Iron Active Center Coordination Reconstruction in Iron Carbide Modified on Porous Carbon for Superior Overall Water Splitting.

In this work, a novel liquid nitrogen quenching strategy is engineered to fulfill iron active center coordination reconstruction within iron carbide (Fe3C) modified on biomass-derived nitrogen-doped porous carbon (NC) for initiating rapid hydrogen and oxygen evolution, where the chrysanthemum tea (elm seeds, corn leaves, and shaddock peel, etc.) is treated as biomass carbon source within Fe3C and NC. Moreover, the original thermodynamic stability is changed through the corresponding force generated by liquid nitrogen quenching and the phase transformation is induced with rich carbon vacancies with the increasing instantaneous temperature drop amplitude. Noteworthy, the optimizing intermediate absorption/desorption is achieved by new phases, Fe coordination, and carbon vacancies. The Fe3C/NC-550 (550 refers to quenching temperature) demonstrates outstanding overpotential for hydrogen evolution reaction (26.3 mV at -10 mA cm-2) and oxygen evolution reaction (281.4 mV at 10 mA cm-2), favorable overall water splitting activity (1.57 V at 10 mA cm-2). Density functional theory (DFT) calculations further confirm that liquid nitrogen quenching treatment can enhance the intrinsic electrocatalytic activity efficiently by optimizing the adsorption free energy of reaction intermediates. Overall, the above results authenticate that liquid nitrogen quenching strategy open up new possibilities for obtaining highly active electrocatalysts for the new generation of green energy conversion systems.

Design of an Internal/External Bicontinuous Conductive Network for High-Performance Asymmetrical Supercapacitors.

High-energy density supercapacitors have attracted extensive attention due to their electrode structure design. A synergistic effect related to core-shell structure can improve the energy storage capacity and power density of electrode materials. The Ni-foam (NF) substrate coupled with polypyrrole (PPy) conductive coating can serve as an internal/external bicontinuous conductive network. In this work, the distinctive PPy@FeNi2S4@NF and PPy@NiCo2S4@NF materials were prepared by a simple two-step hydrothermal synthesis with a subsequent in situ polymerization method. PPy@FeNi2S4@NF and PPy@NiCo2S4@NF could deliver ultrahigh specific capacitances of 3870.3 and 5771.4 F·g-1 at 1 A·g-1 and marvelous cycling capability performances of 81.39% and 93.02% after 5000 cycles. The asymmetric supercapacitors composed of the prepared materials provided a high-energy density of over 47.2 Wh·kg-1 at 699.9 W·kg-1 power density and 67.11 Wh·kg-1 at 800 W·kg-1 power density. Therefore, the self-assembled core-shell structure can effectively improve the electrochemical performance and will have an effective service in advanced energy-storage devices.

Nickel/Cobalt Molybdate Hollow Rods Induced by Structure and Defect Engineering as Exceptional Electrode Materials for Hybrid Supercapacitor.

Oxygen defects and hollow structures positively impact pseudocapacitive properties of diffusion/surface-controlled processes, a component of critical importance when building high-performance supercapacitors. Hence, we fabricated hollow nickel/cobalt molybdate rods with O-defects (D-H-NiMoO4 @CoMoO4 ) through a soft-template and partial reduction method, enhancing D-H-NiMoO4 @CoMoO4 's electrochemical performance, yielding a specific capacitance of 1329 F g-1 , and demonstrating excellent durability with 95.8 % capacity retention after 3000 cycles. D-H-NiMoO4 @CoMoO4 was used as the positive electrode to construct an asymmetric supercapacitor, displaying an energy density of up to 34.13 Wh kg-1 and demonstrating good predisposition towards practical applications. This work presents an effective approach to fabricate and use hollow nickel/cobalt molybdate rods with O-defects as pseudocapacitor material for high-performance capacitive energy storage devices.

Facile Dual-Ligand Modulation Tactic toward Nickel-Cobalt Sulfides/Phosphides/Selenides as Supercapacitor Electrodes with Long-Term Durability and Electrochemical Activity.

