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1.
Realization of ideal molecular sieves, in which the larger gas molecules are completely blocked without sacrificing high adsorption capacities of the preferred smaller gas molecules, can significantly reduce energy costs for gas separation and purification and thus facilitate a possible technological transformation from the traditional energy‐intensive cryogenic distillation to the energy‐efficient, adsorbent‐based separation and purification in the future. Although extensive research endeavors are pursued to target ideal molecular sieves among diverse porous materials, over the past several decades, ideal molecular sieves for the separation and purification of light hydrocarbons are rarely realized. Herein, an ideal porous material, SIFSIX‐14‐Cu‐i (also termed as UTSA‐200), is reported with ultrafine tuning of pore size (3.4 Å) to effectively block ethylene (C2H4) molecules but to take up a record‐high amount of acetylene (C2H2, 58 cm3 cm?3 under 0.01 bar and 298 K). The material therefore sets up new benchmarks for both the adsorption capacity and selectivity, and thus provides a record purification capacity for the removal of trace C2H2 from C2H4 with 1.18 mmol g?1 C2H2 uptake capacity from a 1/99 C2H2/C2H4 mixture to produce 99.9999% pure C2H4 (much higher than the acceptable purity of 99.996% for polymer‐grade C2H4), as demonstrated by experimental breakthrough curves.  相似文献   

2.
Propyne/propylene (C3H4/C3H6) separation is a critical process for the production of polymer‐grade C3H6. However, optimization of the structure of porous materials for the highly efficient removal of C3H4 from C3H6 remains challenging due to their similar structures and ultralow C3H4 concentration. Here, it is first reported that hybrid ultramicroporous materials with pillared inorganic anions (SiF62? = SIFSIX, NbOF52? = NbOFFIVE) can serve as highly selective C3H4 traps for the removal of trace C3H4 from C3H6. Especially, it is revealed that the pyrazine‐based ultramicroporous material with square grid structure for which the pore shape and functional site disposition can be varied in 0.1–0.5 Å scale to match both the shape and interacting sites of guest molecule is an interesting single‐molecule trap for C3H4 molecule. The pyrazine‐based single‐molecule trap enables extremely high C3H4 uptake under ultralow concentration (2.65 mmol g?1 at 3000 ppm, one C3H4 per unit cell) and record selectivity over C3H6 at 298 K (>250). The single‐molecule binding mode for C3H4 within ultramicroporous material is validated by X‐ray diffraction experiments and modeling studies. The breakthrough experiments confirm that anion‐pillared ultramicroporous materials set new benchmarks for the removal of ultralow concentration C3H4 (1000 ppm on SIFSIX‐3‐Ni, and 10 000 ppm on SIFSIX‐2‐Cu‐i) from C3H6.  相似文献   

3.
Sodium‐ion batteries (SIBs) are considered a prospective candidate for large‐scale energy storage due to the merits of abundant sodium resources and low cost. However, a lack of suitable advanced anode materials has hindered further applications. Herein, metal–semiconductor mixed phase twinned hierarchical (MPTH) MoS2 nanowires with an expanded interlayer (9.63 Å) are engineered and prepared using MoO3 nanobelts as a self‐sacrificed template in the presence of a trace amount of (NH4)6Mo7O24·4H2O as initiator. The greatly expanded interlayer spacing accelerates Na+ insertion/extraction kinetics, and the metal–semiconductor mixed phase enhances electron transfer ability and stabilizes electrode structure during cycling. Benefiting from the structural merits, the MPTH MoS2 electrode delivers high reversible capacities of 200 mAh g?1 at 0.1 A g?1 for 200 cycles and 154 mAh g?1 at 1 A g?1 for 2450 cycles in the voltage range of 0.4–3.0 V. Strikingly, the electrode maintains 6500 cycles at a current density of 2 A g?1, corresponding to a capacity retention of 82.8% of the 2nd cycle, overwhelming the all reported MoS2 cycling results. This study provides an alternative strategy to boost SIB cycling performance in terms of reversible capacity by virtue of interlayer expansion and structure stability.  相似文献   

