多室内环流反应器中液体循环量的试验验证与模拟

目的 对液相氧化脱硫多室内环流反应器液体循环量的影响因素进行模拟和验证。方法 采用CFD数值模拟,基于欧拉-欧拉多相流模型,对液相氧化脱硫多室内环流反应器进行气液两相流模拟,考查了酸气流量和空气流量对液体循环量的影响。结果 利用数值模拟得到的液体循环量与利用靶式流量计测得的液体循环量误差小于10%。当酸气中H₂S体积分数不超过3%时,液体循环量(z)与酸气流量(x)、空气流量(y)之间的关系式为：z=-474.996+0.358x+0.487 3y。结论 欧拉-欧拉两相流模型能够准确地预测液相氧化脱硫反应器内液体循环量。     

LaO_x(OH)_y supported platinum catalysts for CO oxidation:Deactivation by formation of lanthanum carbonate

Platinum catalyst for CO oxidation has been studied for decades,due to its high activity and good stability.In this work,we prepared three different lantha num oxide or hydroxide supports(LaO_x(OH)_y),and deposited platinum(Pt) with 0.5 at% via an impregnation approach to synthesize Pt/LaO_x(OH)_y catalysts.However,we find that these catalysts perform a poor stability for the CO oxidation reaction.The fresh and used samples were comprehensively characterized by multiple techniques including power X-ray diffraction(XRD),X-ray absorption fine structure(XAFS),transmission electron microscopy(TEM),temperature-programmed reduction by carbon monoxide(CO-TPR) and thermogravimetric analysis(TGA),to demonstrate that the oxidized platinum atoms or clusters,without any component of Pt-Pt metallic bond,are highly dispersed on the surface of LaO_x(OH)_y.Furthermore,the as-formed lanthanum carbonate(La₂O₂CO₃) during the exposure to ambient circumstances or in the reaction atmosphere of CO+O₂,severely impair the reactivity of Pt/LaO_x(OH)_y.On the basis of the obtained experimental results,we have drawn a conclusion that the oxidized P_tO_x atoms or PtxOy clusters are the active species for CO oxidation,while the formation of lanthanum carbonate is the origin of deactivation on reactivity.     

Thiogenistein—Antioxidant Chemistry,Antitumor Activity,and Structure Elucidation of New Oxidation Products

Isoflavonoids such as genistein (GE) are well known antioxidants. The predictive biological activity of structurally new compounds such as thiogenistein (TGE)–a new analogue of GE–becomes an interesting way to design new drug candidates with promising properties. Two oxidation strategies were used to characterize TGE oxidation products: the first in solution and the second on the 2D surface of the Au electrode as a self-assembling TGE monolayer. The structure elucidation of products generated by different oxidation strategies was performed. The electrospray ionization mass spectrometry (ESI-MS) was used for identifying the product of electrochemical and hydrogen peroxide oxidation in the solution. Fourier transform infrared spectroscopy (FT-IR) with the ATR mode was used to identify a product after hydrogen peroxide treatment of TGE on the 2D surface. The density functional theory was used to support the experimental results for the estimation of antioxidant activity of TGE as well as for the molecular modeling of oxidation products. The biological studies were performed simultaneously to assess the suitability of TGE for antioxidant and antitumor properties. It was found that TGE was characterized by a high cytotoxic activity toward human breast cancer cells. The research was also carried out on mice macrophages, disclosing that TGE neutralized the production of the LPS-induced reactive oxygen species (ROS) and exhibits ABTS (2,2′-azino-bis-3-(ethylbenzothiazoline-6-sulphonic acid) radical scavenging ability. In the presented study, we identified the main oxidation products of TGE generated under different environmental conditions. The electroactive centers of TGE were identified and its oxidation mechanisms were proposed. TGE redox properties can be related to its various pharmacological activities. Our new thiolated analogue of genistein neutralizes the LPS-induced ROS production better than GE. Additionally, TGE shows a high cytotoxic activity against human breast cancer cells. The viability of MCF-7 (estrogen-positive cells) drops two times after a 72-h incubation with 12.5 μM TGE (viability 53.86%) compared to genistein (viability 94.46%).     

Removal of an Azo Dye from Wastewater through the Use of Two Technologies: Magnetic Cyclodextrin Polymers and Pulsed Light

Water pollution by dyes is a huge environmental problem; there is a necessity to produce new decolorization methods that are effective, cost-attractive, and acceptable in industrial use. Magnetic cyclodextrin polymers offer the advantage of easy separation from the dye solution. In this work, the β-CD-EPI-magnetic (β-cyclodextrin-epichlorohydrin) polymer was synthesized, characterized, and tested for removal of the azo dye Direct Red 83:1 from water, and the fraction of non-adsorbed dye was degraded by an advanced oxidation process. The polymer was characterized in terms of the particle size distribution and surface morphology (FE-SEM), elemental analysis (EA), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), infrared spectrophotometry (IR), and X-ray powder diffraction (XRD). The reported results hint that 0.5 g and pH 5.0 were the best conditions to carry out both kinetic and isotherm models. A 30 min contact time was needed to reach equilibrium with a qmax of 32.0 mg/g. The results indicated that the pseudo-second-order and intraparticle diffusion models were involved in the assembly of Direct Red 83:1 onto the magnetic adsorbent. Regarding the isotherms discussed, the Freundlich model correctly reproduced the experimental data so that adsorption was confirmed to take place onto heterogeneous surfaces. The calculation of the thermodynamic parameters further demonstrates the spontaneous character of the adsorption phenomena (ΔG° = −27,556.9 J/mol) and endothermic phenomena (ΔH° = 8757.1 J/mol) at 25 °C. Furthermore, a good reusability of the polymer was evidenced after six cycles of regeneration, with a negligible decline in the adsorption extent (10%) regarding its initial capacity. Finally, the residual dye in solution after treatment with magnetic adsorbents was degraded by using an advanced oxidation process (AOP) with pulsed light and hydrogen peroxide (343 mg/L); >90% of the dye was degraded after receiving a fluence of 118 J/cm²; the discoloration followed a pseudo first-order kinetics where the degradation rate was 0.0196 cm²/J. The newly synthesized β-CD-EPI-magnetic polymer exhibited good adsorption properties and separability from water which, when complemented with a pulsed light-AOP, may offer a good alternative to remove dyes such as Direct Red 83:1 from water. It allows for the reuse of both the polymer and the dye in the dyeing process.     

