Bionic iontronics based on nano-confined structures

The Moore’s law in silicone-based electronics is reaching its limit and the energy efficiency of the most sophisticated electronics to mimic the iontronic logic circuit in single-celled organisms is still inferior to their natural counterpart.Unlike electronics,iontronics is widely present in nature,and provides the fundamentals for many life activities through the transmission and conversion of information and energy via ions.Moreover,as nanotechnology and fabrication processes continue to advance,highly efficient iontronics could be enabled by creation of asymmetry from nano-confined unipolar ion transport through various nanohierarchical structures of materials.The introduction of bionic design and nanostructures has made it possible for ions to demonstrate numerous anomalous behaviours and entirely new mechanisms,which are governed by complex interfacial interactions.In this review,we discuss the origins,development,mechanism,and applications of bionic iontronics and analyze the unique benefits as well as the practicality of iontronics from a variety of perspectives.Iontronics,as an emerging field of research with innumerable challenges and opportunities for exploring the theory and applications of ions as transport carriers,promises to provide new insights in many subjects covering energy and sensing,etc.,and establishes a new paradigm in investigating the ionic-electric signal transduction interface for futuristic iontronic logic circuit and neuromorphic computing.

Nanostructured MXene-based materials for boosting hydrogen sorption properties of Mg/MgH_(2)

Hydrogen holds the advantages of high energy density,great natural abundance and zero emission,making it suitable for large scale and long term energy storage,while its safe and efficient storage is still challenging.Among various solid state hydrogen storage materials,MgH_(2) is promising for industrial applications due to its high gravimetric and volumetric hydrogen densities and the abundance of Mg on earth.However,the practical application of MgH_(2) has been limited by its stable thermodynamics and slow hydrogen desorption kinetics.Nanocatalysis is considered as a promising approach for improving the hydrogen storage performance of MgH_(2) and bringing it closer to the requirements of commercial applications.It is worth mentioning that the recently emerging two-dimensional material,MXene,has showcased exceptional catalytic abilities in modifying the hydrogen storage properties of MgH_(2).Besides,MXene possesses a high surface area,excellent chemical/physical stability,and negatively charged terminating groups,making it an ideal support for the"nanoconfinement"of MgH_(2) or highly active catalysts.Herein,we endeavor to provide a comprehensive overview of recent investigations on MXene-based catalysts and MXene supports for improving the hydrogen sorption properties of Mg/MgH_(2).The mechanisms of hydrogen sorption involved in Mg-MXene based composites are highlighted with special emphases on thermodynamics,kinetics,and catalytic behaviors.The aim of this work is to provide a comprehensive and objective review of researches on the development of high-performance catalysts/supports to improve hydrogen storage performances of Mg/MgH_(2) and to identify the opportunities and challenges for future applications.

Hierarchically porous Fe/N/S/C nanospheres with high-content of Fe-Nx for enhanced ORR and Zn-air battery performance

Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a facile and general melting perfusion and mesopore-confined pyrolysis method was reported to prepare single-atomic Fe/N–S-doped carbon catalyst(FeNx/NC-S) with hierarchically porous structure and well-defined morphology. The FeNx/NC-S exhibited excellent ORR activity with a half-wave potential(E_(1/2)) of 0.92 V, and a lower overpotential of 320 mV at a current density of 10 mA cm^(-2)for OER under alkaline condition. The remarkable electrocatalysis performance can be attributed to the hierarchically porous carbon nanospheres with S doping and high content of Fe-Nx sites(up to 3.7 wt% of Fe), resulting from the nano-confinement effect of the hierarchically porous silica spheres(NKM-5) during the pyrolysis process. The rechargeable Zn-air battery with FeNx/NC-S as a cathode catalyst demonstrated a superior power density of 194.5 mW cm-2charge–discharge stability. This work highlights a new avenue to design advanced SACs for efficient sustainable energy storage and conversion.

