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Covalent organic frameworks (COFs) with flexible periodic skeletons and ordered nanoporous structures have attracted much attention as potential candidate electrode materials for green energy storage and efficient seawater desalination. Further improving the intrinsic electronic conductivity and releasing porosity of COF-based materials is a necessary strategy to improve their electrochemical performance. Herein, the employed graphene as the conductive substrate to in situ grow 2D redox-active COF (TFPDQ-COF) with redox activity under solvent-free conditions to prepare TFPDQ-COF/graphene (TFPDQGO) nanohybrids and explores their application in both supercapacitor and hybrid capacitive deionization (HCDI). By optimizing the hybridization ratio, TFPDQGO exhibits a large specific capacitance of 429.0 F g-1 due to the synergistic effect of the charge transport highway provided by the graphene layers and the abundant redox-active centers contained in the COF skeleton, and the assembled TFPDQGO//activated carbon (AC) asymmetric supercapacitor possesses a high energy output of 59.4 Wh kg-1 at a power density of 950 W kg-1 and good cycling life. Furthermore, the maximum salt adsorption capacity (SAC) of 58.4 mg g-1 and stable regeneration performance is attained for TFPDQGO-based HCDI. This study highlights the new opportunities of COF-based hybrid materials acting as high-performance supercapacitor and HCDI electrode materials.
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Defect engineering is recognized as an attractive method for modulating the electronic structure and physicochemical characteristics of carbon materials. Exploiting heteroatom-doped porous carbon with copious active sites has attracted great attention for capacitive deionization (CDI). However, traditional methods often rely on the utilization of additional heteroatom sources and strong corrosive activators, suffering from low doping efficiency, insufficient doping level, and potential biotoxicity. Herein, hydrogen-bonded organic frameworks (HOFs) are employed as precursors to synthesize N, O co-doped porous carbon via a simple and green reverse defect engineering strategy, achieving controllable heavy doping of heteroatoms. The N, O co-doping triggers significant pseudocapacitive contribution and the surface pore structure supports the formation of the electric double layer. Therefore, when HOF-derived N, O co-doped carbon is used as CDI electrodes, a superior salt adsorption capacity of 32.29 ± 1.42 mg g-1 and an outstanding maximum salt adsorption rate of 10.58 ± 0.46 mg g-1 min-1 at 1.6 V in 500 mg L-1 NaCl solution are achieved, which are comparable to those of state-of-the-art carbonaceous electrodes. This work exemplifies the effectiveness of the reverse nitrogen-heavy doping strategy on improving the carbon structure, shedding light on the further development of rational designed electrode materials for CDI.
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Nowadays, capacitive deionization (CDI) has emerged as a prominent technology in the desalination field, typically utilizing porous carbons as electrodes. However, the precise significance of electrode properties and operational conditions in shaping desalination performance remains blurry, necessitating numerous time-consuming and resource-intensive CDI experiments. Machine learning (ML) presents an emerging solution, offering the prospect of predicting CDI performance with minimal investment in electrode material synthesis and testing. Herein, four ML models are used for predicting the CDI performance of porous carbons. Among them, the gradient boosting model delivers the best performance on test set with low root mean square error values of 2.13 mg g-1 and 0.073 mg g-1 min-1 for predicting desalination capacity and rate, respectively. Furthermore, SHapley Additive exPlanations is introduced to analyze the significance of electrode properties and operational conditions. It highlights that electrolyte concentration and specific surface area exert a substantially more influential role in determining desalination performance compared to other features. Ultimately, experimental validation employing metal-organic frameworks-derived porous carbons and biomass-derived porous carbons as CDI electrodes is conducted to affirm the prediction accuracy of ML models. This study pioneers ML techniques for predicting CDI performance, offering a compelling strategy for advancing CDI technology.
