Ice crystal guided folding of graphene oxides in a confined space: a facile approach to 1D functional graphene structures.

The controlled conformational changes of planar graphene nanosheets are of great importance to the realization of their practical applications. Despite substantial effort in the area, the controlled folding of two-dimensional (2D) graphene sheets into one-dimensional (1D) structures still remains a significant challenge. Here, for the first time, we report an ice crystal guided folding strategy to fabricate 1D folded graphene nanobelts (FGBs), where the formation and growth of ice crystals in a confined space function to guide the folding of 2D graphene oxide (GO) nanosheets into 1D nanobelts (i.e. folded graphene oxide belts, FGOBs), which were subsequently converted to FGBs after annealing. Thin aqueous GO containing films were obtained by blowing air through a GO dispersion in the presence of a surfactant, polyoxypropylenediamine (D400), resulting in a foam containing uniform air bubbles. Subsequent shock cooling of the foam using liquid nitrogen resulted in the facile fabrication of FGOBs. This technique provides a general approach to encapsulate catalytic nanomaterials such as Fe3O4 nanorods, TiO2 and Co3O4 nanoparticles into the folded graphene structure for practical applications such as Li-ion batteries.

Power Generation from the Interaction of a Carbon Foam and Water.

Understanding the interaction mechanisms between the surface of carbon-based materials and water is of great significance for the development of water-based energy storage and energy conversion devices. Herein, a self-supporting electric generator is demonstrated based on water adsorption on the surface of the carbon foam (CF) that works with various water resources, including deionized (DI) water, tap water, wastewater, and seawater. It is revealed that the dissociation of oxygen-containing groups on the surface of CF after water molecule adsorption leads to a reduction of the surface potential of the CF. Through surface modulation techniques such as reduction and oxidation, a balance has been uncovered between the oxygen content and conductivity for the high-performance CFs. The generator can generate an open-circuit voltage of approximately 0.6 V in natural seawater with a power density of up to 0.77 mW g-1. A high voltage of more than 2 V can be achieved easily by assembling components connected in series to drive electronic devices, such as a light-emitting diode (LED). This work demonstrates a simple and low-cost method for electricity harvesting, offering an additional option for self-powered devices.

Preparation of expandable vertically aligned carbon nanotube arrays/polydimethylsiloxane membrane by a modular splicing method and its application in in situ ethanol recovery from ethanol fermentation.

Aligned carbon nanotube (CNT) arrays have been widely used in the preparation of polymer composites. CNT arrays are commonly prepared by chemical vapor deposition (CVD) in a high temperature tubular furnace, and the areas of the aligned CNT/polymer membranes prepared are relatively small (<30 cm2) due to the limitation of the inner diameter of the furnace, which limits its practical application in the field of membrane separation. Herein, the vertically aligned CNT arrays/polydimethylsiloxane (PDMS) membrane with large and expandable area was prepared by a modular splicing method for the first time, with a maximum area of 144 cm2. The addition of CNT arrays with openings at both ends significantly improved the pervaporation performance of the PDMS membrane for ethanol recovery. At 80 °C, the flux (671.6 g m-2 h-1) and separation factor (9.0) of CNT arrays/PDMS membrane were increased by 435.12% and 58.52%, respectively, compared with those of the PDMS membrane. Furthermore, the expandable area enabled the CNT arrays/PDMS membrane to couple with fed-batch fermentation for pervaporation for the first time, which increased the ethanol yield (0.47 g g-1) and productivity (2.34 g L-1 h-1) by 9.3% and 4.9% respectively compared with batch fermentation. Besides, the flux (135.47-166.79 g m-2 h-1) and separation factor (8.83-9.21) of CNT arrays/PDMS membrane remained stable in this process, indicating that this membrane has the potential to be applied in industrial bioethanol production. This work provides a new idea for the preparation of large-area aligned CNT/polymer membranes, and also opens up a new direction for the application of large-area aligned CNT/polymer membranes.

CoSe Nanoparticle Embedded B,N-Codoped Carbon Nanotube Array as a Dual-Functional Host for a High-Performance Li-S Full Battery.

