Recent advances in the nanoconfinement of Mg-related hydrogen storage materials:A minor review

Hydrogen is an ideal clean energy because of its high calorific value and abundance of sources.However,storing hydrogen in a compact,inexpensive,and safe manner is the main restriction on the extensive utilization of hydrogen energy.Magnesium(Mg)-based hydrogen storage material is considered a reliable solid hydrogen storage material with the advantages of high hydrogen storage capacity(7.6wt%),good performance,and low cost.However,the high thermodynamic stability and slow kinetics of Mg-based hydrogen storage materials have to be overcome.In this paper,we will review the recent advances in the nanoconfinement of Mg-related hydrogen storage materials by loading Mg particles on different supporting materials,including carbons,metal-organic frameworks,and other materials.Perspectives are also provided for designing high-performance Mg-based materials using nanoconfinement.

A transient model integrating the nanoconfinement effect and pore structure characteristics of oil transport through nanopores

Understanding the integrated transport behavior of oil in shale nanopores is critical to efficient shale oil development. In this paper, based on the time-dependent Poiseuille flow momentum equation, we present a novel transient model to describe oil transport in unsteady and steady states. The model incorporates the effect of the critical shift density, apparent viscosity, slip length, and alkane property, as well as pore tortuosity and surface roughness. We evaluated our model through a comparison with other models, experiments, and molecular dynamics simulations. The results show that the development rates of the volume flows of C_(6)–C_(12) alkane confined in inorganic nanopores and C_(12) alkane confined in organic nanopores were faster than that of the corresponding bulk alkane. In addition, the critical drift density positively promoted the volume flow development rate in the unsteady state and negatively inhibited the mass flow rate in the steady state. This effect was clearest in pores with a smaller radius and lower-energy wall and in alkane with shorter chain lengths. Furthermore, both the nanoconfinement effect and pore structure determined whether the volume flow enhancement rate was greater than or less than 1. The rate increased or decreased with time and was controlled mainly by the nanoconfinement effect. Moreover, as the wall energy increased, the flow inhibition effect increased;as the carbon number of alkane increased, the flow promotion effect increased. The results indicate that the proposed model can accurately describe oil transport in shale nanopores.

Nanoconfinement effect of nanoporous carbon electrodes for ionic liquid-based aluminum metal anode

Rechargeable aluminum batteries(RABs),which use earth-abundant and high-volumetric-capacity metal anodes(8040 m Ah cm-3),have great potential as next-generation power sources because they use cheaper resources to deliver higher energies,compared to current lithium ion batteries.However,the mechanism of charge delivery in the newly developed,ionic liquid-based electrolytic system for RABs differs from that in conventional organic electrolytes.Thus,targeted research efforts are required to address the large overpotentials and cycling decay encountered in the ionic liquid-based electrolytic system.In this study,a nanoporous carbon(NPC)electrode with well-developed nanopores is used to develop a high-performance aluminum anode.The negatively charged nanopores can provide quenched dynamics of electrolyte molecules in the aluminum deposition process,resulting in an increased collision rate.The fast chemical equilibrium of anionic species induced by the facilitated anionic collisions leads to more favorable reduction reactions that form aluminum metals.The nanoconfinement effect causes separated nucleation and growth of aluminum nanoparticles in the multiple confined nanopores,leading to higher coulombic efficiencies and more stable cycling performance compared with macroporous carbon black and 2D stainless steel electrodes.

