Double pyrovanadates CaMgV2O7: Formation mechanism,phase structure,and thermodynamic properties

A double pyrovanadate CaMgV₂O₇ sample was synthesized via a facile solid-state route under an air atmosphere. The nonequilibrium formation pathways of the CaMgV₂O₇ were investigated via powder X-ray diffraction. A multistep reactions path (metavanadates–pyrovanadates–double pyrovanadate CaMgV₂O₇) was proposed to describe the formation of the CaMgV₂O₇ considering the thermodynamic and kinetic factors. The cell unit parameters of the CaMgV₂O₇ sample indicated the crystallization according to a monoclinic system with space group P12/c1(14), and the lattice parameters of a = 6.756 Å, b = 14.495 Å, c = 11.253 Å, β = 99.12, and V = 108.806 Å³. X-ray photoelectron spectroscopy also confirmed the +5 oxidation state vanadium in CaMgV₂O₇. The endothermic effects at 1033 and 1143 K were related to the incongruent melting and liquidus temperatures of CaMgV₂O₇, respectively. The comprehensive thermodynamic properties of CaMgV₂O₇ were established in both low- and high-temperature regions, utilizing a physical property measurement system and multi-high-temperature calorimetry (96 lines). The heat capacity (200 J mol K⁻¹) and entropy (198 J mol K⁻¹) at 298.15 K were computed based on the low-temperature heat capacity values, and the enthalpy of formation at 298.15 K was also estimated. The fitted high-temperature capacity can be used to obtain the changes in the enthalpy, entropy, and Gibbs free energy. This study is part of building a reliable thermodynamic database of the CaO–MgO–V₂O₅ system.     

Isostructural phase transition (IPT) in CaMoO4 with Scheelite structure

The ceramic compound CaMoO₄ is synthesized via a solid-state reaction technique. Rietveld refinement studies were done on the powder X-ray diffraction data of CaMoO₄ and revealed that the compound is crystallized in the tetragonal Scheelite structure with I4₁/a space group. The differential scanning calorimetry (DSC) studies on CaMoO₄ divulged an anomaly around 440 °C. This anomaly is further probed using the temperature-dependent Raman and dielectric spectroscopic measurements and are corroborating with the results obtained from DSC. A detailed investigation on the temperature-dependent Raman spectroscopic data revealed that the A_1g mode of CaMoO₄ showed a soft phonon behavior up to the phase transition temperature. It is observed that the A_1g mode displayed phonon hardening behavior with further increasing the temperature. The anomaly is attributed to an isostructural phase transition (IPT), a rarely observed phenomenon in the compounds with Scheelite structure. The IPT in CaMoO₄ is elucidated with a phonon softening mechanism.     

基于卷积神经网络的5G蜂窝网络无线定位方法

5G蜂窝网络发展迅猛，其覆盖面积将逐渐增大，因此使用5G蜂窝网络进行定位是有研究潜力的研究方向。本文提出一种新的深度学习技术来实现高效、高精度和低占用的定位，以代替传统指纹定位过程中繁重的指纹库生成以及距离计算。该方法建立了一个特殊的卷积神经网络，并根据5G天线信号的接收信号强度指示、相位和到达角等特征量，选择合适的输入数据格式构造样本组建训练集，对该卷积神经网络进行训练。训练得到的卷积神经网络可以替代指纹定位中的庞大指纹库，非常有利于直接在5G移动设备端实现定位。虽然卷积神经网络在训练过程中需要大量时间，但在训练完毕后直接进行分类定位的速度非常快，可以保障定位实现的实时性。本文所实现的卷积神经网络权重与偏置所占内存不到0.5 MB，且能够在实际应用环境中以95%的定位准确率以及0.1 m的平均定位精度实现高精度定位。     

