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Due to their unique structure and outstanding intrinsic physical properties such as extraordinarily high electrical conductivity, large surface area, and various chemical functionalities, low-dimension-based materials exhibit great potential for application in electrochemical capacitors (ECs). The electrical properties of electrochemical capacitors are determined by the electrode materials. Because energy charge storage is a surface process, the surface properties of the electrode materials greatly influence the electrochemical performance of the cell. Recently, graphene, a single layer of sp(2)-bonded carbon atoms arrayed into two-dimensional carbon nanomaterial, has attracted wide interest as an electrode material for electrochemical capacitor applications due to its unique properties, including a high electrical conductivity and large surface area. Several low-dimensional materials with large surface areas and high conductivity such as onion-like carbons (OLCs), carbide-derived carbons (CDCs), carbon nanotubes (CNTs), graphene, metal hydroxide, transition metal dichalcogenides (TMDs), and most recently MXene, have been developed for electrochemical capacitors. Therefore, it is useful to understand the current issues of low-dimensional materials and their device applications.
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MXenes possess the characteristics required for high-performance supercapacitors, such as high metallic conductivity and electrochemical activity, but their full potential remains unrealized owing to their tendency to self-restack when fabricated into an electrode. Designing an MXene interlayer with an effective intercalant has, therefore, become an important criterion to alleviate the restacking issue while also synergistically interact with MXene to further improve its electrochemical activity. This study reports the intercalation of 1D π-d conjugated coordination polymer (Ni-BTA) within the Ti3 C2 Tx nanosheet for the fabrication of a highly efficient supercapacitor electrode. Ni-BTA, which consists of a nickel center and 1,2,4,5-benzenetetramine (BTA) organic chain, is uniformly intercalated by direct synthesis on the abundant oxygen terminals on the Ti3 C2 Tx nanosheet surface. The intercalated Ni-BTA acts as an effective charge carrier transportation pathway through its 1D stretched delocalized π-d electrons while participating in pseudocapacitive activity with the Ni centers. As a result, the Ni-BTA/MXene film exhibits excellent rate performance and a gravimetric specific capacitance of 264.4 F g-1 at 5 mV s-1 . This magnitude is retained up to 94.6% after 10 000 cycles. The present study provides insights into the design of MXene interlayers for the fabrication of highly robust and stable supercapacitors.
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To achieve a zero-carbon-emission society, it is essential to increase the use of clean and renewable energy. Yet, renewable energy resources present constraints in terms of geographical locations and limited time intervals for energy generation. Therefore, there is a surging demand for developing high-performance energy storage systems (ESSs) to effectively store the energy during the peak time and use the energy during the trough period. To this end, supercapacitors hold great promise as short-term ESSs for rapid power recovery or frequency regulation to improve the quality and reliability of power supply. In particular, the electrical double layer capacitor (EDLC) which offers long and stable cycle retention, high power densities, and fast charge/discharge characteristics with a moderate operating voltage window, is a suitable candidate. Yet, for implementation of the EDLC in ESSs, further research effort is required in terms of increasing the operating voltage and energy densities while maintaining the long-term cycle stability and power densities which are desirable aspects for ESS operation. Here, we examine the advances in EDLC research to achieve a high operating voltage window along with high energy densities, covering from materials and electrolytes to long-term device perspectives for next-generation supercapacitor-based ESSs.
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Thermally doped nitrogen atoms on the sp(2)-carbon network of reduced graphene oxide (rGO) enhance its electrical conductivity. Atomic structural information of thermally annealed graphene oxide (GO) provides an understanding on how the heteroatomic doping could affect electronic property of rGO. Herein, the spectroscopic and microscopic variations during thermal graphitization from 573 to 1,373 K are reported in two different rGO sheets, prepared by thermal annealing of GO (rGO(therm)) and post-thermal annealing of chemically nitrogen-doped rGO (post-therm-rGO(N(2)H(4))). The spectroscopic transitions of rGO(N(2)H(4)) in thermal annealing ultimately showed new oxygen-functional groups, such as cyclic edge ethers and new graphitized nitrogen atoms at 1,373 K. During the graphitization process, the microscopic evolution resolved by scanning tunneling microscopy (STM) produced more wrinkled surface morphology with graphitized nanocrystalline domains due to atomic doping of nitrogen on a post-therm-rGO(N(2)H(4)) sheet. As a result, the post-therm-rGO(N(2)H(4))-containing nitrogen showed a less defected sp(2)-carbon network, resulting in enhanced conductivity, whereas the rGO(therm) sheet containing no nitrogen had large topological defects on the basal plane of the sp(2)-carbon network. Thus, our investigation of the structural evolution of original wrinkles on a GO sheet incorporated into the graphitized N-doped rGO helps to explain how the atomic doping can enhance the electrical conductivity.