A review on nanoconfinement engineering of red phosphorus for enhanced Li/Na/K-ion storage performances

Secondary batteries are widely used in energy storage equipment.To obtain high-performance batteries,the development and utilization of electrode materials with cheap price and ideal theoretical gravimetric and volumetric specific capacities have become particularly important.Naturally abundant and low-cost red phosphorus(RP)is recognized as an anode material with great promise because it has a theoretical capacity of 2596 mA h g^(-1) in lithium-ion batteries(LIBs)and sodium-ion batteries(SIBs).However,owing to the inferior discharging,the capacity of pure RP has a fast decay.Nanoconfinement of RP nanoparticles within porous carbon framework is one of the efficient methods to overcome these problems.In this review,we introduce the recent progress of RP confinement into carbon matrix as an energy storage anode material in LIBs,SIBs and potassium-ion batteries(PIBs).The synthetic strategies,lithiation/sodia tion/potassiation mechanism,and the electrochemical performances of RP/carbon composites(RP/C)with kinds of designed structures and P-C and P-O-C bond by kinds of methods are included.Finally,the challenges and perspectives of RP faced in the application development as anodes for LIBs/SIBs/PIBs are covered.This review will strengthen the understanding of composites of RP nanoparticles in porous carbon materials and aid researchers to carry out future work rationally.

Nitrogen-doped microporous graphite-enhanced copper plasmonic effect for solar evaporation

Water scarcity is a global challenge,and solar evaporation technology offers a promising and eco-friendly solution for freshwater production.Photothermal conversion materials(PCMs)are crucial for solar evaporation.Improving photothermal conversion efficiency and reducing water evaporation enthalpy are the two key strategies for the designing of PCMs.The desired PCMs that combine both of these properties remain a challenging task,even with the latest advancements in the field.Herein,we developed copper nanoparticles(NPs)with different conjugated nitrogen-doped microporous carbon coatings(Cu@C–N)as PCMs.The microporous carbon enveloping layer provides a highly efficient pathway for water transport and a nanoconfined environment that protects Cu NPs and facilitates the evaporation of water clusters,reducing the enthalpy of water evaporation.Meanwhile,the conjugated nitrogen nodes form strong metal-organic coordination bonds with the surface of copper NPs,acting as an energy bridge to achieve rapid energy transfer and provide high solar-to-vapor conversion efficiency.The Cu@C–N exhibited up to 89.4%solar-to-vapor conversion efficiency and an evaporation rate of 1.94 kgm^(−2) h^(−1) under one sun irradiation,outperforming conventional PCMs,including carbon-based materials and semiconductor materials.These findings offer an efficient design scheme for high-performance PCMs essential for solar evaporators to address global water scarcity.

Lamellar water induced quantized interlayer spacing of nanochannels walls

The nanoscale confinement is of great important for the industrial applications of molecular sieve,desalination,and also essential in bio-logical transport systems.Massive efforts have been devoted to the influence of restricted spaces on the properties of confined fluids.However,the situation of channel-wall is crucial but attracts less attention and remains unknown.To fundamentally understand the mechanism of channel-walls in nanoconfinement,we investigated the interaction between the counter-force of the liquid and interlamellar spacing of nanochannel walls by considering the effect of both spatial confinement and surface wettability.The results reveal that the nanochannel stables at only a few discrete spacing states when its confinement is within 1.4 nm.The quantized interlayer spacing is attributed to water molecules becoming laminated structures,and the stable states are corresponding to the monolayer,bilayer and trilayer water configurations,respectively.The results can potentially help to understand the characterized interlayers spacing of graphene oxide membrane in water.Our findings are hold great promise in design of ion filtration membrane and artificial water/ion channels.

Constant charge method or constant potential method:Which is better for molecular modeling of electrical double layers?

In molecular modeling of electrical double layers(EDLs),the constant charge method(CCM)is prized for its computational efficiency but cannot maintain electrode equipotentiality like the more resourceintensive constant potential method(CPM),potentially leading to inaccuracies.In certain scenarios,CCM can yield results identical to CPM.However,there are no clear guidelines to determine when CCM is sufficient and when CPM is required.Here,we conduct a series of molecular simulations across various electrodes and electrolytes to present a comprehensive comparison between CCM and CPM under different charging modes.Results reveal that CCM approximates CPM effectively in capturing equilibrium EDL and current-driven dynamics in open electrode systems featuring ionic liquids or regular concentration aqueous electrolytes,while CPM is indispensable in scenarios involving organic and highly concentrated aqueous electrolytes,nanoconfinement effects,and voltage-driven dynamics.This work helps to select appropriate methods for modeling EDL systems,prioritizing accuracy while considering computationalefficiency.

