Partially oxidized inter-doped RuNi alloy aerogel for the hydrogen evolution reaction in both alkaline and acidic media.

A facile reduction and doping process is employed with the supercritical ethanol drying method to form RuNi alloy aerogels. The optimized heterostructure comprising RuNi metal, RuO2, and NiO phases is synthesized through partial oxidation. When applied to the surface of Ni foam, the multiphase aerogels form a morphology of highly porous 0D colloidal aerogel networks on the surface. RuNi alloy-Ni foam oxidized at 350 °C (RuNi-350@NF) has an overpotential of 89 and 61 mV in 1 M KOH and 0.5 M H2SO4 media at 50 mA cm-2, as well as satisfactory long-term stability. Additionally, the Tafel slopes in alkaline and acidic media are found to be 34 and 30.9 mV dec-1, respectively. Furthermore, it exhibits long-term stability (35 h) in alkaline and acidic media at high current densities of 50 mA cm-2, respectively. This study presents a novel strategy for developing exceptionally efficient and free-standing 3D porous aerogel electrocatalysts with potential applications in hydrogen production.

Harnessing morphological alteration from microflowers to nanoparticles and cations synergy (Co:Ni) in binder-free cobalt nickel vanadate thin film cathodes synthesized via SILAR method for hybrid supercapacitor devices.

Electrode materials must be rationally designed with morphologies and electroactive sites manipulated through cations' synergy in bimetal compounds in order to maximize the performance of energy storage devices. Therefore, the present study emphasizes binder-free scalable preparation of cobalt nickel vanadate (CNV) thin films by a facile successive ionic layer adsorption and reaction (SILAR) approach with specific cations (Co:Ni) alternation. Increasing the Ni cation content in the CNV notably transforms its microflower structure comprising nanoflakes (252 nm) into nanoparticles (74 nm). An optimized S-CNV5 thin film cathode with Co:Ni molar ratio of âˆ¼ 0.4:0.6 and a high specific surface area of 340 m2 g-1, provided the excellent specific capacitance (Csp) and capacity (Csc) of 1382 F g-1 and 691 C g-1, respectively at 1 A g-1 current density. A hybrid aqueous supercapacitor (HASc) device with positive and negative electrodes comprising optimized CNV and reduced graphene oxide (rGO), respectively, in a 1 M KOH electrolyte delivered a Csp of 133 F g-1 and a specific energy (SE) of 53 Wh kg-1 at a specific power (SP) of 2261 kW kg-1. Additionally, a fabricated hybrid solid-state supercapacitor (HSSc) device with the same electrodes applying PVA-KOH gel electrolyte displayed a Csp of 119 F g-1, and SE of 46 Wh kg-1 at SP of 1184 W kg-1. This boosted electrochemical activity is due to the synergetic effects of Ni and Co species in the CNV thin film electrodes, emphasizing the potential of CNV electrodes as cathodes in hybrid energy storage devices.

Mechanically Strengthened Aerogels through Multiscale, Multicompositional, and Multidimensional Approaches: A Review.

In recent decades, aerogels have attracted tremendous attention in academia and industry as a class of lightweight and porous multifunctional nanomaterial. Despite their wide application range, the low mechanical durability hinders their processing and handling, particularly in applications requiring complex physical structures. "Mechanically strengthened aerogels" have emerged as a potential solution to address this drawback. Since the first report on aerogels in 1931, various modified synthesis processes have been introduced in the last few decades to enhance the aerogel mechanical strength, further advancing their multifunctional scope. This review summarizes the state-of-the-art developments of mechanically strengthened aerogels through multicompositional and multidimensional approaches. Furthermore, new trends and future directions for as prevailed commercialization of aerogels as plastic materials are discussed.

One-Pot Sol-Gel Synthesis of Highly Insulative Hybrid P(AAm-CO-AAc)-Silica Aerogels with Improved Mechanical and Thermal Properties.

