Strong Chemisorption Research Articles

An o-Phenylenediamine and MWCNT-Based Electrochemical Sensor for the Detection of Triclosan by Cyclic Voltammetry

Selectivity and sensitivity are the two key parameters for construction of a sensor. In this work, a novel electrochemical sensor based on molecularly-imprinted composites synthesized from o-phenylenediamine (o-PD) and multiwalled carbon nanotube (MWCNT) to detect triclosan is reported. Two different sensors were developed MIC/GC and MIC/cf-MWCNT/GC. To fabricate MIC/GC, molecularly imprinted composite (MIC) was synthesized by cyclic voltammetry using o-PD, COOH-functionalized MWCNT (cf-MWCNT) and triclosan on glassy carbon (GC) electrode, following removal of surface triclosan. MIC/cf-MWCNT/GC was fabricated by synthesizing MIC on cf-MWCNT coated GC. Template removal was performed using NaOH solution. MIC/GC could detect triclosan till 40 ppb while using MIC/cf-MWCNT/GC, 10 ppb of limit of detection (LOD) was achieved. Adsorption isotherms were constructed for both the films. Langmuir adsorption isotherm gave the best fit for MIC/cf-MWCNT/GC with -ΔGads value of 54.952 kJ mol−1 indicating stronger chemisorption. To understand the role of cf-MWCNT in detection of triclosan, electrochemical band gap studies, electrochemical impedance spectroscopy, and cyclic voltammetry studies were conducted. Both the sensors were found to be efficient for detection of triclosan in the presence of interfering ions.

Interfacial redox modulation of polysulfides with ferrocene functionalized separator in Al–S batteries

Despite the bright future of aluminum-sulfur (Al–S) batteries due to the ultrahigh energy-to-price ratios, the development of this new energy storage system is plagued by the shutting of polysulfides and sluggish kinetics during redox conversions. Herein, ferrocene as efficient polysulfide mediators and electrocatalysts is covalently grafted onto glass fiber (GF) membranes, which serves as separators in Al–S batteries. Attributed to the strong chemisorption and catalytic effect of metallocene toward polysulfide conversions, Al–S cells assembled with the grafted separators deliver an ultrahigh initial capacity of 1347.9 mAh g−1 (at 200 mA g−1) and desirable rate performance (328.1 mAh g−1 at 500 mA g−1). As validated by theoretical calculations, effective polysulfide binding is achieved through beneficial cation-π interactions between Al3+ in polysulfides and the negatively charged cyclopentadienyl ligands in ferrocene, providing novel insights into the exploration of metal-sulfur chemistries for stable energy storage.

Pd-Adsorbed SiN3 Monolayer as a Promising Gas Scavenger for SF6 Partial Discharge Decomposition Components: Insights from the First-Principles Study.

Gas-insulated switchgear (GIS) equipment must be protected by detecting and eliminating the toxic SF6 partial discharge decomposition components. This study employs first-principles calculations to thoroughly investigate the interaction between a Pd-adsorbed SiN3 monolayer (Pd-SiN3) and four typical SF6 decomposition gases (H2S, SO2, SOF2, and SO2F2). The study also investigates the associated geometric, electrical, and optical characteristics along with the sensing sensitivity and desorption efficiency. The ab initio molecular dynamics (AIMD) simulations demonstrated the favorable stability of the Pd-SiN3 monolayer. Furthermore, the Pd-SiN3 monolayer exhibited strong chemisorption behavior toward H2S, SO2, SOF2, and SO2F2 gases because of the higher adsorption energies of -2.717, -2.917, -2.457, and -2.025 eV, respectively. Furthermore, significant changes occur in the electronic and optical characteristics of the Pd-SiN3 monolayer following the adsorption of these gases, resulting in remarkable sensitivity of the Pd-SiN3 monolayer in relation to electrical conductivity and optical absorption. Meanwhile, all of these gas adsorption systems exhibited extremely long recovery times. The aforementioned theoretical findings suggest that the Pd-SiN3 monolayer has the potential to be an effective gas scavenger for the storage or removal of the SF6 decomposition components. Additionally, it might function as a reliable one-time sensor for detecting these gases. The results potentially provide valuable theoretical guidance for maintaining the normal operation of the SF6 insulation devices.

