Recent Developments and Future Perspectives of Molybdenum Borides and MBenes.

Metal borides have received a lot of attention recently as a potentially useful material for a wide range of applications. In particular, molybdenum-based borides and MBenes are of great significance, due to their remarkable properties like good electronic conductivity, considerable stability, high surface area, and environmental harmlessness. Therefore, in this article, the progress made in molybdenum-based borides and MBenes in recent years is reviewed. The first step in understanding these materials is to begin with an overview of their structural and electronic properties. Then synthetic technologies for the production of molybdenum borides, such as high-temperature/pressure methods, physical vapor deposition (PVD), chemical vapor deposition (CVD), element reaction route, molten salt-assisted, and selective etching methods are surveyed. Then, the critical performance of these materials in numerous applications like energy storage, catalysis, biosensors, biomedical devices, surface-enhanced Raman spectroscopy (SERS), and tribology and lubrication are summarized. The review concludes with an analysis of the current progress of these materials and provides perspectives for future research. Overall, this review will offer an insightful reference for the understanding molybdenum-based borides and their development in the future.

Construction of Nickel Molybdenum Sulfide/Black Phosphorous 3D Hierarchical Structure Toward High Performance Supercapacitor Electrodes.

Supercapacitors (SCs) with outstanding versatility have a lot of potential applications in next-generation electronics. However, their practical uses are limited by their short working potential window and ultralow-specific capacity. Herein, the facile one-step in-situ hydrothermal synthesis is employed for the construction of a NiMo3S4/BP (black phosphorous) hybrid with a 3D hierarchical structure. After optimization, the NiMo3S4/BP hybrid displays a high specific capacitance of 830 F/g at 1 A/g compared to the pristine NiMo3S4 electrode. The fabricated NiMo3S4/BP//NiCo2S4/Ti3C2Tx asymmetric supercapacitor exhibits a better specific capacitance of 120 F/g at 0.5 A/g, which also demonstrates a high energy density of 54 Wh/kg at 1148.53 W/kg and good cycle stability with capacity retention of 86% and 97% of Coulombic efficiency after 6000 cycles. Further from the DFT simulations, the hybrid NiMo3S4/BP structure shows higher conductivity and quantum capacitance, which demonstrate greater charge storage capability, due to enhanced electronic states near the Fermi level. The lower diffusion energy barrier for the electrolyte K+ ions in the hybrid structure is facilitated by improved charge transfer performance for the hybrid NiMo3S4/BP. This work highlights the potential significance of hybrid nanoarchitectonics and compositional tunability as an emerging method for improving the charge storage capabilities of active electrodes.

Experimental and Theoretical Insights of Anion Regulation in MOF-Derived Ni-Co-Based Nanosheets for Supercapacitors and Anion Exchange Membrane Water Electrolyzers.

The anionic components have a significant role in regulating the electrochemical properties of mixed transition-metal (MTM)-based materials. However, the relationship between the anionic components and their inherent electrochemical properties in MTM-based materials is still unclear. Herein, we report the anion-dependent supercapacitive and oxygen evolution reaction (OER) properties of in situ grown binary Ni-Co-selenide (Se)/sulfide (S)/phosphide (P) nanosheet arrays (NAs) over nickel foam starting from MOF-derived Ni-Co layered double hydroxide precursors. Among them, the Ni-Co-Se NAs exhibited the best specific capacity (289.6 mA h g-1 at 4 mA cm-2). Furthermore, a hybrid device constructed with Ni-Co-Se NAs delivered an excellent energy density (74 W h kg-1 at 525 W kg-1) and an ultra-high power density (10 832 W kg-1 at 46 W h kg-1) with outstanding durability (∼94%) for 10 000 cycles. Meanwhile, the Ni-Co-Se NAs showed superior electrocatalytic OER outputs with the lowest overpotential (235 mV at 10 mA cm-2) and Tafel slope. In addition, Ni-Co-Se NAs outperformed IrO2 as an anode in an anion exchange membrane water electrolyzer at a high current density (>1.0 A cm-2) and exhibited a stable performance up to 48 h with a 99% Faraday efficiency. Theoretical analyses validate that the Se promotes OH adsorption and improves the electrochemical activity of the Ni-Co-Se through a strong electronic redistribution/hybridization with an active metal center due to its valence 4p and inner 3d orbital participations. This study will provide in-depth knowledge of bifunctional activities in MTM-based materials with different anionic substitutions.