Silica aerogels and their derivatives have outstanding thermal properties with exceptional values in the thermal insulation industry. However, their brittle nature restricts their large-scale commercialization. Thus, enhancing their mechanical strength without affecting their thermal insulating properties is essential. Therefore, for the first time, highly thermally stable poly(acrylamide-co-acrylic acid) partial sodium salt is used as a reinforcing polymer to synthesize hybrid P(AAm-CO-AAc)-silica aerogels via epoxy ring-opening polymerization in the present study. Functional groups in P(AAm-CO-AAc) partial sodium salts, such as CONH2 and COOH, acted as nucleophiles for the epoxy ring-opening reaction with (3-glycidyloxypropyl)trimethoxysilane, which resulted in a seven-fold enhancement in mechanical strength compared to that of pristine silica aerogel while maintaining thermal conductivity at less than 30.6 mW/mK and porosity of more than 93.68%. Moreover, the hybrid P(AAm-CO-AAc)-silica aerogel demonstrated improved thermal stability up to 343 °C, owing to the synergetic effect between the P(AAm-CO-AAc) and the silica aerogel, corresponding to the thermal stability and strong covalent bonding among them. These excellent results illustrate that this new synthetic approach for producing hybrid P(AAm-CO-AAc)-silica aerogels is useful for enhancing the mechanical strength of pristine silica aerogel without impairing its thermal insulating property and shows potential as an industrial heat insulation material.

Square-Facet Nanobar MOF-Derived Co3O4@Co/N-doped CNT Core-Shell-based Nanocomposites as Cathode Materials for High-Performance Supercapacitor Studies.

The binary as well as ternary nanocomposites of the square-facet nanobar Co-MOF-derived Co3O4@Co/N-CNTs (N-CNTs: nitrogen-doped carbon nanotubes) with Ag NPs and rGO have been synthesized via an easy wet chemical route, and their supercapacitor behavior was then studied. At a controlled pH of the precursor solution, square-facet nanobars of Co-MOF were first synthesized by the solvothermal method and then pyrolyzed under a controlled nitrogen atmosphere to get a core-shell system of Co3O4@Co/N-CNTs. In the second step, different compositions of Co3O4@Co/N-CNT core-shell structures were formed by an ex-situ method with Ag NPs and rGO moieties. Among several bare, binary, and ternary compositions tested in 6 M aqueous KOH electrolyte, a ternary nanocomposite having a 7.0:1.5:1.5 stoichiometric ratio of Co3O4@Co/N-CNT, Ag NPs, and rGO, respectively, reported the highest specific capacitance (3393.8 F g-1 at 5 mV s-1). The optimized nanocomposite showed the energy density, power density, and Coulombic efficiency of 74.1 W h.kg-1, 443.7 W.kg-1, and 101.3%, respectively, with excellent electrochemical stability. After testing an asymmetrical supercapacitor with a Co3O4@Co/N-CNT/Ag NPs/rGO/nickel foam cathode and an activated carbon/nickel foam anode, it showed 4.9 W h.kg-1 of energy density and 5000.0 W.kg-1 of power density.

Highly Dispersed Pt Clusters on F-Doped Tin(IV) Oxide Aerogel Matrix: An Ultra-Robust Hybrid Catalyst for Enhanced Hydrogen Evolution.

Dispersing the minuscule mass loading without hampering the high catalytic activity and long-term stability of a noble metal catalyst results in its ultimate efficacy for the electrochemical hydrogen evolution reaction (HER). Despite being the most efficient HER catalyst, the use of Pt is curtailed due to its scarcity and tendency to leach out in the harsh electrochemical reaction environment. In this study, we combined F-doped tin(IV) oxide (F-SnO2) aerogel with Pt catalyst to prevent metallic corrosion and to achieve abundant Pt active sites (approximately 5 nm clusters) with large specific surface area (321 cm2·g-1). With nanoscopic Pt loading inside the SnO2 aerogel matrix, the as-synthesized hybrid F-SnO2@Pt possesses a large specific surface area and high porosity and, thus, exhibits efficient experimental and intrinsic HER activity (a low overpotential of 42 mV at 10 mA·cm-2 in 0.5 M sulfuric acid), a 22-times larger turnover frequency (11.2 H2·s-1) than that of Pt/C at 50 mV, and excellent robustness over 10,000 cyclic voltammetry cycles. The existing metal support interaction and strong intermolecular forces between Pt and F-SnO2 account for the catalytic superiority and persistence against corrosion of F-SnO2@Pt compared to commercially used Pt/C. Density functional theory analysis suggests that hybridization between the Pt and F-SnO2 orbitals enhances intermediate hydrogen atom (H*) adsorption at their interface, which improves the reaction kinetics.