Porous FeNi Prussian blue cubes derived carbon-based phosphides as superior sulfur hosts for high-performance lithium–sulfur batteries

In contrast to lithium-ion batteries, lithium–sulfur batteries have higher theoretical energy density and lower cost, so they would become competitive in the practical application. However, the shuttle effect of polysulfides and slow oxidation–reduction kinetics can degrade their electrochemical performance and cycle life. In this work, we have first developed the porous FeNi Prussian blue cubes as precursors. The calcination in different atmospheres was employed to make precursors convert into common pyrolysis products or novel carbon-based phosphides, and sulfides, labeled as FeNiP/A-C, FeNiP/A-P, and FeNiP/A-S. When these products serve as host materials in the sulfur cathode, the electrochemical performance of lithium–sulfur batteries is in the order of S@FeNiP/A-P > S@FeNiP/A-S > S@FeNiP/A-C. Specifically, the initial discharge capacity of S@FeNiP/A-P can reach 679.1 mAh g−1 at 1 C, and the capacity would maintain 594.6 mAh g−1 after 300 cycles. That is because the combination of carbon-based porous structure and numerous well-dispersed Ni2P/Fe2P active sites contribute FeNiP/A-P to obtain larger lithium-ion diffusion, lower resistance, stronger chemisorption, and more excellent catalytic effect than other samples. This work may deliver that metal–organic framework-derived carbon-based phosphides are more suitable to serve as sulfur hosts than carbon-based sulfides or common pyrolysis products for enhancing Li–S batteries’ performance.

Mg-MOF-74 Derived Defective Framework for Hydrogen Storage at Above-Ambient Temperature Assisted by Pt Catalyst.

Metal-organic frameworks (MOFs) are promising candidates for room-temperature hydrogen storage materials after modification, thanks to their ability to chemisorb hydrogen. However, the hydrogen adsorption strength of these modified MOFs remains insufficient to meet the capacity and safety requirements of hydrogen storage systems. To address this challenge, a highly defective framework material known as de-MgMOF is prepared by gently annealing Mg-MOF-74. This material retains some of the crystal properties of the original Mg-MOF-74 and exhibits exceptional hydrogen storage capacity at above-ambient temperatures. The MgO5 knots around linker vacancies in de-MgMOF can adsorb a significant amount of dissociated and nondissociated hydrogen, with adsorption enthalpies ranging from -22.7 to -43.6kJmol-1, indicating a strong chemisorption interaction. By leveraging a spillover catalyst of Pt, the material achieves a reversible hydrogen storage capacity of 2.55wt.% at 160°C and 81bar. Additionally, this material offers rapid hydrogen uptake/release, stable cycling, and convenient storage capabilities. A comprehensive techno-economic analysis demonstrates that this material outperforms many other hydrogen storage materials at the system level for on-board applications.

Pt decorated Janus WSSe monolayer: A gas-sensitive material candidate for SF6 decomposition gases based on the first-principles

