Architecting the High-Entropy Oxides on 2D MXene Nanosheets by Rapid Microwave-Heating Strategy with Robust Photoelectrochemical Oxygen Evolution Performance.

High-entropy oxides (HEO) have recently concerned interest as the most promising electrocatalytic materials for oxygen evolution reactions (OER). In this work, a new strategy to the synthesis of HEO nanostructures on Ti3 C2 Tx MXene via rapid microwave heating and subsequent calcination at a low temperature is reported. Furthermore, the influence of HEO loading on Ti3 C2 Tx MXene is investigated toward OER performance with and without visible-light illumination in an alkaline medium. The obtained HEO/Ti3 C2 Tx -0.5 hybrid exhibited an outstanding photoelectrochemical OER ability with a low overpotential of 331 mV at 10 mA cm-2 and a small Tafel slope of 71 mV dec-1 , which exceeded that of a commercial IrO2 catalyst (340 mV at 10 mA cm-2 ). In particular, the fabricated water electrolyzer with the HEO/Ti3 C2 Tx -0.5 hybrid as anode required a less potential of 1.62 V at 10 mA cm-2 under visible-light illumination. Owing to the strong synergistic interaction between the HEO and Ti3 C2 Tx MXene, the HEO/Ti3 C2 Tx hybrid has a great electrochemical surface area, many metal active sites, high conductivity, and fast reaction kinetics, resulting in an excellent OER performance. This study offers an efficient strategy for synthesizing HEO-based materials with high OER performance to produce high-value hydrogen fuel.

Fabrication of ß-CoV3O8 nanorods embedded in graphene sheets and their application for electrochemical charge storage electrode.

The fabrication of ß-CoV3O8 nanorods embedded in graphene sheets and their application as electrochemical charge storage electrodes is reported. From the surfactant treatment of raw graphite, graphene was directly prepared and its nanocomposite with ß-CoV3O8 nanorods distributed between graphene layers (ß-CoV3O8-G) was synthesized by a hydrothermal method. When applied as an anode in lithium-ion batteries, the ß-CoV3O8-G anode exhibits greatly improved charge and discharge capacities of 790 and 627 mAh · g-1, respectively, with unexpectedly high initial efficiency of 82%. The observed discharge capacity reflected that at least 3.7 mol of Li+ is selectively accumulated within the ß-CoV3O8 phase (LixCoV3O8, x > 3.7), indicative of significantly improved Li+ uptake when compared with aggregated ß-CoV3O8 nanorods. Moreover, very distinct peak plateaus and greatly advanced cycling performance are observed, showing more improved Li+ storage within the ß-CoV3O8 phase. As a supercapacitor electrode, moreover, our composite electrode exhibits very high peak pseudocapacitances of 2.71 F · cm-2 and 433.65 F · g-1 in the ß-CoV3O8 phase with extremely stable cycling performance. This remarkably enhanced performance in the individual electrochemical charge storage electrodes is attributed to the novel phase formation of ß-CoV3O8 and its optimized nanocomposite structure with graphene, which yield fast electrical conduction through graphene, easy accessibility of ions through the open multilayer nanosheet structure, and a relaxation space between the ß-CoV3O8-G.

Aloe vera-derived graphene-coupled phenosafranin photocatalyst for generation and regeneration of ammonia and NADH by mimicking natural photosynthetic route.

Aloe vera-derived graphene (ADG) coupled system photocatalyst, mimicking natural photosynthesis, is one of the most promising ways for converting solar energy into ammonia (NH3 ) and nicotinamide adenine dinucleotide (NADH) that have been widely used to make the numerous chemicals such as fertilizer and fuel. In this study, we report the synthesis of the aloe vera-derived graphene-coupled phenosafranin (ADGCP) acting as a highly efficient photocatalyst for the generation of NH3 and regeneration of NADH from nitrogen (N2 ) and oxidized form of nicotinamide adenine dinucleotide (NAD+ ). The results show a benchmark instance for mimicking natural photosynthesis activity as well as the practical applications for the solar-driven selective formation of NH3 and the regeneration of NADH by using the newly designed photocatalyst.

Moving beyond Ti2C3Tx MXene to Pt-Decorated TiO2@TiC Core-Shell via Pulsed Laser in Reshaping Modification for Accelerating Hydrogen Evolution Kinetics.