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Graphene is of considerable interest as a next-generation semiconductor material to serve as a possible substitute for silicon. For real device applications with complete circuits, effective n-type graphene field effect transistors (FETs) capable of operating even under atmospheric conditions are necessary. In this study, we investigated n-type reduced graphene oxide (rGO) FETs of photoactive metal oxides, such as TiO(2) and ZnO. These metal oxide doped FETs showed slight n-type electric properties without irradiation. Under UV light these photoactive materials readily generated electrons and holes, and the generated electrons easily transferred to graphene channels. As a result, the graphene FET showed strong n-type electric behavior and its drain current was increased. These n-doping effects showed saturation curves and slowly returned back to their original state in darkness. Finally, the n-type rGO FET was also highly stable in air due to the use of highly resistant metal oxides and robust graphene as a channel.
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A simple chemical method to obtain bulk quantities of N-doped, reduced graphene oxide (rGO) sheets (see figure) as an n-type semiconductor through the treatment of as-prepared GO sheets with the commonly used reducing reagent hydrazine, followed by rapid thermal annealing (RTA) is described.
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Synthesizing layered transition-metal carbides, MXenes, with a mesoporous structure remains challenging but is highly useful because it converts the laminated two-dimensional structures into versatile porous materials. Hydrogen bonds between intercalated H2O molecules and oxygen terminal groups on the surface are formed in aqueous solution processes, and this is a determining factor of surface area. We developed an extraction method to remove intercalated water molecules based on a simple intermolecular force attraction strategy in a co-solvent system using a combination of polar-protic/-aprotic and non-polar solvents. As a result, self-aggregated mesoporous Ti3C2Tx was realized without any additives. The dipole-dipole interaction between H2O and CHCl3 molecules under non-polar solvent conditions assists the extraction of intercalated H2O from the MXene suspension, which can form a self-aggregated morphology (not re-stacked horizontally). The process yields Ti3C2Tx with a layered structure of embedded mesopores and a specific surface area that is 13-fold higher than that of standard MXene. Electrodes made with the resulting MXene exhibited a larger specific capacitance of 224 F/g (1 A/g), with an improved cyclic retention of 96.4%@10,000 cycles. This intermolecular attraction-induced approach, involving the manipulation of morphology, is simple to mass-produce and can be used for MXene-based electrochemical applications.
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We report a laser-pyrolyzed carbon (LPC) electrode prepared from a black photoresist for an on-chip microsupercapacitor (MSC). An interdigitated LPC electrode was fabricated by direct laser writing using a high-power carbon dioxide (CO2) laser to simultaneously carbonize and pattern a spin-coated black SU-8 film. Due to the high absorption of carbon blacks in black SU-8, the laser-irradiated SU-8 surface was directly exfoliated and carbonized by a fast photo-thermal reaction. Facile laser pyrolysis of black SU-8 provides a hierarchically macroporous, graphitic carbon structure with fewer defects (ID/IG = 0.19). The experimental conditions of CO2 direct laser writing were optimized to fabricate high-quality LPCs for MSC electrodes with low sheet resistance and good porosity. A typical MSC based on an LPC electrode showed a large areal capacitance of 1.26 mF cm-2 at a scan rate of 5 mV/s, outperforming most MSCs based on thermally pyrolyzed carbon. In addition, the results revealed that the high-resolution electrode pattern in the same footprint as that of the LPC-MSCs significantly affected the rate performance of the MSCs. Consequently, the proposed laser pyrolysis technique using black SU-8 provided simple and facile fabrication of porous, graphitic carbon electrodes for high-performance on-chip MSCs without high-temperature thermal pyrolysis.