In gas insulated switchgear, unavoidable partial discharge faults cause SF6 to decompose various low-fluorine compounds. These compounds react with micro-water to form acids, leading to gas insulated switchgear corrosion as well as reduced insulation properties. For this reason, on-line monitoring of SF6 decomposition gases is essential. In this work, based on density functional theory, the structures of pristine WSSe and platinum doped WSSe monolayer are established, and eight adsorption systems of SO2, SO2F2, SOF2 and HF gas molecules on pristine WSSe and Pt-WSSe monolayer are constructed by geometrical optimization. By analyzing parameters such as adsorption energy, charge density, density of states, orbital theory, conductivity, sensing response and recovery time, the adsorption performance and gas-sensing mechanism of each adsorption system were investigated. The analytical results showed that both intrinsic WSSe and Pt-WSSe were unsuitable for HF gas detection and exhibited physical adsorption. The adsorption energies of Pt-WSSe for SO2, SO2F2, and SOF2 were −1.596 eV, −1.702 eV, and −2.288 eV, respectively, which showed strong chemisorption. At the optimum operating temperature, the Pt-WSSe/SO2F2 system has a fast recovery time of 1.928 s, a high response of 28.436 and a strong resistivity change, and this gas-sensitive material is well suited for the detection of this gas molecule. The Pt-WSSe/SO2 system has a small response value of 1.928 and the Pt-WSSe/SOF2 system has a strong adsorption energy of −2.288 eV. Therefore, the Pt-WSSe monolayer is not suitable as a gas-sensitive material for SO2 and SOF2 detection. This work provides theoretical guidance for the future development of low power, highly sensitive, fast response gas sensors for gas insulated switchgear fault detection.

Adsorption and sensing properties of greenhouse gases (CO2, CH4, N2O and SF6) on pristine and Cr modified WSe2 monolayer based on density functional theory

With the increasing global warming, monitoring and reducing the content of greenhouse gases in the atmosphere has become a top priority. In this study, we investigated the adsorption and sensing performances of pristine and two Cr-modified WSe2 (Cr-doped and Cr-substituted) monolayers on four greenhouse gases (CO2, CH4, N2O, and SF6) based on DFT, and explored their application prospects as a greenhouse gas sensor. The mechanism of gas sensing was analyzed from the aspects of adsorption energy, charge transfer, density of states (DOS), band structure, sensitivity, desorption time, etc. The experimental results show that both Cr modification methods could significantly improve the adsorption capacity of the intrinsic WSe2 monolayer. The two Cr-WSe2 monolayers possess strong chemisorption on all four gases according to high adsorption energy and charge transfer, so they can be used to purify CO2, CH4, N2O, and SF6 in the atmosphere. In addition, Cr-WSe2 monolayers have good desorption behavior to CO2 and CH4 at high temperatures, which makes them possible to be used as gas-sensing material for recycling under certain conditions. Our research has some theoretical implications for exploring potential sensing materials for the recovery of greenhouse gases.

Chemistry of the Au-Thiol Interface through the Lens of Single-Molecule Flicker Noise Measurements.

Chemistry of the Au-S interface at the nanoscale is one of the most complex systems to study, as the nature and strength of the Au-S bond change under different experimental conditions. In this study, using mechanically controlled break junction technique, we probed the conductance and analyzed Flicker noise for several aliphatic and aromatic thiol derivatives and thioethers. We demonstrate that Flicker noise can be used to unambiguously differentiate between stronger chemisorption (Au-SR) and weaker physisorption (Au-SRR') type interactions. The Flicker noise measurements indicate that the gold rearrangement in chemisorbed Au-SR junctions resembles that of the Au rearrangement in pure Au-Au metal contact breaking, which is independent of the molecular backbone structure and the resulting conductance. In contrast, thioethers showed the formation of a weaker physisorbed Au-SRR' type bond, and the Flicker noise measurement indicates the changes in the Au-anchoring group interface but not the Au-Au rearrangement like that in the Au-SR case. Additionally, by employing single-molecular conductance and Flicker noise analysis, we have probed the interfacial electric field-catalyzed ring-opening reaction of cyclic thioether under mild environmental conditions, which otherwise requires harsh chemical conditions for cleavage of the C-S bond. All of our conductance measurements are complemented by NEGF transport calculations. This study illustrates that the single-molecule conductance, together with the Flicker noise measurements can be used to tune and monitor chemical reactions at the single-molecule level.

Chemoselective Heterogeneous Hydrogenation of Sulfur Containing Quinolines under Mild Conditions.

