Synthesis,thermal properties,conductivity and lifetime of proton conductors based on nanocrystalline cellulose surface-functionalized with triazole and imidazole

A new proton conductor based on 1H-1,2,3-triazole doped nanocrystalline cellulose (2.66 CNC-Tri) has been synthesized for possible use as an electrolyte in proton exchange membrane (PEM) cells. The physicochemical properties of 2.66 CNC-Tri were determined and compared with those of imidazole-doped nanocrystalline (1.17 CNC-Im) and pure nanocrystalline cellulose (CNC). The composites were obtained in the form of a film and their synthesis proceeded under vacuum. The maximum conductivity of 2.66 CNC-Tri was measured to be 0.1 × 10⁻⁴ S/m at 175 °C and that of 1.17 CNC-Im to be 1.6 × 10⁻² S/m at 155 °C, in the anhydrous state. The composite 2.66 CNC-Tri, compared to 1.17 CNC-Im, has much better thermal properties manifested as stability of the matrix and durability of the heterocyclic molecule. The lifetimes of 2.66 CNC-Tri fulfills the requirements of the U.S. Department of Energy for the minimum lifetimes of a PEM based fuel cell for cars.     

Precise Molecular Sieving Architectures with Janus Pathways for Both Polar and Nonpolar Molecules

Precise molecular sieving architectures with Janus superhighways are constructed via a molecularly engineered interfacial reaction between cyclodextrin (CD) and trimesoyl chloride (TMC). Interestingly, the CD/TMC nanofilms constructed with both hydrophobic inner cavities and hydrophilic channels exhibit exceptionally high permeances for both polar and nonpolar solvents. The precise molecular sieving functions are determined by the type of CD building blocks and the inner cavities of intrinsic 3D hollow bowls. Positron annihilation spectroscopy (PAS) confirms that a larger inner CD cavity tends to generate a larger free volume and higher microporosity. Based on the rejection ratio of various dyes, the estimated molecular weight cutoff of CD/TMC nanofilms follows the trend of α‐CD/TMC (320 Da) <β‐CD/TMC (400 Da) <γ‐CD/TMC (550 Da), which is in strict accordance with the orders of their free volumes measured by PAS and inner cavity sizes of α‐CD <β‐CD <γ‐CD. This kind of novel CD/TMC molecular sieving membrane with intrinsic microporosity containing tunable pore size and sharp pore‐size distribution can effectively discriminate molecules with different 3D sizes.     

羟基(—OH)对煤自燃侧链活性基团氧化反应特性的影响

针对煤结构及其氧化反应机理不明等问题,以羟基(—OH)和煤自燃侧链活性基团—OCH,—CHOHCH 3和—OCH 3为研究对象,采用密度泛函理论(DFT)的B3LYP-311G(d,p)方法,构建出了羟基(—OH)处于侧链活性结构邻位的小分子结构模型。基于前线轨道理论和量子化学理论,采用Gaussian 16软件对小分子模型的静电势、前线轨道的能级和电荷分布及煤氧复合反应过程中的热力学参数进行了模拟计算,探究了侧链活性基团的低温氧化特性和羟基(—OH)对其的影响。计算结果显示,在侧链活性结构中,氢原子周边呈强正电势,为亲核反应活性位点,而氧原子附近呈强负电势,为亲电反应活性位点。当羟基(—OH)处于侧链活性基团邻位时,会削弱侧链活性基团的亲电反应能力,增加—CHO和—CHOHCH 3的亲核反应能力,而使—OCH 3的亲核反应能力消失;通过分析各活性基团最高占据轨道(HOMO:Highest Occupied Molecular Orbital)和最低未占轨道(LUMO:Lowest Unoccupied Molecular Orbital)可知,侧链活性基团的稳定性与其前线轨道的成键能力并不一致,而活性基团与氧气发生复合反应的难易程度主要取决于该基团前线轨道中LUMO的成键能力,成键能力越强,复合反应越容易发生;由于羟基(—OH)改变了侧链活性基团前线轨道上的电子特性,故当其与侧链基团共存时,会使—CHO和—CHOHCH 3与氧气的复合反应更容易发生,而使—OCH 3与氧气的复合由自发的放热反应转变为非自发的吸热反应。该研究成果可为揭示煤自燃微观作用机理和研发煤自燃新型高效阻化材料提供参考。     