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Although energy-storage devices based on Li ions are considered as the most prominent candidates for immediate application in the near future, concerns with regard to their stability, safety, and environmental impact still remain. As a solution, the development of all-solid-state energy-storage devices with enhanced stability is proposed. A new eco-friendly polymer electrolyte has been synthesized by incorporating lithium trifluoromethanesulfonate into chemically modified methyl cellulose (LiTFS-LiSMC). The transparent and flexible electrolyte exhibits a good conductivity of near 1â mS cm-1 . An all-solid-state supercapacitor fabricated from 20â wt % LiTFS-LiSMC shows comparable specific capacitances to a standard liquid-electrolyte supercapacitor and an excellent stability even after 20 000 charge-discharge cycles. The electrolyte is also compatible with patterned carbon, which enables the simple fabrication of micro-supercapacitors. In addition, the LiTFS-LiSMC electrolyte can be recycled and reused more than 20â times with negligible change in its performance. Thus, it is a promising material for sustainable energy-storage devices.
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To gain the target functionality of graphene for gas detection, nonfocused and large-scale compatible MeV electron beam irradiation on graphene with Ag patterns is innovatively adopted in air for chemical patterning of graphene. This strategy allows the metal-assisted site-specific oxidation of graphene to realize monolithically integrated graphene-chemically patterned graphene (CPG)-graphene homojunction-based gas sensors. The size-tunable CPG patterns can be mediated by regulating the size of Ag prepatterns. The impacts of highly energetic electron irradiation (HEEI) on graphene are summarized as follows: (i) the selective p-type doping and the defect generation of graphene by the HEEI-induced oxidation, (ii) the resistance of the homojunction devices manipulated by the HEEI dose, (iii) the band gap opening of graphene as well as the lowering of the Fermi level, (iv) the work function values for pristine graphene and CPG corresponding to 4.14 and 4.88 eV, respectively, and (v) graphene-CPG-graphene homojunction for NO2 gas, revealing an 839% enhanced gas response compared with that of the pristine graphene-based gas sensor.
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Single source precursors for coating and subsequent thermal decomposition processes enable a large-scale, low-cost synthesis of two-dimensional transition metal dichalcogenides (TMDs). However, practical applications based on two-dimensional TMDs have been limited by the lack of applicable single source precursors for the synthesis of p-type TMDs including layered tungsten diselenide (WSe2). We firstly demonstrate the simple and facile synthesis of WSe2 layers using a newly developed precursor that allows improved dispersibility and lower decomposition temperature. We study the thermal decomposition mechanism of three types of (Cat+)2[WSe4] precursors to assess the most suitable precursor for the synthesis of WSe2 layers. The resulting chemical and structural exploration of solution-processed WSe2 layers suggests that the (CTA)2[WSe4] may be a promising precursor because it resulted in the formation of high-crystalline WSe2. In addition, this study verifies the capability of WSe2 layers for multifunctional applications in optoelectronic and electronic devices. The photocurrent of WSe2-based photodetectors shows an abrupt switching behavior under periodic illumination of visible or IR light. The extracted photoresponsivity values for WSe2-based photodetectors recorded at 0.5 V correspond to 26.3 mA W-1 for visible light and 5.4 mA W-1 for IR light. The WSe2-based field effect transistors exhibit unipolar p-channel transistor behavior with a carrier mobility of 0.45 cm2 V-1 s-1 and an on-off ratio of â¼10.
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Low-dimensional nanostructures and their complementary hybridization techniques are in the vanguard of technological advances for applications in transparent and flexible nanoelectronics due to the intriguing electrical properties related to their atomic structure. In this study, we demonstrated that welding of Ag nanowires (NWs) encapsulated in graphene was stimulated by flux-optimized, high-energy electron beam irradiation (HEBI) under ambient conditions. This methodology can inhibit the oxidation of Ag NWs which is induced by the inevitably generated reactive ozone as well as improve of their electrical conductivity. We have systematically explored the effects of HEBI on Ag NWs and graphene. The optimized flux for HEBI welding of the Ag NWs with graphene was 150 kGy, which decreased the sheet resistance of the graphene/Ag NWs to 12 Ohm/sq. Following encapsulation with graphene, the initial chemical states of the Ag NWs were well-preserved after flux-tuned HEBI, whereas graphene underwent local HEBI-induced defect generation near the junction area. We further employed resonant Raman spectroscopy to follow the structural evolution of the sacrificial graphene in the hybrid film after HEBI. Notably, the sheet resistance of the welded Ag NWs encapsulated with graphene after HEBI was well-maintained even after 85 days.