Enhanced reversible hydrogen storage properties of wrinkled graphene microflowers confined LiBH_(4) system with high volumetric hydrogen storage capacity

LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nanoconfinement is effective in achieving low dehydrogenation temperature and favorable reversibility.Besides,graphene can serve as supporting materials for LiBH_(4)catalysts and also destabilize LiBH_(4)via interfacial reaction.However,graphene has never been used alone as a frame material for nanoconfining LiBH_(4).In this study,graphene microflowers with large pore volumes were prepared and used as nanoconfinement framework material for LiBH_(4),and the nanoconfinement effect of graphene was revealed.After loading 70 wt%of LiBH_(4) and mechanically compressed at 350 MPa,8.0 wt% of H2 can be released within 100 min at 320C,corresponding to the highest volumetric hydrogen storage density of 94.9 g H2 L^(-1)ever reported.Thanks to the nanoconfinement of graphene,the rate-limiting step of dehydrogenation of nanoconfined LiBH_(4) was changed and its apparent activation energy of the dehydrogenation(107.3 kJ mol^(-1))was 42%lower than that of pure LiBH_(4).Moreover,the formation of the intermediate Li_(2)B_(12)H_(12) was effectively inhibited,and the stable nanoconfined structure enhanced the reversibility of LiBH_(4).This work widens the understanding of graphene's nanoconfinement effect and provides new insights for developing high-density hydrogen storage materials.

Weakly hydrophobic nanoconfinement by graphene aerogels greatly enhances the reactivity and ambient stability of reactivity of MIL-101-Fe in Fenton-like reaction

In the pursuit of heterogeneous catalysts with high reactivity,metal organic framework(MOF)nanomaterials have received tremendous attentions.However,many MOF catalysts especially Fe-based MOFs need to be utilized immediately after synthesis or being activated using high temperature,because of the easy loss of reactivity in humid environments resulting from the occupation of active Fe sites by water molecules.Here,we describe an inspiring strategy of growing MIL-101-Fe nanoparticles inside the three-dimensional confined space of graphene aerogel(GA),generating shapeable GA/MIL-101-Fe nanocomposite convenient for practical use.Compared to MIL-101-Fe,GA/MIL-101-Fe as catalyst demonstrates much higher reactivity in Fenton-like reaction,attributing to smaller MIL-101-Fe particle size,presence of active Fe(II)sites,and abundant defects in GA.Strikingly,the weakly hydrophobic nature of the composite greatly inhibits the loss of catalytic reactivity after being stored in humid air and accelerates the recovery of reactivity in mild temperature,by resisting the entrance of water molecules and helping to exclude water molecules.This work demonstrates that a delicate design of nanocomposite structure could not only improve the reactivity of the catalytic component,but also overcome its intrinsic drawback by taking advantage of the properties of host.We hope this functional nanoconfinement strategy could be extended to more scenarios in other fields.

Physical Properties of Polymers under Soft and Hard Nanoconfinement: A Review

Polymeric materials under nanoconfinements have substantially deviated physical properties with respect to the bulk,especially glass transition temperature,physical aging,and crystallization behavior.Here we highlight the leading methods for creating various confinement systems.Upon these systems,recent advances on hard and soft confinement effect for glass transition,physical aging,mechanical properties and crystallization of polymers are reviewed in details.Furthermore,as nanoconfined systems in extreme conditions are experimentally inaccessible,simulation results describing confinement effect on such systems are also discussed.