Sulfur, alongside oxygen and nitrogen, holds a prominent position as one of the key heteroatoms in nature and medicinal chemistry. Its significance stems from its ability to adopt different oxidation states, rendering it valuable as both a polarity handle and a hydrogen bond donor/acceptor. Nevertheless, the poisonous nature of its free electron pairs makes sulfur containing substrates inaccessible for many catalytic protocols. Strong and (at low temperatures) irreversible chemisorption to the catalyst's surface is in particular detrimental for heterogeneous catalysts, possessing only few catalytically active sites. Herein, we present a novel heterogeneous Ru-S catalyst that tolerates multiple sulfur functionalities, including thioethers, thiophenes, sulfoxides, sulfones, sulfonamides, and sulfoximines, in the hydrogenation of quinolines. The utility of the products was further demonstrated by subsequent diversifications of the sulfur functionalities.

A sulfur-rich copolymer hybrid cathode for anchoring polysulfides and accelerating redox reaction in lithium sulfur batteries

In lithium-sulfur batteries (LSBs), sulfur-rich copolymers have attracted wide attention due to the reduced dissolution of active material and alleviated self-discharge problem through the efficient chemical interaction between polysulfide and carbon. Herein, we present an effective strategy to encapsulate sulfur-rich copolymer into NiCo2S4 encapsulated hierarchical porous N/O dual-doped graphitic carbon nanocages (GCNs), named S-DIB@NiCo2S4@PDA@rGO-GCNs. The host NiCo2S4@PDA@rGO-GCNs matrix can not only provide the “lithiophilic”-rich polar sites and tight anchored LiPSnon the N/O dual-doped GCNs surface, and “sulfphilic” NiCo2S4 electrocatalyst for accelerated sulfur electrochemistry, but also offer abundant hierarchical pores for accommodating sulfur and cushioning its volume expansion. Both of the experimental and theoretical analyses reveal the S-DIB@NiCo2S4@PDA@rGO-GCNs possesses the strong chemisorptions and catalytic ability with the synergetic mechanism, suppressing the self-discharge problem. As a proof-of-concept study, the assembled LSBs cells show excellent discharge capacities of 486 and 324 mA h g−1 at 5C and 10C after 1000 cycles, respectively. The corresponding capacity loss rate is as low as 0.032 % and 0.030 % per cycle, respectively. Thanks to the exceptional lithiophilic and sulfiphilic characteristic, the LSBs pouch cell also demonstrates high cycling stability. The proposed hierarchical encapsulation strategy with synergetic chemisorptions and catalytic ability shows great potential for developing advanced electrodes for next-generation high-performance rechargeable batteries.

An Artificial Olfactory Chemical‐Resistant Synapse for Training‐Free Gas Recognition

AbstractTransferring the concept of chemical‐driven responses into artificial intelligence technology holds the key to mimicking olfactory for neuromorphic computing of chemical recognition. Currently, artificial olfactory systems are designed based on chemical sensor arrays. Time‐dependent responses of the sensor arrays are processed by artificial neural networks for recognition. However, the sensors generate instantly volatile responses, and algorithms for the processing of the time‐dependent responses have not been involved. The recognition accuracy and speed are severely impeded. A sensor array can only achieve an accuracy of 90% after at least 5 training epochs. Herein an artificial olfactory chemical‐resistant synapse consisting of 3D hierarchical WO3@WO3 nanofibers are demonstrated. The nanofibers exhibit persistent resistance responses through chemical exposures due to the strong chemisorption of water molecules. Typical synaptic behaviors including paired‐pulse facilitation, long‐term −1 short‐term memory, and learning experience have been achieved. Next, a recurrent neural network that is committed to processing the time‐dependent data is used to identify gas‐phase chemicals of 3‐hydroxy‐2‐butanone, triethylamine, and trimethylamine. Training‐free gas recognition has been realized by a WO3@WO3 nanofiber synapse only, in which the accuracy is above 90% at the first epoch. The results have great potential to satisfy stringent performance requirements on artificial perception systems.