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Despite many encouraging properties of transition metal dichalcogenides (TMDs), a central challenge in the realm of industrial applications based on TMD materials is to connect the large-scale synthesis and reproducible production of highly crystalline TMD materials. Here, the primary aim is to resolve simultaneously the two inversely related issues through the synthesis of MoS2(1- x ) Se2 x ternary alloys with customizable bichalcogen atomic (S and Se) ratio via atomic-level substitution combined with a solution-based large-area compatible approach. The relative concentration of bichalcogen atoms in the 2D alloy can be effectively modulated by altering the selenization temperature, resulting in 4 in. scale production of MoS1.62 Se0.38 , MoS1.37 Se0.63 , MoS1.15 Se0.85 , and MoS0.46 Se1.54 alloys, as well as MoS2 and MoSe2 . Comprehensive spectroscopic evaluations for vertical and lateral homogeneity in terms of heteroatom distribution in the large-scale 2D TMD alloys are implemented. Se-stimulated strain effects and a detailed mechanism for the Se substitution in the MoS2 crystal are further explored. Finally, the capability of the 2D alloy for industrial application in nanophotonic devices and hydrogen evolution reaction (HER) catalysts is validated. Substantial enhancements in the optoelectronic and HER performances of the 2D ternary alloy compared with those of its binary counterparts, including pure-phase MoS2 and MoSe2 , are unambiguously achieved.
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MXenes - two dimensional, 2D, early transition metal, M, carbides and nitrides, X - are the latest addition to the 2D materials' world. Herein, we report on a facile low temperature solution chemical synthesis method to reduce Ti3C2Tx multilayered, ML, MXenes. Using X-ray photoelectron spectroscopy, electron spin resonance, magnetization measurements and other techniques, we concluded that immersing Ti3C2Tx MLs in the reducing agent Li-ethylenediamine (Li-EDA) - held at temperatures varying from room to 120 °C - reduces the 2D layers creating Ti3+ ions and oxygen vacancies. Above a temperature (T) of ≈10 K, the magnetic susceptibilities, χ, are temperature independent, implying that the resulting powders are Pauli paramagnetic. The loss of the magnetic signal upon intercalation of Li+ or EDA, together with a Curie-like increase in χ at T < 10 K, is consistent with that of a disordered metal that is close to a metallic to insulator transition and proves that the magnetism is associated with the 2D flakes. This result is the first evidence of any magnetism of any MXene.
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Herein, we report on an unprecedented synthetic method for single-layered GO that takes just a few tens of minutes. This rationally designed solid-state oxidation based on alkali metal carbonates (Li2CO3, Na2CO3, K2CO3) involves a molten salt reaction, which enables the effective exfoliation and oxidation of graphene layers without using H2SO4 and KMnO4. The advantage of this approach is not only the ability to avoid the introduction of strong acid reactants in the reaction process, but this approach also leads to a 4.2 times larger specific surface area than conventional GO. For these reasons, we anticipate that this green, safe, fast and effective approach enables practical applications in graphene-based energy storage and light-absorbing black materials.