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A paucity of redox centers, poor charge transport properties, and low structural stability of organic materials obstruct their use in practical applications. Herein, these issues have been addressed through the use of a redox-active salen-based framework polymer (RSFP) containing multiple redox-active centers in π-conjugated configuration for applications in lithium-ion batteries (LIBs). Based on its unique architecture, RSFP exhibits a superior reversible capacity of 671.8 mAh g-1 at 0.05 A g-1 after 168 charge-discharge cycles. Importantly, the lithiation/de-lithiation performance is enhanced during operation, leading to an unprecedented reversible capacity of 946.2 mAh g-1 after 3500 cycles at 2 A g-1. The structural evolution of RSFP is studied ex situ using X-ray photoelectron spectroscopy, revealing multiple active CâN, CâO, and CâO sites and aromatic sites such as benzene rings. Remarkably, the emergence of CâO originated from CâO is triggered by an electrochemical process, which is beneficial for improving reversible lithiation/delithiation behavior. Furthermore, the respective strong and weak binding interactions between redox centers and lithium ions, corresponding to theoretical capacities of 670.1 and 938.2 mAh g-1, have been identified by density functional theory calculations manifesting 14-electron redox reactions. This work sheds new light on routes for the development of redox-active organic materials for energy storage applications.
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Graphynes (GYs) are a novel type of carbon allotrope composed of sp and sp2 hybridized carbon atoms, boasting both a planar conjugated structure akin to graphene and a pore-like configuration in three-dimensional space. Graphdiyne (GDY), the first successfully synthesized member of GYs family, has gained much interest due to its fascinating electrochemical properties including a greater theoretical capacity, high charge mobility and advanced electronic transport properties, making it a promising material for energy storage applications for lithium-ion and hydrogen storage. Various methods, including heteroatom substitution, embedding, strain, and nanomorphology control, have been employed to further enhance the energy storage performance of GDY. Despite the potential of GDY in energy storage applications, there are still challenges to overcome in scaling up mass production. This review summarizes recent progress in the synthesis and application of GDY in lithium-ion and hydrogen storage, highlighting the obstacles faced in large-scale commercial application of GDY-based energy storage devices. Suggestions on possible solutions to overcome these hurdles have also been provided. Overall, the unique properties of GDY make it a promising material for energy storage applications in lithium-ion and hydrogen storage devices. The findings presented here will inspire further development of energy storage devices utilizing GDY.
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The open NASICON framework and high reversible capacity enable Na3V2(PO4)3 (NVP) to be a highly promising cathode candidate for sodium-ion batteries (SIBs). Nevertheless, the unsatisfied cyclic stability and degraded rate capability at low temperatures due to sluggish ionic migration and poor conductivity become the main challenges. Herein, excellent sodium storage performance for the NVP cathode can be received by partial potassium (K) substitution and multiwalled carbon nanotube (MWCNT) cross-linking to modify the ionic diffusion and electronic conductivity. Consequently, the as-fabricated Na3-xKxV2(PO4)3@C/MWCNT can maintain a capacity retention of 79.4% after 2000 cycles at 20 C. Moreover, the electrochemical tests at -20 °C manifest that the designed electrode can deliver 89.7, 73.5, and 64.8% charge of states, respectively, at 1, 2, and 3 C, accompanied with a capacity retention of 84.3% after 500 cycles at 20 C. Generally, the improved electronic conductivity and modified ionic diffusion kinetics resulting from K doping and MWCNT interconnecting endows the resultant Na3-xKxV2(PO4)3@C/MWCNT with modified electrochemical polarization and improved redox reversibility, contributing to superior performance at low temperatures. Generally, this study highlights the potential of alien substitution and carbon hybridization to improve the NASICON-type cathodes toward high-performance SIBs, especially at low temperatures.
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The design of high-performance electrode materials with excellent desalination ability has always been a research goal for efficient capacitive deionization (CDI). Herein, a hybrid architecture with Cu/Cu2O nanospheres anchored on porous carbon nanosheets (Cu/Cu2O/C) was first synthesized by pyrolyzing a two-dimensional (2D) Cu-based metal-organic framework and then evaluated as a cathode for hybrid CDI. The as-prepared Cu/Cu2O/C exhibits a hierarchically porous structure with a high specific surface area of 305 m2 g-1 and large pore volume of 0.55 cm3 g-1, which is favorable to accelerating ion migration and diffusion. The porous carbon nanosheet matrix with enhanced conductivity will facilitate the Faradaic reactions of Cu/Cu2O nanospheres during the desalination process. The Cu/Cu2O/C hybrid architecture displays a high specific capacitance of 142.5 F g-1 at a scan rate of 2 mV s-1 in 1 M NaCl solution. The hybrid CDI constructed using the Cu/Cu2O/C cathode and a commercial activated carbon anode exhibits a high desalination capacity of 16.4 mg g-1 at an operation voltage of 1.2 V in 500 mg L-1 NaCl solution. Additionally, the hybrid CDI exhibits a good cycling stability with 18.3% decay in the desalination capacity after 20 electrosorption-desorption cycles. Thus, the Cu/Cu2O/C composite is expected to be a promising cathode material for hybrid CDI.