The lithium polysulfide (LiPSs) shuttling and slow chemical reactions at the sulfur cathode and the formation of dendritic lithium in metal anodes severely hinder the popularization of lithium-sulfur batteries. Here, a B,N-codoped carbon nanotube (BNCNTs) array decorated with sulfilic and lithiophilic CoSe nanoparticles grown on a carbon cloth (CoSe@BNCNTs/CC) as both a sulfur and a lithium host is reported. Density functional theory (DFT) calculations, simulations, and electrochemical performance determinations demonstrate that CoSe@BNCNTs/CC can simultaneously exert catalytic effects for accelerating LiPSs conversion and realize smooth and uniform lithium deposition to regulate the S and Li electrochemistry. Moreover, the unique structure of the BNCNTs array provides sufficient storage space for sulfur and homogenizes the distribution of Li ions and the electric field of the electrode. The assembled Li-S full battery with a CoSe@BNCNTs/CC dual-functional host exhibits a long-term cycling stability (800 cycles at 0.5 C with a decay rate of 0.066% per cycle) and a high rate capacity (684 mAh g-1 at 2 C). Even at a high sulfur loading of 7.9 mg cm-2, the Li-S full battery has a high areal capacity of 9.76 mAh cm-2 at 0.2 C. This study proposes a viable strategy to solve the challenges of both S and Li electrodes for practical Li-S full batteries.

Urea-Mediated Monoliths Made of Nitrogen-Enriched Mesoporous Carbon Nanosheets for High-Performance Aqueous Zinc Ion Hybrid Capacitors.

Aqueous zinc ion hybrid capacitors (aZHCs) are of great potential for large-scale energy storage and flexible wearable devices, of which the specific capacity and energy density need to be further enhanced for practical applications. Herein, a urea-mediated foaming strategy is reported for the efficient synthesis of monoliths consisting of nitrogen-enriched mesoporous carbon nanosheets (NPCNs) by prefoaming drying a solution made of polyvinylpyrrolidone, zinc nitrate, and urea at low temperatures, foaming and annealing at high temperatures, and subsequent acid etching. NPCNs have a large lateral size of ≈40 µm, thin thickness of ≈55 nm, abundant micropores and mesopores (≈3.8 nm), and a high N-doping value of 9.7 at.%. The NPCNs as the cathode in aZHCs provide abundant zinc storage sites involving both physical and chemical adsorption/desorption of Zn2+  ions, and deliver high specific capacities of 262 and 115 mAh g-1 at 0.2 and 10 A g-1 , and a remarkable areal capacity of ≈0.5 mAh cm-2  with a mass loading of 5.3 mg cm-2 , outperforming most carbon cathodes reported thus far. Moreover, safe and flexible NPCNs based quasi-solid-state devices are fabricated, which can withstand drilling and mechanical bending, suggesting their potential applications in wearable devices.

Ni@Ni3N Embedded on Three-Dimensional Carbon Nanosheets for High-Performance Lithium/Sodium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are recognized as one of the most promising next-generation energy storage devices, but their practical application is greatly limited by several obstacles, such as the highly insulating nature and sluggish redox kinetics of sulfur and the dissolution of lithium polysulfides. Herein, three-dimensional carbon nanosheet frameworks anchored with Ni@Ni3N heterostructure nanoparticles (denoted Ni@Ni3N/CNS) are designed and fabricated by a chemical blowing and thermal nitridation strategy. It is demonstrated that the Ni@Ni3N heterostructure can effectively accelerate polysulfide conversion and promote the chemical trapping of polysulfides. Meanwhile, the carbon nanosheet frameworks of Ni@Ni3N/CNS establish a highly conductive network for fast electron transportation. The cells with Ni@Ni3N heterostructures as the catalyst in the cathode show excellent electrochemical performance, revealing stable cycling over 600 cycles with a low-capacity fading rate of 0.04% per cycle at 0.5 C and high-rate capability (594 mAh g-1 at 3 C). Furthermore, Ni@Ni3N/CNS can also work well in room-temperature sodium-sulfur (RT-Na/S) batteries, delivering a high specific capacity (454 mAh g-1 after 400 cycles at 0.5 C). This work provides a rational way to prepare the metal-metal nitride heterostructures to enhance the performance both of Li-S and RT-Na/S batteries.

