Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.     

Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

Decorating surface charge of graphite nanoplate using an electrostatic coupling agent for 3-dimensional polymer nanocomposite

Here, we report a facile approach to electrostatically couple the surface charges of graphite nanoplate (GNP) fillers and poly(methyl methacrylate) (PMMA) polymer particles using ethylene maleic anhydride (EMA) copolymer as an electrostatic coupling agent. Our strategy involved switching the intrinsic repulsive electrostatic interactions between the directly exfoliated GNPs fillers and the PMMA particles to attractive electrostatic surface interactions for preparing core(PMMA)-shell (GNP) precursor in order to optimizing 3-dimensionally dispersed polymer nanocomposite. As a result, the electrical conductivity of the composites dramatically increased by a factor of 16.7 in the EMA-coupled GNP/PMMA composites compared with that of the EMA-free GNP/PMMA composites. In addition, the percolation threshold was also notably reduced from 0.32 to 0.159 vol% after electrostatic coupling of the GNPs fillers and PMMA particles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48390.     

Microwave dielectric properties of ultra-low loss Li2MgTi0.7(Mg1/3Nb2/3)0.3O4 ceramics sintered at low temperature by LiF addition

In this work, ultra-low loss Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄ ceramics were successfully prepared via the conventional solid-state method. X-ray photoelectron spectroscopy (XPS), thermally stimulated depolarization current (TSDC) and bond energy were used to determine the distinction between intrinsic and extrinsic dielectric loss in (Mg_1/3Nb_2/3)⁴⁺ ions substituted ceramics. The addition of (Mg_1/3Nb_2/3)⁴⁺ ions enhances the bond energy in unit cell without changing the crystal structure of Li₂MgTiO₄, which results in high Q·f value as an intrinsic factor. The extrinsic factors such as porosity and grain size influence the dielectric loss at lower sintering temperature, while the oxygen vacancies play dominant role when the ceramics densified at 1400?°C. The Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄ ceramics sintered at 1400?°C can achieve an excellent combination of microwave dielectric properties: ε_r =?16.19, Q·f?=?160,000?GHz and τ_f =??3.14?ppm/°C. In addition, a certain amount of LiF can effectively lower the sintering temperature of the matrix, and the Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄-3?wt% LiF ceramics sintered at 1100?°C possess balanced properties with ε_r?=?16.32, Q·f?=?145,384?GHz and τ_f =??16.33?ppm/°C.     

丙烷脱沥青装置调合前沥青的综合利用

在丙烷脱沥青装置加热炉试烧装置自产调合前沥青,通过观察油枪雾化沥青的能力、火嘴的燃烧情况以及燃烧后的烟尘状况,筛选出适合沥青燃烧的油枪,最终实现调合前沥青直接做加热炉燃料、减少重油出厂量的目的。     

含煤盆地深层“超饱和”煤层气形成条件

中国深层煤层气资源丰富，但总体勘探和认识程度较低，尚未形成较为系统的深层煤层气地质理论。通过解剖分析准噶尔盆地白家海凸起和鄂尔多斯盆地临兴区块深层"超饱和"煤层气井的试气/生产动态，估算原地游离气的含气量，分析了深层"超饱和"煤层气的形成条件。研究表明：①深层"超饱和"煤层气储层中除吸附气外，还含有原地游离气，用常规试气方法可直接获得气流，煤层气的产出不明显依赖于排水降压；②埋藏超过一定深度，在煤阶和温度的综合作用下，煤的吸附能力将随埋深的继续增加而降低，煤层中吸附气的饱和度有增加的趋势，在达到吸附饱和后，出现原地游离气并形成"超饱和"煤层气，盆地深层具有"超饱和"煤层气形成的优势条件；③由于地温梯度和压力梯度的不同，不同盆地"超饱和"煤层气出现的临界深度不同，异常高压和异常高热流可以降低深层"超饱和"煤层气形成的临界深度；④深层"超饱和"煤层气开发具有大大缩短见气时间、充分利用地层能量和累积产水量低等优势，有望成为未来煤层气勘探开发的一个重要领域。     

Sparse non-convex Lp regularization for cone-beam X-ray luminescence computed tomography

Cone-beam X-ray luminescence computed tomography (CB-XLCT) is an attractive hybrid imaging modality, and it has the potential of monitoring the metabolic processes of nanophosphors-based drugs in vivo. However, the XLCT imaging suffers from a severe ill-posed problem. In this work, a sparse nonconvex L_p (0?p?L₁ regularization. Further, an iteratively reweighted split augmented lagrangian shrinkage algorithm (IRW_SALSA-L_p) was proposed to efficiently solve the non-convex L_p (0?p?p-values (1/16, 1/8, 1/4, 3/8, 1/2, 5/8, 3/4, 7/8) in both 3D digital mouse experiments and in vivo experiments. The results demonstrate that the proposed non-convex methods outperform L₂ and L₁ regularization in accurately recovering sparse targets in CB-XLCT. And among all the non-convex p-values, our L_p(1/4?p?相似文献   

甲基氯硅烷精馏流程的模拟与优化

采用Aspen plus软件对工业七塔精馏过程进行全流程建模与模拟，优化工艺参数，研究了新的精馏节能工艺。对一甲塔等7个精馏塔采用双因素水平的灵敏度分析，考察了塔釜采出率、回流比、进料位置和塔顶压力对产品浓度和热负荷的影响，确定一甲塔最优的工艺参数：塔釜摩尔采出率为0.92，摩尔回流比为130，塔顶压力为0.18 MPa，总理论板数为400，在210块理论板位置进料。在此基础上，针对高能耗的脱高塔/脱低塔，模拟研究了双效精馏新工艺，新工艺可节省39.70%的年总成本；针对一甲塔模拟研究了热泵精馏新工艺，新工艺可降低41.42%的年总成本。