A balance between catalysis and nanoconfinement towards enhanced hydrogen storage performance of NaAlH_(4)

Owing to its favorable thermodynamics and high density,NaAlH_(4) has been widely regarded as a potential hydrogen storage material,but its practical application is hindered by the sluggish kinetics,high operating temperature and poor cycling stability.Here,taking advantage of Co-doped nanoporous carbon scaffolds as structural host,we develop a new strategy to balance the synergistic effect between the catalytic role of Co nanoparticles and the nanoconfinement role of porous carbon scaffolds via the controllable etching of Co nanoparticles towards enhanced hydrogen storage performance of NaAlH_(4).The etching of Co nanoparticles creates extra void spaces nearby catalytically active Co nanoparticles,which not only exerts the catalytic effect of Co nanoparticles,but also improves the nanoconfinement role in maintaining the cycling stability towards increased loading ratio and hence high systematic capacity.Induced by this balanced synergistic effect,the peak temperature for the dehydrogenation of NaAlH_(4) could be reduced to 164°C,97°C lower than the bulk counterpart,even under an ultrahigh loading ratio of 67%,and more importantly,the reversible systematic hydrogen storage capacity could still reach 3.3 wt.%after 5 cycles.This work opens up a new avenue to improve the hydrogen storage performance of various complex hydrides.

利用商用凝胶型离子交换树脂实现超微纳米颗粒的大规模生产与高效水处理

纳米技术为深度水处理提供了新的机遇。然而,高活性超微(<5 nm)纳米颗粒材料的大规模生产仍存在挑战,且超微材料在实际水处理中也存在操作困难等问题,阻碍了纳米技术在水污染控制领域的推广应用。针对这些问题,我们提出了一种简便的解决方法,即以商用凝胶型离子交换树脂N201为载体合成超微纳米颗粒。N201是一种季铵化的毫米级聚(苯乙烯二乙烯基苯共聚)小球。在N2O1中通过简单的浸渍-沉淀获得了水合氧化铁(HFO)、水合氧化锰(HMO)、硫化镉(CdS)和零价铁(ZVI)等纳米颗粒,所有纳米颗粒的尺寸都小于5 nm。中试生产表明该合成方法可方便放大,并制备了大量亚5 nm HFO颗粒。关于超微纳米颗粒的合成机理,我们认为在每个在水中溶胀的N201小球内都包含连续均匀水相,使反应物可快速地扩散到树脂球内部(7 s内从小球表面扩散到中心),从而实现纳米颗粒的爆发成核,形成超窄尺寸分布的晶核。此外,交联聚合物链间还可形成狭窄的孔隙(直径<5 nm),可防止在其中形成的纳米颗粒过度生长。由于N201载体具有毫米级尺寸,所制备复合的纳米材料可方便用于连续流装置中。批次实验和柱吸附测试表明,超微HFO颗粒对As(Ⅲ/Ⅴ)的吸附性能比约17 nm的HFO显著增强。本研究有望进一步促进纳米技术在实际水处理中的推广应用。

Affinity-Engineered Flexible Scaffold toward Energy-Dense, Highly Reversible Na Metal Batteries

The practical deployment of metallic anodes in the energy-dense batteries is impeded by the thermodynamically unstable interphase in contact with the aprotic electrolyte,structural collapse of the substrates as well as their insufficient affinity toward the metallic deposits.Herein,the mechanical flexible,lightweight(1.2 mg cm^(−2))carbon nanofiber scaffold with the monodispersed,ultrafine Sn_(4)P_(3) nanoparticles encapsulation(Sn_(4)P_(3)NPs@CNF)is proposed as the deposition substrate toward the high-areal-capacity sodium loadings up to 4 mAh cm^(−2).First-principles calculations manifest that the alloy intermediates,namely the Na_(15)Sn_(4) and Na_(3)P matrix,exhibit the intimate Na affinity as the“sodiophilic”sites.Meanwhile,the porous CNF regulates the heterogeneous alloying process and confines the deposit propagation along the nanofiber orientation.With the precise control of pairing mode with the NaVPO4F cathode(8.7 mg cm^(−2)),the practical feasibility of the Sn_(4)P_(3) NPs@CNF anode(1^(*)Na excess)is demonstrated in 2 mAh single-layer pouch cell prototype,which achieves the 95.7%capacity retention for 150 cycles at various mechanical flexing states as well as balanced energy/power densities.