Electrolyte/Structure-Dependent Cocktail Mediation Enabling High-Rate/Low-Plateau Metal Sulfide Anodes for Sodium Storage.

As promising anodes for sodium-ion batteries, metal sulfides ubiquitously suffer from low-rate and high-plateau issues, greatly hindering their application in full-cells. Herein, exemplifying carbon nanotubes (CNTs)-stringed metal sulfides superstructure (CSC) assembled by nano-dispersed SnS2 and CoS2 phases, cocktail mediation effect similar to that of high-entropy materials is initially studied in ether-based electrolyte to solve the challenges. The high nano-dispersity of metal sulfides in CSC anode underlies the cocktail-like mediation effect, enabling the circumvention of intrinsic drawbacks of different metal sulfides. By utilizing ether-based electrolyte, the reversibility of metal sulfides is greatly improved, sustaining a long-life effectivity of cocktail-like mediation. As such, CSC effectively overcomes low-rate flaw of SnS2 and high-plateau demerit of CoS2, simultaneously realizes a high rate and a low plateau. In half-cells, CSC delivers an ultrahigh-rate capability of 327.6 mAh g-1anode at 20 A g-1, far outperforming those of monometallic sulfides (SnS2, CoS2) and their mixtures. Compared with CoS2 phase and SnS2/CoS2 mixture, CSC shows remarkably lowered average charge voltage up to ca. 0.62 V. As-assembled CSC//Na1.5VPO4.8F0.7 full-cell shows a good rate capability (0.05 ~ 1.0 A g-1, 120.3 mAh g-1electrode at 0.05 A g-1) and a high average discharge voltage up to 2.57 V, comparable to full-cells with alloy-type anodes. Kinetics analysis verifies that the cocktail-like mediation effect largely boosts the charge transfer and ionic diffusion in CSC, compared with single phase and mixed phases. Further mechanism study reveals that alternative and complementary electrochemical processes between nano-dispersed SnS2 and CoS2 phases are responsible for the lowered charge voltage of CSC. This electrolyte/structure-dependent cocktail-like mediation effect effectively enhances the practicability of metal sulfide anodes, which will boost the development of high-rate/-voltage sodium-ion full batteries.

Balanced kinetics between electrodes by carbon cloth@ZIF-8 for high rate performance zinc-ion hybrid capacitors.

Herein, ZIF-8 pre-grown on carbon cloth (CC) leads to preferential and homogenizing Zn deposition to accelerate Zn-ion diffusion. CC with uniform Zn deposits induced from ZIF-8 promotes rapid Zn plating, resulting in balanced kinetics between electrodes. The as-assembled ZICs show a high specific capacitance of 302 F g-1 at 0.5 A g-1, an outstanding rate performance of 188 F g-1 at 20 A g-1 and 100% capacitance retention after 10000 cycles.

Preparation of nitrogen-doped hollow carbon nanosphere/graphene composite aerogel for efficient removal of quinoline from wastewater.

The deep removal of quinoline from coking wastewater is a prerequisite for reducing its potential threat to environmental safety. Therefore, it is urgent to develop advanced materials for efficient removal of quinoline in wastewater. In this work, a nitrogen-doped hollow carbon nanosphere/graphene composite aerogel (HCNS/NGA) was prepared by in-situ reduction self-assembly strategy, in which HCNS prevents the agglomeration of graphene oxide (GO) nanosheets, and a special sphere-sheet mutual support structure is formed to ensure the structural stability. As-prepared HCNS/NGA exhibits large specific surface area, hierarchical pore structure, and excellent conductivity. Large cavity inside and hierarchically porous structure that primarily consists of micropores, resulting in high quinoline adsorption performance (138.37 ± 2.58 mg g-1 at 298 K). Furthermore, in a fixed-bed column adsorption system, the partition coefficient at 10% breakthrough reaches up to 35.19 mg g-1 µM-1. More importantly, HCNS/NGA, as a conductive monolithic sorbent, can realize easy solid-liquid separation, as well as efficient regeneration in situ by electrochemically assisted regeneration. After ten regeneration cycles, the adsorption capacity retention is 91.54%. In short, as an efficient adsorbent, HCNS/NGA has an enormous application potential in wastewater treatment.