4.
Exploring high‐rate electrode materials with excellent kinetic properties is imperative for advanced sodium‐storage systems. Herein, novel cubic‐like X? Fe (X = Co, Ni, Mn) Prussian blue analogs (PBAs), as cathodes materials, are obtained through as‐tuned ionic bonding, delivering improved crystallinity and homogeneous particles size. As expected, Ni‐Fe PBAs show a capacity of 81 mAh g?1 at 1.0 A g?1, mainly resulting from their physical–chemical stability, fast kinetics, and “zero‐strain” insertion characteristics. Considering that the combination of elements incorporated with carbon may increase the rate of ion transfer and improve the lifetime of cycling stability, they are expected to derive binary metal‐selenide/nitrogen‐doped carbon as anodes. Among them, binary Ni0.67Fe0.33Se2 coming from Ni‐Fe PBAs shows obvious core–shell structure in a dual‐carbon matrix, leading to enhanced electron interactions, electrochemical activity, and “metal‐like” conductivity, which could retain an ultralong‐term stability of 375 mAh g?1 after 10 000 loops even at 10.0 A g?1. The corresponding full‐cell Ni‐Fe PBAs versus Ni0.67Fe0.33Se2 deliver a remarkable Na‐storage capacity of 302.2 mAh g?1 at 1.0 A g?1. The rational strategy is anticipated to offer more possibilities for designing advanced electrode materials used in high‐performance sodium‐ion batteries.  相似文献   

5.
Molybdenum ditelluride nanosheets encapsulated in few‐layer graphene (MoTe2/FLG) are synthesized by a simple heating method using Te and Mo powder and subsequent ball milling with graphite. The as‐prepared MoTe2/FLG nanocomposites as anode materials for lithium‐ion batteries exhibit excellent electrochemical performance with a highly reversible capacity of 596.5 mAh g?1 at 100 mA g?1, a high rate capability (334.5 mAh g?1 at 2 A g?1), and superior cycling stability (capacity retention of 99.5% over 400 cycles at 0.5 A g?1). Ex situ X‐ray diffraction and transmission electron microscopy are used to explore the lithium storage mechanism of MoTe2. Moreover, the electrochemical performance of a MoTe2/FLG//0.35Li2MnO3·0.65LiMn0.5Ni0.5O2 full cell is investigated, which displays a reversible capacity of 499 mAh g?1 (based on the MoTe2/FLG mass) at 100 mA g?1 and a capacity retention of 78% over 50 cycles, suggesting the promising application of MoTe2/FLG for lithium‐ion storage. First‐principles calculations exhibit that the lowest diffusion barrier (0.18 eV) for lithium ions along pathway III in the MoTe2 layered structure is beneficial for improving the Li intercalation/deintercalation property.  相似文献   

6.
LiV3O8 nanorods with controlled size are successfully synthesized using a nonionic triblock surfactant Pluronic‐F127 as the structure directing agent. X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy techniques are used to characterize the samples. It is observed that the nanorods with a length of 4–8 µm and diameter of 0.5–1.0 µm distribute uniformly. The resultant LiV3O8 nanorods show much better performance as cathode materials in lithium‐ion batteries than normal LiV3O8 nanoparticles, which is associated with the their unique micro–nano‐like structure that can not only facilitate fast lithium ion transport, but also withstand erosion from electrolytes. The high discharge capacity (292.0 mAh g?1 at 100 mA g?1), high rate capability (138.4 mAh g?1 at 6.4 A g?1), and long lifespan (capacity retention of 80.5% after 500 cycles) suggest the potential use of LiV3O8 nanorods as alternative cathode materials for high‐power and long‐life lithium ion batteries. In particular, the synthetic strategy may open new routes toward the facile fabrication of nanostructured vanadium‐based compounds for energy storage applications.  相似文献   

