free, low-cost, high-yield and scalable single-step ball milling process is developed to construct 2D MoS2/graphene hybrid electrodes for lithium-ion batteries. Electron microscopy investigation reveals that the obtained hybrid electrodes consist of numerous nanosheets of MoS2 and graphene which are randomly distributed. The MoS2/graphene hybrid anodes exhibit excellent cycling stability with high reversible capacities (442 mA h g-1 for MoS2/graphene (40 h); 553 mA h g-1 for MoS2/graphene (20 h); 342 mA h g-1 for MoS2/graphene (10 h)) at a high current rate of 250 mA g-1 after 100 cycles, whereas the pristine MoS2 electrode shows huge capacity fading with a retention of 37 mA h g-1 at 250 mA g-1 current after 100 cycles. The incorporation of graphene into MoS2 has an extraordinary effect on its electrochemical performance. This work emphasises the importance of the construction of the 2D MoS2/graphene hybrid structure to prevent capacity fading issues with the MoS2 anode in lithium-ion batteries.

Atomically Thin Boron Nitride as an Ideal Spacer for Metal-Enhanced Fluorescence.

Metal-enhanced fluorescence (MEF) considerably enhances the luminescence for various applications, but its performance largely depends on the dielectric spacer between the fluorophore and plasmonic system. It is still challenging to produce a defect-free spacer having an optimized thickness with a sub-nanometer accuracy that enables reusability without affecting the enhancement. In this study, we demonstrate the use of atomically thin hexagonal boron nitride (BN) as an ideal MEF spacer owing to its multifold advantages over the traditional dielectric thin films. With rhodamine 6G as a representative fluorophore, it largely improves the enhancement factor (up to ∼95 ± 5), sensitivity (10-8 M), reproducibility, and reusability (∼90% of the plasmonic activity is retained after 30 cycles of heating at 350 °C in air) of MEF. This can be attributed to its two-dimensional structure, thickness control at the atomic level, defect-free quality, high affinities to aromatic fluorophores, good thermal stability, and excellent impermeability. The atomically thin BN spacers could increase the use of MEF in different fields and industries.

Highly Compressive Boron Nitride Nanotube Aerogels Reinforced with Reduced Graphene Oxide.

Boron nitride nanotubes (BNNTs), structural analogues of carbon nanotubes, have attracted significant attention due to their superb thermal conductivity, wide bandgap, excellent hydrogen storage capacity, and thermal and chemical stability. Despite considerable progress in the preparation and surface functionalization of BNNTs, it remains a challenge to assemble one-dimensional BNNTs into three-dimensional (3D) architectures (such as aerogels) for practical applications. Here, we report a highly compressive BNNT aerogel reinforced with reduced graphene oxide (rGO) fabricated using a freeze-drying method. The reinforcement effect of rGO and 3D honeycomb-like framework offer the BNNTs/rGO aerogel with a high compression resilience. The BNNTs/rGO aerogels were then infiltrated with polyethylene glycol to prepare a kind of phase change materials. The prepared phase change material composites show zero leakage even at 100 °C and enhanced thermal conductivity, due to the 3D porous structure of the BNNTs/rGO aerogel. This work provides a simple method for the preparation of 3D BNNTs/rGO aerogels for many potential applications, such as high-performance polymer composites.

Boron Radicals Identified as the Source of the Unexpected Catalysis by Boron Nitride Nanosheets.

Atomically thin boron nitride (BN) nanosheets were generally considered to be chemically inert until the recent discovery of the surprising catalysis. However, the origin of this unusual catalytic activity remains unclear. We have observed the free boron radicals at the edges and defective sites of BN nanosheets and demonstrated with both experimental and theoretical approaches that the boron radicals in the nanosheets can catalyze the chromogenic reaction of 3,5,3',5'-tetramethylbenzidine and serve as a source of reactive radicals for the co-reactant electrogenerated chemiluminescence of tris(2,2'-bipyridine)ruthenium(2+). These findings suggest BN nanosheets as a type of nonmetal catalyst.

K-ion and Na-ion storage performances of Co3O4-Fe2O3 nanoparticle-decorated super P carbon black prepared by a ball milling process.