A C-S-C Linkage-Triggered Ultrahigh Nitrogen-Doped Carbon and the Identification of Active Site in Triiodide Reduction.

An efficient chemical synthesis route, with an aim of reaching an ultrahigh nitrogen (N)-doping level in carbon materials can provide a platform where the type and amount of N dopant can be tuned over a wide range. We propose a C-S-C linkage-triggered confined-pyrolysis strategy for the high-efficiency in situ N-doping into carbon matrix and an ultrahigh doping level up to 13.5 at %, which is close to the theoretical upper limit (15.2 at %) is realized at a high carbonization temperature of 1000 °C. The pyridinic N is dominant with a maximum percent of 48.7 %. By using I3 - reduction as an example, the resultant NCM-5 exhibits the best activity with a power conversion efficiency of 8.77 %. A pyridinic N site-dependent activity is demonstrated in which the amount of active sites increases with the increase of pyridinic N, and the carbon atom adjacent to electron-withdrawing pyridinic N at the armchair edge acts as the most favorable site for the adsorption of I2 .

Enabling a Large Accessible Surface Area of a Pore-Designed Hydrophilic Carbon Nanofiber Fabric for Ultrahigh Capacitive Deionization.

Although porous carbons have been widely used for capacitive deionization, the low accessible surface area because of the hydrophobic microporous structure results in unsatisfied desalination capacity, which drastically hinders their practical application. Herein, a novel carbon nanofiber fabric with a large accessible surface area was prepared by electrospinning using the uniformly dispersed ferrocene as a pore former. The carbon nanofiber fabric with good mechanical strength and flexibility can be directly used as a filter membrane to filter simulated sandy seawater. The high content of heteroatoms increases the surface polarity of the carbon nanofiber, while the well-controlled interconnected mesoporous structure of the optimized sample facilitates fast transport and adsorption of hydrated Na+ and Cl-. Thus, the hydrophilic carbon nanofiber fabric shows a Brunauer-Emmett-Teller surface area of 922 m2 g-1 and a large accessible surface area of 405 m2 g-1, leading to a high capacitance of 263 F g-1 in the NaCl electrolyte. Most importantly, it shows an ultrahigh desalination capacity of 19.34 mg g-1, which is much higher than most of the previously reported carbon materials. The high desalination capacity, fast adsorption rate, and good cycle stability make the as-prepared carbon nanofiber fabric an attractive candidate for practical application.

A novel robust adsorbent for efficient oil/water separation: Magnetic carbon nanospheres/graphene composite aerogel.

Recently, graphene aerogels (GAs) have attracted considerable research attention in oil/water separation owing to their remarkable properties. However, the serious stacking of graphene oxide nanosheets (GO) would lead to low adsorption capacity and poor recyclability. For the first time, with alkaline ammonium citrate as reducing agent and nitrogen source, the point-to-face contact between magnetic carbon nanospheres (MCNS) and graphene sheets was adopted to effectively inhibit the aggregation of graphene sheets. Nitrogen-doped magnetic carbon nanospheres/graphene composite aerogels (MCNS/NGA) were fabricated under weakly alkaline conditions by one-step hydrothermal in-situ electrostatic self-assembling strategy. The aerogels have low density, super-elasticity (up to 95 % compression), high specific surface area (787.92 m2 g-1) and good magnetic properties. Therefore, they exhibit adsorption capacity in the range of 187-537 g g-1 towards various organic solvents and oils, superior to most reported materials to date. In addition, thanks to their good mechanical properties, excellent thermal stability and flame retardancy, they can be regenerated by squeezing, distillation and combustion. More importantly, magnetic control technology can be adopted to realize oriented adsorption and facilitate recycling of organic solvents and oils in extreme environments.

3D Carbon Frameworks for Ultrafast Charge/Discharge Rate Supercapacitors with High Energy-Power Density.