7.
With the unique‐layered structure, MXenes show potential as electrodes in energy‐storage devices including lithium‐ion (Li+) capacitors and batteries. However, the low Li+‐storage capacity hinders the application of MXenes in place of commercial carbon materials. Here, the vanadium carbide (V2C) MXene with engineered interlayer spacing for desirable storage capacity is demonstrated. The interlayer distance of pristine V2C MXene is controllably tuned to 0.735 nm resulting in improved Li‐ion capacity of 686.7 mA h g?1 at 0.1 A g?1, the best MXene‐based Li+‐storage capacity reported so far. Further, cobalt ions are stably intercalated into the interlayer of V2C MXene to form a new interlayer‐expanded structure via strong V–O–Co bonding. The intercalated V2C MXene electrodes not only exhibit superior capacity up to 1117.3 mA h g?1 at 0.1 A g?1, but also deliver a significantly ultralong cycling stability over 15 000 cycles. These results clearly suggest that MXene materials with an engineered interlayer distance will be a rational route for realizing them as superstable and high‐performance Li+ capacitor electrodes.  相似文献   

8.
Using interfacial reaction systems for biphasic catalytic reactions is attracting more and more attention due to their simple reaction process and low environmental pollution. Yolk–shell structured materials have broad applications in biomedicine, catalysis, and environmental remediation owing to their open channels and large space for guest molecules. Conventional methods to obtain yolk–shell mesoporous materials rely on costly and complex hard‐template strategies. In this study, a mild and convenient nonsacrificial self‐template strategy is developed to construct yolk–shell magnetic periodic mesoporous organosilica (YS‐mPMO) particles by using the unique swelling–deswelling property of low‐crosslinking density resorcinol formaldehyde (RF). The obtained YS‐mPMO microspheres possess an amphiphilic outer shell, high surface area (393 m2 g?1), uniform mesopores (2.58 nm), a tunable middle hollow space (50–156 nm), and high superparamagnetism (34.4–37.1 emu g?1). By tuning the synthesis conditions, heterojunction structured yolk–shell Fe3O4@RF@void@PMO particles with different morphologies can be produced. Owing to the amphipathy of PMO framworks, the YS‐mPMO particles show great emulsion stabilization ability and recyclability under a magnetic field. YS‐mPMO microspheres with immobilized Au nanoparticles (≈3 nm) act as both solid emulsifier for dispersing styrene (St) in water and interface catalysts for selective conversion of St into styrene oxide with a high selectivity of 86%, and yields of over 97%.  相似文献   

9.
Aqueous zinc‐ion batteries are promising candidates for grid‐scale energy storage because of their intrinsic safety, low cost, and high energy intensity. However, lack of suitable cathode materials with both excellent rate performance and cycling stability hinders further practical application of aqueous zinc‐ion batteries. Here, a nanoflake‐self‐assembled nanorod structure of Ca0.28MnO2·0.5H2O as Zn‐insertion cathode material is designed. The Ca0.28MnO2·0.5H2O exhibits a reversible capacity of 298 mAh g?1 at 175 mA g?1 and long‐term cycling stability over 5000 cycles with no obvious capacity fading, which indicates that the per‐insertion of Ca ions and water can significantly improve reversible insertion/extraction stability of Zn2+ in Mn‐based layered type material. Further, its charge storage mechanism, especially hydrogen ions, is elucidated. A comprehensive study suggests that the intercalation of hydrogen ions in the first discharge plat is controled by both pH value and type of anion of electrolyte. Further, it can stabilize the Ca0.28MnO2·0.5H2O cathode and facilitate the following insertion of Zn2+ in 1 m ZnSO4/0.1 m MnSO4 electrolyte. This work can enlighten and promote the development of high‐performance rechargeable aqueous zinc‐ion batteries.  相似文献   

10.
Two-dimensional (2D) materials have attracted enormous attention due to their functional applications in energy storage. In this work, a low-temperature molten-salt chemical exfoliation methodology is developed for producing free-standing 2D mesoporous Si through deintercalation of CaSi2 in excess molten AlCl3 at 195 °C. The average dimension of these sheets is 1.5 μm, and the thickness of a single sheet is approximately 10 nm. The as-prepared 2D Si has a Brunauer–Emmett–Teller surface area of 154 m2·g?1 and an average pore size of 5.87 nm. With this unique structure, the 2D Si exhibits superior Li-storage performance, including a reversible capacity of 2,974 mA·h·g?1 at 0.2 C, reversible capacities of 2,162, 1,947, and 1,527 mA·h·g?1 at 0.8, 2, and 5 C after 200 cycles, and a capacity retention of 357 mA·h·g?1 even at 30 C (90 A·g?1).
  相似文献   

