A universal and scalable transformation of bulk metals into single-atom catalysts in ionic liquids.

Single-atom catalysts (SACs) with maximized metal atom utilization and intriguing properties are of utmost importance for energy conversion and catalysis science. However, the lack of a straightforward and scalable synthesis strategy of SACs on diverse support materials remains the bottleneck for their large-scale industrial applications. Herein, we report a general approach to directly transform bulk metals into single atoms through the precise control of the electrodissolution-electrodeposition kinetics in ionic liquids and demonstrate the successful applicability of up to twenty different monometallic SACs and one multimetallic SAC with five distinct elements. As a case study, the atomically dispersed Pt was electrodeposited onto Ni3N/Ni-Co-graphene oxide heterostructures in varied scales (up to 5 cm × 5 cm) as bifunctional catalysts with the electronic metal-support interaction, which exhibits low overpotentials at 10 mA cm-2 for hydrogen evolution reaction (HER, 30 mV) and oxygen evolution reaction (OER, 263 mV) with a relatively low Pt loading (0.98 wt%). This work provides a simple and practical route for large-scale synthesis of various SACs with favorable catalytic properties on diversified supports using alternative ionic liquids and inspires the methodology on precise synthesis of multimetallic single-atom materials with tunable compositions.

Dual-Parasitic Effect Enables Highly Reversible Zn Metal Anode for Ultralong 25,000 Cycles Aqueous Zinc-Ion Batteries.

The use of electrolyte additives is an efficient approach to mitigating undesirable side reactions and dendrites. However, the existing electrolyte additives do not effectively regulate both the chaotic diffusion of Zn2+ and the decomposition of H2O simultaneously. Herein, a dual-parasitic method is introduced to address the aforementioned issues by incorporating 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIm]OTf) as cosolvent into the Zn(OTf)2 electrolyte. Specifically, the OTf- anion is parasitic in the solvent sheath of Zn2+ to decrease the number of active H2O. Additionally, the EMIm+ cation can construct an electrostatic shield layer and a hybrid organic/inorganic solid electrolyte interface layer to optimize the deposition behavior of Zn2+. This results in a Zn anode with a reversible cycle life of 3000 h, the longest cycle life of full cells (25,000 cycles), and an extremely high initial capacity (4.5 mA h cm-2), providing a promising electrolyte solution for practical applications of rechargeable aqueous zinc-ion batteries.

Ultrarapid Gelation of Porous Ti3C2Tx MXene Monoliths Induced by Ionic Liquids.

Gelation is a promising method to assemble 3D macroscopic structures from MXene sheets for various applications. However, the fine control and scalable manufacturing of 3D MXene monoliths remains a great challenge. Herein, the controllable gelation of Ti3C2Tx MXene initiated by various ionic liquids (ILs) is first proposed, where the IL serve as linkers to bond the nanosheets together through electrostatic and hydrogen bonding interactions, forming 3D monoliths with well-adjustable structure. Furthermore, density functional theory calculations and experiments further reveal the cross-linking effect of different ILs. Typically, 3D porous structure with high specific surface area, suitable pore size, and improved electrolyte affinity is designed through the cross-linking of Ti3C2Tx with 1-vinyl-3-ethylimidazole bromide ([C2VIm]Br-Ti3C2Tx). Due to the strong coupling, the as-synthesized monolith possesses excellent rate performance and high energy density. The methodology is quite flexible, controllable, and universal that provides a new perspective for promoting innovative applications of 2D materials.

Single-Particle Imaging Reveals the Electrical Double-Layer Modulated Ion Dynamics at Crowded Interface.

The dynamics of ion transport at the interface is the critical factor for determining the performance of an electrochemical energy storage device. While practical applications are realized in concentrated electrolytes and nanopores, there is a limited understanding of their ion dynamic features. Herein, we studied the interfacial ion dynamics in room-temperature ionic liquids by transient single-particle imaging with microsecond-scale resolution. We observed slowed-down dynamics at lower potential while acceleration was observed at higher potential. Combined with simulation, we found that the microstructure evolution of the electric double layer (EDL) results in potential-dependent kinetics. Then, we established a correspondence between the ion dynamics and interfacial ion composition. Besides, the ordered ion orientation within EDL is also an essential factor for accelerating interfacial ion transport. These results inspire us with a new possibility to optimize electrochemical energy storage through the good control of the rational design of the interfacial ion structures.

Ionic liquids intercalation in titanium carbide MXenes: A first-principles investigation.

