Yolk–shell structured iron carbide/N-doped carbon composite as highly efficient and stable oxygen reduction reaction electrocatalyst

We report a simple route to synthesize iron carbide/carbon yolk–shell composite via a facile two-step process including polymerization of pyrrole using Fe₃O₄ as a sacrificial template to form a Fe₃O₄/polypyrrole composite, followed by annealing at high temperature in N₂ atmosphere. The yolk–shell composite, with iron carbide (Fe_2.5C) embedded in nitrogen-doped carbon layers, shows impressively high catalytic activity and stability for oxygen reduction reaction in alkaline solution. Both the pyridinic-N and graphic-N in the shell of Fe₃O₄–PPy-700, together with the Fe_2.5C confined in carbon layers are believed to be the active sites for the ORR.     

Performance investigation on a novel 3D wave flow channel design for PEMFC

Flow field structure can largely determine the output performance of Polymer electrolyte membrane fuel cell. Excellent channel configuration accelerates electrochemical reactions in the catalytic layer, effectively avoiding flooding on the cathode side. In present study, a three-dimensional, multi-phase model of PEMFC with a 3D wave flow channel is established. CFD method is applied to optimize the geometry constructions of three-dimensional wave flow channels. The results reveal that 3D wave flow channel is overall better than straight channel in promoting reactant gases transport, removing liquid water accumulated in microporous layer and avoiding thermal stress concentration in the membrane. Moreover, results show the optimal flow channel minimum depth and wave length of the 3D wave flow channel are 0.45 mm and 2 mm, respectively. Due to the periodic geometric characteristics of the wave channel, the convective mass transfer is introduced, improving gas flow rate in through-plane direction. Furthermore, when the cell output voltage is 0.4 V, the current density in the novel channel is 23.8% higher than that of conventional channel.     

Three Ln(III)-2,3,5-trichlorobenzoate coordination polymers (Ln = Tb,Ho and Er): Syntheses,structures and magnetic properties

Three novel lanthanide polymers, [Ln(III)(L)₃EtOH]_n (Ln = Tb(1), Ho(2), Er(3), HL = 2,3,5-trichlorobenzoic acid), have been solvothermal synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy and element analyses. The three polymers crystallize in triclinic space group P-1. The Ln(III) ions are in turn bridged by double and quadruple carboxylate of L⁻ ligands to form one-dimensional (1D) chains. Magnetic studies reveal that polymer 1 demonstrates dominant ferromagnetic behavior, polymer 2 shows antiferromagnetic behavior, and polymer 3 present spin-canting behavior.     

Nickel foam-supported Fe,Ni-Polyporphyrin microparticles: Efficient bifunctional catalysts for overall water splitting in alkaline media

Developing highly active, stable and sustainable electrocatalysts for overall water splitting is of great importance to generate renewable H₂ for fuel cells. Herein, we report the synthesis of electrocatalytically active, nickel foam-supported, spherical core-shell Fe-poly(tetraphenylporphyrin)/Ni-poly(tetraphenylporphyrin) microparticles (FeTPP@NiTPP/NF). We also show that FeTPP@NiTPP/NF exhibits efficient bifunctional electrocatalytic properties toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Electrochemical tests in KOH solution (1 M) reveal that FeTPP@NiTPP/NF electrocatalyzes the OER with 100 mA cm⁻² at an overpotential of 302 mV and the HER with 10 mA cm⁻² at an overpotential of 170 mV. Notably also, its catalytic performance for OER is better than that of RuO₂, the benchmark OER catalyst. Although its catalytic activity for HER is slightly lower than that of Pt/C (the benchmark HER electrocatalyst), it shows greater stability than the latter during the reaction. The material also exhibits electrocatalytic activity for overall water splitting reaction at a current density of 10 mA cm⁻² with a cell voltage of 1.58 V, along with a good recovery property. Additionally, the work demonstrates a new synthetic strategy to an efficient, noble metal-free-coordinated covalent organic framework (COF)-based, bifunctional electrocatalyst for water splitting.     

Use of conditioning time to investigate the mechanisms of interactions of selected fatty acids on hematite Part II laboratory investigations

It is the aim of this paper to examine the effects of conditioning time on the flotation of hematite using three technical grade fatty acid reagents as providing additional evidence on their mechanism of interaction with the hematite surface. Various mechanisms have been postulated as occurring as conditioning time is increased. Both physical (e.g. conditioning time and power input) and chemical (nature, dispersion and solubility of the adsorbing species) contribute to the mechanisms of attachment of collector. In this paper, the mechanism of attachment of oleate to hematite can be readily explained by chemisorption, but the mechanism of attachment of lauric acid appears to be physical adsorption at neutral pH. The flotation of hematite with a mixture of tallow-type fatty acids (palmitic, stearic and oleic acids) is very sensitive to conditioning time, and suggests that, even though flotation is very effective at short conditioning times, it is very susceptible to the presence of fines and their associated high surface areas. It is therefore obvious that both the physical and chemical conditions contribute to the mechanisms of adsorption of fatty acids on iron-containing oxide minerals and must be understood in order to optimise the flotation of these minerals in an industrial situation.     