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A facile methodology for the large-scale production of layer-controlled MoS2 layers on an inexpensive substrate involving a simple coating of single source precursor with subsequent roll-to-roll-based thermal decomposition is developed. The resulting 50 cm long MoS2 layers synthesized on Ni foils possess excellent long-range uniformity and optimum stoichiometry. Moreover, this methodology is promising because it enables simple control of the number of MoS2 layers by simply adjusting the concentration of (NH4 )2 MoS4 . Additionally, the capability of the MoS2 for practical applications in electronic/optoelectronic devices and catalysts for hydrogen evolution reaction is verified. The MoS2 -based field effect transistors exhibit unipolar n-channel transistor behavior with electron mobility of 0.6 cm2 V-1 s-1 and an on-off ratio of ≈10³. The MoS2 -based visible-light photodetectors are fabricated in order to evaluate their photoelectrical properties, obtaining an 100% yield for active devices with significant photocurrents and extracted photoresponsivity of ≈22 mA W-1 . Moreover, the MoS2 layers on Ni foils exhibit applicable catalytic activity with observed overpotential of ≈165 mV and a Tafel slope of 133 mV dec-1 . Based on these results, it is envisaged that the cost-effective methodology will trigger actual industrial applications, as well as novel research related to 2D semiconductor-based multifaceted applications.
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A generation of reactive oxygen species (ROS) from TiO2 under solar light has been long sought since the ROS can disinfect organic pollutants. We found that newly developed crystalline/amorphous reduced TiO2 (rTiO2) that has low energy bandgap can effectively generate ROS under solar light and successfully remove a bloom of algae. The preparation of rTiO2 is a one-pot and mass productive solution-process reduction using lithium-ethylene diamine (Li-EDA) at room temperature. Interestingly only the rutile phase of TiO2 crystal was reduced, while the anatase phase even in case of both anatase/rutile phased TiO2 was not reduced. Only reduced TiO2 materials can generate ROS under solar light, which was confirmed by electron spin resonance. Among the three different types of Li-EDA treated TiO2 (anatase, rutile and both phased TiO2), the both phased rTiO2 showed the best performance to produce ROS. The generated ROS effectively removed the common green algae Chlamydomonas. This is the first report on algae degradation under solar light, proving the feasibility of commercially available products for disinfection.
Assuntos
Chlamydomonas/efeitos dos fármacos , Desinfecção/métodos , Luz , Oxidantes/metabolismo , Fotólise , Titânio/metabolismo , Chlamydomonas/fisiologia , Espécies Reativas de Oxigênio/metabolismoRESUMO
Although there are numerous reports of high performance supercapacitors with porous graphene, there are few reports to control the interlayer gap between graphene sheets with conductive molecular linkers (or molecular pillars) through a π-conjugated chemical carbon-carbon bond that can maintain high conductivity, which can explain the enhanced capacitive effect of supercapacitor mechanism about accessibility of electrolyte ions. For this, we designed molecularly gap-controlled reduced graphene oxides (rGOs) via diazotization of three different phenyl, biphenyl, and para-terphenyl bis-diazonium salts (BD1-3). The graphene interlayer sub-nanopores of rGO-BD1-3 are 0.49, 0.7, and 0.96 nm, respectively. Surprisingly, the rGO-BD2 0.7 nm gap shows the highest capacitance in 1 M TEABF4 having 0.68 nm size of cation and 6 M KOH having 0.6 nm size of hydrated cation. The maximum energy density and power density of the rGO-BD2 were 129.67 W h kg(-1) and 30.3 kW kg(-1), respectively, demonstrating clearly that the optimized sub-nanopore of the rGO-BDs corresponding to the electrolyte ion size resulted in the best capacitive performance.
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Encapsulation of electronic devices such as dye-sensitized solar cells (DSSCs) is prone to degradation under normal atmospheric conditions, even with hermetic barriers on the metal electrodes. Overcoming this problem is crucial to increasing DSSC lifetimes and making them commercially viable. Herein, we report a new impermeable flexible liquid barrier film using polyvinyl alcohol (PVA) and partially reduced graphene oxide (PrGO), which dramatically enhances the lifetime of Ag metal electrodes (typically used in DSSCs) immersed in a highly acidic iodolyte solution. The Ag metal electrode encapsulated by the PVA/PrGO film survived for over 500 hrs, superior to existing barriers of glass frits, epoxy resins and polymers. The PVA/PrGO film strongly adheres to the Ag metal surface, and the resulting PVA/PrGO/Ag electrode is stable even on a curved substrate, with a sheet resistance nearly independent of curvature. These results give new insight for the design of high-performance and solution-processable flexible liquid barrier films for a wide range of applications, in particular for the encapsulation of electronic devices with liquid electrolytes.