Efficient Polytelluride Anchoring for Ultralong-Life Potassium Storage: Combined Physical Barrier and Chemisorption in Nanogrid-in-Nanofiber

HighlightsThe hierarchical nanogrid-in-nanofiber-structured dual-type carbon-confined CoTe2 nanodots (CoTe2@NC@NSPCNFs) were synthesized via facile templates and an electrospinning approach.Hierarchical nanogrid-in-nanofiber structure effectively suppresses the volume change of CoTe2 and the shuttle of potassium polytelluride (K-pTex) through robust physical restraint and strong chemisorption.CoTe2@NC@NSPCNFs hybrid achieves ultralong lifespan potassium-storage performance over 3500 cycles, and the deep mechanisms underlying the evolution, dissolution, and shuttle of K-pTex have been clearly revealed.

Adsorption of rare bases on transition metal doped γ-graphyne nanosheets: a DFT study.

Detection of rare bases (RBs) is key to understanding biological complexity, rapidly diagnosing genetic diseases and advancing personalized medicine. Electrochemical sensors are one of the most promising methods for RB detection, but their low responsiveness limits their effectiveness. Therefore, enhancing selectivity and sensitivity is necessary. γ-Graphyne (γ-GY) has garnered significant attention due to its sp2 and sp hybrid carbon bonds and layered two-dimensional planar structure, as well as its extensive conjugated system, and sizable triangular hole. In this study, the structural characteristics, electronic properties, and sensing parameters of the adsorption involving RBs with both γ-GY and transition metal (Fe, Co, and Ni)-doped γ-graphyne (TM-GY) nanosheets are investigated using density functional theory calculations to evaluate the potential of nanosheets for sequencing RBs in DNA. The result shows that the adsorption interaction between RBs and γ-GY is weak physical adsorption, making it difficult to distinguish RBs. In contrast, the adsorption of RBs with TM-GY is stronger chemisorption and can be completely separated by translocation time and sensing response. Through translocation time calculations, we demonstrate the high selectivity of Ni-GY for RBs. Furthermore, sensitivity analysis reveals that Fe-GY exhibits excellent responsiveness to RBs. Our work reveals that the TM-GY nanosheets hold promise for detecting RBs compared with the γ-GY, and may provide valuable insights for the design of graphyne-based biosensors and catalysts.

Computational investigations of different iron oxide–coronene nanoclusters: a DFT study

Abstract This study utilizes density functional theory (DFT) to investigate the adsorption of iron oxide clusters on the surface of coronene nanocages. The study explores five different adsorption geometries (P1–P5) using the B3PW91/6-311G (d, p) approach, comparing them to pure coronene. Electronic properties, including energy (hf), HOMO, LUMO, Fermi level, HOMO–LUMO gap, vertical ionization potential, electron affinity, chemical hardness, softness, and chemical potential, were analyzed compared to native coronene nanocages. The calculations revealed strong chemisorption in P1, attributed to significant charge transfer from coronene to the metal atom, resulting in altered positions of HOMOs and LUMOs and a reduced HOMO–LUMO gap (E gap). Across all geometries (P1–P5), electronic densities in HOMOs were concentrated on iron oxides, while in LUMOs, the electronic cloud was distributed throughout the structure. The diffusion of d-electrons from iron contributed to a more diffuse structure and a lower HOMO–LUMO gap (E gap), indicating N-type conduction. Global indices demonstrated increased reactivity of iron oxide–adsorbed coronene nanocages compared to native, unbound coronene.

Role of Chemisorbing Species in Growth at Liquid Metal-Electrolyte Interfaces Revealed by in Situ X-Ray Scattering

