锡量子点制备及其电催化还原二氧化碳产甲酸性能

锡基材料在自然界含量丰富、价格低廉, 在电催化还原CO₂制液体燃料反应中具有巨大潜力。但是较低的产物选择性和较差的稳定性限制了其应用。本工作制备的锡量子点电催化剂(Sn-QDs), 具有高效、高稳定性和高选择性的电催化还原CO₂产HCOOH活性。Sn-QDs的平均颗粒尺寸仅为2~3 nm, 结晶性良好。小的颗粒尺寸增大了电化学活性面积(ECSA), Sn-QDs的ECSA约为锡颗粒的4.4倍。ECSA增大以及CO₂还原反应动力学加速, 促进了CO₂电化学转化。在-1.0 V (vs RHE)下, Sn-QDs/CN催化剂的HCOOH法拉第效率(FE_HCOOH)达到95%, 并且在宽约0.5 V的电势范围内能够保持在83%以上。此外, Sn-QDs/CN可以在24 h内保持良好的电化学稳定性。     

柱淋滤模式下生活垃圾焚烧炉渣中Cu2+和Zn2+浸出规律

垃圾焚烧炉渣是一种活性材料，在其储存、预处理及应用等过程与雨水频繁接触时，炉渣中重金属随着水域环境发生迁移和浸出现象。本研究采用连续柱淋滤试验装置模拟自然降雨，开展了0～5mm和5～10mm焚烧炉渣的动态淋滤毒性浸出分析，重点研究了pH和降雨强度对Cu²⁺和Zn²⁺的浸出影响。结果表明，动态淋滤过程中，淋滤液pH变化对Cu²⁺和Zn²⁺的浸出水平影响显著，且在酸性较强淋滤液作用下Cu²⁺浸出水平比Zn²⁺更强，与Ⅴ类地表水环境浓度限值对比，在整个淋滤时间内Cu²⁺浸出浓度严重超标，在炉渣工程应用时需预防相关的环境风险；原生炉渣粒径大小与重金属浸出水平无直接相关性，但是0～5mm细炉渣中可浸出Zn²⁺含量更高，这与细颗粒物中Zn赋存形态和可溶出态含量较高有关；淋滤强度对重金属浸出水平影响主要反应了动态淋滤过程液固比和水分运移速率情况，当较低淋滤强度时具有低液固比，溶出液中重金属含量较高。     

PdCoNi nanoparticles supported on nitrogen-doped porous carbon nanosheets for room temperature dehydrogenation of formic acid

The development of cost-effective heterogeneous catalysts for the dehydrogenation of formic acid (FA) is the key challenge for the commercialization of FA as a hydrogen-storage medium. Herein, PdCoNi nanoparticles (NPs) with different element ratios supported on N-doped carbon nanosheets (N-CN) were designed, which exhibit excellent catalytic dehydrogenation performance for FA. Compared with PdCoNi NPs loaded on the carbon nanosheets (CN), the introduction of pyrrolic N to CN induces the formation of ultrafine, monodispersed and amorphous Pd_0.6Co_0.2Ni_0.2 NPs with a size of 1.60 nm, which significantly increases the number of active sites and the instant contact between FA and catalysts. The as-prepared Pd_0.6Co_0.2Ni_0.2/N-CN catalyst shows more than 99% conversion and 100% H₂ selectivity at room temperature, with a record-high initial turnover frequency (TOF_initial) of 1249.0 h⁻¹ among non-noble containing Pd-based catalysts, which demonstrates the high potential of Pd_0.6Co_0.2Ni_0.2/N-CN as a practical catalyst for the hydrogen generation from FA.     

Two-dimensional polymer nanosheets for efficient energy storage and conversion

As a promising graphene analogue, two-dimensional (2D) polymer nanosheets with unique 2D features, diversified topological structures and as well as tunable electronic properties, have received extensive attention in recent years. Here in this review, we summarized the recent research progress in the preparation methods of 2D polymer nanosheets, mainly including interfacial polymerization and solution polymerization. We also discussed the recent research advancements of 2D polymer nanosheets in the fields of energy storage and conversion applications, such as batteries, supercapacitors, electrocatalysis and photocatalysis. Finally, on the basis of their current development, we put forward the existing challenges and some personal perspectives.