Herein, we present a density functional theory with dispersion correction (DFT-D) calculations that focus on the intercalation of ionic liquids (ILs) electrolytes into the two-dimensional (2D) Ti3C2Tx MXenes. These ILs include the cation 1-ethyl-3-methylimidazolium (Emim+), accompanied by three distinct anions: bis(trifluoromethylsulfonyl)imide (TFSA-), (fluorosulfonyl)imide (FSA-) and fluorosulfonyl(trifluoromethanesulfonyl)imide (FTFSA-). By altering the surface termination elements, we explore the intricate geometries of IL intercalation in neutral, negative, and positive pore systems. Accurate estimation of charge transfer is achieved through five population analysis models, such as Hirshfeld, Hirshfeld-I, DDEC6 (density derived electrostatic and chemical), Bader, and VDD (voronoi deformation density) charges. In this work, we recommend the DDEC6 and Hirshfeld-I charge models, as they offer moderate values and exhibit reasonable trends. The investigation, aimed at visualizing non-covalent interactions, elucidates the role of cation-MXene and anion-MXene interactions in governing the intercalation phenomenon of ionic liquids within MXenes. The magnitude of this role depends on two factors: the specific arrangement of the cation, and the nature of the anionic species involved in the process.

A "Zn2+ in Salt" Interphase Enabling High-Performance Zn Metal Anodes.

Zinc metal is a promising anode candidate for aqueous zinc ion batteries due to its high theoretical capacity, low cost, and high safety. However, its application is currently restricted by hydrogen evolution reactions (HER), by-product formation, and Zn dendrite growth. Herein, a "Zn2+ in salt" (ZIS) interphase is in situ constructed on the surface of the anode (ZIS@Zn). Unlike the conventional "Zn2+ in water" working environment of Zn anodes, the intrinsic hydrophobicity of the ZIS interphase isolates the anode from direct contact with the aqueous electrolyte, thereby protecting it from HER, and the accompanying side reactions. More importantly, it works as an ordered water-free ion-conducting medium, which guides uniform Zn deposition and facilitates rapid Zn2+ migration at the interface. As a result, the symmetric cells assembled with ZIS@Zn exhibit dendrite-free plating/striping at 4500 h and a high critical current of 14 mA cm-2. When matched with a vanadium-based (NVO) cathode, the full battery exhibits excellent long-term cycling stability, with 88% capacity retention after 1600 cycles. This work provides an effective strategy to promote the stability and reversibility of Zn anodes in aqueous electrolytes.

Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO2.

The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO2 (400 ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO2 insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400 ppm) CO2 from gas mixtures via O─C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using 13C-labeled CO2 sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40 kJ mol-1 between CO2 and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO2 release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO2 insertion. The as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO2 in crystalline scaffolds.

Elimination of Intragrain Defect to Enhance the Performance of FAPbI3 Perovskite Solar Cells by Ionic Liquid.

Ionic liquids have been widely used to improve the efficiency and stability of perovskite solar cells (PSCs), and are generally believed to passivate defects on the grain boundaries of perovskites. However, few studies have focused on the relevant effects of ionic liquids on intragrain defects in perovskites which have been shown to be critical for the performance of PSCs. In this work, the effect of ionic liquid 1-hexyl-3-methylimidazolium iodide (HMII) on intragrain defects of formamidinium lead iodide (FAPbI3) perovskite is investigated. Abundant {111}c intragrain planar defects in pure FAPbI3 grains are found to be significantly reduced by the addition of the ionic liquid HMII, shown by using ultra-low-dose selected area electron diffraction. As a result, longer charge carrier lifetimes, higher photoluminescence quantum yield, better charge carrier transport properties, lower Urbach energy, and current-voltage hysteresis are achieved, and the champion power conversion efficiency of 24.09% is demonstrated. These observations suggest that ionic liquids significantly improve device performance resulting from the elimination of {111}c intragrain planar defects.

Bioinspired Synaptic Branched Network within Quasi-Solid Polymer Electrolyte for High-Performance Microsupercapacitors.