Effects of CH_(4)/CO_(2) multi-component gas on components and properties of tight oil during CO_(2) utilization and storage: Physical experiment and composition numerical simulation

An essential technology of carbon capture, utilization and storage-enhanced oil recovery (CCUS-EOR) for tight oil reservoirs is CO_(2) huff-puff followed by associated produced gas reinjection. In this paper, the effects of multi-component gas on the properties and components of tight oil are studied. First, the core displacement experiments using the CH_(4)/CO_(2) multi-component gas are conducted to determine the oil displacement efficiency under different CO_(2) and CH_(4) ratios. Then, a viscometer and a liquid density balance are used to investigate the change characteristics of oil viscosity and density after multi-component gas displacement with different CO_(2) and CH_(4) ratios. In addition, a laboratory scale numerical model is established to validate the experimental results. Finally, a composition model of multi-stage fractured horizontal well in tight oil reservoir considering nano-confinement effects is established to investigate the effects of multi-component gas on the components of produced dead oil and formation crude oil. The experimental results show that the oil displacement efficiency of multi-component gas displacement is greater than that of single-component gas displacement. The CH_(4) decreases the viscosity and density of light oil, while CO_(2) decreases the viscosity but increases the density. And the numerical simulation results show that CO_(2) extracts more heavy components from the liquid phase into the vapor phase, while CH_(4) extracts more light components from the liquid phase into the vapor phase during cyclic gas injection. The multi-component gas can extract both the light components and the heavy components from oil, and the balanced production of each component can be achieved by using multi-component gas huff-puff.

Realizing nano-confinement of magnesium for hydrogen storage using vapour transport deposition

A new approach was developed to successfully load Mg into the nanometre-sized pores of an anodic aluminium oxide（AAO） template for realizing the nano-confinement of Mg. Structural characterization shows that Mg nano-particles are nucleated along the AAO pipe wall together with the formation of MgO and Mg17Al12 as byproducts. The flow rate of argon gas, the temperature of the AAO template and the transporting distance between the Mg vapour source and the AAO template were optimized to achieve the confinement of Mg nano-particles with larger loading rate. Under optimized deposition conditions, the particle size of the loaded Mg is less than 100 nm and the effective filling factor is about 35 wt%. The confined Mg/MgH2 even after 10 de-/hydrogenation cycles still shows favourable kinetics. Furthermore, the slight reduction in hydrogen desorption enthalpy and entropy of MgH2 from（74.42 ± 0.12） to（73.21 ± 0.04） k J·mol^-1 and（130.98 ±0.05） to（130.11 ± 0.24） Jámol^-1·K^-1 is also found in the present nano-confinement.

Nano-confinement of biomolecules： Hydrophilic confinement promotes structural order and enhances mobility of water molecules

Molecular dynamics simulations have been used to investigate the confinement packing characteristics of small hydrophilic （N-acetyl-glycine-methylamide, Nagma） and hydrophobic （N-acetyl-leucine-methylamide, Nalma） biomolecules in large diameter single-wall carbon nanotubes （SWCNTs）. We find that hydrophilic biomolecules easily fill the nanotube and self organize into a geometrical configuration which reminds the water structural organization under SWCNT confinement. The packing of hydrophilic biomolecules inside the cylinder confines all water molecules in its core, which enhances their mobility. Conversely, hydrophobic biomolecules accommodate into the nanotubes with a trend for homogeneous filling, which generate unstable small pockets of water and drive toward a state of dehydration. These results shed light on key parameters important for the encapsulation of biomolecules with direct relevance for long-term storage and prevention of degradation.

Robust architecture of 2D nano Mg-based borohydride on graphene with superior reversible hydrogen storage performance