The use of high electrochemical active binary nickel-cobalt sulfides/phosphides/selenides (Ni-Co-X, X = S, P, Se) as electrochemical energy storage materials still has a space for improvement because they become electrochemically unstable during long-term use. Herein, a facile and cost-effective dual-ligand synergistic modulation tactic is described to substantially improve the durability of Ni-Co-X (X = S, P, Se) at the atomic level by partially substituting S, P, and Se ligands into the nickel-cobalt hydroxide precursor, respectively. Remarkably, the dual-ligand electrodes on Ni-foam achieve superior durability and high electrochemical activity when used as positive electrodes in supercapacitors. Impressively, the density functional theory calculations demonstrate that the OH ligand in NiCo2(MOH)x (M = S, P, Se) could attract electrons from metal-S/metal-P/metal-Se bonds to the metal-O bond, enhancing the binding energy of metal-S/metal-P/metal-Se bonds and improving the long-term durability of Ni-Co-X (X = S, P, Se) in alkaline electrolytes. Moreover, OH and S/P/Se ligands could effectively alter the electron structure and result in favorable electrochemical activity. Overall, this tactic could offer an exciting avenue to achieve long-term durability and electrochemical activity of supercapacitor electrodes simultaneously.

Freestanding hierarchical nickel molybdate@reduced graphene oxide@nickel aluminum layered double hydroxides nanoarrays assembled from well-aligned uniform nanosheets as binder-free electrode materials for high performance supercapacitors.

Herein, the hierarchical nickel molybdate@reduced graphene oxide@nickel aluminum layered double hydroxides (NiMoO4@rGO@NiAl-LDHs) architecture assembled from well-aligned nanosheets is successfully constructed on Ni-foam through a three-step strategy. For the first time, ultrathin graphene nanosheets are introduced by a novel spraying process to avoid the stack. NiAl-LDHs is prepared via situ growth procedure in which NiAl-LDH self-assembles on the surface of graphene to prevent graphene from aggregating, resulting in an enlarged specific surface area. Electrochemical analysis manifests that NiMoO4@rGO@NiAl-LDHs yields exceptional specific capacitance (3396 Fg-1 at 1 Ag-1), favorable charge/discharge rate and approving long-term stability. Furthermore, the NiMoO4@rGO@NiAl-LDHs//AC device delivers superior specific capacitance (137.2 Fg-1 at 1 Ag-1), high energy density (48.7 Whkg-1) associated with pleasurable power output (7987 Wkg-1). Importantly, the well-aligned NiMoO4@rGO@NiAl-LDHs provides a prospective conception constructing hierarchical structural materials in the area of supercapacitor.

Polypyrrole/cobalt ferrite/multiwalled carbon nanotubes as an adsorbent for removing uranium ions from aqueous solutions.

A novel rod-like, dual-shell structural adsorbent of polypyrrole/cobalt ferrite/multiwalled carbon nanotubes (PPy/CoFe2O4/MWCNTs) was successfully synthesized by a hydrothermal method, which could easily separate uranium(vi) ions with an external magnetic field. The structure and morphology of PPy/CoFe2O4/MWCNTs were characterized by VSM, XRD, XPS TEM and FT-IR. The results proved that the dual-shell structure was obtained in which a shell of cobalt ferrite and polypyrrole formed around the MWCNTs core. In batch adsorption experiments, including pH, equilibrium time and temperature on uranium adsorption, were investigated. The main results show that the PPy/CoFe2O4/MWCNTs composite has a higher affinity towards the uptake of uranium(vi) from aqueous solutions. The highest adsorption capacity reached was 148.8 mg U per g at pH 7. A kinetic analysis showed that the adsorption process was best described by a pseudo-second-order kinetic model. The uranium sorption equilibrium data correlated well with the Langmuir sorption isotherm model in the thermodynamic analysis. 0.5 mol per L NaHCO3 was used as the desorbent and good adsorption properties were shown after the desorption procedures were repeated three times. Thus, PPy/CoFe2O4/MWCNTs was an excellent adsorbent for removing uranium(vi) ions.

Preparation of magnetic core-shell iron oxide@silica@nickel-ethylene glycol microspheres for highly efficient sorption of uranium(VI).

We report a facile approach for the formation of magnetic core-shell iron oxide@silica@nickel-ethylene glycol (Fe3O4@SiO2@Ni-L) microspheres. The structure and morphology of Fe3O4@SiO2@Ni-L are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen sorption isotherm. The composite possesses a high specific surface area of 382 m(2) g(-1). The obtained core/shell structure is composed of a superparamagnetic core with a strong response to external fields, which are recovered readily from aqueous solutions by magnetic separation. When used as the adsorbent for uranium(vi) in water, the as-prepared Fe3O4@SiO2@Ni-L multi-structural microspheres exhibit a high adsorption capacity, which is mainly attributed to the large specific surface area and typical mesoporous characteristics of Fe3O4@SiO2@Ni-L microspheres. This work provides a promising approach for the design and synthesis of multifunctional microspheres, which can be used for water treatment, as well as having other potential applications in a variety of biomedical fields including drug delivery and biosensors.