The branched network-driven ion solvating quasi-solid polymer electrolytes (QSPEs) are prepared via one-step photochemical reaction. A poly(ethylene glycol diacrylate) (PEGDA) is combined with an ion-conducting solvate ionic liquid (SIL), where tetraglyme (TEGDME), which acts like interneuron in the human brain and creates branching network points, is mixed with EMIM-NTf2 and Li-NTf2. The QSPE exhibits a unique gyrified morphology, inspired by the cortical surface of human brain, and features well-refined nano-scale ion channels. This human-mimicking method offers excellent ion transport capabilities through a synaptic branched network with high ionic conductivity (σDC ≈ 1.8 mS cm-1 at 298 K), high dielectric constant (εs ≈ 125 at 298 K), and strong ion solvation ability, in addition to superior mechanical flexibility. Furthermore, the interdigitated microsupercapacitors (MSCs) based on the QSPE present excellent electrochemical performance of high energy (E  =  5.37 µWh cm-2) and power density (P  =  2.2 mW cm-2), long-term cycle stability (≈94% retention after 48 000 cycles), and mechanical stability (>94% retention after continuous bending and compressing deformation). Moreover, these MSC devices have flame-retarding properties and operate effectively in air and water across a wide temperature range (275 to 370 K), offering a promising foundation for high-performance, stable next-generation all-solid-state energy storage devices.

Amphiphilic Nanoscale Antifog Coatings: Improved Chemical Robustness by Continuous Assembly of Polymers.

Designing effective antifog coatings poses challenges in resisting physical and chemical damage, with persistent susceptibility to decomposition in aggressive environments. As their robustness is dictated by physicochemical structural features, precise control through unique fabrication strategies is crucial. To address this challenge, a novel method for crafting nanoscale antifog films with simultaneous directional growth and cross-linking is presented, utilizing solid-state continuous assembly of polymers via ring-opening metathesis polymerization (ssCAPROMP). A new amphiphilic copolymer (specified as macrocross-linker) is designed by incorporating polydimethylsiloxane, poly(2-(methacryloyloxy)ethyl) trimethylammonium chloride (PMETAC), and polymerizable norbornene (NB) pendant groups, allowing ssCAPROMP to produce antifog films under ambient conditions. This novel approach results in distinctive surface and molecular characteristics. Adjusting water-absorption and nanoscale assembly parameters produced ultra-thin (≤100 nm) antifog films with enhanced durability, particularly against strong acidic and alkaline environments, surpassing commercial antifog glasses. Thickness loss analysis against external disturbances further validated the stable surface-tethered chemistries introduced through ssCAPROMP, even with the incorporation of minimal content of cross-linkable NB moieties (5 mol%). Additionally, a potential zwitter-wettability mechanism elucidates antifog observations. This work establishes a unique avenue for exploring nanoengineered antifog coatings through facile and robust surface chemistries.

Ternary Heteroatomic Doping Induced Microenvironment Engineering of Low Fe-N4-Loaded Carbon Nanofibers for Bifunctional Oxygen Electrocatalysis.

Fabricating highly efficient and long-life redox bifunctional electrocatalysts is vital for oxygen-related renewable energy devices. To boost the bifunctional catalytic activity of Fe-N-C single-atom catalysts, it is imperative to fine-tune the coordination microenvironment of the Fe sites to optimize the adsorption/desorption energies of intermediates during oxygen reduction/evolution reactions (ORR/OER) and simultaneously avoid the aggregation of atomically dispersed metal sites. Herein, a strategy is developed for fabricating a free-standing electrocatalyst with atomically dispersed Fe sites (≈0.89 wt.%) supported on N, F, and S ternary-doped hollow carbon nanofibers (FeN4 -NFS-CNF). Both experimental and theoretical findings suggest that the incorporation of ternary heteroatoms modifies the charge distribution of Fe active centers and enhances defect density, thereby optimizing the bifunctional catalytic activities. The efficient regulation isolated Fe centers come from the dual confinement of zeolitic imidazole framework-8 (ZIF-8) and polymerized ionic liquid (PIL), while the precise formation of distinct hierarchical three-dimensional porous structure maximizes the exposure of low-doping Fe active sites and enriched heteroatoms. FeN4 -NFS-CNF achieves remarkable electrocatalytic activity with a high ORR half-wave potential (0.90 V) and a low OER overpotential (270 mV) in alkaline electrolyte, revealing the benefit of optimizing the microenvironment of low-doping iron single atoms in directing bifunctional catalytic activity.

Ionic Liquids Modulating Local Microenvironment of Ni-Fe Binary Single Atom Catalyst for Efficient Electrochemical CO2 Reduction.

