Cold plasma-assisted regeneration of biochar for dye adsorption.

Environmental remedies, including adsorption-based water purification, are now being asked to meet the requirement for a low-carbon circular economy requiring low energy and low material consumption. In this regard, we tested the possibility of regenerating adsorbents via cold plasma (CP) treatment for less use of adsorbents and no washing solution. In the adsorption of methylene blue (MB) using carbonized rice husk (CRH) and five successive regeneration cycles by CP treatment, the removal efficiencies were maintained at a moderate level (∼70% of the initial performance), unlike five consecutive adsorption without CP treatment (∼9-13% of the initial performance). The regeneration of CRH by CP treatment was also double-checked by the FESEM, EDS, BET, FTIR, XPS, and surface zeta potential measurements. The successfully recovered adsorption capability is related to the remediation of adsorption sites. It is also worth noting that the required power consumption for recycling by CP treatment was about 6.4 times lower than carbonizing new rice husks. This work provides insights into recovering adsorbents using CP without rigorous, costly, and energy-intensive processes.

Homogeneous Elongation of N-Doped CNTs over Nano-Fibrillated Hollow-Carbon-Nanofiber: Mass and Charge Balance in Asymmetric Supercapacitors Is No Longer Problematic.

The hurdle of fabricating asymmetric supercapacitor (ASC) devices using a faradic cathode and a double layer anode is challenging due to the required large amount of active mass of anodic material compared to that of the cathodic material during mass balancing due to the large difference in capacitance values of the two electrodes. Here, the problem is addressed by engineering a negative electrode that furnishes an ultrahigh capacitance. An in situ developed metal-organic framework (MOF)-based thermal treatment is adopted to grow highly porous N-doped carbon nanotubes (CNTs) containing submerged Co nanoparticles over nano-fibrillated electrospun hollow carbon nanofibers (HCNFs). The optimized CNT@HCNF-1.5 furnishes an ultrahigh capacitance approaching 712 F g-1 with excellent rate capability. The capacitance reported from this work is the highest for any carbonaceous material reported to date. The CNT@HCNF-1.5 is further used to fabricate symmetric supercapacitors (SSCs), as well as ASC devices. Remarkably, both the SSC and ASC devices furnish incredible performances in all aspects of SCs, such as a high energy density, long cycle life, and high rate capability, displaying decent practical applicability. The energy density of the SSC device reaches as high as 20.13 W h kg-1 , whereas that of ASC approaches 87.5 W h kg-1 .

Polypyrrole Nanotunnels with Luminal and Abluminal Layered Double Hydroxide Nanosheets Grown on a Carbon Cloth for Energy Storage Applications.

The structural design of transition metal-based electrode materials with gigantic energy storage capabilities is a crucial task. In this work, we report an assembly of thin layered double hydroxide (LDH) nanosheets arrayed throughout the luminal and abluminal parts of polypyrrole tunnels fastened onto both sides of a carbon cloth as a battery-type energy storage system. Electron microscopy images reveal that the resulting electrode (NiCo-LDH@H-PPy@CC, where H-PPy@CC represents carbon cloth-supported hollow polypyrrole fibers) is constructed by combining luminal and abluminal NiCo-LDH nanosheets onto a long polypyrrole tunnel on a carbon cloth. The primary sample shows an excellent specific capacity of 149.16 mAh g-1 at 1.0 mA cm-2, a remarkable rate capability of 80.45%, and comprehensive cyclic stability (93.4%). The improved performance is mainly attributed to the strategic organization of the electrode materials with superior Brunauer-Emmett-Teller (BET) surface area and conductivity. Moreover, an asymmetric supercapacitor device assembled with NiCo-LDH@H-PPy@CC and vanadium phosphate-incorporated carbon nanofiber (VPO@CNFs900) electrodes contributes a specific energy density of 32.42 Wh kg-1 at 3 mA cm-2 with a specific power density of 359.16 W kg-1. When the current density is increased by 6-fold, the specific power density reaches 1999.89 W kg-1 at a specific energy density of 20.06 Wh kg-1. This is a simple, cost-effective, and convenient synthetic strategy for the synthesis of porous nanosheet arrays assimilated into hollow fiber architectures, which can illuminate the ideal approach for the fabrication of novel materials with an immense potential for energy storage.