The hybridisation of Co3O4 and Fe2O3 nanoparticles dispersed in a super P carbon matrix is proposed as a favourable approach to improve the electrochemical performance (reversible capacity, cycling stability and rate capability) of the metal oxide electrodes in metal-ion batteries. Hybrid Co3O4-Fe2O3/C is prepared by a simple, cheap and easily scalable molten salt method combined with ball-milling and used in sodium-ion and potassium-ion batteries for the first time. The electrode exhibits excellent cycling stability and superior rate capability in sodium-ion cells with a capacity recovery of 440 mA h g-1 (93% retention) after 180 long-term cycles at 50-1000 mA g-1 and back to 50 mA g-1. In contrast, Co3O4-Fe2O3, Co3O4 and Fe2O3 electrodes display unsatisfactory electrochemical performance. The hybrid Co3O4-Fe2O3/C is also reactive with potassium and capable of delivering a reversible capacity of 220 mA h g-1 at 50 mA g-1 which is comparable with the most reported anode materials for potassium-ion batteries. The obtained results broaden the range of transition metal oxide-based hybrids as potential anodes for K-ion and Na-ion batteries, and suggest that further studies of these materials with potassium and sodium are worthwhile.

Gas Protection of Two-Dimensional Nanomaterials from High-Energy Impacts.

Two-dimensional (2D) materials can be produced using ball milling with the help of liquid surfactants or solid exfoliation agents, as ball milling of bulk precursor materials usually produces nanosized particles because of high-energy impacts. Post-milling treatment is thus needed to purify the nanosheets. We show here that nanosheets of graphene, BN, and MoS2 can be produced by ball milling of their bulk crystals in the presence of ammonia or a hydrocarbon ethylene gas and the obtained nanosheets remain flat and maintain their single-crystalline structure with low defects density even after a long period of time; post-milling treatment is not needed. This study does not just demonstrate production of nanosheets using ball milling, but reveals surprising indestructible behaviour of 2D nanomaterials in ammonia or hydrocarbon gas under the high-energy impacts; in other milling atmospheres such as air, nitrogen or argon the same milling treatment produces nanosized particles. A systematic study reveals chemisorption of ammonia and hydrocarbon gases and chemical reactions occurring at defect sites, which heal the defects by saturating the dangling bonds. Density functional theory was used to understand the mechanism of mechanochemical reactions. Ball milling in ammonia or hydrocarbon is promising for mass-production of pure nanosheets.

Boron Nitride Nanosheet-Veiled Gold Nanoparticles for Surface-Enhanced Raman Scattering.

Atomically thin boron nitride (BN) nanosheets have many properties desirable for surface-enhanced Raman spectroscopy (SERS). BN nanosheets have a strong surface adsorption capability toward airborne hydrocarbon and aromatic molecules. For maximized adsorption area and hence SERS sensitivity, atomically thin BN nanosheet-covered gold nanoparticles have been prepared for the first time. When placed on top of metal nanoparticles, atomically thin BN nanosheets closely follow their contours so that the plasmonic hot spots are retained. Electrically insulating BN nanosheets also act as a barrier layer to eliminate metal-induced disturbances in SERS. Moreover, the SERS substrates veiled by BN nanosheets show an outstanding reusability in the long term. As a result, the sensitivity, reproducibility, and reusability of SERS substrates can be greatly improved. We also demonstrate that large BN nanosheets produced by chemical vapor deposition can be used to scale up the proposed SERS substrate for practical applications.

Boron Nitride Nanosheets Improve Sensitivity and Reusability of Surface-Enhanced Raman Spectroscopy.

Surface enhanced Raman spectroscopy (SERS) is a useful multidisciplinary analytic technique. However, it is still a challenge to produce SERS substrates that are highly sensitive, reproducible, stable, reusable, and scalable. Herein, we demonstrate that atomically thin boron nitride (BN) nanosheets have many unique and desirable properties to help solve this challenge. The synergic effect of the atomic thickness, high flexibility, stronger surface adsorption capability, electrical insulation, impermeability, high thermal and chemical stability of BN nanosheets can increase the Raman sensitivity by up to two orders, and in the meantime attain long-term stability and extraordinary reusability not achievable by other materials. These advances will greatly facilitate the wider use of SERS in many fields.