Liquid-liquid interfaces offer intriguing possibilities for nanomaterials growth. Especially, growth at liquid metal surfaces has recently received renewed interest. Here, fundamental interface-related mechanisms that control the growth behavior in these systems are studied for the case of Pb halide compound formation at the interface between liquid mercury electrode and aqueous salt solutions, using in situ X-ray reflectivity and grazing incidence X-ray diffraction, supplemented by electrochemical measurements and optical microscopy. The nucleation and growth of these compounds at potentials in the regime of Pb de-amalgamation was investigated in NaX + PbX2 (X = F, Cl, Br) to systematically explore the role of the halide species. X-ray reflectivity studies reveal the rapid formation of well-defined ultrathin precursor adlayers in Cl- and Br-containing solution. This adlayer formation is followed by subsequent quasi-epitaxial growth of Pb(OH)X bulk crystals, that are oriented with the c-axis along the surface normal. In contrast, growth in F-containing solution proceeds by slow formation of a more disordered deposit, resulting in random bulk crystal orientations on the Hg surface. A detailed structural analysis of the Pb(OH)Br and Pb(OH)Cl precursor adlayers reveals that they determine the orientation of the subsequently formed bulk crystals, with the arrangement in the adlayer providing a template. Together with our previous results on the pseudo-epitaxial growth of PbFBr on Hg (A. Elsen, et al., Proc.Nat.Acad.Sci., 2013, 110, 6663), these data reveal the decisive role of the interface chemistry, especially the strong chemisorption of the anions bromide and chloride, in steering the formation of these textured deposits at the liquid metal surface.

Adsorption behavior of Rh-doped graphdiyne monolayer towards various gases: A quantum mechanical analysis

In this study, the conformational properties of pure Graphdiyne (GDY) and Rh-doped (Rh-GDY) for the CO, NO, and NH3 gases are investigated using DFT computations. The doping site is optimized, and the structure parameters and electronic properties of Rh-GDY were evaluated. It is found that Rh-dosing at the optimal site (CII) increases the electrical conductivity due to decreasing of gap energy. The tendency of pure GDY toward CO, NO, and NH3 gases is low and not suitable for sensing due to physical adsorption of gases. However, Rh-GDY demonstrates exceptional performance as a gas sensor due to its strong chemisorption of CO, NO, and NH3 gases through hybridization and chemical reactions with the gas molecular orbital. As a result, Rh-GDY represents a potential gas detection sensor material with notable monitoring capabilities for gases such as CO, NO, and NH3. This research provides valuable information for advancing the creation of innovative and effective gas detection sensor technologies.

Fluorinated bamboo-structure carbon nanotubes: as attractive substrates for the cathodes of lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries have gained considerable attention for high theoretical specific capacity and energy density. However, their development is hampered by the poor electrical conductivity of sulfur and the shuttle of polysulfides. Herein, the acidified bamboo-structure carbon nanotubes (BCNTs) were mixed with polyvinylidene difluoride and pyrolyzed at high-temperature to obtain the fluorinated bamboo-structure carbon nanotubes (FBCNTs), which were compounded with sulfur as the cathode. The prepared S@FBCNTs with sulfur loading reaching 74.2 wt.% shows a high initial specific capacity of 1407.5 mAh·g−1 at the discharge rate of 0.1 C. When the discharge rate was increased to 5 C, the capacity could be maintained at 622.3 mAh·g−1. The electrical conductivity of carbon nanotubes is effectively improved by semi-ionic C–F bonds formed by the doped F atoms and carbon atoms. Simultaneously, the surface of the F-containing carbon tubes exhibits strong polarity and strong chemisorption effect on polysulfides, which inhibits the shuttle effect of Li–S batteries.

Molecular modeling of Si60 fullerene and Nb-doped Si60 fullerene nanomaterials for SO2, NO2 and CO2 gas sensing