Heterostructure of polyoxometalate/zinc-iron-oxide nanoplates as an outstanding bifunctional electrocatalyst for the hydrogen and oxygen evolution reaction.

Electrocatalysts play an important role to increase the energy conversion efficiency of electrolysis processes. In this study, a heterostructure of zinc iron oxide (ZnFe2O4) and polyoxometalate (POM) nanoplates (POM-ZnFe2O4) was fabricated for the first time by a hydrothermal process. The hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) analysis of POM-ZnFe2O4 furnished low overpotentials of 268 and 356 mV, and 220 and 290 mV to achieve current densities of 20 and 50 mA cm-2, respectively. In addition, an electrolytic cell composed of a POM-ZnFe2O4 cathode and anode required an operating voltage of 1.53 V to deliver a current of 10 mA cm-2. The improved electrochemical performance of POM-ZnFe2O4 compared to commercial and recently reported catalysts is attributed to the high electrocatalytically active surface area, modulation in the electronic and chemical properties and the formation of heterojunction of ZnFe2O4 and POM, which are vital for accelerating HER and OER activity.

Ruthenium nanoparticles integrated bimetallic metal-organic framework electrocatalysts for multifunctional electrode materials and practical water electrolysis in seawater.

There is still a significant technical hurdle in the integration of better electrocatalysts with coordinated functional units and morphological integrity that improves reversible electrochemical activity, electrical conductivity, and mass transport capabilities. In this work, ruthenium-integrating porous bimetallic transition metal nanoarrays are efficiently generated from metal-organic framework-covered three-dimensional platforms such as carbon cloth using a simple solution-based deposition technique followed by calcination. Heterostructure ruthenium-cobalt-iron hollow nanoarrays are built to permit exceptionally effective multifunctional activities in reactions including the oxygen evolution reaction, hydrogen evolution reaction, and oxygen reduction reaction. As presumed, the as-synthesized porous nanostructured arrays show remarkable electrochemical performance due to the benefits of copious active reaction sites, and efficient electron and ion transport channels. The oxygen reduction reaction of the porous nanostructured array electrocatalyst has a half-wave potential of 0.875 V vs. reversible hydrogen electrode and can achieve a current density of 10 mA cm-2 at low overpotentials of 220 and 50 mV for the oxygen and hydrogen evolution reactions, respectively, and the needed cell voltage for total water splitting is just 1.49 V at a current density of 10 mA cm-2. The fabricated electrolyzer coupling splits seawater at relatively low cell voltages of 1.54 V at ambient temperature.

Three-dimensional nano assembly of nickel cobalt sulphide/polyaniline@polyoxometalate/reduced graphene oxide hybrid with superior lithium storage and electrocatalytic properties for hydrogen evolution reaction.

Engineering hierarchical nanostructures with enhanced charge storage capacity and electrochemical activity are vital for the advancement of energy devices. Herein, a highly ordered mesoporous three-dimensional (3D) nano-assembly of Nickel Cobalt Sulphide/Polyaniline @Polyoxometalate/Reduced Graphene Oxide (NiCo2S4/PANI@POM/rGO) is prepared first time via a simple route of oxidative polymerization followed by a hydrothermal method. Morphological analysis of the resulting hybrid reveals the sheet-like structures containing a homogeneous assembly of PANI@POM and NiCo2S4 on the graphene exterior maintaining huge structural integrity, large surface area and electrochemically active centres. The electrochemical analysis of the nanohybrid as the anode of the lithium-ion battery (LIB) has delivered ultra-huge reversible capacity of 735.5 mA h g-1 (0.1 A g-1 after 200 cycles), superb capacity retention (0.161% decay/per cycle at 0.5 A g-1 for 1000 cycles), and significant rate capability (355.6 mA h g-1 at 2 A g-1). The hydrogen evolution reaction (HER) measurement also proves remarkable activity, extremely low overpotential and high durability. The extraordinary performance of the nanohybrid is due to the presence of abundant electroactive centres, high surface area and a large number of ion exchange channels. These outstanding results prove the advantages of a combination of NiCo2S4, graphene sheets, and PANI@POM in energy devices.