The Ni and Fe dual-atom catalysts still undergo strikingly attenuation under high current density and high overpotential. To ameliorate the issue, the ionic liquids with different cations or anions are used in this work to regulate the micro-surface of nitrogen-doped carbon supported Ni and Fe dual-atom sites catalyst (NiFe-N-C) by an impregnation method. The experimental data reveals the dual function of ionic liquids, which enhances CO2 adsorption ability and modulates electronic structure, facilitating CO2 anion radical (CO2 •¯) stabilization and decreasing onset potential. The theoretical calculation results prove that the attachment of ionic liquids modulates electronic structure, reduces energy barrier of CO2 •¯ formation, and enhances overall ECR performance. Based on these merits, BMImPF6 modified NiFe-N-C (NiFe-N-C/BMImPF6) achieves the high CO faradaic efficiency of 91.9% with a CO partial current density of -120 mA cm-2 at -1.0 V. When the NiFe-N-C/BMImPF6 is assembled as cathode of Zn-CO2 battery, it delivers the highest power density of 2.61 mW cm-2 at 2.57 mA cm-2 and superior cycling stability. This work will afford a direction to modify the microenvironment of other dual-atom catalysts for high-performance CO2 electroreduction.

Stabilizing High-Valence Copper(I) Sites with Cu-Ni Interfaces Enhances Electroreduction of CO2 to C2+ Products.

In this study, the copper-nickel (Cu-Ni) bimetallic electrocatalysts for electrochemical CO2 reduction reaction(CO2RR) are fabricated by taking the finely designed poly(ionic liquids) (PIL) containing abundant Salen and imidazolium chelating sites as the surficial layer, wherein Cu-Ni, PIL-Cu and PIL-Ni interaction can be readily regulated by different synthetic scheme. As a proof of concept, Cu@Salen-PIL@Ni(NO3)2 and Cu@Salen-PIL(Ni) hybrids differ significantly in the types and distribution of Ni species and Cu species at the surface, thereby delivering distinct Cu-Ni cooperation fashion for the CO2RR. Remarkably, Cu@Salen-PIL@Ni(NO3)2 provides a C2+ faradaic efficiency (FEC2+) of 80.9% with partial current density (jC 2+) of 262.9 mA cm-2 at -0.80 V (versus reversible hydrogen electrode, RHE) in 1 m KOH in a flow cell, while Cu@Salen-PIL(Ni) delivers the optimal FEC2+ of 63.8% at jC2+ of 146.7 mA cm-2 at -0.78 V. Mechanistic studies indicates that the presence of Cu-Ni interfaces in Cu@Salen-PIL@Ni(NO3)2 accounts for the preserve of high-valence Cu(I) species under CO2RR conditions. It results in a high activity of both CO2-to-CO conversion and C-C coupling while inhibition of the competitive HER.

Assessing Solid Catalysts with Ionic Liquid Layers (SCILL) from Molecular Dynamics Simulations: On the role of local charge polarization.

Recent developments in molecular mechanics modelling of metal catalyst surfaces with interfaces to complex ad-layers or bulk liquids enable the study of 10 nm scale systems by molecular dynamics simulations of up to microseconds. Therein, electronic polarization as otherwise benchmarked by quantum calculations is mimicked via atom-centered partial charges that are adjusted dynamically to account for changes in local environment. Apart from thermal fluctuations, this encompasses molecule association and dissociation processes as well as externally applied voltage. Here, we elaborate the concept of employing the charge equilibration method to the molecular dynamics simulation of solid catalysts, namely metal surfaces and substrate-supported metal nanoparticles. This showcases the association of reactants and their interplay with local charge polarization upon co-adsorption of ionic liquids or application of external voltage - thus paving the way to understanding complex interfaces in (electro-)catalysis from molecular dynamics simulation.

Replacement of Toxic Hydrazines in Satellite Propulsion with Greener Dinitramide-Based Energetic Ionic Liquid Candidates.

Satellite propulsion uses liquid mono or bi-propellants composed of a hydrazine in combination with a strong oxidant. However, hydrazines are highly toxic. As a result, many research efforts for more environmentally compatible propellants have been made over the past decade. In this study we evidence green formulations that retain high propulsive performances. They are based on the dinitramide anion. From an initial library of 37 ammonium dinitramides 3 best candidates were selected after evaluation of their potential syntheses, calculated theoretical performances, experimental synthesis optimizations and decomposition temperatures. These three salts were then formulated to obtain acceptable sensitivities and melting points, which eventually led to only one formulation being retained: a 40 : 60 mixture of dimethylammonium dinitramide and ammonium dinitramide phlegmatized by 10 % of glycerol.

Tailoring the Properties of Gel Polymer Electrolytes for Sodium-Ion Batteries Using Ionic Liquids: A Review.