Carbon-based electric double layer capacitors (EDLCs) hold tremendous potentials due to their high-power performance and excellent cycle stability. However, the practical use of EDLCs is limited by the low energy density in aqueous electrolyte and sluggish diffusion kinetics in organic or/and ionic liquids electrolyte. Herein, 3D carbon frameworks (3DCFs) constructed by interconnected nanocages (10-20 nm) with an ultrathin wall of ca. 2 nm have been fabricated, which possess high specific surface area, hierarchical porosity and good conductive network. After deoxidization, the deoxidized 3DCF (3DCF-DO) exhibits a record low IR drop of 0.064 V at 100 A g-1 and ultrafast charge/discharge rate up to 10 V s-1. The related device can be charged up to 77.4% of its maximum capacitance in 0.65 s at 100 A g-1 in 6 M KOH. It has been found that the 3DCF-DO has a great affinity to EMIMBF4, resulting in a high specific capacitance of 174 F g-1 at 1 A g-1, and a high energy density of 34 Wh kg-1 at an ultrahigh power density of 150 kW kg-1 at 4 V after a fast charge in 1.11 s. This work provides a facile fabrication of novel 3D carbon frameworks for supercapacitors with ultrafast charge/discharge rate and high energy-power density.

Pulse electrochemical synthesis of polypyrrole/graphene oxide@graphene aerogel for high-performance supercapacitor.

A novel electroactive polypyrrole/graphene oxide@graphene aerogel (PGO@GA) was synthesized for the first time by pulse electropolymerization. The off-time in this technique allows polypyrrole (PPy) to go through a more stable structural arrangement, meanwhile its electronic transmission performance is enhanced by immobilizing graphene oxide between PPy chains. Moreover, graphene aerogel provides a three-dimensional structure with high conductivity to protect PPy from swelling and shrinking during the capacitive testing. Under these synergistic effects, PGO@GA presents exceptional capacitive performances including high specific capacitance (625 F g-1 at 1 A g-1), excellent rate capability (keeping 478 F g-1 at 15 A g-1 with retention rate of 76.5%), and excellent cycling life (retaining 85.7% of its initial value when cycling 5000 times at 10 A g-1). Therefore, the strategy adopted by this research provides a good reference for preparing other PPy-based electrode materials applied in the fields of catalysis, sensing, adsorption and energy storage.

Tuned Fabrication of the Aligned and Opened CNT Membrane with Exceptionally High Permeability and Selectivity for Bioalcohol Recovery.

Synthetic membranes usually suffer from a ubiquitous trade-off between permeability and selectivity. Carbon nanotube (CNT)-based hybrid materials have shown attractive properties in high-performance membrane preparation; however, the aggregation of random CNTs in polymer remains a great challenge. Herein, the aligned and open-ended CNT/(polydimethylsiloxane) PDMS membranes are controllably fabricated to form a hamburger-like structure that possesses nanochannels (∼10 nm) in the intermediate layer as well as angstrom cavities in the embedded PDMS. These aligned CNT membranes surpass the filling content limitation of the nonaligned CNT/PDMS membrane (37.4 wt % versus ∼10 wt %), leading to excellent mechanical properties and a multiplying performance increase of mass flux and selectivity for the separation of alcohols. The membranes break the permeability-selectivity trade-off with both parameters remarkably increasing (maximum 9 times) for bioalcohol separation. The established pervaporative-ultrafiltration mechanism indicates that the penetrant molecules preferentially pass through CNT internal nanochannels with increasing membrane permeability, thereby paving a way to nanoscale design of highly efficient channeled membranes for separation application.

Microporous MOFs Engaged in the Formation of Nitrogen-Doped Mesoporous Carbon Nanosheets for High-Rate Supercapacitors.

Nitrogen-doped mesoporous carbon nanosheets (NMCS) have been fabricated from zinc-based microporous metal-organic frameworks (ZIF-8) by pyrolysis in a molten salt medium. The as-prepared NMCS exhibit significantly improved specific capacitance (NMCS-8: 232 F g-1 at 0.5 A g-1 ) and capacitance retention ratio (75.9 % at 50 A g-1 ) compared with the micropore-dominant nitrogen-doped porous carbon polyhedrons (NPCP-5: 178 F g-1 at 0.5 A g-1 , 15.9 % at 20 A g-1 ) obtained by direct pyrolysis of nanocrystalline ZIF-8. The excellent capacitive performance and high rate performance of the NMCS can be attributed to their unique combination of structure and composition, that is, the two-dimensional and hierarchically porous structure provides a short ion-transport pathway and facilitates the supply of electrolyte ions, and the nitrogen-doped polar surface improves the interface wettability when used as an electrode.