Oxygen Vacancy-Rich 2D TiO_(2) Nanosheets:A Bridge Toward High Stability and Rapid Hydrogen Storage Kinetics of Nano-Confined MgH_(2)

MgH_(2) has attracted intensive interests as one of the most promising hydrogen storage materials.Nevertheless,the high desorption temperature,sluggish kinetics,and rapid capacity decay hamper its commercial application.Herein,2D TiO_(2) nanosheets with abundant oxygen vacancies are used to fabricate a flower-like MgH_(2)/TiO_(2) heterostructure with enhanced hydrogen storage performances.Particularly,the onset hydrogen desorption temperature of the MgH_(2)/TiO_(2) heterostructure is lowered down to 180℃(295℃ for blank MgH_(2)).The initial desorption rate of MgH_(2)/TiO_(2) reaches 2.116 wt% min^(-1) at 300℃,35 times of the blank MgH_(2) under the same conditions.Moreover,the capacity retention is as high as 98.5% after 100 cycles at 300℃,remarkably higher than those of the previously reported MgH_(2)-TiO_(2) composites.Both in situ HRTEM observations and ex situ XPS analyses confirm that the synergistic effects from multi-valance of Ti species,accelerated electron transportation caused by oxygen vacancies,formation of catalytic Mg-Ti oxides,and stabilized MgH_(2) NPs confined by TiO_(2) nanosheets contribute to the high stability and kinetically accelerated hydrogen storage performances of the composite.The strategy of using 2D substrates with abundant defects to support nano-sized energy storage materials to build heterostructure is therefore promising for the design of high-performance energy materials.

Hierarchically porous S-scheme CdS/UiO-66 photocatalyst for efficient 4-nitroaniline reduction

Unveiling the pore-size performance of metal organic frameworks(MOFs)is imperative for controllable design of sophisticated catalysts.Herein,UiO-66 with distinct macropores and mesopores were intentionally created and served as substrates to create advanced CdS/UiO-66 catalysts.The pore size impacted the spatial distribution of CdS nanoparticles(NPs):CdS tended to deposit on the external surface of mesoporous UiO-66,but spontaneously penetrated into the large cavity of macroporous UiO-66 nanocage.Normalized to unit amount of CdS,the photocatalytic reaction constant of macroporous CdS/UiO-66 over 4-nitroaniline reduction was~3 folds of that of mesoporous counterpart,and outperformed many other reported state-of-art CdS-based catalysts.A confinement effect of CdS NPs within UiO-66 cage could respond for its high activity,which could shorten the electron-transport distance of NPs-MOFs-reactant,and protect the active CdS NPs from photocorrosion.The finding here provides a straightforward paradigm and mechanism to rationally fabricate advance NPs/MOFs for diverse applications.

Molecular insights on Ca^(2+)/Na+separation via graphene-based nanopores:The role of electrostatic interactions to ionic dehydration

Ca^(2+)/Na+separation is a common problem in industrial applications,biological and medical fields.However,Ca^(2+)and Na+have similar ionic radii and hydration radii,thus Ca^(2+)/Na+separation is challenging.Inspired by biological channels,group modification is one of the effective methods to improve the separation performance.In this work,molecular dynamics simulations were performed to investigate the effects of different functional groups(COO,NH3+)on the separation performance of Ca^(2+)and Na+through graphene nanopores under an electric field.The pristine graphene nanopore was used for comparison.Results showed that three types of nanopores preferred Ca^(2+)to Na+,and Ca^(2+)/Na+selectivity followed the order of GE-COO(4.06)>GE(1.85)>GE-NH3+(1.63).Detailed analysis of ionic hydration microstructure shows that different nanopores result in different hydration factors for the second hydration layer of Ca^(2+)and the first layer of Na+.Such different hydration factors corresponding to the dehydration ability can effectively evaluate the separation performance.In addition,the breaking of hydrogen bonds between water molecules due to electrostatic effects can directly affect the dehydration ability.Therefore,the electrostatic effect generated by group modification will affect the ionic hydration microstructure,thus reflecting the differences in dehydration ability.This in turn affects the permeable and separation performance of cations.The results of this work provide perceptive guidelines for the application of graphene-based membranes in ion separation.