Phase engineering of nanocatalysts on specific facets is critical not only for enhancing catalytic activity but also for intensely understanding the impact of facet-based phase engineering on electrocatalytic reactions. In this study, we successfully reshaped a two-dimensional (2D) MXene (Ti3C2Tx) obtained by etching Ti3AlC2 MAX via a pulsed laser irradiation in liquid (PLIL) process. We produced a TiO2@TiC core-shell structure in spheres with sizes of 200-350 nm, and then ∼2 nm ultrasmall Pt NPs were decorated on the surface of the TiO2@TiC core-shell using the single-step PLIL method. These advances allow for a significant increase in electrocatalytic hydrogen evolution reaction (HER) activity under visible light illumination. The effect of optimal Pt loading on PLIL time was identified, and the resulting Pt/TiO2@TiC/Pt-5 min sample demonstrated outstanding electrochemical and photoelectrochemical performance. The photoelectrochemical HER activity over Pt/TiO2@TiC/Pt-5 min catalyst exhibits a low overpotential of 48 mV at 10 mA/cm2 and an ultralow Tafel slope of 54.03 mV/dec with excellent stability of over 50 h, which is hydrogen production activity even superior to that of the commercial Pt/C catalysts (55 mV, 62.45 mV/dec). This investigation not only serves as a potential for laser-dependent phase engineering but also provides a reliable strategy for the rational design and fabrication of highly effective nanocatalysts.

Nanoscale Assembly of 2D Materials for Energy and Environmental Applications.

Rational design of 2D materials is crucial for the realization of their profound implications in energy and environmental fields. The past decade has witnessed significant developments in 2D material research, yet a number of critical challenges remain for real-world applications. Nanoscale assembly, precise control over the orientational and positional ordering, and complex interfaces among 2D layers are essential for the continued progress of 2D materials, especially for energy storage and conversion and environmental remediation. Herein, recent progress, the status, future prospects, and challenges associated with nanoscopic assembly of 2D materials are highlighted, specifically targeting energy and environmental applications. Geometric dimensional diversity of 2D material assembly is focused on, based on novel assembly mechanisms, including 1D fibers from the colloidal liquid crystalline phase, 2D films by interfacial tension (Marangoni effect), and 3D nanoarchitecture assembly by electrochemical processes. Relevant critical advantages of 2D material assembly are highlighted for application fields, including secondary batteries, supercapacitors, catalysts, gas sensors, desalination, and water decontamination.

Polyhedral Au nanocrystals exclusively bound by {110} facets: the rhombic dodecahedron.

The rhombic dodecahedral Au nanocrystals enclosed by 12 {110} facets could be readily prepared without the use of any seeds, surfactants, or foreign metal ions but only with N,N-dimethylformamide as both reductant and solvent.

High-Energy Efficiency Membraneless Flowless Zn-Br Battery: Utilizing the Electrochemical-Chemical Growth of Polybromides.

Aqueous Zn-Br batteries (ZBBs) offer promising next-generation high-density energy storage for energy storage systems, along with distinctive cost effectiveness particularly in membraneless and flowless (MLFL) form. Unfortunately, they generally suffer from uncontrolled diffusion of corrosive bromine components, which cause serious self-discharge and capacity fade. An MLFL-ZBB is presented that fundamentally tackles the problem of bromine crossover by converting bromine to the polybromide anion using protonated pyridinic nitrogen doped microporous carbon decorated on graphite felt (NGF). The NGF electrodes efficiently capture bromine and polybromide anions at the abundant protonated nitrogen dopant sites within micropores and facilitate effective conversion of bromine into polybromides through electrochemical-chemical growth mechanism. The MLFL-ZBBs with NGF exhibit an extraordinary stability over 1000 charge/discharge cycles, with an energy efficiency over 80%, the highest value ever reported among membraneless Zn-Br batteries. Judicious engineering of an atomistically designed nanostructured electrode offers a novel design platform for low cost, high voltage, long-life cycle aqueous hybrid Zn-Br batteries.

Metal Oxide/Graphene Composites for Supercapacitive Electrode Materials.

Graphene composites with metal or metal oxide nanoparticles have been extensively investigated owing to their potential applications in the fields of fuel cells, batteries, sensing, solar cells, and catalysis. Among them, much research has focused on supercapacitor applications and have come close to realization. Composites include monometal oxides of cobalt, nickel, manganese, and iron, as well as their binary and ternary oxides. In addition, their morphological control and hybrid systems of carbon nanotubes have also been investigated. This review presents the current trends in research on metal oxide/graphene composites for supercapacitors. Furthermore, methods are suggested to improve the properties of electrochemical capacitor electrodes.

ZrO2-SiO2 nanosheets with ultrasmall WO3 nanoparticles and their enhanced pseudocapacitance and stability.

We report on the first synthesis of porous ZrO2-SiO2 sheets with well-defined ultrasmall WO3 nanoparticles for energy storage performance. In our system, for improving the surface deterioration of electrode, we use the ZrO2-SiO2 sheets using graphene oxide as a template to access electrode substrate. The synthesized electrode with about 20 nm thickness and about 10 nm pores, has a maximum value of 313 F/g at current density of 1 A/g and a minimum value of 160 F/g at current density of 30 A/g in the specific capacitance. In addition, over 90% of its initial specific capacitance is retained when they are cycled up to 2500 cycles.

Diameter-controlled and surface-modified Sb2Se3 nanowires and their photodetector performance.

