Influence of metal-support interactions on reaction pathways over Ni/CeZrOx–Al2O3 catalysts for ethanol steam reforming

This work investigates selective Ni locations over Ni/CeZrO_x–Al₂O₃ catalysts at different Ni loading contents and their influences on reaction pathways in ethanol steam reforming (ESR). Depending on the Ni loading contents, the added Ni selectively interacts with CeZrO_x–Al₂O₃, resulting in the stepwise locations of Ni over CeZrO_x–Al₂O₃. This behavior induces a remarkable difference in hydrogen production and coke formation in ESR. The selective interaction between Ni and CeZrO_x for 10-wt.% Ni generates more oxygen vacancies in the CeZrO_x lattice. The Ni sites near the oxygen vacancies enhance reforming via steam activation, resulting in the highest hydrogen production rate of 1863.0 μmol/g_cat·min. In contrast, for 15 and 20-wt.% Ni, excessive Ni is additionally deposited on Al₂O₃ after the saturation of Ni–CeZrO_x interactions. These Ni sites on Al₂O₃ accelerate coking from the ethylene produced on the acidic sites, resulting in a high coke amount of 19.1 mg_c/g_cat·h (20Ni/CZ-Al).     

Preparation of high-activity coal char-based catalysts from high metals containing coal gangue and lignite for catalytic decomposition of biomass tar

The potential of using high metals containing coal gangue and lignite to prepare high-activity coal char-based catalysts is investigated for effective biomass tar decomposition. Loose structure and rough surface are formed for these char-based catalysts with heterogeneous distribution of a large number of inorganic particles. In the biomass tar decomposition, the performance of the coal char-based catalysts is significantly influenced by the content of the metals in the raw materials and coal gangue char (GC) with the ash content as high as 50.80% exhibits the highest activity in this work. A high biomass tar conversion efficiency of 93.5% is achieved at 800 °C along with a significant increase in the fuel gas product. During the five-time consecutive tests, the catalytic performance of GC increases a little at the second or third times reuse and remains relatively stable, showing the remarkable stability of the catalyst in biomass tar decomposition applications.     

Extraction and characterization of hydroxyapatite-based materials from grey triggerfish skin and black scabbardfish bones

The conversion of food industry by-products to compounds with high added value is nowadays a significant topic, for social, environmental, and economic reasons. In this paper, calcium phosphate-based materials were obtained from black scabbardfish (Aphanopus carbo) bones and grey triggerfish (Balistes capriscus) skin, which are two of the most abundant fish by-products of Madeira Island. Different calcination temperatures between 400 and 1000°C were employed. Materials obtained from calcination of bones of black scabbard fish were composed by homogeneous mixtures of hydroxyapatite (Ca₁₀(PO4)₆(OH)₂, HAp) and β-tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP). Because of the high biocompatibility of HAp and the good resorbability of β-TCP, these natural biphasic materials could be very relevant in the field of biomaterials, as bone grafts. The ratio between HAp and β-TCP in the biphasic compound was dependent on the calcination temperature. Differently, the material obtained from skin of grey triggerfish contained HAp as the main phase, together with small amounts of other mineral phases, such as halite and rhenanite, which are known to enhance osteogenesis when used as bone substitutes. In both cases, the increase of calcination temperature led to an increase in the particles size with a consequent decrease in their specific surface area. These results demonstrate that from the fish by-products of the most consumed fishes in Madeira Island it is possible to obtain bioceramic materials with tunable composition and particle morphology, which could be promising materials for the biomedical field.     

Phase composition,microstructure, and properties of Al4O4C–(Al2OC)1-x(AlN)x –Zr2Al3C4–Al2O3 refractories prepared at high temperatures in nitrogen

The novel Al₄O₄C–(Al₂OC)_1-x(AlN)_x–Zr₂Al₃C₄–Al₂O₃ refractories with ultra-low carbon content have been successfully prepared by constructing the core-shell structure of aluminum at 1300–1700°C in nitrogen. The phase composition, microstructure, and properties of the novel refractories are deeply investigated. The cracking temperature on the core-shell structure of aluminum is further explored and the reaction mechanism of Zr₂Al₃C₄ has also added explanation. The results show that the novel refractories have excellent physical properties and cannot be corroded by molten iron. There exist two different Al₂OC solid solutions in the novel refractories, Al₂OC-rich (Al₂OC)_1-x(AlN)_x and AlN-rich (Al₂OC)_1-x(AlN)_x. The temperatures affect their relative content. When temperatures are less than 1600°C, the relative content of Al₂OC-rich (Al₂OC)_1-x(AlN)_x is more than that of AlN-rich (Al₂OC)_1-x(AlN)_x. When temperatures are above 1700°C, the relative content of AlN-rich (Al₂OC)_1-x(AlN)_x is more than that of Al₂OC-rich (Al₂OC)_1-x(AlN)_x. The core-shell structure of aluminum fully ruptures at about 1200°C. Zr₂Al₃C₄ begins to form at about 1000°C and generates in large at 1200°C.     