Integrating the Essence of a Metal-Organic Framework with Electrospinning: A New Approach for Making a Metal Nanoparticle Confined N-Doped Carbon Nanotubes/Porous Carbon Nanofibrous Membrane for Energy Storage and Conversion.

The fabrication of an economic and efficient multifunctional advanced nanomaterial with a rational composition and configuration by a facile methodology is a crucial challenge. Herein, we are the first to report the growth of Co nanoparticle-integrated nitrogen-doped carbon nanotubes (N-CNTs) on porous carbon nanofibers by simply heating in the situ-developed metal-organic framework (MOF)-based electrospun nanofibrous membrane with no need for an external supply of any additional precursors and reducing gases. The long and entangled N-CNTs originating from highly porous and graphitic carbon nanofibers offer good flexibility, large surface area, high porosity, high conductivity, the homogeneous incorporation of heteroatoms and metallic constituents, and an abundant exposure of active nanocatalytic sites. The as-developed nanoassembly demonstrates attractive characteristics for electrocatalytic hydrogen and oxygen evolution reactions and electrochemical energy storage. This strategy of integrating the essence of an MOF with electrospinning offers a new, direct, and cost-effective approach for making N-doped CNT-based multifunctional membranes.

Fabrication of Nonmetal-Modulated Dual Metal-Organic Platform for Overall Water Splitting and Rechargeable Zinc-Air Batteries.

The fast development of portable water-splitting devices has led to a great deal of work on rechargeable metal-air batteries or solar cells; however, the lack of affordable multifunctional electrocatalysts still hampers their widespread applications. Herein, a well-aligned ternary metal (oxy)hydroxide nanostructure is a sacrificial pseudomorphic transformation template of an integrated metal-organic network on the carbon cloth (CC) surface, that is, the Fe-doped metal-organic framework (MOF) ZnNiCoSe@CC nanosheet network, exhibiting powerful and efficient multifunctional electrocatalysts such as the oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction in alkaline media combined with desirable electrode kinetics. As a proof-of-concept observational study, the nanostructured Fe-doped MOF ZnNiCoSe@CC could be used as air-cathode materials in the rechargeable metal-air battery. The fabricated device delivered higher open-circuit voltage, higher capacity, and peak power density, excellent discharge-charge performance, and long cycle life. Thus, our research creates a unique perspective on the development of highly portable air electrodes with a favorable electrocatalytic application of overall water-splitting reaction.

Vertically Aligned Metal-Organic Framework Derived from Sacrificial Cobalt Nanowire Template Interconnected with Nickel Foam Supported Selenite Network as an Integrated 3D Electrode for Overall Water Splitting.

The development of bifunctional, highly active electrocatalysts for an overall water splitting reaction remains a major challenge. Here, the sacrificial template-assisted transformation of cobalt hydroxide nanowire (Co(OH)2 NW) into a metal-organic framework network (MOF) is conceived as a porous structure that provides extremely active and durable electrochemical energy conversion characteristics. After this, the 1D MOF modified Co NWs can be further transformed into a hybrid structure (MOF CoSeO3 NWs) by selenization. The self-template transformation strategy allows the interconnected porous conductive network to be exposed to abundant reactive sites and to improve electronic conductivity/structural integrity. Thus, the obtained catalyst established by electrocatalytic activity in the course of the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in 1 M KOH solution requires overpotentials (η) of 290 and 150 mV to achieve a current density of 50 and 10 mA cm-2 for both OER and HER. Interestingly, as a full cell water electrolyzer (MOF CoSeO3 NWs (+) // MOF CoSeO3 NWs (-)), the MOF CoSeO3 NW's modified electrode exhibits an affordable cell voltage of 1.675 V at a current density of 100 mA cm-2. This work involves a viable and systematic strategy to prepare many other functional integrated MOFs that can be used for energy storage and conversion in multiple applications.