Ligand-Controlled Growth of Different Morphological Bimetallic Metal-Organic Frameworks for Enhanced Charge-Storage Performance and Quasi-Solid-State Hybrid Supercapacitors.

The present research work facilitates a ligand-mediated effective strategy to achieve different morphological surface structures of bimetallic (Ni and Co) metal-organic frameworks (MOFs) by utilizing different types of organic ligands like terephthalic acid (BDC), 2-methylimidazole (2-Melm), and trimesic acid (BTC). Different morphological structures, rectangular-like nanosheets, petal-like nanosheets, and nanosheet-assembled flower-like spheres (NSFS) of NiCo MOFs, are confirmed from the structural characterization for ligands BDC, 2-Melm, and BTC, respectively. The basic characterization studies like scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and Brunauer-Emmett-Teller revealed that the NiCo MOF prepared by using trimesic acid as the ligand (NiCo MOF_BTC) with a long organic linker exhibits a three-dimensional architecture of NSFS that possesses higher surface area and pore dimensions, which enables better ion kinetics. Also, the NiCo MOF_BTC delivered the highest capacity of 1471.4 C g-1 (and 408 mA h g-1) at 1 A g-1 current density, compared to the other prepared NiCo MOFs and already reported different NiCo MOF structures. High interaction of trimesic acid with the metal ions confirmed from ultraviolet-visible spectroscopy and X-ray photoelectron spectroscopy leads to a NSFS structure of NiCo MOF_BTC. For practical application, an asymmetric supercapacitor device (NiCo MOF_BTC//AC) is fabricated by taking NiCo MOF_BTC and activated carbon as the positive and negative electrode, respectively, where the PVA + KOH gel electrolyte serves as a separator as well as an electrolyte. The device delivered an outstanding energy density of 78.1 Wh kg-1 at a power density of 750 W kg-1 in an operating potential window of 1.5 V. In addition, it displays a long cycle life of 5000 cycles with only 12% decay of the initial specific capacitance. Therefore, these findings manifest the morphology control of MOFs by using different ligands and the mechanism behind the different morphologies that will provide an effective way to synthesize differently structured MOF materials for future energy-storage applications.

Rational Design of Perforated Bimetallic (Ni, Mo) Sulfides/N-doped Graphitic Carbon Composite Microspheres as Anode Materials for Superior Na-Ion Batteries.

Highly conductive 3D ordered mesoporous Ni7 S6 -MoS2 /N-doped graphitic carbon (NGC) composite (P-NiMoS/C) microspheres are prepared as anode materials for Na-ion batteries. The rationally designed nanostructure comprises stable Ni7 S6 - and MoS2 -phases along with the homogeneously distributed ordered mesopores (ϕ = 50 nm) over the external and internal structures generated through thermal decomposition of polystyrene nanobeads (ϕ = 100 nm). Therefore, the P-NiMoS/C microspheres deliver initial discharge capacities of 662, 419, 373, 300, 231, 181, and 146 mA h g-1 at current densities of 0.5, 1, 2, 4, 6, 8, and 10 A g-1 , respectively. Furthermore, P-NiMoS/C exhibits a stable discharge capacity of 444 mA h g-1 at the end of the 150th cycle at a current density of 0.5 A g-1 , indicating higher cycling stability than the filled, that is, non-mesoporous, Ni3 S2 -MoS2 /NGC (F-NiMoS/C) microspheres and filled carbon-free Ni3 S2 -MoS2 (F-NiMoS) microspheres. The superior electrochemical performance of P-NiMoS/C microspheres is attributed to the rapid Na+ ion diffusion, alleviation of severe volume stress during prolonged cycling, and higher electrical conductivity of NGC, which results in fast charge transfer during the redox processes. The results in the present study can provide fundamental knowledge for the development of multicomponent, porous, and highly conductive anodes for various applications.

Facile In Situ Synthesis of Co(OH)2-Ni3S2 Nanowires on Ni Foam for Use in High-Energy-Density Supercapacitors.