11.
Core–shell magnetic porous microspheres have wide applications in drug delivery, catalysis and bioseparation, and so on. However, it is great challenge to controllably synthesize magnetic porous microspheres with uniform well‐aligned accessible large mesopores (>10 nm) which are highly desired for applications involving immobilization or adsorption of large guest molecules or nanoobjects. In this study, a facile and general amphiphilic block copolymer directed interfacial coassembly strategy is developed to synthesize core–shell magnetic mesoporous microspheres with a monolayer of mesoporous shell of different composition (FDUcs‐17D), such as core–shell magnetic mesoporous aluminosilicate (CS‐MMAS), silica (CS‐MMS), and zirconia‐silica (CS‐MMZS), open and large pores by employing polystyrene‐block‐poly (4‐vinylpyridine) (PS‐b‐P4VP) as an interface structure directing agent and aluminum acetylacetonate (Al(acac)3), zirconium acetylacetonate, and tetraethyl orthosilicate as shell precursors. The obtained CS‐MMAS microspheres possess magnetic core, perpendicular mesopores (20–32 nm) in the shell, high surface area (244.7 m2 g?1), and abundant acid sites (0.44 mmol g?1), and as a result, they exhibit superior performance in removal of organophosphorus pesticides (fenthion) with a fast adsorption dynamics and high adsorption capacity. CS‐MMAS microspheres loaded with Au nanoparticles (≈3.5 nm) behavior as a highly active heterogeneous nanocatalyst for N‐alkylation reaction for producing N‐phenylbenzylamine with a selectivity and yields of over 90% and good magnetic recyclability.  相似文献   

12.
Supercapacitors have received increasing interest as energy storage devices due to their rapid charge–discharge rates, high power densities, and high durability. In this work, novel conjugated microporous polymer (CMP) networks are presented for supercapacitor energy storage, namely 3D polyaminoanthraquinone (PAQ) networks synthesized via Buchwald–Hartwig coupling between 2,6‐diaminoanthraquinone and aryl bromides. PAQs exhibit surface areas up to 600 m2 g?1, good dispersibility in polar solvents, and can be processed to flexible electrodes. The PAQs exhibit a three‐electrode specific capacitance of 576 F g?1 in 0.5 m H2SO4 at a current of 1 A g?1 retaining 80–85% capacitances and nearly 100% Coulombic efficiencies (95–98%) upon 6000 cycles at a current density of 2 A g?1. Asymmetric two‐electrode supercapacitors assembled by PAQs show a capacitance of 168 F g?1 of total electrode materials, an energy density of 60 Wh kg?1 at a power density of 1300 W kg?1, and a wide working potential window (0–1.6 V). The asymmetric supercapacitors show Coulombic efficiencies up to 97% and can retain 95.5% of initial capacitance undergo 2000 cycles. This work thus presents novel promising CMP networks for charge energy storage.  相似文献   

13.
Potassium‐ion batteries (KIBs) are promising alternatives to lithium‐ion batteries because of the abundance and low cost of K. However, an important challenge faced by KIBs is the search for high‐capacity materials that can hold large‐diameter K ions. Herein, copper oxide (CuO) nanoplates are synthesized as high‐performance anode materials for KIBs. CuO nanoplates with a thickness of ≈20 nm afford a large electrode–electrolyte contact interface and short K+ ion diffusion distance. As a consequence, a reversible capacity of 342.5 mAh g?1 is delivered by the as‐prepared CuO nanoplate electrode at 0.2 A g?1. Even after 100 cycles at a high current density of 1.0 A g?1, the capacity of the electrode remains over 206 mAh g?1, which is among the best values for KIB anodes reported in the literature. Moreover, a conversion reaction occurs at the CuO anode. Cu nanoparticles form during the first potassiation process and reoxidize to Cu2O during the depotassiation process. Thereafter, the conversion reaction proceeds between the as‐formed Cu2O and Cu, yielding a reversible theoretical capacity of 374 mAh g?1. Considering their low cost, easy preparation, and environmental benignity, CuO nanoplates are promising KIB anode materials.  相似文献   