Ta/Ta2O5/Cu结构制备及应用性能研究

介绍了以Ta/Ta₂O₅/Cu为结构的平板MIM电容器的制备方法和性能测试,探究金属Cu直接作为钽电解电容器阴极层的可行性。通过阳极氧化法在钽箔表面制备非晶态的Ta₂O₅薄膜,以化学镀铜、磁控溅射镀铜两种镀铜工艺制备Ta/Ta₂O₅/Cu结构,并对所得结构进行结构表征和性能测试。实验结果表明：不同镀铜方式制备的Ta/Ta₂O₅/Cu结构在电学性能测试过程中都没有表现出电容特性,正负极之间的电阻仅有0.7Ω;以金属Cu直接作为钽电容器的阴极层会导致金属铜在测试过程中被氧化成铜离子从而进入Ta₂O₅介质层中,进而导致Ta₂O₅的击穿,因此金属铜不适合直接作为钽电容的阴极层。     

Recent Advances in Porphyrin-Based Systems for Electrochemical Oxygen Evolution Reaction

Oxygen evolution reaction (OER) plays a pivotal role in the development of renewable energy methods, such as water-splitting devices and the use of Zn–air batteries. First-row transition metal complexes are promising catalyst candidates due to their excellent electrocatalytic performance, rich abundance, and cheap price. Metalloporphyrins are a class of representative high-efficiency complex catalysts owing to their structural and functional characteristics. However, OER based on porphyrin systems previously have been paid little attention in comparison to the well-described oxygen reduction reaction (ORR), hydrogen evolution reaction, and CO₂ reduction reaction. Recently, porphyrin-based systems, including both small molecules and porous polymers for electrochemical OER, are emerging. Accordingly, this review summarizes the recent advances of porphyrin-based systems for electrochemical OER. Firstly, the electrochemical OER for water oxidation is discussed, which shows various methodologies to achieve catalysis from homogeneous to heterogeneous processes. Subsequently, the porphyrin-based catalytic systems for bifunctional oxygen electrocatalysis including both OER and ORR are demonstrated. Finally, the future development of porphyrin-based catalytic systems for electrochemical OER is briefly prospected.     

Carbon Metabolism of a Soilborne Mn(II)-Oxidizing Escherichia coli Isolate Implicated as a Pronounced Modulator of Bacterial Mn Oxidation

Mn(II)-oxidizing microorganisms are generally considered the primary driving forces in the biological formation of Mn oxides. However, the mechanistic elucidation of the actuation and regulation of Mn oxidation in soilborne bacteria remains elusive. Here, we performed joint multiple gene-knockout analyses and comparative morphological and physiological determinations to characterize the influence of carbon metabolism on the Mn oxide deposit amount (MnODA) and the Mn oxide formation of a soilborne bacterium, Escherichia coli MB266. Different carbon source substances exhibited significantly varied effects on the MnODA of MB266. A total of 16 carbon metabolism-related genes with significant variant expression levels under Mn supplementation conditions were knocked out in the MB266 genome accordingly, but only little effect on the MnODA of each mutant strain was accounted for. However, a simultaneous four-gene-knockout mutant (namely, MB801) showed an overall remarkable MnODA reduction and an initially delayed Mn oxide formation compared with the wild-type MB266. The assays using scanning/transmission electron microscopy verified that MB801 exhibited not only a delayed Mn-oxide aggregate processing, but also relatively smaller microspherical agglomerations, and presented flocculent deposit Mn oxides compared with normal fibrous and crystalline Mn oxides formed by MB266. Moreover, the Mn oxide aggregate formation was highly related to the intracellular ROS level. Thus, this study demonstrates that carbon metabolism acts as a pronounced modulator of MnODA in MB266, which will provide new insights into the occurrence of Mn oxidation and Mn oxide formation by soilborne bacteria in habitats where Mn(II) naturally occurs.     

乙烯裂解炉炉管失效原因分析

利用金相显微镜、X射线衍射仪、光谱分析仪等测试仪器,通过对炉管的材质、外观形貌、金相组织、组分组成等方面进行检测,分析了乙烯裂解炉炉管失效的原因.结果表明,材质为Incoloy 800 H合金的裂解炉管可满足乙烯裂解工况的工艺要求,炉管失效主要是由于高温过热引起的氧化腐蚀破坏所致,另外管内介质对腐蚀也有促进作用.