Metal chlorides-promoted ammonia absorption of deep eutectic solvent

Ammonia is considered as a promising hydrogen or energy carrier. Ammonia absorption or adsorption is an important aspect for both ammonia removal, storage and separation applications. To these ends, a wide range of solid and liquid sorbents have been investigated. Among these, the deep eutectic solvent (DES) is emerging as a promising class of ammonia absorbers. Herein, we report a novel type of DES, i.e., metal-containing DESs for ammonia absorption. Specifically, the NH₃ absorption capacity is enhanced by ca. 18.1–36.9% when a small amount of metal chlorides, such as MgCl₂, MnCl₂ etc., are added into a DES composed of resorcinol (Res) and ethylene glycol (EG). To our knowledge, the MgCl₂/Res/EG (0.1:1:2) DES outperforms most of the reported DESs. The excellent NH₃ absorption performances of metal–containing DESs have been attributed to the synergy of Lewis acid–base and hydrogen bonding interactions. Additionally, good reversibility and high NH₃/CO₂ selectivity are achieved over the MgCl₂/Res/EG (0.1:1:2) DES, which enables it to be a potential NH₃ absorber for further investigations.     

Thermal properties of hierarchical YSZ and LZO ceramic microspheres with multi-scaled voids investigated by using theoretical,experimental and simulation methods

Heat transfer within ceramic feedstock powders is still unclear, which impedes optimization of the thermal and mechanical properties of the thermal sprayed coatings. The microspheres (yttria-stabilized zirconia YSZ and lanthanum zirconate LZO) were prepared via the electro-spraying assisted phase inversion method (ESP). The thermal properties of the two ESP microspheres and a commercial hollow spherical powder (HOSP) were investigated by using theoretical, experimental, and simulation methods. Thermal conductivity of the single microsphere was estimated via a novel nest model that was derived from the Maxwell-Eucken 1 and the EMT model. Thermal conductivity of a single YSZ/LZO-ESP microsphere prepared at 1100–1200 °C was within 0.36–0.75 W/m K, which was ～ 20 % lower than that of a single YSZ-HOSP microsphere with a similar porosity. Heat flux simulation showed that high tortuosity around the multi-scaled voids of the ESP microsphere led to a more efficient decrease in thermal conductivity compared with total porosity.     

Adenine-functionalized conjugated polymer as an efficient photocatalyst for hydrogen evolution from water

Conjugated polymers have emerged as a promising class of organic photocatalysts for photocatalytic hydrogen evolution from water splitting due to their adjustable chemical structures and electronic properties. However, developing highly efficient organic polymer photocatalysts with high photocatalytic activity for hydrogen evolution remains a significant challenge. Herein, we present an efficient approach to enhance the photocatalytic performance of linear conjugated polymers by modifying the surface chemistry via introducing a hydrophilic adenine group into the side chain. The adenine unit with five nitrogen atoms could enhance the interaction between the surface of polymer photocatalyst and water molecules through the formation of hydrogen bonding, which improves the hydrophilicity and dispersity of the resulting polymer photocatalyst in the photocatalytic reaction solution. In addition, the strong electron-donating ability of adenine group with plentiful nitrogen atoms could promote the separation of light-induced electrons and holes. As a result, the adenine-functionalized conjugated polymer PF6A-DBTO2 shows a high photocatalytic activity with a hydrogen evolution rate (HER) of 25.21 mmol g^?1 h^?1 under UV-Vis light irradiation, which is much higher than that of its counterpart polymer PF6-DBTO2 without the adenine group (6.53 mmol g^?1 h^?1). More importantly, PF6A-DBTO2 without addition of a Pt co-catalyst also exhibits an impressive HER of 21.93 mmol g^?1 h^?1 under visible light (λ > 420 nm). This work highlights that it is an efficient strategy to improve the photocatalytic activity of conjugated polymer photocatalysts by the modification of surface chemistry.     