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Mn-based oxides are efficient pseudocapacitive electrode materials and have been investigated for capacitive deionization (CDI). However, their poor conductivity seriously affects their desalination performance. In this work, polyaniline coated Mn2O3 nanorods (PANI/Mn2O3) are synthesized by oxidizing a Mn-based metal organic framework (MOF) and subsequent in-situ chemical polymerization. The polyaniline not only acts as a conductive network for faradaic reactions of Mn2O3, but also enhances the desalination rate. PANI/Mn2O3 has a specific capacitance of 87 F g-1 (at 1 A g-1), superior to that of Mn2O3 nanorod (52 F g-1 at 1 A g-1). The hybrid CDI cell constructed with a PANI/Mn2O3 cathode and an active carbon anode shows a high desalination capacity of 21.6 mg g-1, superior recyclability with only 11.3% desalination capacity decay after 30 desalination cycles and fast desalination rate of 2.2 mg g-1 min-1. PANI/Mn2O3 is a potential candidate for high performance CDI applications.
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Ionic conductive hydrogel electrolyte is considered to be an ideal electrolyte candidate for flexible supercapacitor due to its flexibility and high conductivity. However, due to the lack of effective recycling methods, a large number of ineffective flexible hydrogel supercapacitors caused by some irreversible damages and dryness of hydrogel electrolyte are abandoned, which would induce heavy economic and environmental protection problems. Herein,a smart ionic conductive hydrogel (SPMA-Zn: ZnSO4 /sodium alginate/polymethylacrylic acid) is developed for flexible hybrid supercapacitor (SPMA-ZHS). The SPMA-Zn exhibits an excellent self-healing ability and can recover its electrochemical performance after multiple mechanical damages. More importantly, it possesses an outstanding powder self-healable property, which could easily regenerate the hydrogel electrolyte after powdering, and maintain stable electrochemical performance of SPMA-ZHS. Besides, the SPMA-ZHS displays excellent electrochemical performance with a wide and stable working voltage range of 0-2.2 V, high energy density of 164.13 Wh kg-1 at the power density of 1283.44 Wh kg-1 and good stability with a capacity retention of 95.3% after 5000 charge/discharge cycles at 10 A g-1 . The strategy in this work would provide a new insight in exploring flexible hydrogel electrolyte-based supercapacitor with good sustainability and high energy density for flexible wearable electronic devices.
Assuntos
Eletrólitos , Hidrogéis , Alginatos , Condutividade Elétrica , PósRESUMO
Wearable strain sensors based on nanomaterial/elastomer composites have potential applications in flexible electronic skin, human motion detection, human-machine interfaces, etc. In this research, a type of high performance strain sensors has been developed using fragmentized carbon nanotube/polydimethylsiloxane (CNT/PDMS) composites. The CNT/PDMS composites were ground into fragments, and a liquid-induced densification method was used to fabricate the strain sensors. The strain sensors showed high sensitivity with gauge factors (GFs) larger than 200 and a broad strain detection range up to 80%, much higher than those strain sensors based on unfragmentized CNT/PDMS composites (GF < 1). The enhanced sensitivity of the strain sensors is ascribed to the sliding of individual fragmentized-CNT/PDMS-composite particles during mechanical deformation, which causes significant resistance change in the strain sensors. The strain sensors can differentiate mechanical stimuli and monitor various human body motions, such as bending of the fingers, human breathing, and blood pulsing.
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Hierarchically porous carbon (HPC) materials with interconnected porous texture are produced from a porous poly(divinylbenzene) precursor, which is synthesized by polymerizing high-internal-phase emulsions. After carbonation, the macroporous structures of the poly(divinylbenzene) precursor are preserved and enormous micro-/mesopores via carbonation with KOH are produced, resulting in an interconnected hierarchically porous network. The prepared HPC has a maximum specific surface area of 2189 m2 g-1. The electrode materials for supercapacitors and capacitive deionization devices employing the formed HPC exhibit a high specific capacity of 88 mA h g-1 through a voltage range of 1 V (319 F g-1 at 1 A g-1) and a superior electrosorption capacity of 21.3 mg g-1 in 500 mg L-1 NaCl solution. The excellent capacitive performance could be ascribed to the combination of high specific surface area and favorable hierarchically porous structure.
