Correlation and extrapolation scheme for the composition and temperature dependence of viscosity of binary gaseous mixtures: Carbon dioxide + ethane

Experimental viscosity data of ethane, carbon dioxide, and three mole fractions of the binary system carbon dioxide + ethane in the temperature range 293.15<T633.15 K and in the density range 0.010.05 mol·L^–1 reported earlier were evaluated simultaneously to find out a useful correlation and extrapolation scheme for the viscosity of binary systems in the range of moderate densities. A procedure based on the ideas of the modified Enskog theory has been found to give the best results. Dependent on temperature, the collision diameters related to the equilibrium radial distribution function at contact are fitted to viscosity values of the pure substances and of at least one mixture. The results are compared with experimental data from the literature. A recommendation is given concerning the density range in which the first density contribution to the viscosity coefficient of the system carbon dioxide + ethane is sufficient to be included.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

考虑天然气混氢的园区综合能源系统电制氢优化配置

电制氢和天然气混氢技术在促进可再生能源消纳、降低系统碳排放量方面具有良好的理论研究和工程应用前景。面向含高比例可再生能源的园区综合能源系统,提出一种计及天然气混氢及跨季节存储的电制氢优化配置方法。首先梳理了含氢园区综合能源系统的运行框架和能量流动关系,建立园区内部能源生产、转换与存储设备的数学模型,其次以设备的年化投资成本、园区综合能源系统的年度运行成本和碳交易成本最优为目标,提出电制氢优化配置模型。最后通过算例分析表明电制氢及天然气混氢技术的引入可提升可再生能源的消纳能力,降低系统的整体经济成本和碳排放量,并分析了电解槽投资成本、混氢体积分数上限以及经济性和低碳性成本权重系数变化对规划运行结果的影响。关键词：园区综合能源系统;电制氢;天然气混氢;碳交易;跨季节储氢;优化配置 中图分类号：TM732     

基于微纳电离的有毒有害气体传感器

为了有效避免有害气体浓度的超标对经济效益和人类生命财产安全造成损害,提出并设计了一种新型检测方法,通过对微纳电离型传感器进行一系列的测试,设计的传感器展现了较强的抗弯能力及较快的响应-恢复能力。在室温常压、相对湿度75%的实验条件下,对多个浓度的苯、甲苯气体展开了测试,并基于特征噪声强度识别气体的浓度,构建了对应的识别模型。实验结果表明：传感器对有害气体检测时的测量值和真实值的拟合度可达99%以上,体现了较高的检测精度,且在检测有害气体时传感器处于可逆电离平衡状态,重复性良好,不需要进行预热、安全无毒,因此适合于应用到苯类气体的检测中,能够满足效率、精度的要求,具备了一定的实用性。     

Reaching the Fundamental Limitation in CO2 Reduction to CO with Single Atom Catalysts

The electrochemical CO₂ reduction reaction (CO₂RR) to value-added chemicals with renewable electricity is a promising method to decarbonize parts of the chemical industry. Recently, single metal atoms in nitrogen-doped carbon (MNC) have emerged as potential electrocatalysts for CO₂RR to CO with high activity and faradaic efficiency, although the reaction limitation for CO₂RR to CO is unclear. To understand the comparison of intrinsic activity of different MNCs, two catalysts are synthesized through a decoupled two-step synthesis approach of high temperature pyrolysis and low temperature metalation (Fe or Ni). The highly meso-porous structure results in the highest reported electrochemical active site utilization based on in situ nitrite stripping; up to 59±6% for NiNC. Ex situ X-ray absorption spectroscopy (XAS) confirms the penta-coordinated nature of the active sites. The catalysts are amongst the most active in the literature for CO₂ reduction to CO. The density functional theory calculations (DFT) show that their binding to the reaction intermediates approximates to that of Au surfaces. However, it is found that the turnover frequencies (TOFs) of the most active catalysts for CO evolution converge, suggesting a fundamental ceiling to the catalytic rates.     

Hybrid Catalyst Coupling Zn Single Atoms and CuNx Clusters for Synergetic Catalytic Reduction of CO2

Reverse water-gas shift (RWGS) reaction is the initial and necessary step of CO₂ hydrogenation to high value-added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnN_x@C-N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four-coordinate Zn-N₄ sites and low valence CuN_x clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn-N₄ and N₄ structures, which show strong Lewis basicity and has strong adsorption for *CO₂ and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO₂ conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO₂ conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu-ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO₂. In the catalytic process, CuN_x not only adsorbs and activates H₂, but also cooperates with the adjacent Zn-N₄ and N₄ structures to jointly activate CO₂ molecules and further promotes the hydrogenation of CO₂. This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts.     

Pre-Activation of CO2 at Cobalt Phthalocyanine-Mg(OH)2 Interface for Enhanced Turnover Rate

Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO₂RR), but the molecule/substrate interaction is still pending for clarification and optimization to maximize the reaction kinetics. Herein, a CO₂RR catalyst is fabricated by affixing CoPc onto the Mg(OH)₂ substrate primed with conductive carbon, demonstrating an ultra-low overpotential of 0.31 ± 0.03 V at 100 mA cm⁻² and high faradaic efficiency of >95% at a wide current density range for CO production, as well as a heavy-duty operation at 100 mA cm⁻² for more than 50 h in a membrane electrode assembly. Mechanistic investigations employing in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectroscopy unravel that Mg(OH)₂ plays a pivotal role to enhance the CO₂RR kinetics by facilitating the first-step electron transfer to form anionic *CO₂⁻ intermediates. DFT calculations further elucidate that introducing Lewis acid sites help to polarize CO₂ molecules absorbed at the metal centers of CoPc and consequently lower the activation barrier. This work signifies the tailoring of catalyst-support interface at molecular level for enhancing the turnover rate of CO₂RR.     

Nano-Engineered Carbon Fibre-Based Piezoelectric Smart Composites for Energy Harvesting and Self-Powered Sensing

The integration of piezoelectric materials onto carbon fiber (CF) can add energy harvesting and self-power sensing capabilities enabling great potential for “Internet of Things” (IoT) applications in motion tracking, environmental sensing, and personal portable electronics. Herein, a CF-based smart composite is developed by integrating piezoelectric poly(3,4-ethylenedioxythiophene) (PEDOT)/CuSCN-coated ZnO nanorods onto the CF surfaces with no detrimental effect on the mechanical properties of the composite, forming composites using two different polymer matrices: highly flexible polydimethylsiloxane (PDMS) and more rigid epoxy. The PDMS-coated piezoelectric smart composite can serve as an energy harvester and a self-powered sensor for detecting variations in impact acceleration with increasing output voltage from 1.4 to 7.6 V under impact acceleration from 0.1 to 0.4 m s⁻². