Project description:AbstractThe catalytic behaviour of Co3Mo3C, Co6Mo6C, Co3Mo3N and Co6Mo6N for methane cracking has been studied to determine the relationship between the methane cracking activity and the chemical composition. The characterisation of post-reaction samples showed a complex phase composition with the presence of Co3Mo3C, α-Co and β-Mo2C as catalytic phases and the deposition of different forms of carbon during reaction.Graphical abstract
Project description:Transition metal carbides have numerous applications and are known to excel in terms of hardness, thermal stability and conductivity. In particular, the Pt-like behavior of Mo and W carbides has led to the popularization of metal carbides in catalysis, ranging from electrochemically-driven reactions to thermal methane coupling. Herein, we show the active participation of carbidic carbon in the formation of C2 products during methane coupling at high temperature that is associated with the dynamics of Mo and W carbides. A detailed mechanistic study reveals that the catalyst performance of these metal carbides can be traced back to its carbon diffusivity and exchange capability upon interaction with methane (gas phase carbon). A stable C2 selectivity over time on stream for Mo carbide (Mo2C) can be rationalized by fast carbon diffusion dynamics, while W carbide (WC) shows loss of selectivity due to slow diffusion leading to surface carbon depletion. This finding showcases that the bulk carbidic carbon of the catalyst plays a crucial role and that the metal carbide is not only responsible for methyl radical formation. Overall, this study evidences the presence of a carbon equivalent to the Mars-Van Krevelen type mechanism for non-oxidative coupling of methane.
Project description:Efficient flexible energy storage systems have received tremendous attention due to their enormous potential applications in self-powering portable electronic devices, including roll-up displays, electronic paper, and "smart" garments outfitted with piezoelectric patches to harvest energy from body movement. Unfortunately, the further development of these technologies faces great challenges due to a lack of ideal electrode materials with the right electrochemical behavior and mechanical properties. MXenes, which exhibit outstanding mechanical properties, hydrophilic surfaces, and high conductivities, have been identified as promising electrode material candidates. In this work, taking 2D transition metal carbides (TMCs) as representatives, we systematically explored several influencing factors, including transition metal species, layer thickness, functional group, and strain on their mechanical properties (e.g., stiffness, flexibility, and strength) and their electrochemical properties (e.g., ionic mobility, equilibrium voltage, and theoretical capacity). Considering potential charge-transfer polarization, we employed a charged electrode model to simulate ionic mobility and found that ionic mobility has a unique dependence on the surface atomic configuration influenced by bond length, valence electron number, functional groups, and strain. Under multiaxial loadings, electrical conductivity, high ionic mobility, low equilibrium voltage with good stability, excellent flexibility, and high theoretical capacity indicate that the bare 2D TMCs have potential to be ideal flexible anode materials, whereas the surface functionalization degrades the transport mobility and increases the equilibrium voltage due to bonding between the nonmetals and Li. These results provide valuable insights for experimental explorations of flexible anode candidates based on 2D TMCs.
Project description:A facile, highly efficient approach to obtain molybdenum trioxide (MoO3)-doped tungsten trioxide (WO3) is reported. An annealing process was used to transform ammonium tetrathiotungstate [(NH4)2WS4] to WO3 in the presence of oxygen. Ammonium tetrathiomolybdate [(NH4)2MoS4] was used as a dopant to improve the film for use in an electrochromic (EC) cell. (NH4)2MoS4 at different concentrations (10, 20, 30, and 40 mM) was added to the (NH4)2WS4 precursor by sonication and the samples were annealed at 500 °C in air. Raman, X-ray diffraction, and X-ray photoelectron spectroscopy measurements confirmed that the (NH4)2WS4 precursor decomposed to WO3 and the (NH4)2MoS4-(NH4)2WS4 precursor was transformed to MoO3-doped WO3 after annealing at 500 °C. It is shown that the MoO3-doped WO3 film is more uniform and porous than pure WO3, confirming the doping quality and the privileges of the proposed method. The optimal MoO3-doped WO3 used as an EC layer exhibited a high coloration efficiency of 128.1 cm2/C, which is larger than that of pure WO3 (74.5 cm2/C). Therefore, MoO3-doped WO3 synthesized by the reported method is a promising candidate for high-efficiency and low-cost smart windows.
Project description:A layered titanate, K2Ti4O9, is intercalated with various n-alkylamines through ion-exchange reaction in aqueous medium. On heating, the intercalated amine is partially deintercalated, yielding nitrogen-doped amine-intercalated titanates. The modified titanates are studied as catalysts in methylene blue degradation under UV irradiation. Heat-treated long-chain amine titanates exhibit better photocatalytic activity in comparison to short chain amine titanates. The improved catalytic activity could be attributed to two factors: (i) increased surface access as the titanate layers are well separated, pillared by the alkylamine chains and (ii) nitrogen doping.
Project description:Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the interactions between the sulfur pi-orbitals of arene dithiolates and high-valent transition metals as minimum molecular models of the active site features of pyranopterin MoW enzymes. The compounds (Tp*)MoO(bdt) (compound 1), Cp(2)Mo(bdt) (compound 2), and Cp(2)Ti(bdt) (compound 3) [where Tp* is hydrotris(3,5-dimethyl-1-pyrazolyl)borate, bdt is 1,2-benzenedithiolate, and Cp is eta(5)- cyclopentadienyl] provide access to three different electronic configurations of the metal, formally d(1), d(2), and d(0), respectively. The gas-phase photoelectron spectra show that ionizations from occupied metal and sulfur based valence orbitals are more clearly observed in compounds 2 and 3 than in compound 1. The observed ionization energies and characters compare very well with those calculated by density functional theory. A "dithiolate-folding-effect" involving an interaction of the metal in-plane and sulfur-pi orbitals is proposed to be a factor in the electron transfer reactions that regenerate the active sites of molybdenum and tungsten enzymes.
Project description:For the practical application of dynamic holography using updatable dyed materials, optical transparency and an enlarged sample size with a uniform dispersion of the dye and no air bubbles are crucial. The holographic films were prepared by applying a dyeing method comprising application, curing, dyeing, and washing to an unsaturated polyester (UP) resin film. The unsaturated polyester (UP) resin film with high optical transparency was dyed with a 3-[(4-cyanophenyl)azo]-9H-carbazole-9-ethanol (CACzE) (azo-carbazole) dye via the surfactant, polyoxyethylene (5) docosyl ether, in an aqueous solution. The amount of dye uptake obtained via the dyeing process ranged from 0.49 to 6.75 wt.%. The dye concentration in the UP resin was proportional to the dye concentration in the aqueous solution and the immersion time. The UP resin film with 3.65 wt.% dye exhibited the optical diffraction property η₁ of 0.23% with a response time τ of 5.9 s and a decay time of 3.6 s. The spectroscopic evaluation of the UP resin film crosslinking reaction and the dyeing state in the UP resin film are discussed. Furthermore, as an example of its functionality, the dynamic holographic properties of the dye-doped UP resin film are discussed.
Project description:Coordination polymers (CPs) are an assorted class of coordination complexes that are gaining attention for the safe and sustainable removal of organic dyes from wastewater discharge by either adsorption or photocatalytic degradation. Herein, three different coordination polymers with compositions [Ni(HL)(H2O)2·1.9H2O] (1), [Mn3(HL)(L)(μ3-OH)(H2O)(phen)2·2H2O] (2), and [Cd(HL)4(H2O)]·H2O (3) (H3L = 2-(3,5-dicarboxyphenyl)-6-carboxybenzimidazole; phen = 1,10-phenanthroline) have been synthesized and characterized spectroscopically and by single crystal X-ray diffraction. Single crystal X-ray diffraction results indicated that 1 forms a 2D layer-like framework, while 2 exhibits a 3-connected net with the Schläfli symbol of (44.6), and 3 displays a 3D supramolecular network in which two adjacent 2D layers are held by π···π interactions. All three compounds have been used as photocatalysts to catalyze the photodegradation of antibiotic dinitrozole (DTZ) and rhodamine B (RhB). The photocatalytic results suggested that the Mn-based CP 2 exhibited better photodecomposition of DTZ (91.1%) and RhB (95.0%) than the other two CPs in the time span of 45 min. The observed photocatalytic mechanisms have been addressed using Hirshfeld surface analyses.
Project description:In this contribution, the synthesis of the metal-organic framework (MOF) based on lanthanum that exhibits trigonal prism shape is presented. The length of a single side of this structure ranges from 2 to 10 μm. The carbonized lanthanum-based organic framework (CMOF-La) maintained the original shape. However, the lanthanum oxide was reshaped in the form of rods during the carbonization. It resulted in the creation of parallel arranged channels. The unique structure of the carbonized structure motivated us to reveal its adsorption performance. Therefore, the adsorption kinetics of acid red 18 onto a carbonized metal-organic framework were conducted. Various physicochemical parameters such as initial dye concentration and pH of dye solution were investigated in an adsorption process. The adsorption was found to decrease with an increase in initial dye concentration. In addition, the increase in adsorption capacity was noticed when the solution was changed to basic. Optimal conditions were obtained at a low pH. Kinetic adsorption data were analyzed using the pseudo-first-order kinetic model, the pseudo-second-order kinetic model and the intraparticle diffusion model. The adsorption kinetics were well fitted using a pseudo-second-order kinetic model. It was found that the adsorption of anionic dye onto CMOF-La occurs by hydrophobic interactions between carbonized metal-organic framework and acid red 18.
Project description:The potential disrupting effects of Azo dye on wastewater nutrients removal deserved more analysis. In this study, 15 days exposure experiments were conducted with alizarin yellow R (AYR) as a model dye to determine whether the dye caused adverse effects on biological removal of both the dye and nutrients in acclimated anaerobic-aerobic-anoxic sequencing batch reactors. The results showed that the AYR removal efficiency was, respectively, 85.7% and 66.8% at AYR concentrations of 50 and 200 mg l-1, while higher AYR inlet (400 mg l-1) might inactivate sludge. Lower removal of AYR at 200 mg l-1 of AYR was due to the insufficient support of electron donors in the anaerobic process. However, the decolorized by-products p-phenylenediamine and 5-aminosalicylic were completely decomposed in the following aerobic stage at both 50 and 200 mg l-1 of AYR concentrations. Compared with the absence of AYR, the presence of 200 mg l-1 of AYR decreased the total nitrogen removal efficiency from 82.4 to 41.1%, and chemical oxygen demand (COD) removal efficiency initially decreased to 68.1% and then returned to around 83.4% in the long-term exposure time. It was also found that the inhibition of AYR, nitrogen and COD removal induced by a higher concentration of AYR was due to the increased intracellular reactive oxygen species production, which caused the rise of oxidation-reduction potential value and decreased ammonia monooxygenase and nitrite oxidoreductase activities.