14.
The development of high‐capacity, Earth‐abundant, and stable cathode materials for robust aqueous Zn‐ion batteries is an ongoing challenge. Herein, ultrathin nickel cobaltite (NiCo2O4) nanosheets with enriched oxygen vacancies and surface phosphate ions (P–NiCo2O4‐x) are reported as a new high‐energy‐density cathode material for rechargeable Zn‐ion batteries. The oxygen‐vacancy and surface phosphate‐ion modulation are achieved by annealing the pristine NiCo2O4 nanosheets using a simple phosphating process. Benefiting from the merits of substantially improved electrical conductivity and increased concentration of active sites, the optimized P–NiCo2O4‐x nanosheet electrode delivers remarkable capacity (309.2 mAh g?1 at 6.0 A g?1) and extraordinary rate performance (64% capacity retention at 60.4 A g?1). Moreover, based on the P–NiCo2O4‐x cathode, our fabricated P–NiCo2O4‐x//Zn battery presents an impressive specific capacity of 361.3 mAh g?1 at the high current density of 3.0 A g?1 in an alkaline electrolyte. Furthermore, extremely high energy density (616.5 Wh kg?1) and power density (30.2 kW kg?1) are also achieved, which outperforms most of the previously reported aqueous Zn‐ion batteries. This ultrafast and high‐energy aqueous Zn‐ion battery is promising for widespread application to electric vehicles and intelligent devices.  相似文献   

15.
Owing to the advantages of high safety, low cost, high theoretical volumetric capacities, and environmental friendliness, magnesium‐ion batteries (MIBs) have more feasibility for large‐scale energy storage compared to lithium‐ion batteries. However, lack of suitable cathode materials due to sluggish kinetics of magnesium ion is one of the biggest challenges. Herein, water‐pillared sodium vanadium bronze nanowires (Na2V6O16·1.63H2O) are reported as cathode material for MIBs, which display high performance in magnesium storage. The hydrated sodium ions provide excellent structural stability. The charge shielding effect of lattice water enables fast Mg2+ diffusion. It exhibits high specific capacity of 175 mAh g?1, long cycle life (450 cycles), and high coulombic efficiency (≈100%). At high current density of 200 mA g?1, the capacity retention is up to 71% even after 450 cycles (compared to the highest capacity), demonstrating excellent long‐term cycling performance. The nature of charge storage kinetics is explored. Furthermore, a highly reversible structure change during the electrochemical process is proved by comprehensive electrochemical analysis. The remarkable electrochemical performance makes Na2V6O16·1.63H2O a promising cathode material for low‐cost and safe MIBs.  相似文献   

16.
3D cube‐shaped composites and carbon microparticles with hierarchically porous structure are prepared by a facile template‐free synthesis route. Via the coordination of zinc acetate dihydrate and squaric acid, porous 3D cubic crystalline particles of zinc squarate can be obtained. These are easily transformed into the respective zinc oxide carbon composites under preservation of the macromorphology by heat treatment. Washing of the composite materials results in hierarchically porous carbons with high surface areas (1295 m2 g–1) and large pore volumes (1.5 cm3 g?1) under full retention of the cube‐like architecture of the initial crystals. The materials are shown to be promising electrode materials for supercapacitor applications with a specific capacitance of 133 F g?1 in H2SO4 at a scan rate of 5 mV s?1, while 67% of this specific capacitance is retained, when increasing the scan rate to 200 mV s?1.  相似文献   