CO2, NO2 and SO2 are by-products from the petrochemical industries that have been associated with both global warming and several respiratory dysfunctions. Hence, several efforts are being put forth to detect their excesses at minimal concentrations. In this regard, this study presents a theoretical analysis based on quantum and molecular mechanical calculations of the sensing efficacy of silicon nanostructures towards the effective detection of these gases at low concentrations. To enhance the attributes of the nanomaterial, transition metal (Nb) was endohedrally doped on the silicon Si60 nanomaterial to enhance the surface conductivity and sensitivity. The results indicate that the metal-doped nanostructures have improved sensitivity towards the studied gases. The adsorption of NO2, SO2 and CO2 followed a declining trend; NO2@NbdopSi59 > SO2@NbdopSi59 > CO2@NbdopSi59 > NO2@Si60 > SO2@Si60 > CO2@Si60 respectively. The computed adsorption enthalpies were found to be −25.36, −136.26 and −183.67 kcal/mol respectively for CO2@NbdopSi59, NO2@NbdopSi59 and SO2@NbdopSi59 systems. Comparatively, SO2 and NO2 preferred to be adsorbed on Si60 than CO2. The results of other electronic properties such as energy gap and conductivity were also found to be in tandem with the adsorption and stability studies. The sensing mechanism and computed desorption times were also found to be within 1.02 s to 2.72 s, clearly indicating a quick desorption from the metal-doped surface. Contrary, desorption from the pristine nanocluster was found to be slower due to strong chemisorption bonds between the gases and surface. While the electronic properties affirmed the conducting and stable nature of the surfaces, molecular dynamics simulation was further employed for stability evaluation. These results also unveiled the stable nature of the nanocluster and confirmed that the studied metal-doped nanoclusters possess the ideal properties to be employed as sensors for SO2 NO2 and CO2 gases.

Metallic Ti4O7 with strong polybromide chemisorption ability as polar host for zinc–bromine batteries

Membraneless and flowless zinc-bromine batteries (MLFL-ZBBs) have emerged as a compelling solution for energy storage due to their cost-effectiveness, high cell voltage, and high safety. However, challenges persist in maintaining long-term stability and efficiency, primarily attributed to the inadequate adsorption of carbon-based host materials in ZBBs to soluble polybromides. Here, we report a highly conductive, inherently polar Ti4O7 as the host material and demonstrate how it improves MLFL-ZBBs stability. Density functional theory calculations suggest the electron densities of Br atoms within polybromides are significantly intertwined with Ti atoms in Ti4O7, resulting in the formation of robust Ti-Br bonding, which are absent as for carbon and bromine interactions. Visual discrimination, UV–Vis, and X-ray photoelectron spectroscopy collectively confirm the substantial adsorption capabilities of Ti4O7 towards polybromides. The Coulombic efficiency of MLFL-ZBBs with Ti4O7 as host materials remain 93.8% after 2,000 cycles, which is more than three times that with traditional carbon-based host.

Temperature-dependent Viscoelastic Liquid MOFs Based Cellulose Gel Electrolyte for Advanced Lithium-Sulfur Batteries Over an Extensive Temperature Range

The uncontrolled growth of lithium dendrites severely limits the practical use of Li-S batteries. Additionally, cell temperature increases during operation, accelerating dendrite growth and side reactions. To stabilize the anode over a wide temperature range, we proposed a promising solution of a novel temperature-dependent viscoelastic liquid UiO66 MOFs-based cellulose gel electrolyte. This specially engineered electrolyte demonstrated superior stabilization of the anode. It adopted the “blocking anions and promoting Li+ transfer” strategy, resulting in a uniform Li+ flux deposition and the formation of a stable and dense solid electrolyte interphase layer, effectively suppressing dendrite growth. To further improve the cycling performance of the cell, a hollow transition bi-metal selenide (FeCo-Se2/NC) was developed as the sulfur host material. This complex exhibited a strong chemisorption capacity for polysulfides and a high catalytic ability to expedite the conversion process of lithium polysulfides. The final cell achieved a high capacity of 687.2 mAh g−1 after 500 cycles at 3 C with a minimal fading rate of 0.04% per cycle. It also demonstrated a high area capacity of 5.78 mAh cm−2 at a high sulfur loading of 6.2 mg cm−2, along with excellent cycling stability under temperature-varying conditions. The findings not only highlighted the commercialization potential of Li-S batteries but also underscored the effectiveness of porous liquid MOFs as a modified layer, effectively stabilizing the Li anode and reducing interfacial impedance between the electrolyte and electrode. Our research paved the way for advanced energy storage solutions that could significantly contribute to a sustainable and eco-friendly future.