Investigation of production parameters in fracture behavior of hot-pressed Al2O3–SiC/graphite fibrous monolithic ceramics: Fibers orientation and cell boundary fraction

Fibrous monoliths (FMs) exhibit graceful failure in flexure and have higher toughness values. In this research, a mixture of Al₂O₃ and SiC as the core and graphite as the shell material of fibers were produced by extrusion-molding technique and after aligning along intended directions (0°, 90°, and 0°/90°) were sintered using the hot-pressing method at the temperature of 1500°C under pressure of 35 MPa for 1 hour. The significance of fibers orientation angle and the cell to cell boundary volume ratio in defining the fracture behavior of the FMs was detected. Because of the extensive crack interactions with graphite cell boundary such as crack deflection and delamination, with increasing cell boundary content from 25 to 30 vol%, the fracture toughness was enhanced. The highest flexural strength (184.8 ± 0.61 MPa) obtained from samples with 0° fibers orientation compared to 0°/90°. Since in the transverse plies (layers with 90° aligning), the properties of matrix phase are dominant, hence the strength in specimens with 0°/90° fibers orientation decreased considerably due to weak graphite matrix phase. In addition, the fracture toughness value increased up to 8.35 ± 0.74 MPa·m^1/2 for the unidirectional architecture of (0°) in comparison with cross-ply (0°/90°) architecture.     

Molecularly imprinted macroporous polymer monolithic layers for L-phenylalanine recognition in complex biological fluids

In present work, the development of macroporous monolithic layers bearing the artificial recognition sites toward L-phenylalanine has been carried out. The set of macroporous poly(2-aminoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) materials with average pore size ranged in 340–1200 nm was synthesized. The applicability of Hildebrand's and Hansen's theories for the prediction of polymer compatibility with porogenic solvents was evaluated. The dependences of average pore size on theoretically calculated parameters were plotted. The linear trend detected for Hansen's theory has indicated the high suitability of this approach to select appropriate porogens. The synthesized monolithic MIP layers were tested toward the ability to rebind phenylalanine-derivative in microarray format. The influence of such factors as average pore size of the material, the concentration of template molecule in polymerization mixture, interaction time of analyte with its imprinted sites on binding efficiency were studied. The developed materials demonstrated good analyte rebinding from buffer solution with recognition factors 2.5–3.4 depending on the MIP sample. The comparable rebinding efficiency was also detected when the analysis was carried using complex biological media. The selectivity of phenylalanine binding from the equimolar mixture of structural analogues was 81.9% for free amino acid and 91.2% for labeled one.     

Improvement in the properties of low carbon MgO-C refractories through the addition of graphite-SiC micro-composite

Graphite–SiC micro-composites have been prepared in–house by carbothermal reduction process. Controlling the process parameters including the weight ratio of SiO₂ to graphite as well as carbothermal reduction temperature during the micro-composite preparation favors the homogeneous formation of SiC with preferred morphologies like ribbons and whiskers/fibers. The micro-composite modified low carbon MgO-C refractories have exhibited significantly improved bulk properties over the standard composition. To understand the beneficial role of SiC reinforcement on hot strength performance under air oxidizing conditions, we propose a scaling parameter known as strength factor (fs) based on the ratio of hot strength (HMOR) to cold strength (CCS). Correlating the strength factor data (fs) with oxidative damage provides new insights into the reinforcing effects of distinct SiC morphologies in this new class of micro-composite fortified refractory systems over the standard compositions.     

通过晶种胶作导向剂的凝胶预陈化路线合成多级孔道FAU/α-Al2O3整体材料

以整体型α-Al2O3为载体，晶种胶作导向剂，通过凝胶预陈化路线合成了多级孔道FAU整体材料。对合成的样品进行了FT-IR、XRD、SEM和N2吸附脱附表征。根据实验结果确定了晶种胶、凝胶预处理及预陈化步骤的作用，同时提出了不同路线生成氧化铝复合物可能的合成机理。结果发现：负载的FAU沸石的粒径、形状及数量可通过改变晶化凝胶的组成，并且α-Al2O3载体的结构没有明显改变。具有简单、可重现且易将三重孔道结构融于成型的整体材料中的特点，通过晶种胶预处理的凝胶预陈化路线可加强载体内表面与沸石间的界面作用，形成纯相FAU晶体沉积在α-Al2O3载体骨架表面的形貌。另外，该方法可为其他的多级孔道沸石的合成提供思路。                                  

Unique structure of fibrous ZSM-5 catalyst expedited prolonged hydrogen atom restoration for selective production of propylene from methanol

A unique mesostructured fibrous silica@ZSM-5 (HSi@ZSM-5) catalyst was synthesized via microemulsion ZSM-5 zeolite seed assisted synthesis method and successfully applied in enhanced propylene formation in methanol to olefin (MTO) process. Characterization of the catalysts were carried out by FESEM, TEM, XRD, TGA, N₂ adsorption-desorption, NH₃ and KBr probed FTIR. Catalytic performance of as-synthesized catalyst was examined using a micro-pulse reactor and compared with the commercial HZSM-5. The reaction mechanism was elucidated by in-situ methanol FTIR spectroscopy. It was found that HSi@ZSM-5 produced higher propylene selectivity (56%) and was stable for long time on stream (80 h), nearly three-fold higher than that of commercial HZSM-5. In addition, HSi@ZSM-5 displayed higher rate of methanol dehydration, surface methoxy species generation and olefin methylation, indicating that alkene catalytic cycle is the dominant reaction mechanism. The higher selectivity towards propylene was correlated to the existence of moderate acidity which impeded the formation of paraffins and polymethylbenzene intermediates. These observations are further supported by KBr probed FTIR findings which revealed negligible paraffinic carbon species on HSi@ZSM-5. Thus, the unique fibrous silica@ZSM-5 retarded coke deposition due to suppression of undesired side reactions thereby signifying intensified propylene formation, which is highly desirable in commercial MTO processes.     

3D Macroscopic Architectures from Self‐Assembled MXene Hydrogels

Assembly of 2D MXene sheets into a 3D macroscopic architecture is highly desirable to overcome the severe restacking problem of 2D MXene sheets and develop MXene‐based functional materials. However, unlike graphene, 3D MXene macroassembly directly from the individual 2D sheets is hard to achieve for the intrinsic property of MXene. Here a new gelation method is reported to prepare a 3D structured hydrogel from 2D MXene sheets that is assisted by graphene oxide and a suitable reductant. As a supercapacitor electrode, the hydrogel delivers a superb capacitance up to 370 F g^?1 at 5 A g^?1, and more promisingly, demonstrates an exceptionally high rate performance with the capacitance of 165 F g^?1 even at 1000 A g^?1. Moreover, using controllable drying processes, MXene hydrogels are transformed into different monoliths with structures ranging from a loosely organized porous aerogel to a dense solid. As a result, a 3D porous MXene aerogel shows excellent adsorption capacity to simultaneously remove various classes of organic liquids and heavy metal ions while the dense solid has excellent mechanical performance with a high Young's modulus and hardness.     

Ultra‐High Pyridinic N‐Doped Porous Carbon Monolith Enabling High‐Capacity K‐Ion Battery Anodes for Both Half‐Cell and Full‐Cell Applications

An ultrahigh pyridinic N‐content‐doped porous carbon monolith is reported, and the content of pyridinic N reaches up to 10.1% in overall material (53.4 ± 0.9% out of 18.9 ± 0.4% N content), being higher than most of previously reported N‐doping carbonaceous materials, which exhibit greatly improved electrochemical performance for potassium storage, especially in term of the high reversible capacity. Remarkably, the pyridinic N‐doped porous carbon monolith (PNCM) electrode exhibits high initial charge capacity of 487 mAh g^?1 at a current density of 20 mA g^?1, which is one of the highest reversible capacities among all carbonaceous anodes for K‐ion batteries. Moreover, the K‐ion full cell is successfully assembled, demonstrating a high practical energy density of 153.5 Wh kg^?1. These results make PNCM promising for practical application in energy storage devices and encourage more investigations on a similar potassium storage system.     

Challenges and Advances in the Fabrication of Monolithic Bioseparation Materials and their Applications in Proteomics Research

High‐performance liquid chromatography integrated with tandem mass spectrometry (HPLC–MS/MS) has become a powerful technique for proteomics research. Its performance heavily depends on the separation efficiency of HPLC, which in turn depends on the chromatographic material. As the “heart” of the HPLC system, the chromatographic material is required to achieve excellent column efficiency and fast analysis. Monolithic materials, fabricated as continuous supports with interconnected skeletal structure and flow‐through pores, are regarded as an alternative to particle‐packed columns. Such materials are featured with easy preparation, fast mass transfer, high porosity, low back pressure, and miniaturization, and are next‐generation separation materials for high‐throughput proteins and peptides analysis. Herein, the recent progress regarding the fabrication of various monolithic materials is reviewed. Special emphasis is placed on studies of the fabrication of monolithic capillary columns and their applications in separation of biomolecules by capillary liquid chromatography (cLC). The applications of monolithic materials in the digestion, enrichment, and separation of phosphopeptides and glycopeptides from biological samples are also considered. Finally, advances in comprehensive 2D HPLC separations using monolithic columns are also shown.     

Methane coupling to acetylene over Pt-coated monoliths at millisecond contact times

We have studied the adiabatic and autothermal oxidative coupling of methane over Pt on -Al₂O₃ monoliths at space velocities above 10⁵ h^-1. The selectivity to C₂ hydrocarbons (primarily acetylene) reaches a maximum of around 20% at low fuel to oxygen ratios, low dilution, and high space velocities. These conditions promote a large temperature gradient in the monolith, with an exit temperature of nearly 1500°C and an entrance temperature of less than 200°C. This temperature gradient appears to be the driving force for C₂ hydrocarbon formation under these conditions. Both homogeneous and heterogeneous reactions may be involved in producing coupling products, and a combustion model predicts C₂ selectivities similar to those observed.