2D-2D lattice engineering route for intimately coupled nanohybrids of layered double hydroxide and potassium hexaniobate: Chemiresistive SO2 sensor.

2D-2D lattice engineering route is used to synthesize intimately coupled nanohybrids of layered double hydroxide (LDH) and potassium hexaniobate. The 2D-2D lattice engineering route is based on the electrostatically derived self-assembly of delaminated zinc-chromium-layered double hydroxide (ZC-LDH) nanosheets and potassium hexaniobate (HNb) nanosheets (ZCNb nanohybrids). The 2D-2D lattice-engineered ZCNb nanohybrids display expanded surface area, mesoporous anchored nanosheets network morphology, and intimate coupling between nanosheets. The 2D-2D lattice engineered ZCNb nanohybrids are used for the low temperature operated gas sensor. The ZCNb nanohybrids display outstanding selectivity for the SO2, with the high response of 61.5% compared to pristine ZC-LDH (28.08%) and potassium niobate (8%) at 150 °C. Moreover, ZCNb sensors demonstrate superior response and recovery periods of 6 and 167 s at 150 °C, respectively. This result underscores the exceptional functionality of the ZCNb nanohybrids as efficient SO2 sensors. Moreover, these findings vividly demonstrate that the 2D-2D lattice-engineered ZCNb nanohybrids are quite effective not only in improving the gas sensor activity but also in developing of new type of intimately coupled mesoporous LDH-metal-oxide based hybrid materials.

Binder free cobalt iron phosphate thin films as efficient electrocatalysts for overall water splitting.

Designing nanostructure based robust catalyst for the electrochemical water splitting is the great task in the energy conversion field to accomplish high electrical conductivity, low overpotential and long lasting activity. Herein, the electrochemical overall water splitting is reported by using the hydrothermally synthesized binder free cobalt iron phosphate thin films on low cost stainless steel substrates as a conducting backbone for the first time. The effect of composition ratio variation of cobalt and iron was studied on the structural, compositional, morphological, and surface electronic properties by conducting various characterizations which results in amorphous hydrous cobalt iron phosphate having mesoporosity. The as synthesized cobalt iron phosphate having composition ratio (50:50 of Co:Fe) exhibits excellent electrochemical OER and HER catalytic water splitting performance. Best performing electrode exhibits smallest overpotentials of 251.9 mV and 55.5 mV for OER and HER respectively at 10 mA/cm2 current density. To split water molecule into the H2 and O2 by overall water splitting in same alkaline medium, the potential of 1.75 V was required after long duration (100 h) catalysis. Overall analysis confirms the cobalt iron phosphate thin films are outstanding and robust for the hydrogen production as clean renewable energy source.

Influence of Tin Doped TiO2 Nanorods on Dye Sensitized Solar Cells.

The one-step hydrothermal method was used to synthesize Sn-doped TiO2 (Sn-TiO2) thin films, in which the variation in Sn content ranged from 0 to 7-wt % and, further, its influence on the performance of a dye-sensitized solar cell (DSSC) photoanode was studied. The deposited samples were analyzed by X-ray diffraction (XRD) and Raman spectroscopy, which confirmed the existence of the rutile phase of the synthesized samples with crystallite size ranges in between 20.1 to 22.3 nm. In addition, the bare and Sn-TiO2 thin films showed nanorod morphology. A reduction in the optical band gap from 2.78 to 2.62 eV was observed with increasing Sn content. The X-ray photoelectron spectroscopy (XPS) analysis confirmed Sn4+ was successfully replaced at the Ti4+ site. The 3-wt % Sn-TiO2 based DSSC showed the optimum efficiency of 4.01%, which was superior to 0.87% of bare and other doping concentrations of Sn-TiO2 based DSSCs. The present work reflects Sn-TiO2 as an advancing material with excellent capabilities, which can be used in photovoltaic energy conversion devices.

Fabrication of a High-Performance Hybrid Supercapacitor Based on Hydrothermally Synthesized Highly Stable Cobalt Manganese Phosphate Thin Films.