Stability of Y-TZP during hydrothermal treatment: neutron experiments and stability considerations

The degradation of yttria-stabilised zirconia in humid atmospheres at temperatures around 250 °C is influenced by a number of microstructural parameters. The corrosive attack starts from the surface and is associated with the tetragonal to monoclinic transformation. In order to investigate structural changes chemically homogeneous single phase t-powders had been hydrothermally treated in a D₂O-atmosphere and subsequently investigated by neutron diffraction. Slight structural changes were observed after water treatment: a general contraction of both a and c parameters, hence, the “free” structural z(oxygen) parameter as well as the c/a-ratio are closer to the values of cubic zirconia. In this paper the structural changes due to the penetration of water radicals during hydrolysis are discussed. They give rise to stresses which then have an impact on the energy balance between the tetragonal and the monoclinic phase (martensitic transformations). Since the powder state can be assumed to be mostly free from macro-straining, the changes of the lattice constants were used to deduct a shape change tensor. Hence assuming linear elastic behaviour (isotropic elastic modulus of 200 GPa for both a surface grain and its environment) maximum stresses of 328 MPa for the a-axis and 488 MPa for the c-axis were found. Thus, water radicals basically lead to further tensile stresses in the surface which increase the energy difference between the t and m phase, i.e. a further destabilisation.     

Effect of surfactant microstructures on photocatalytic degradation of phenol and chlorophenols

The effect of hexadecyltrimethylammonium bromide (HTAB) on the photocatalytic degradation of phenol (Phe), 2,5-dichlorophenol (2,5-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) in the presence of aqueous TiO₂ suspensions at pH ca. 5 was investigated using a laboratory photoreactor equipped with a medium-pressure mercury lamp. Inhibition of substrate decomposition was observed for phenol, both below and above the surfactant critical micellar concentration, whereas a more complex behaviour was exhibited by chlorophenols. It was found that adsorption of these compounds onto the surfactant-modified semiconductor particles facilitates their faster decomposition, but the competitive partition of substrates between adsorbed surfactant structures and micellar aggregates tends to limit the beneficial kinetic effects at higher amphiphile concentrations. The crucial influence of surfactant adsorption was clearly evidenced in some runs performed at pH 3. Relevant inhibition of chloride release from chlorophenols, observed in the presence of HTAB, indicates a higher persistence of reaction intermediates in the reaction media, suggesting the need for a careful investigation of surfactant effects on all the degradation steps of the process.     

A dinuclear copper(II) complex and a zigzag chain iron(II) polymer based on the 4-antipyrine derived Schiff base ligands: The hydroxylation and redox occurred under the solvothermal conditions

A new dinuclear copper(II) compound, [Cu₂(L1-O)₂] (1) (L1 = (4E)-4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one), and zigzag chain polymer, {[FeCl₂(L2)]}_n (2) (L2 = 1,5-dimethyl-2-phenyl-4-{[(1E)-pyridine-4-ylmethylene]amino}-1,2-dihydro-3H-pyrazol-3-one), were synthesized by solvothermal reactions and structurally characterized. The methyl group hydroxylation and the redox have been observed in the preparation of 1 and 2, respectively.     

Study on polyurethane-acrylate/cerium dioxide modified by 3-(Methylacryloxyl)propyltrimethoxy silane and its UV absorption property

Firstly, cerium dioxide(CeO₂) was modified by 3-(Methylacryloxyl)propyltrimethoxy silane (KH-570), and modified CeO₂ (mCeO₂) was prepared. Then poly (urethane-acrylate) was modified by mCeO₂, and poly (urethane-acrylate)/modified CeO₂ (PUA/mCeO₂) composites with ultraviolet absorption property were prepared. The morphology, thermal hydrophobicity, mechanical properties, optical properties, and UV-absorption properties of PUA/mCeO₂ composites were studied. XRD and SEM analysis showed that the modified CeO₂ had better dispersion in the matrix than that of pure CeO₂. Ultraviolet–visible spectrum and thermogravimetric analysis were used to characterize the optical properties and thermal stability of PUA/mCeO₂ composites. The results showed that with the increasing of the mCeO₂ content, the UV-absorption property of PUA/mCeO₂ composites was improved gradually. When the content of mCeO₂ is 3%, the absorption of ultraviolet of PUA/mCeO2 composites is about 5 times of pure PUA film, and the absorption band is mainly in the UVA section. The thermal stability of PUA/mCeO₂ composites was improved with the adding of mCeO₂. With the increasing of mCeO₂ content, the contact angle of PUA/mCeO₂ composites increased significantly. And the UV-absorption mechanism of PUA/mCeO₂ Composites was studied. UV-curable PUA/mCeO₂ composites have good UV absorption property and water resistance. They will be used in the sun screen and protect people's skin.