Ni3S2 nanowires were synthesized in situ using a one-pot hydrothermal reaction on Ni foam (NF) for use in supercapacitors as a positive electrode, and various contents (0.3-0.6 mmol) of Co(OH)2 shells were coated onto the surfaces of the Ni3S2 nanowire cores to improve the electrochemical properties. The Ni3S2 nanowires were uniformly formed on the smooth NF surface, and the Co(OH)2 shell was formed on the Ni3S2 nanowire surface. By direct NF participation as a reactant without adding any other Ni source, Ni3S2 was formed more closely to the NF surface, and the Co(OH)2 shell suppressed the loss of active material during charging-discharging, yielding excellent electrochemical properties. The Co(OH)2-Ni3S2/Ni electrode produced using 0.5 mmol Co(OH)2 (Co0.5-Ni3S2/Ni) exhibited a high specific capacitance of 1837 F g-1 (16.07 F cm-2) at a current density of 5 mA cm-2, and maintained a capacitance of 583 F g-1 (16.07 F cm-2) at a much higher current density of 50 mA cm-2. An asymmetric supercapacitor (ASC) with Co(OH)2-Ni3S2 and active carbon displayed a high-power density of 1036 kW kg-1 at an energy density of 43 W h kg-1 with good cycling stability, indicating its suitability for use in energy storage applications. Thus, the newly developed core-shell structure, Co(OH)2-Ni3S2, was shown to be efficient at improving the electrochemical performance.

Porous SnO2/C Nanofiber Anodes and LiFePO4/C Nanofiber Cathodes with a Wrinkle Structure for Stretchable Lithium Polymer Batteries with High Electrochemical Performance.

Stretchable lithium batteries have attracted considerable attention as components in future electronic devices, such as wearable devices, sensors, and body-attachment healthcare devices. However, several challenges still exist in the bid to obtain excellent electrochemical properties for stretchable batteries. Here, a unique stretchable lithium full-cell battery is designed using 1D nanofiber active materials, stretchable gel polymer electrolyte, and wrinkle structure electrodes. A SnO2/C nanofiber anode and a LiFePO4/C nanofiber cathode introduce meso- and micropores for lithium-ion diffusion and electrolyte penetration. The stretchable full-cell consists of an elastic poly(dimethylsiloxane) (PDMS) wrapping film, SnO2/C and LiFePO4/C nanofiber electrodes with a wrinkle structure fixed on the PDMS wrapping film by an adhesive polymer, and a gel polymer electrolyte. The specific capacity of the stretchable full-battery is maintained at 128.3 mAh g-1 (capacity retention of 92%) even after a 30% strain, as compared with 136.8 mAh g-1 before strain. The energy densities are 458.8 Wh kg-1 in the released state and 423.4 Wh kg-1 in the stretched state (based on the electrode), respectively. The high capacity and stability in the stretched state demonstrate the potential of the stretchable battery to overcome its limitations.

Golden Bristlegrass-Like Hierarchical Graphene Nanofibers Entangled with N-Doped CNTs Containing CoSe2 Nanocrystals at Each Node as Anodes for High-Rate Sodium-Ion Batteries.

Golden bristlegrass-like unique nanostructures comprising reduced graphene oxide (rGO) matrixed nanofibers entangled with bamboo-like N-doped carbon nanotubes (CNTs) containing CoSe2 nanocrystals at each node (denoted as N-CNT/rGO/CoSe2 NF) are designed as anodes for high-rate sodium-ion batteries (SIBs). Bamboo-like N-doped CNTs (N-CNTs) are successfully generated on the rGO matrixed nanofiber surface, between rGO sheets and mesopores, and interconnected chemically with homogeneously distributed rGO sheets. The defects in the N-CNTs formed by a simple etching process allow the complete phase conversion of Co into CoSe2 through the efficient penetration of H2 Se gas inside the CNT walls. The N-CNTs bridge the vertical defects for electron transfer in the rGO sheet layers and increase the distance between the rGO sheets during cycles. The discharge capacity of N-CNT/rGO/CoSe2 NF after the 10 000th cycle at an extremely high current density of 10 A g-1 is 264 mA h g-1 , and the capacity retention measured at the 100th cycle is 89%. N-CNT/rGO/CoSe2 NF has final discharge capacities of 395, 363, 328, 304, 283, 263, 246, 223, 197, 171, and 151 mA h g-1 at current densities of 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, and 20 A g-1 , respectively.

Facile and scalable synthesis of silicon nanowires from waste rice husk silica by the molten salt process.