Two-dimensional graphene-like N, Co-codoped carbon nanosheets derived from ZIF-67 polyhedrons for efficient oxygen reduction reactions.

Two-dimensional graphene-like N, Co-codoped carbon nanosheets (N, Co-CNSs), which exhibit excellent stability, competitive catalytic activity and superior methanol tolerance compared to the commercial Pt/C catalyst, have been successfully fabricated using Co-based zeolitic imidazolate framework (ZIF-67) polyhedrons as precursors in a molten salt medium.

Flexible Paper-like Free-Standing Electrodes by Anchoring Ultrafine SnS2 Nanocrystals on Graphene Nanoribbons for High-Performance Sodium Ion Batteries.

Ultrafine SnS2 nanocrystals-reduced graphene oxide nanoribbon paper (SnS2-RGONRP) has been created by a well-designed process including in situ reduction, evaporation-induced self-assembly, and sulfuration. The as-formed SnS2 nanocrystals possess an average diameter of 2.3 nm and disperse on the surface of RGONRs uniformly. The strong capillary force formed during evaporation leads to a compact assembly of RGONRs to give a flexible paper structure with a high density of 0.94 g cm-3. The as-prepared SnS2-RGONRP composite could be directly used as free-standing electrode for sodium ion batteries. Due to the synergistic effects between the ultrafine SnS2 nanocrystals and the conductive, tightly connected RGONR networks, the composite paper electrode exhibits excellent electrochemical performance. A high volumetric capacity of 508-244 mAh cm-3 was obtained at current densities in the range of 0.1-10 A g-1. Discharge capacities of 334 and 255 mAh cm-3 were still kept, even after 1500 cycles tested at current densities of 1 and 5 A g-1, respectively. This strategy provides insight into a new pathway for the creation of free-standing composite electrodes used in the energy storage and conversion.

Carbon-Stabilized Interlayer-Expanded Few-Layer MoSe2 Nanosheets for Sodium Ion Batteries with Enhanced Rate Capability and Cycling Performance.

Sodium ion batteries (SIBs) have been considered as a promising alternative to lithium ion batteries, owing to the abundant reserve and low-cost accessibility of the sodium source. To date, the pursuit of high-performance anode materials remains a great challenge for the SIBs. In this work, carbon-stabilized interlayer-expanded few-layer MoSe2 nanosheets (MoSe2@C) have been fabricated by an oleic acid (OA) functionalized synthesis-polydopamine (PDA) stabilization-carbonization strategy, and their structural, morphological, and electrochemical properties have been carefully characterized and compared with the carbon-free MoSe2. When evaluated as anode for sodium ion half batteries, the MoSe2@C exhibits a remarkably enhanced rate capability of 367 mA h g-1 at 5 A g-1, a high reversible discharge capacity of 445 mA h g-1 at 1 A g-1, and a long-term cycling stability over 100 cycles. To further explore the potential applications, the MoSe2@C is assembled into sodium ion full batteries with Na3V2(PO4)3 (NVP) as cathode materials, showing an impressively high reversible capacity of 421 mA h g-1 at 0.2 A g-1 after 100 cycles. Such results are primarily attributed to the unique carbon-stabilized interlayer-expanded few-layer MoSe2 nanosheets structure, which facilitates the permeation of electrolyte into the inner of MoSe2 nanosheets, promoting charge transfer efficiency among MoSe2 nanosheets, and accommodating the volume change from discharge-charge cycling.

Self-assembled sulfur/reduced graphene oxide nanoribbon paper as a free-standing electrode for high performance lithium-sulfur batteries.

Flexible, interconnected sulfur/reduced graphene oxide nanoribbon paper (S/RGONRP) is synthesized through S2- reduction and evaporation induced self-assembly processes. The in situ formed sulfur atoms chemically bonded with the surface of reduced graphene oxide nanoribbons and were physically trapped by the compact assembly, which make the hybrid a suitable cathode material for lithium-sulfur batteries.