In the present study, cobalt manganese phosphate (H-CMP-series) thin films with different compositions of Co/Mn are prepared on stainless steel (SS) substrate via a facile hydrothermal method and employed as binder-free cathode electrodes in a hybrid supercapacitor. The XRD study reveals a monoclinic crystal structure, and the FE-SEM analysis confirmed that H-CMP-series samples displayed a nano/microarchitecture (microflowers to nanoflakes) on the surface of SS substrate with excess available surfaces and unique sizes. Interestingly, the synergy between cobalt and manganese species in the cobalt manganese phosphate thin film electrode demonstrates a maximum specific capacitance of 571 F g-1 at a 2.2 A g-1 current density in 1 M KOH. Besides, the nano/microstructured cobalt manganese phosphate was able to maintain capacitance retention of 88% over 8000 charge-discharge cycles. More importantly, the aqueous/all-solid-state asymmetric supercapacitor manufactured with the cobalt manganese phosphate thin film as the cathode and reduced graphene oxide (rGO) as the anode displays a high operating potential window of 1.6 V. The aqueous asymmetric device exhibited a maximum specific capacitance of 128 F g-1 at a current density of 1 A g-1 with an energy density of 45.7 Wh kg-1 and a power density of 1.65 kW kg-1. In addition, the all-solid-state asymmetric supercapacitor device provides a high specific capacitance of 37 F g-1 at 1 A g-1 with 13.3 Wh kg-1 energy density and 1.64 kW kg-1 power density in a polymer gel (PVA-KOH) electrolyte. The long cyclic life of both devices (87 and 84%, respectively, after 6000 cycles) and practical demonstration of the solid-state device (lighting of a LED lamp) suggest another alternative choice for cathode materials to develop stable energy storage devices with high energy density. Furthermore, the aforementioned study paves the way to investigate phosphate-based materials as a new class of materials for supercapacitor applicability.

Facile Synthesis of SnO2 Aerogel/Reduced Graphene Oxide Nanocomposites via in Situ Annealing for the Photocatalytic Degradation of Methyl Orange.

SnO2 aerogel/reduced graphene oxide (rGO) nanocomposites were synthesized using the sol⁻gel method. A homogeneous dispersion of graphene oxide (GO) flakes in a tin precursor solution was captured in a three-dimensional network SnO2 aerogel matrix and successively underwent supercritical alcohol drying followed by the in situ thermal reduction of GO, resulting in SnO2 aerogel/rGO nanocomposites. The chemical interaction between aerogel matrix and GO functional groups was confirmed by a peak shift in the Fourier transform infrared spectra and a change in the optical bandgap of the diffuse reflectance spectra. The role of rGO in 3D aerogel structure was studied in terms of photocatalytic activity with detailed mechanism of the enhancement such as electron transfer between the GO and SnO2. In addition, the photocatalytic activity of these nanocomposites in the methyl orange degradation varied depending on the amount of rGO loading in the SnO2 aerogel matrix; an appropriate amount of rGO was required for the highest enhancement in the photocatalytic activity of the SnO2 aerogel. The proposed nanocomposites could be a useful solution against water pollutants.

Polypropylene/Silica Aerogel Composite Incorporating a Conformal Coating of Methyltrimethoxysilane-Based Aerogel.

Silica aerogels possess low thermal conductivity but have a brittle nature, while their polymers tend to exhibit enhanced mechanical properties. In this study, we introduce a new approach to overcoming this brittle property of silica aerogels. Polypropylene/silica aerogel composites were prepared by thermally induced phase separation followed by a supercritical CO2 drying method. Silica aerogel was formed onto a polypropylene scaffold using a two-step sol-gel process with methyltrimethoxysilane as the silica precursor. Enhancement of the mechanical properties of the polypropylene/silica aerogel composite compared with a pristine methyltrimethoxysilane-based silica aerogel was observed. The effects of the latter on the microstructure and physical properties of the polypropylene/silica aerogel (hereafter referred to as the polymer matrix aerogel) composite were investigated. Compared with the polypropylene monolith, the polymer matrix aerogel composite demonstrated enhanced surface-chemical and microporous-structural properties such as higher hydrophobicity (135°), pore volume (0.18 cm³/g), average pore diameter (12.55 nm), and specific surface area (57.2 m²/g). This novel approach of incorporating methyltrimethoxysilane-based silica aerogel onto polypropylene when synthesizing the polymer matrix aerogel composite shows great potential as a durable superhydrophobic and corrosion resistant thermal insulating material.