Progress in molecular-simulation-based research on the effects of interface-induced fluid microstructures on flow resistance

In modern chemical engineering processes, solid interface involvement is the most important component of process intensification techniques, such as nanoporous membrane separation and heterogeneous catalysis. The fundamental mechanism underlying interfacial transport remains incompletely understood given the complexity of heterogeneous interfacial molecular interactions and the high nonideality of the fluid involved. Thus, understanding the effects of interface-induced fluid microstructures on flow resistance is the first step in further understanding interfacial transport. Molecular simulation has become an indispensable method for the investigation of fluid microstructure and flow resistance. Here, we reviewed the recent research progress of our group and the latest relevant works to elucidate the contribution of interface-induced fluid microstructures to flow resistance.We specifically focused on water, ionic aqueous solutions, and alcohol–water mixtures given the ubiquity of these fluid systems in modern chemical engineering processes. We discussed the effects of the interfaceinduced hydrogen bond networks of water molecules, the ionic hydration of ionic aqueous solutions, and the spatial distributions of alcohol and alcohol–water mixtures on flow resistance on the basis of the distinctive characteristics of different fluid systems.

Bioinspired ionic control for energy and information flow

The control of ion transport by responding to stimulus is a necessary condition for the existence of life.Bioinspired iontronics could enable anomalous ion dynamics in the nano-confined spaces,creating many efficient energy systems and neuromorphic in-sensor computing networks:Unlike tradi-tional electronics based on von Neumann computing architec-ture,the Boolean logic computing based on the iontronics could avoid complex wiring with higher energy efficiency and programmable neuromorphic logic.Here,a systematic summary on the state of art in bioinspired iontronics is pre-sented and the stimulus from chemical potentials,electric fields,light,heat,piezo and magnetic fields on ion dynamics are reviewed.Challenges and perspectives are also addressed in the aspects of iontronic integrated systems.It is believed that comprehensive investigations in bioinspired ionic control will accelerate the development on more efficient energy and information flow for the futuristic human-machine interface.

Semiempirical equations of state of H_(2)O/CO_(2) binary mixtures in graphite nanoslits

The existence of confining walls limits the prediction accuracy of nanoconfined fluids using macroscopic equations of state(EOSs);moreover,appropriate EOSs for multicomponent mixture fluids in nanoconfined spaces are missing.Here,we derive the EOS of multicomponent mixture fluids confined in nanospaces at high temperatures and pressures,mainly considering the nanoconfinement effect and the competitive adsorption effect between different components.Then,the EOSs are validated through comparison with the molecular dynamics-simulated Pv T data of CO_(2)/H_(2)O mixtures in graphite nanoslits.To consider the above effects,we derive two EOSs via two modeling methods:EOS I is obtained through modification of the actual component occupation volume in the Peng-Robinson equation of state(PR EOS)by fitting the binary component interaction coefficient and the number of adsorbed molecules according to a selectivity coefficient,while EOS II is obtained by considering the decreased pressure of the fluids in PR EOS by adding an attractive term between components and walls.With the simulation results as a benchmark,the two EOSs exhibited good prediction accuracies under low CO_(2) concentrations,and generally,EOS II was more accurate than EOS I.This study fills the gap in the EOSs of nanoconfined mixture fluids,and the obtained equations can help to further describe the thermodynamic properties of confined mixture fluids.

The Rise and Promise of Molecular Nanotopology

Molecular nanotopology—a term we coined recently—is a rapidly developing field of research that is emerging out of the confluence of chemical topology with the mechanical bond.When perusing the increased research activities in this field,it is clear that a new discipline is ready to receive recognition in its own right.In this Mini-Review,we address the historical development of chemical topology and describe how the rational design and practical synthesis of molecular links and knots with mechanical bonds.