17.
Manganese oxides (MnOx) are promising anode materials for lithium ion batteries, but they generally exhibit mediocre performances due to intrinsic low ionic conductivity, high polarization, and poor stability. Herein, yolk–shell nanorods comprising of nitrogen‐doped carbon (N–C) coating on manganese monoxide (MnO) coupled with zinc manganate (ZnMn2O4) nanoparticles are manufactured via one‐step carbonization of α‐MnO2/ZIF‐8 precursors. When evaluated as anodes for lithium ion batteries, MnO@ZnMn2O4/N–C exhibits an reversible capacity of 803 mAh g?1 at 50 mA g?1 after 100 cycles, excellent cyclability with a capacity of 595 mAh g?1 at 1000 mAg?1 after 200 cycles, as well as better rate capability compared with those non‐N–C shelled manganese oxides (MnOx). The outstanding electrochemical performance is attributed to the unique yolk–shell nanorod structure, the coating effect of N–C and nanoscale size.  相似文献   

18.
In the present investigation, we report the synthesis of ruthenium oxide (RuO2 · nH2O) thin films by simple chemical bath deposition (CBD) method at low temperature on the stainless steel substrate. The prepared thin films are characterized for their structural and morphological properties by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT–IR) and scanning electron microscopy (SEM). The structural study revealed that the ruthenium oxide thin films are amorphous. Scanning electron microscopy study shows compact morphology with small overgrown particles on the surface of the substrate. FT–IR study confirms the formation of RuO2 · nH2O material. The supercapacitor behaviour of RuO2 · nH2O thin film was studied using cyclic voltammetry (CV) technique in 0 · 5 M H2SO4electrolyte. RuO2 · nH2O film showed maximum specific capacitance of 192 F · g? 1at a scan rate of 20 mV · s? 1. The charge–discharge studies of RuO2 · nH2O carried out at 300 μA · cm? 2current density revealed the specific power of 1 · 5 kW.kg? 1and specific energy of 41 · 6 Wh.kg? 1with 95% coulombic efficiency.  相似文献   

19.
A high capacity cathode is the key to the realization of high‐energy‐density lithium‐ion batteries. The anionic oxygen redox induced by activation of the Li2MnO3 domain has previously afforded an O3‐type layered Li‐rich material used as the cathode for lithium‐ion batteries with a notably high capacity of 250–300 mAh g?1. However, its practical application in lithium‐ion batteries has been limited due to electrodes made from this material suffering severe voltage fading and capacity decay during cycling. Here, it is shown that an O2‐type Li‐rich material with a single‐layer Li2MnO3 superstructure can deliver an extraordinary reversible capacity of 400 mAh g?1 (energy density: ≈1360 Wh kg?1). The activation of a single‐layer Li2MnO3 enables stable anionic oxygen redox reactions and leads to a highly reversible charge–discharge cycle. Understanding the high performance will further the development of high‐capacity cathode materials that utilize anionic oxygen redox processes.  相似文献   

20.
Light hydrocarbons are important raw materials for industrial products and fine chemicals. The storage and separation of C1–C3 hydrocarbons are vital to their practical use. Here, we report efficient C1–C3 hydrocarbon adsorption and separation with a NbO-type anionic copper metal–organic framework with uncoordinated –COO? groups ([Cu2(L)·(H2O)2]·2H2O·3DMA·(CH3)2NH2) (1). Complex 1 exhibited large C2H2 (190 cm3 g?1), C2H4 (147 cm3 g?1), C2H6 (156 cm3 g?1), C3H6 (170 cm3 g?1), and C3H8 (173 cm3 g?1) uptakes and high selectivities for C2H2/CH4 (32.3), C3H6/CH4 (152), and C3H8/CH4 (127) under ambient conditions. The excellent cycling performance of the material was reflected by only 9.2 and 10.9% losses of the C2H2 and C3H6 storage capacities even after ten cycles of adsorption–desorption tests. First-principles calculations and Grand canonical Monte Carlo simulations further revealed that not only the open metal sites but also the –COO? groups played a key role in the high C2–C3 hydrocarbon uptakes. The results obtained in this study suggest that anionic 1 is a promising candidate for light hydrocarbon adsorption and natural gas purification at room temperature.  相似文献   

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