Due to its direct and narrow band gap, high chemical stability, and high Seebeck coefficient (1800 µVK(-1)), antimony selenide (Sb2Se3) has many potential applications, such as in photovoltaic devices, thermoelectric devices, and solar cells. However, research on the Sb2Se3 materials has been limited by its low electrical conductivity in bulk state. To overcome this challenge, we suggest two kinds of nano-structured materials, namely, the diameter-controlled Sb2Se3 nanowires and Ag2Se-decorated Sb2Se3 nanowires. The photocurrent response of diameter-controlled Sb2Se3, which depends on electrical conductivity of the material, increases non-linearly with the diameter of the nanowire. The photosensitivity factor (K = I(light)/I(dark)) of the intrinsic Sb2Se3 nanowire with diameter of 80-100 nm is highly improved (K = 75). Additionally, the measurement was conducted using a single nanowire under low source-drain voltage. The dark- and photocurrent of the Ag2Se-decorated Sb2Se3 nanowire further increased, as compared to that of the intrinsic Sb2Se3 nanowire, to approximately 50 and 7 times, respectively.

Synthesis of noble metal/graphene nanocomposites without surfactants by one-step reduction of metal salt and graphene oxide.

We carried out hydrazine-free, surfactant-free synthesis of noble metal/graphene nanocomposites. The reduction of the noble metals and GO was carried out simultaneously in hot water using ascorbic acid as a reductant. In the noble metal/graphene nanocomposites of Pd, Pt, Au, and Ag nanoparticles, the GO and metal salts were reduced completely by this synthetic method. In addition, the Pd/graphene nanocomposites showed good catalytic activity in the Suzuki coupling reaction and could be reused many times without loss of catalytic activity.

Direct synthesis of noble metal/graphene nanocomposites from graphite in water: photo-synthesis.

We report on the direct and facile method for noble metal/graphene nano-composites from graphite without reducing agents. In this system, the irradiant white-light instead of the chemical reducing agent exerts the influence on the synthesis of noble metal nanoparticles on graphene. Noble metal salts adsorbed on graphene flakes which were functionalized with ionic surfactants were reduced by irradiation with white light. In particular, noble metal nanoparticles were more evenly distributed on the surface of graphene which was functionalized with SDS than with CTAB.

High-yield synthesis of multi-branched gold nanoparticles and their surface-enhanced Raman scattering properties.

Multi-branched gold nanoparticles were synthesized in high-yield through the reduction of HAuCl(4) by using hydrazine as a reducing agent. Practically 100% of the particles have numerous branches. The high reduction capability of hydrazine is found to be crucial for the formation of these branched gold nanoparticles. Their size can be controlled from 20 to 130 nm by varying the amounts of hydrazine. The prepared nanoparticles exhibit efficient surface-enhanced Raman scattering (SERS) properties and the SERS activity of the particles depends on the aspect ratio of their branches, which are most likely related to a great increase in the localized electromagnetic field enhancement from their unique sharp surface features arising from the branches.

Crystal structure of a methylamine sorption complex of fully dehydrated fully Ca2+ -exchanged zeolite X, |Ca46(CH3NH2)16|[Si100Al92O384]-FAU.

The structure of a methylamine sorption complex of fully dehydrated fully Ca2+-exchanged zeolite X, |Ca46(CH3NH2)16|[Si100Al92O384]-FAU, has been determined in the cubic space group Fd3 at 21(1) degrees C (a = 24.994(4) angstroms) by single-crystal X-ray diffraction techniques. The crystal was prepared by ion exchange in a flowing stream of 0.05 M aqueous Ca(NO3)2 for 3 days, followed by dehydration at 480 degrees C and 2 x 10(-6) Torr for 2 days, and exposure to 160 Torr of zeolitically dry methylamine gas at 21(1) degrees C. The structure was determined in this atmosphere and was refined, using the 739 reflections for which I > 0, to the final error indices R1 = 0.152 and R2 = 0.061. In this structure, Ca2+ ions occupy three crystallographic sites. Sixteen Ca2+ ions fill the octahedral site at the centers of hexagonal prisms (Ca-O = 2.429(7) angstroms). The remaining 30 Ca2+ ions are found at two nonequivalent sites II (in the supercages) with occupancies of 14 and 16 ions. Each of these Ca2+ ions coordinates to three framework oxygens, either at 2.296(7) or 2.334(7) angstroms, respectively. Sixteen methylamine molecules have been sorbed per unit cell, two per supercage. Each coordinates to one of the latter 16 site-II Ca2+ ions: N-Ca = 2.30(9) angstroms. The imprecisely determined N-C bond length, 1.48(23) angstroms, differs insignificantly from that in methylamine(g), 1.474(5) angstroms. The positions of the hydrogen atoms were calculated. One of the amino hydrogen atoms hydrogen bonds to a 6-ring oxygen, and the other forms a bifurcated hydrogen bond to two other 6-ring oxygens. The methyl group does not hydrogen bond to anything.