Investigation on thermal conductivity and mechanical properties of Si3N4 ceramics via one-step sintering

High thermal conductivity Si₃N₄ ceramics were fabricated using a one-step method consisting of reaction-bonded Si₃N₄ (RBSN) and post-sintering. The influence of Si content on nitridation rate, β/(α+β) phase rate, thermal conductivity and mechanical properties was investigated in this work. It is of special interest to note that the thermal conductivity showed a tendency to increase first and then decrease with increasing Si content. This experimental result shows that the optimal thermal conductivity and fracture toughness were obtained to be 66 W (m K)^-1 and 12.0 MPa m^1/2, respectively. As a comparison, the nitridation rate and β/(α+β) phase rate in a static pressure nitriding system, i.e., 97% (MS10), 97% (MS15), 97% (MS20) and 8.3% (MS10), 8.3% (MS15), 8.9% (MS20), respectively, have obvious advantages over those in a flowing nitriding system, i.e., 91% (MS10), 91% (MS15), 93% (MS20) and 3.1% (MS10), 3.3% (MS15), 3.3% (MS20), respectively. Moreover, high lattice integrity of the β-Si₃N₄ phase was observed, which can effectively confine O atoms into the β-Si₃N₄ lattice using MgO as a sintering additive. This result indicates that one-step sintering can provide a new route to prepare Si₃N₄ ceramics with a good combination of thermal conductivity and mechanical properties.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Structural Basis for the Function of the C-Terminal Proton Release Pathway in the Calcium Pump

The calcium pump (sarco/endoplasmic reticulum Ca²⁺-ATPase, SERCA) plays a major role in calcium homeostasis in muscle cells by clearing cytosolic Ca²⁺ during muscle relaxation. Active Ca²⁺ transport by SERCA involves the structural transition from a low-Ca²⁺ affinity E2 state toward a high-Ca²⁺ affinity E1 state of the pump. This structural transition is accompanied by the countertransport of protons to stabilize the negative charge and maintain the structural integrity of the transport sites and partially compensate for the positive charges of the two Ca²⁺ ions passing through the membrane. X-ray crystallography studies have suggested that a hydrated pore located at the C-terminal domain of SERCA serves as a conduit for proton countertransport, but the existence and function of this pathway have not yet been fully characterized. We used atomistic simulations to demonstrate that in the protonated E2 state and the absence of initially bound water molecules, the C-terminal pore becomes hydrated in the nanosecond timescale. Hydration of the C-terminal pore is accompanied by the formation of water wires that connect the transport sites with the cytosol. Water wires are known as ubiquitous proton-transport devices in biological systems, thus supporting the notion that the C-terminal domain serves as a conduit for proton release. Additional simulations showed that the release of a single proton from the transport sites induces bending of transmembrane helix M5 and the interaction between residues Arg762 and Ser915. These structural changes create a physical barrier against full hydration of the pore and prevent the formation of hydrogen-bonded water wires once proton transport has occurred through this pore. Together, these findings support the notion that the C-terminal proton release pathway is a functional element of SERCA and also provide a mechanistic model for its operation in the catalytic cycle of the pump.     

Impact of gypsum on flotation of scheelite and fluorite using sodium oleate as collector

ABSTRACT

In this study, effect of calcium and gypsum on scheelite and fluorite was investigated using sodium oleate as collector. Micro-flotation and contact angle results showed that the adsorption of calcium could inhibit the hydrophobicity of scheelite and fluorite. Moreover, sulfate could enhance the inhibition. FT-IR results showed that calcium could be priori precipitated into calcium oleate and adsorb on mineral surface. The adsorption of calcium could increase the scheelite potential to IEP, while it showed limited effect on fluorite potential. However, the interaction of calcium on scheelite and fluorite in gypsum solution was more complex than that in calcium solution.     

Experimental study of crystal anisotropy based on ultra-precision cylindrical turning of single-crystal calcium fluoride

To realize ultimately efficient signal processing, it is necessary to replace electrical signal processing circuits with optical ones. The optical micro-resonator, which localizes light at a certain spot, is an essential component in optical signal processing. Single-crystal calcium fluoride (CaF₂) is the most suitable material for a highly efficient optical micro-resonator. The CaF₂ resonator can only be manufactured by ultra-precision machining processes, because its crystal anisotropy does not allow the application of chemical etching. However, the optical micro-resonator's performance depends definitely on the surface integrity.This study investigated the relationship between surface quality after ultra-precision machining and crystal anisotropy. Firstly, crack initiation was investigated on the (1 0 0), (1 1 0), and (1 1 1) planes using the micro-Vickers hardness test. Secondly, brittle-ductile transition was investigated by orthogonal cutting tests. Finally, cutting performance of cylindrical turning was evaluated, which could be a suitable method for manufacturing the CaF₂ resonator. The most difficult point in cylindrical turning of CaF₂ is that the crystalline plane and cutting direction vary continuously. In order to manufacture the CaF₂ optical micro-resonator more efficiently, analysis was conducted on crack initiation and surface quality of all crystallographic orientations from the perspective of slip system and cleavage.