Predictive association of metal–organic systems in the solid-state: the molecular electrostatic potential based approach

Designing crystalline solids with improved properties or performances remains a challenging task, despite great strides that have been made within the field of crystal engineering since its birth several decades ago. Herein, we are bringing examples that illustrate recent successes in taking supramolecular synthetic guidelines from the organic crystal engineering and adjusting those to metal-containing systems, particularly to the lower-dimensional ones. The versatility of calculated molecular electrostatic potential (MEP) as a new crystal engineering tool is demonstrated.     

膨胀机主轴缝隙腐蚀的电化学分析

为探究膨胀机主轴的缝隙腐蚀行为,搭建了模拟缝隙腐蚀实验装置。通过电化学测试,确定了不同缝隙位置处的自腐蚀电位随时间的变化规律,并揭示了缝隙内腐蚀反应的发展过程。结果表明:缝隙内腐蚀反应经历双电层形成-氧浓差电池形成-金属水解三个反应过程。在富氧条件下,腐蚀产物的主要成分为Fe(OH)2。随着氧气的耗尽,氧浓差电池形成,腐蚀产物逐渐向FeOOH和Fe3O4转变。     

前和煤业东胶带运输大巷钻孔卸压围岩控制技术

为有效解决前和煤业3#煤层东胶带大巷在原有锚网索支护下围岩变形量大的问题,结合巷道变形特征,确定采用钻孔卸压技术,采用理论分析和数值模拟的方式确定卸压钻孔在修巷作业前,垂直于巷帮打设,钻孔深度为8 m,结合巷道的具体条件确定巷道采用卸压钻孔+让压支护的围岩控制方案,并采用矿压监测验证支护效果。结果表明:支护方案实施后,顶底板和两帮的最大移近量分别为141 mm和132 mm,有效解决了巷道两帮及底板鼓起量大的问题,保证了巷道围岩的稳定性。     

大采高综放工作面强动压端头顶板控制技术

为了解决大采高综放工作面回风侧端头顶板控制问题,针对马道头矿8211工作面的地质情况,通过对回风顺槽超前注浆加固,提高超前支护范围和支护强度,并对回风侧端头三角区煤壁和顶板进行化学浆加固的技术方案,有效控制了顺槽超前区围岩变形和工作面回风侧端头三角区煤壁片帮,保证了工作面端头区顶板安全。     

PAM-粉煤灰体系在煤泥水絮凝沉降过程中的作用及机理

以煤泥水COD、SS、动电位、污泥比阻为切入点,分析了煤泥水的特点及难以絮凝沉降的原因,并研究了PAM-粉煤灰体系在混凝沉降作用中的机理。研究结果表明:PAM-粉煤灰法在最优条件下,清水分离率47%、沉降速度0.357 mm/s;上清液:pH=7.35,SS=55.57 mg/L,COD=37.72 mg/L;污泥比阻为0.062×10^15 m/kg,满足煤泥水循环标准。     

Critical state model for structured soil

Structure is an evident determinant for macroscopic behaviors of soils. However, this is not taken into account in most constitutive models, as structure is a rather complex issue in models. For this, it is important to develop and implement simple models that can reflect this important aspect of soil behavior. This paper tried to model structured soils based on well-established concepts, such as critical state and sub-loading. Critical state is the core of the classic Cam Clay model. The sub-loading concept implies adoption of an inner (sub-loading) yield surface, according to specific hardening rules for some internal strain-like state variables. Nakai and co-workers proposed such internal variables for controlling density (ρ) and structure (ω), using a modified stress space, called t_ij. Herein, similar variables are used in the context of the better-known invariants (p and q) of the Cam Clay model. This change requires explicit adoption of a non-associated flow rule for the sub-loading surface. This is accomplished by modifying the dilatancy ratio of the Cam Clay model, as a function of the new internal variables. These modifications are described and implemented under three-dimensional (3D) conditions. The model is then applied to simulating laboratory tests under different stress paths and the results are compared to experiments reported for different types of structured soils. The good agreements show the capacity and potential of the proposed model.