Ionic liquids are an extraordinary group of compounds, fully ionic in structure like inorganic salts but with low melting points, that resemble organic molecular solvents. Their chemical, electrochemical, and thermal stability is what draws the attention and enables their use in many applications, including electrochemical power sources. Even though they are no longer considered eco-friendly because of nonnegligible toxicity and long bioaccumulation, they can still be efficiently recovered, purified, and reused. These attributes can be harvested to enhance the properties of gel polymer electrolytes for the emerging sodium-ion batteries. The variety of anions and cations for ILs and their influence on the final properties of the compound opens the road to tuning the properties of gel polymer electrolytes. Ionic liquids as plasticizers constitute a major part of gel polymer electrolytes (average of 70 wt%) and hence, they affect the fundamental properties of gel electrolytes like ionic conductivity and electrochemical window. They also improve the safety features of sodium-ion batteries, which is relevant for their anticipated applications in stationary energy storage and electric vehicles. The presented review paper aims to explain the relationship between the cation and anion in ionic liquid and the properties of gel electrolytes for sodium-ion batteries.

Confining Ionic Liquids in Developing Quasi-Solid-State Electrolytes for Lithium Metal Batteries.

The concept of confining ionic liquids (ILs) in developing quasi-solid-state electrolytes (QSSEs) has been proposed, where ILs are dispersed in polymer networks/backbones and/or filler/host pores, forming the so-called confinement, and great research progress and promising research results have been achieved. In this review, the progress and achievement in developing QSSEs using IL-confinement for lithium metal batteries (LMBs), together with advanced characterizations and simulations, were surveyed, summarized, and analyzed, where the influence of specific parameters, such as IL (type, content, etc.), substrate (type, structure, surface properties, etc.), confinement methods, and so on, was discussed. The confinement concept was further compared with the conventional one in other research areas. It indicates that the IL-confinement in QSSEs improves the performance of electrolytes, for example, increasing the ionic conductivity, widening the electrochemical window, and enhancing the cycle performance of the assembled cells, and being different from those in other areas, that is, the IL-confinement concept in the battery area is in a broad extent. Finally, insights into developing QSSEs in LMBs with the confinement strategy were provided to promote the development and application of QSSE LMBs.

Remarkably High Separation of Neodymium from Praseodymium by Selective Dissolution from their Oxide Mixture using an Ionic Liquid Containing aß-Diketone.

A simple, efficient, direct and economical method for the mutual separation of Nd and Pr was developed by the selective dissolution of Nd2O3 from their oxide mixtures in an ionic liquid containing 2-thenoyltrifluoroacetone (HTTA) resulting in an unprecedented separation factor (ßNd/Pr)>500, which is 277 times more than the thus far reported ßNd/Pr values. The proposed mechanism was supported by DFT computations.

Fluorinated Linkers Enable High-Voltage Pyrrolidinium-based Dicationic Ionic Liquid Electrolytes.

Novel fluorinated, pyrrolidinium-based dicationic ionic liquids (FDILs) as high-performance electrolytes in energy storage devices have been prepared, displaying unprecedented electrochemical stabilities (up to 7 V); thermal stability (up to 370 °C) and ion transport (up to 1.45 mS cm­1). FDILs were designed with a fluorinated ether linker and paired with TFSI/FSI counterions. To comprehensively asess the impact of the fluorinated spacer on their electrochemical, thermal, and physico-chemical properties, a comparison with their non-fluorinated counterparts was conducted. With a specific focus on their application as electrolytes in next-generation high-voltage lithium-ion batteries, the impact of the Li-salt on the characteristics of dicationic ILs was systematically evaluated. The incorporation of a fluorinated linker demonstrates significantly superior properties compared to their non-fluorinated counterparts, presenting a promising alternative towards next-generation high-voltage energy storage systems.

Molecular Insights of 5-Hydroxymethylfurfural in a Mixture of Ionic Liquids and Alkylated Phenolic Solvents.

This paper presents all-atom molecular dynamics to understand the separation behavior of 5-hydroxymethylfurfural (5-HMF) from 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM]+[BF4]- using alkylated phenols as extractants. We have utilized four solvents such as  4-methyl phenol (4-MP), 4-ethyl phenol (4-EP), 4-propyl phenol (4-PP), and 4-butyl phenol (4-BP). We perform structural, dynamic, and rigorous thermodynamic analyses of 5-HMF in the mixture of ILs and solvents. The [BMIM]+[BF4]- show a strong interactions with phenols. The self-diffusion coefficient of 5-HMF shows a 3-fold increase with a decrease in the methyl group on the phenol. The solvation-free energy (DGsolv) of 5-HMF shows favorable in phenols. On the other hand, the transfer free energy (DGtransfer) of 5-HMF presents favorable from ILs to phenols. The partition coefficient (log P) values shows favorability for separation of 5-HMF using phenols. Overall, the molecular level analysis provides the role of the alkyl group effect on the phenols for extracting 5-HMF from the ILs.