Designing nanostructured silicon, such as in the form of nanoparticles, wires, and porous structures, for high-performance Li-ion electrodes, has progressed significantly. These approaches have largely overcome the capacity fading of silicon electrodes from volume expansion during lithiation/de-lithiation. However, they involve high costs, complex processes, and hazardous precursors. Herein, we propose an electrochemical fabrication of silicon nanowires from waste rice husks via a molten salt process based on electrodeoxidation. The addition of NiO as an electric conductor improved the production efficiency and created pores in the nanowires after washing. The electrically produced high-purity silicon yielded high capacity, and the nanowires provided sufficient free volume to accommodate silicon electrode expansion, resulting in improved cycle life. The converted silicon nanowires from the molten salt process will help develop sustainable energy storage materials.

Boosting the Conversion Efficiency Over 20% in MAPbI3 Perovskite Planar Solar Cells by Employing a Solution-Processed Aluminum-Doped Nickel Oxide Hole Collector.

Recently, nickel oxide (NiOx) thin films have been used as an efficient and robust hole transport layer (HTL) in inverted planar perovskite solar cells (IP-PSCs) to replace costly and unstable organic transport materials. However, the power conversion efficiency (PCE) of most IP-PSCs using NiOx HTLs is rather limited below 20% due to insufficient electronic conductivity of the NiOx. In this work, solution-processed Al-doped NiOx (ANO) films are suggested as HTLs for low-cost and stable IP-PSCs. The electrical conductivity of the NiOx film is significantly enhanced by Al doping, which effectively reduces the nonradiative recombination losses at the HTL-perovskite interfaces and boosts hole extraction/transportation. The device with undoped NiOx shows the best PCE of 16.56%, whereas ANO HTL (5% doping) contributes to achieving a PCE of 20.84%, which outperforms other CH3NH3PbI3 IP-PSCs with NiOx-based HTLs reported to date. Moreover, a reliability test (1728 h storage) shows that the performance stability is enhanced by approximately 11% by employing ANO HTLs. This investigation into ANO HTLs provides a new guideline for the further development of highly efficient and reliable IP-PSCs using low-cost and robust metal oxide HTLs.

Preparation of Highly Porous PAN-LATP Membranes as Separators for Lithium Ion Batteries.

Separators are a vital component to ensure the safety of lithium-ion batteries. However, the commercial separators employed in lithium ion batteries are inefficient due to their low porosity. In the present study, a simple electrospinning technique is adopted to prepare highly porous polyacrylonitrile (PAN)-based membranes with a higher concentration of lithium aluminum titanium phosphate (LATP) ceramic particles, as a viable alternative to the commercialized separators used in lithium ion batteries. The effect of the LATP particles on the morphology of the porous membranes is demonstrated through Field emission scattering electron microscopy. X-ray diffraction and Fourier transform infrared spectra studies suitably demonstrate the mixing of PAN and LATP particles in the polymer matrix. PAN with 30 wt% LATP (P-L30) exhibits an enhanced porosity of 90% and is more thermally stable, with the highest electrolyte uptake among all the prepared membranes. Due to better electrolyte uptake, the P-L30 membrane demonstrates an improved ionic conductivity of 1.7 mS/cm. A coin cell prepared with a P-L30 membrane and a LiFePO4 cathode demonstrates the highest discharge capacity of 158 mAh/g at 0.5 C-rate. The coin cell with the P-L30 membrane also displays good cycling stability by retaining 97.5% of the initial discharge capacity after 200 cycles of charging and discharging at a 1C rate.

Improving of the Photovoltaic Characteristics of Dye-Sensitized Solar Cells Using a Photoelectrode with Electrospun Porous TiO2 Nanofibers.

Porous TiO2 nanofibers (PTFs) and dense TiO2 nanofibers (DTFs) were prepared using simple electrospinning for application in dye-sensitized solar cells (DSSCs). TiO2 nanoparticles (TNPs) were prepared using a hydrothermal reaction. The as-prepared PTFs and DTFs (with a fiber diameter of around 200 nm) were mixed with TNPs such as TNP-PTF and TNP-DTF nanocomposites used in photoelectrode materials or were coated as light scattering layers on the photoelectrodes to improve the charge transfer ability and light harvesting effect of the DSSCs. The as-prepared TNPs showed a pure anatase phase, while the PTFs and DTFs showed both the anatase and rutile phases. The TNP-PTF composite (TNP:PTF = 9:1 wt.%) exhibited an enhanced short circuit photocurrent density (Jsc) of 14.95 ± 1.03 mA cm-2 and a photoelectric conversion efficiency (PCE, η) of 5.4 ± 0.17% because of the improved charge transport and accessibility for the electrolyte ions. In addition, the TNP/PTF photoelectrode showed excellent light absorption in the visible region because of the mountainous nature of light induced by the PTF light scattering layer. The TNP/PTF photoelectrode showed the highest Jsc (16.96 ± 0.79 mA cm-2), η (5.9 ± 0.13%), and open circuit voltage (Voc, 0.66 ± 0.02 V).