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Highly conductive, crystalline, polymer electrolytes, ß-cyclodextrin (ß-CD)-polyethylene oxide (PEO)/LiAsF6 and ß-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, ß-CD, and LiAsF6 /NaAsF6 . The assembled ß-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion.
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With the gradually increasing requirement for freshwater, capacitive deionization (CDI) as a burgeoning desalination technique has gained wide attention owing to its merits of easy operation, high desalination efficiency, and environmental friendliness. To enhance the desalination performance of CDI, different CDI architectures are designed, such as membrane CDI, hybrid CDI, and flow-electrode CDI. However, these CDI systems have their own drawbacks, such as the high cost of membranes, capacity limitation of carbon materials and slurry blockage, which severely limit their practical application. Notably, rocking-chair CDI (RCDI) composed of symmetric electrode materials delivers excellent desalination performance because of its special dual chamber structure, which can not only break through the capacity limitations of carbon materials, but also deliver a continuous desalination process. Although RCDI showcases high promise for efficient desalination, few works systematically summarize the advantages and applications of RCDI in the desalination field. This review offers a thorough analysis of RCDI, focusing on its electrode materials, structure designs and desalination applications. Furthermore, the desalination performances of RCDI and other CDI architectures are compared to demonstrate the advantages of RCDI and the prospect of RCDI is elucidated.
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Covalent organic frameworks (COFs) with customizable geometry and redox centers are an ideal candidate for supercapacitors and hybrid capacitive deionization (HCDI). However, their poor intrinsic conductivity and micropore-dominated pore structures severely impair their electrochemical performance, and the synthesis process using organic solvents brings serious environmental and cost issues. Herein, a 2D redox-active pyrazine-based COF (BAHC-COF) was anchored on the surface of graphene in a solvent-free strategy for heterointerface regulation. The as-prepared BAHC-COF/graphene (BAHCGO) nanohybrid materials possess high-speed charge transport offered by the graphene carrier and accelerated electrolyte ion migration within the BAHC-COF, allowing ions to effectively occupy ion storage sites inside BAHC. As a result, the BAHCGO//activated carbon asymmetric supercapacitor achieves a high energy output of 61.2 W h kg-1 and a satisfactory long-term cycling life. More importantly, BAHCGO-based HCDI possesses a high salt adsorption capacity (SAC) of 67.5 mg g-1 and excellent long-term desalination/regeneration stability. This work accelerates the application of COF-based materials in the fields of energy storage and water treatment.
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As an emerging class of layered transition metal carbides/nitrides/carbon-nitrides, MXenes have been one of the most investigated anode subcategories for sodium ion batteries (SIBs), due to their unique layered structure, metal-like conductivity, large specific surface area and tunable surface groups. In particular, different MAX precursors and synthetic routes will lead to MXenes with different structural and electrochemical properties, which actually gives MXenes unlimited scope for development. In this feature article, we systematically present the recent advances in the methods and synthetic routes of MXenes, together with their impact on the properties of MXenes and also the advantages and disadvantages. Subsequently, the sodium storage mechanisms of MXenes are summarized, as well as the recent research progress and strategies to improve the sodium storage performance. Finally, the main challenges currently facing MXenes and the opportunities in improving the performance of SIBs are pointed out.
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As a cost-effective photocatalyst, carbon nitride (g-C3N4) holds tremendous promise for addressing energy shortages and environmental pollution. However, its application is limited by disadvantages such as low specific surface area and easy recombination of photogenerated electron-hole pairs. This study introduces C and O co-doped g-C3N4 with a three-dimensional (3D) structure achieved through a straightforward one-step calcination process, demonstrating excellent photocatalytic activity of hydrogen production and oxytetracycline degradation, with superoxide radicals as the primary active species. We propose a plausible enhanced mechanism based on systematic characterizations and density functional theory calculations. The 3D structure confers a substantial specific surface area, enhancing both the adsorption area and active sites of catalysts while bolstering structural stability. Co-doping optimizes the band structure and electric conductivity of the catalyst, facilitating rapid migration of photogenerated charges. The synergistic effects of these enhancements significantly elevate the photocatalytic performance. This study presents a convenient and feasible method for the preparation of dual-regulated photocatalysts with outstanding performance.