Phytic acid controlled in situ synthesis of amorphous cobalt phosphate/carbon composite as anode materials with a high mass loading for symmetrical supercapacitor: amorphization of the electrode to boost the energy density.

Transition metal phosphate (TMPi)-based composites as anode electrode materials in supercapacitor applications are less reported. Herein, we report a phytic acid (PA)-assisted in situ-formed amorphous cobalt phosphate/carbon (CoPi/C) composite grown on a flexible woven carbon cloth (CC) via a simple one-step carbonization approach. The tunable synthesis of amorphous and crystalline composites is shown by simply controlling the concentration of the cobalt salts. The strategy for high mass loading to 12 mg cm-2 is also shown in this report. Importantly, the resulting amorphous electrode materials exhibit electric double-layer capacitance (EDLC) behavior that works over a wide potential range from -1.4 to +0.5 V in an aqueous solution of potassium hydroxide (2 M KOH) and from -1.5 to +1.5 V in sodium sulfate (1 M Na2SO4). The amorphous electrode as an anode is capable of delivering an areal capacitance up to 2.15 F cm-2 at a current density of 4 mA cm-2 (gravimetric capacitance up to 606.1 F g-1 at 1 Ag-1) and has a retention of 94.2% at 10 000 cycles. The flexible solid-state symmetric device fabricated shows an energy density of approximately 620.0 µW h cm-2 at a power density of 4.7 mW cm-2 (31.1 W h kg-1 at 476.0 W kg-1). This study offers a novel route for the generation of metal phosphate-based anode materials with high capacitance for symmetrical supercapacitor device with high energy density.

Three-dimensional porous carbonaceous network with in-situ entrapped metallic cobalt for supercapacitor application.

Herein, we outline the fabrication of highly porous three-dimensional carbon-fiber network anchored with uniform metallic cobalt (Co) via electrospinning and subsequent post-modification approaches. First, cobalt acetate solution saturated electrospun polyacrylonitrile (PAN) nanofibrous mat was subjected to sodium borohydride (NaBH4) solution which results in the fabrication of three dimensional (3D) hierarchical multilayer network. Restructuring of the 2D mat into multilayered sponges with metal particles entrapment is attributed to the in-situ generated hydrogen gas into the interconnected pores of the fibrous network simultaneous with reduction of cobalt salt into metallic cobalt by NaBH4. The resulting mesh was stabilized and carbonization at inert atmosphere to obtain metallic cobalt (Co) embedded 3D carbon nanofibrous networks (Co@3D-CNFs). Physicochemical characterization and electrochemical analysis were performed. Results show carbon network was found to be expanded with bubbling like structures often embedded metallic Co nanoparticles. X-ray diffraction (XRD) pattern confirms the existence of the metallic cobalt particles on the carbon fiber networks. Furthermore, we establish a resulting composite (Co@3D-CNFs) identify the enhanced electrochemical performance having specific capacitance 762 F g-1 compared to 173 and 180 F g-1 for corresponding @3D-CNFs and 2D carbon nanofiber network with cobalt doped (Co@2D-CNFs) counterparts, respectively. The assembled Co2@3D-CNFs//NGH ASC device exhibits a high energy density 24.6 W h Kg-1 at 797 W kg-1 power density with an operating voltage of 1.6 V (vs Ag/AgCl). The device further shows good capacitance retention (90.1%) after 5000 cycles. This research shows the simple and cost-effective strategy to make metallic particles embedded 3D porous carbonaceous electrode materials which can have great potential for energy storage application.