Coral-Like Yolk-Shell-Structured Nickel Oxide/Carbon Composite Microspheres for High-Performance Li-Ion Storage Anodes.

In this study, coral-like yolk-shell-structured NiO/C composite microspheres (denoted as CYS-NiO/C) were prepared using spray pyrolysis. The unique yolk-shell structure was characterized, and the formation mechanism of the structure was proposed. Both the phase separation of the polyvinylpyrrolidone and polystyrene (PS) colloidal solution and the decomposition of the size-controlled PS nanobeads in the droplet played crucial roles in the formation of the unique coral-like yolk-shell structure. The CYS-NiO/C microspheres delivered a reversible discharge capacity of 991 mAh g-1 after 500 cycles at the current density of 1.0 A g-1. The discharge capacity of the CYS-NiO/C microspheres after the 1000th cycle at the current density of 2.0 A g-1 was 635 mAh g-1, and the capacity retention measured from the second cycle was 91%. The final discharge capacities of the CYS-NiO/C microspheres at the current densities of 0.5, 1.5, 3.0, 5.0, 7.0, and 10.0 A g-1 were 753, 648, 560, 490, 440, and 389 mAh g-1, respectively. The synergetic effect of the coral-like yolk-shell structure with well-defined interconnected mesopores and highly conductive carbon resulted in the excellent Li+-ion storage properties of the CYS-NiO/C microspheres.

Methanol metabolism and archaeal community changes in a bioelectrochemical anaerobic digestion sequencing batch reactor with copper-coated graphite cathode.

In this study, the metabolism of methanol and changes in an archaeal community were examined in a bioelectrochemical anaerobic digestion sequencing batch reactor with a copper-coated graphite cathode (BEAD-SBRCu). Copper-coated graphite cathode produced methanol from food waste. The BEAD-SBRCu showed higher methanol removal and methane production than those of the anaerobic digestion (AD)-SBR. The methane production and pH of the BEAD-SBRCu were stable even under a high organic loading rate (OLR). The hydrogenotrophic methanogens increased from 32.2 to 60.0%, and the hydrogen-dependent methylotrophic methanogens increased from 19.5 to 37.7% in the bulk of BEAD-SBRCu at high OLR. Where methanol was directly injected as a single substrate into the BEAD-SBRCu, the main metabolism of methane production was hydrogenotrophic methanogenesis using carbon dioxide and hydrogen released by the oxidation of methanol on the anode through bioelectrochemical reactions.

Electro-deposition and re-oxidation of carbon in carbonate-containing molten salts.

The electrochemical deposition and re-oxidation of solid carbon were studied in CO3(2-) ion-containing molten salts (e.g. CaCl2-CaCO3-LiCl-KCl and Li2CO3-K2CO3) at temperatures between 500 and 800 °C under Ar, CO2 or N2-CO2 atmospheres. The electrode reactions were investigated by thermodynamic analysis, cyclic voltammetry and chronopotentiometry in a three-electrode cell under various conditions. The findings suggest that the electro-reduction of CO3(2-) is dominated by carbon deposition on all three tested working electrodes (Ni, Pt and mild steel), but partial reduction to CO can also occur. Electro-re-oxidation of the deposited carbon in the same molten salts was investigated for potential applications in, for example, direct carbon fuel cells. A brief energy and cost analysis is given based on results from constant voltage electrolysis in a two-electrode cell.

Pyrolysis kinetics of coking coal mixed with biomass under non-isothermal and isothermal conditions.

To investigate the kinetic characteristics of coking coal mixed with biomass during pyrolysis, thermogravimetric (TG) and thermo-balance reactor (TBR) analyses were conducted under non-isothermal and isothermal condition. Yellow poplar as a biomass (B) was mixed with weak coking coal (WC) and hard coking coal (HC), respectively. The calculated activation energies of WC/B blends were higher than those of HC/B blends under non-isothermal and isothermal conditions. The coal/biomass blends show increased reactivity and decreased activation energy with increasing biomass blend ratio, regardless of the coking properties of the coal. The different char structures of the WC/B and HC/B blends were analyzed by BET and SEM.