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Heterojunctions photocatalysts play a crucial role in achieving high solar-hydrogen conversion efficiency. In this work, we mainly focus on the charge transfer dynamics and pathways for sulfides-based Schottky junctions in the photocatalytic water splitting process to clarify the mechanism of heterostructures photocatalysis. Sulfides-based Schottky junctions (CdS/CoP and CdS/1T-MoS2) were successfully constructed for photocatalytic water splitting. Because of the higher work function of CdS than that of CoP and 1T-MoS2, the direction of the built-in electric field is from CoP or 1T-MoS2 to semiconductor. Therefore, CoP and 1T-MoS2 can act as electrons acceptors to accelerate the transfer of photo-generated electron on the surface of CdS, thus improving the charge utilization efficiency. Meanwhile, CoP and 1T-MoS2 as active sites can also promote the water dissociation and lower the H+ reduction overpotential, thus contributing to the excellent photocatalytic hydrogen production activity (23.59 mmol·h-1·g-1 and 1195.8 mol·h-1·g-1 for CdS/CoP and CdS/1T-MoS2).
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Aqueous sodium-ion batteries (ASIBs) show great promise as candidates for large-scale energy storage. However, the potential of ASIB is impeded by the limited availability of suitable anode types and the occurrence of dissolution side reactions linked to hydrogen evolution. In this study, we addressed these challenges by developing a Bi-coating modified anode based on a sodium titanium phosphate (NTP)-carbon fibers (CFs) hybrid electrode (NTP-CFs/Bi). The Bi-coating effectively mitigates the localized enrichment of hydroxyl anion (OH-) near the NTP surface, thus addressing the dissolution issue. Notably, the Bi-coating not only restricts the local abundance of OH- to inhibit dissolution but also ensures a higher capacity compared with other NTP-based anodes. Consequently, the NTP-CFs/Bi anode demonstrates an impressive specific capacity of 216.8 mAh/g at 0.2 mV/s and maintains a 90.7 % capacity retention after 1000 cycles at 6.3 A/g. This achievement sets a new capacity record among NTP-based anodes for sodium storage. Furthermore, when paired with a cathode composed of hydroxy nickel oxide directly grown on Ni foam, we assembled a seawater-based cell exhibiting high energy and power densities, surpassing the most recently reported ASIBs. This groundbreaking work lays the foundation for a potential method to develop long-life NTP-based anodes.
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Currently, the development of economical and effective non-noble metal electrocatalysts is vital for advancing hydrogen evolution reaction (HER) and enabling its widespread applications. The customizable pore structure and enormous surface area of metal-organic frameworks (MOFs) have made them to become promising non-noble metal electrocatalysts for HER. However, MOFs have some challenges, including low conductivity and instability, which can result in them having high overpotentials and slow reaction kinetics in electrocatalytic processes. In this work, we present an innovative approach for synthesizing cost-effective and high-efficient Zr-MOF-derived pH-universal electrocatalysts for HER. It entails creating the interfaces of the electrocatalysts with suitable proportions of phosphide nanostructures. Zr-MOF/Ni2P@nickel foam (NF) electrodes with interface regulated by Ni2P nanostructures were successfully developed for high-efficient pH-universal HER electrocatalysts. The presence of Ni2P nanostructures with abundant active sites at the Zr-MOFs@NF interfaces boosted the electronic conductivity and local charge density of the hybrid electrocatalysts. This helped to improve their reaction kinetics and electrocatalytic activity. By optimizing the Ni2P amount, Zr-MOF/Ni2P@NF demonstrated impressive stability and superior HER activities, with a low overpotential of 149 mV (acidic electrolytes) and 143 mV (alkaline electrolytes) at 10 mA cm-2. The proven strategy in this work can be expanded to many types of MOF-based materials for wider practical applications.
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Bi2O3 was successfully synthesized via microwave-assisted reaction of Bi2O3 precursor in aqueous solution using a microwave system. Their morphologies, structures and photocatalytic performances in the degradation of methylene blue (MB) were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, photoluminescence spectroscopy and UV-vis absorption spectroscopy, respectively. The results show that Bi2O3 synthesized at pH value of 7 exhibits an optimal photocatalytic performance with the MB degradation rate of 76% at 240 min under visible light irradiation due to its higher visible light absorption and comparatively low electron-hole pair recombination.