Numerical study of strain development in high-density polyethylene geomembrane liner system in landfills using a new constitutive model for municipal solid waste

Tensile strain development in high-density polyethylene (HDPE) geomembrane (GMB) liner systems in landfills was numerically investigated. A new constitutive model for municipal solid waste (MSW) that incorporates both mechanical creep and biodegradation was employed in the analyses. The MSW constitutive model is a Cam-Clay type of plasticity model and was implemented in the finite difference computer program FLAC?. The influence of the friction angle of the liner system interfaces, the biodegradation of MSW, and the MSW filling rate on tensile strains were investigated. Several design alternatives to reduce the maximum tensile strain under both short- and long-term waste settlement were evaluated. Results of the analyses indicate that landfill geometry, interface friction angles, and short- and long-term waste settlement are key factors in the development of tensile strains. The results show that long-term waste settlement can induce additional tensile strains after waste placement is complete. Using a HDPE GMB with a friction angle on its upper interface that is lower than the friction angle on the underlying interface, increasing the number of benches, and reducing the slope inclination are shown to mitigate the maximum tensile strain caused by waste placement and waste settlement.     

Revealing active species of CePO4 catalyst for selective catalytic reduction of NOx with NH3

Revealing the active species of the catalyst is conducive to the design of more efficient catalyst. Herein, we tried to demonstrate the roles of amorphous and crystalline structures on CePO₄ catalyst during selective catalytic reduction (SCR) of NO_x by NH₃. Higher calcination temperature promotes the transfer of amorphous structure to crystalline structure on the surface of CePO₄. Both amorphous and crystalline CePO₄ species on CePO-X samples can provide acid sites for NH₃ adsorption, but the former can provide more acid sites. The superior redox property of surface amorphous CePO₄ species contributes to its high NH₃-SCR activity at low temperature, but it also leads to the decrease of high temperature (>350 °C) NH₃-SCR activity due to the oxidation of NH₃. In contrast, crystalline CePO₄ species shows high activity only at high temperature because of its poor redox property. Therefore, it can be inferred that amorphous and crystalline structures on CePO₄ catalyst can be the efficient active species of NH₃-SCR at low and high temperature, respectively.     

In-situ measurement of mineral phase transition and kinetics in roasting process of Bayan Obo mixed rare earth concentrate by sodium carbonate

In this study, the Bayan Obo rare earth concentrates mixed with Na₂CO₃ were used for roasting research. The phase change process of each firing stage was analyzed. The kinetic mechanism model of the continuous heating process was calculated. This study aims to recover valuable elements and optimize the production process to provide a certain theoretical basis. Using X-ray diffraction (XRD), Fourier infrared spectroscopy, scanning electron microscopy with energy dispersive spectrometry, the reaction process and the existence of mineral phases were analyzed. The variable temperature XRD and thermogravimetric method were used to calculate the roasting kinetics. The phase transition results show that carbonate-like substances first decompose into fine mineral particles, and CaO, MgO, and SiO₂ react to form silicates, causing hardening. Further, REPO₄ and NaF can directly generate CeF₃ and CeF₄ at high temperatures, and a part of CeF₄ and NaF forms a solid solution substance Na₃CeF₇. Rare earth oxides calcined at a high temperature of 750 °C were separated to produce Ce_0.6Nd_0.4O_1.8, Ce₄O₇, and LaPrO_3+x. Then, BaSO₄, Na₂CO₃, and Fe₂O₃ react to form barium ferrite BaFe₁₂O₁₉; the kinetic calculation results show that during the continuous heating process, the apparent activation energy E reaches the minimum in the entire reaction stage in the temperature range of 440–524 °C, and the reaction order n reaches the maximum, which indicates that the decomposition product REFO significantly impacts the reaction system and reduces the activation energy. The mechanism function is F(α) = [?ln (1?α)]^1/3. The reaction order n reaches the minimum in the temperature range of 680–757 °C, and the apparent activation energy E is large. The difficulty of the reaction increases during the final stage. The reaction mechanism function is F(α) = [1?(1?α)^1/3]². Observing the entire reaction stage, the step of controlling the reaction rate changes from random nucleation to three-dimensional diffusion (spherical symmetry).