     

Tailoring the chemical heterogeneity of Mn-modified 0.75BiFeO3-0.25BaTiO3 ceramics for piezoelectric sensor applications

The Mn-modified 0.75BiFeO₃-0.25BaTiO₃ (75BFBTMn) piezoelectric ceramic possesses a high depolarization temperature of 500 °C and a large piezoelectric coefficient of 110 pC/N, showing the potential for high temperature piezoelectric sensors. However, 75BFBTMn ceramic usually suffers dielectric degradation and abrupt drop of piezoelectric coefficient in the range of 300 °C to 500 °C. Combined the high-energy synchrotron X-ray diffraction analysis with Backscatter-SEM results, it is demonstrated that the electrical thermal instability is owing to the existence of chemical inhomogeneity. The Air-annealing treatment is able to decrease the volume fraction of pseudo-cubic phase and the lattice distortion, removes the chemical inhomogeneity in the grain and free Bi₂O₃ at grain boundary, and then eliminates dielectric anomalies and piezoelectric degradation with temperature. These results indicate that air-annealing is a simple but effective method to eliminate the chemical inhomogeneity in 75BFBTMn ceramics, thereby improving the property thermal stability for high temperature piezoelectric sensor applications.     

Stabilization and superconductivity of AlB2-type nonstoichiometric molybdenum diboride by Sc doping

Molybdenum diboride is unique among transition metal diborides because it exists in both hexagonal (AlB₂-type) and rhombohedral structures. However, it is difficult to stabilize the superconducting AlB₂-type phase, which requires either extreme synthesis condition or suitable chemical doping. Here we report the structural and physical properties of Sc-doped nonstoichiometric molybdenum diborides (Mo_0.95Sc_0.05)_1-xB₂ and (Mo_1-ySc_y)_0.71B₂ prepared by the common arc melting method. The AlB₂-type phase is found to form over wide ranges of 0 ≤ x ≤ 0.29 and 0.025 ≤ y ≤ 0.30 for the first time, and bulk superconductivity with T_c up to 7.9 K is observed. T_c increases with increasing x in the (Mo_0.95Sc_0.05)_1-xB₂ series, but evolves nonmonotonically with varying y in the (Mo_1-ySc_y)_0.71B₂ series. Despite this contrast, T_c of both borides follows nearly the same linear dependence on the electron-phonon coupling constant, suggesting that it is mainly controlled by the electron-phonon interaction. In addition, the stabilization of AlB₂-type structure is attributed to the decrease in the number of d electrons as a consequence of Sc doping, which suggests that a similar effect may be achieved by substituting Mo with other d electron-poorer metal elements.     

A lattice Boltzmann exploration of two-phase displacement in 2D porous media under various pressure boundary conditions

While experimental designs developed in recent decades have contributed to research on dynamic nonequilibrium effects in transient two-phase flow in porous media, this problem has been seldom investigated using direct numerical simulation (DNS). Only a few studies have sought to numerically solve Navier–Stokes equations with level-set (LS) or volume-of-fluid (VoF) methods, each of which has constraints in terms of meniscus dynamics for various flow velocities in the control volume (CV) domain. The Shan–Chen multiphase multicomponent lattice Boltzmann method (SC-LBM) has a fundamental mechanism to separate immiscible fluid phases in the density domain without these limitations. Therefore, this study applied it to explore two-phase displacement in a single representative elementary volume (REV) of two-dimensional (2D) porous media. As a continuation of a previous investigation into one-step inflow/outflow in 2D porous media, this work seeks to identify dynamic nonequilibrium effects on capillary pressure–saturation relationship (P_c–S) for quasi-steady-state flow and multistep inflow/outflow under various pressure boundary conditions. The simulation outcomes show that P_c, S and specific interfacial area (a_nw) had multistep-wise dynamic effects corresponding to the multistep-wise pressure boundary conditions. With finer adjustments to the increase in pressure over more steps, dynamic nonequilibrium effects were significantly alleviated and even finally disappeared to achieve quasi-steady-state inflow/outflow conditions. Furthermore, triangular wave-formed pressure boundary conditions were applied in different periods to investigate dynamic nonequilibrium effects for hysteretical P_c–S. The results showed overshoot and undershoot of P_c to S in loops of the nonequilibrium hysteresis. In addition, the flow regimes of multistep-wise dynamic effects were analyzed in terms of Reynolds and capillary numbers (Re and Ca). The analysis of REV-scale flow regimes showed higher Re (1 < Re < 10) for more significant dynamic nonequilibrium effects. This indicates that inertia is critical for transient two-phase flow in porous media under dynamic nonequilibrium conditions.     

深度融合特征提取网络及其在化工过程软测量中的应用

复杂化工过程的观测数据往往同时包含非线性和强动态特性,而传统的化工过程软测量方法无法准确提取观测数据的非线性动态特征,以至影响数据建模和质量预报的准确性。提出了一种基于变分自编码器的深度融合特征提取网络(deep fusion features extraction network, DFFEN)。在变分自编码器框架下,通过构建潜隐特征信息传递通道,提取非线性动态潜隐变量。并利用自注意力机制(self-attention)融合关键的隐层信息,优化因信息传递通道过长而导致的潜在特征被遗忘的问题。此外,在后端网络构建潜隐变量和关键质量变量之间的回归模型,以实现关键质量变量的预报。最后,通过数值案例和实际的合成氨过程验证了所提出的DFFEN模型的可行性和有效性。