Efficient technical strategies to synthesize hydrides with high capacity and favorable reversibility are significant for the development of novel energy materials.Herein,nano Mg-based borohydride,Mg(BH_(4))_(2),with robust architecture was designed and prepared by confining on graphene through a solution selfconfinement method.The Mg(BH_(4))_(2) confined on graphene displays a wrinkled 2D nano layer morphology within 8.8 nm thickness.Such 2D nano Mg(BH_(4))_(2) can start dehydrogenation at 67.9℃ with a high capacity of 12.0 wt.%,which is 190.5℃ lower than pristine Mg(BH_(4))_(2).The isothermal dehydrogenation tests and kinetics fitting results indicate the 2D nano Mg(BH_(4))_(2) possesses much-enhanced dehydrogenation kinetics of 31.3 kJ/mol activation energy,which is only half of pristine Mg(BH_(4))_(2).The thermodynamics of the 2D nano Mg(BH_(4))_(2) is also verified by PCT tests,of which Gibbs free energy value for the confined 2D nano Mg(BH_(4))_(2) is estimated to be-18.01 kJ/mol H_(2),lower than-16.36 kJ/mol H_(2) of pristine Mg(BH_(4))_(2).Importantly,the reversibility of the confined 2D nano Mg(BH_(4))_(2) is significantly enhanced to over 90%capacity retention with relatively kinetics stability during 10 cycles.The mechanism analyses manifest that Mg(BH_(4))_(2) exhibits stable 2D nano morphology during 10 cyclic tests,resulting in the greatly reduced H diffusion path and the improved de/rehydrogenation kinetics of the 2D nano Mg(BH_(4))_(2).Based on theoretical calculations of Mg(BH_(4))_(2) and the intermediate MgB12H12 confined on graphene,the charge transfer status of both samples is modified to facilitate de/rehydrogenation,thus leading to the significant thermodynamic improvements of the reversible hydrogen storage performances for 2D nano Mg(BH_(4))_(2).Such investigation of the Mg-based borohydride will illuminate prospective technical research of energy storage materials.

Recyclable nanocellulose-confined palladium nanoparticles with enhanced room-temperature catalytic activity and chemoselectivity

We describe the synthesis of even-dispersed palladium nanoparticles(Pd NPs)confined within a cellulose nanofiber(CNF)matrix for developing a high-performance and recyclable catalyst.The CNF matrix was composed of CNF-assembled mesoporous nanosheets and appeared as soft and hydrophilic foam.Ultrafine Pd NPs(∼6 nm)with high-loading(9.6 wt%)were in situ grown on these mesoporous nanosheets,and their dense spatial distributions were likely to generate nano-confinement catalytic effects on the reactants.Consequently,the CNF-confined Pd NPs(CNF-Pd)exhibited an enhanced room-temperature catalytic activity on the model reaction of 4-nitrophenol hydrogenation with a highest rate constant of 8.8×10^−3 s^−1 and turnover frequency of 2640 h The CNF Pd catalyst possessed good chemical stability and recyclability in aqueous media which could be reused for at least six cycles without losing activity.Moreover,chemoselective reduction of 3 nitrostyrene was achieved with high yield(80%–98%)of 3-aminostyrene in alcohol/water cosolvent.Overall,this work demonstrates a positive nanoconfinement effect of CNFs for developing stable and recyclable metal NP catalysts.

Oscillating friction of nanoscale capillary bridge

The presence of a capillary bridge between solid surfaces is ubiquitous under ambient conditions.Usually,it leads to a continuous decrease of friction as a function of bridge height.Here,using molecular dynamics we show that for a capillary bridge with a small radius confined between two hydrophilic elastic solid surfaces,the friction oscillates greatly when decreasing the bridge height.The underlying mechanism is revealed to be a periodic ordered-disordered transition at the liquid–solid interfaces.This transition is caused by the balance between the surface tension of the liquid–vapor interface and the elasticity of the surface.This balance introduces a critical size below which the friction oscillates.Based on the mechanism revealed,a parameter-free analytical model for the oscillating friction was derived and found to be in excellent agreement with the simulation results.Our results describe an interesting frictional phenomenon at the nanoscale,which is most prominent for layered materials.

Storage dynamics of ions on graphene

Carbon has been widely utilized as electrode in electrochemical energy storage,relying on the interaction between ions and electrode.The performance of a carbon electrode is determined by a variety of factors including the structural features of carbon material and the behavior of ions adsorbed on the carbon surface in the specific environment.As the fundamental unit of graphitic carbons,graphene has been employed as a model to understand the energy storage mechanism of carbon materials through various experimental and computational methods,ex‐situ or in‐situ.In this article,we provide a succinct overview of the state‐of‐the‐art proceedings on the ion storage mechanism on graphene.Topics include the structure engineering of carbons,electric gating effect of ions,ion dynamics on the interface or in the confined space,and specifically lithium‐ion storage/reaction on graphene.Our aim is to facilitate the understanding of electrochemistry on carbon electrodes.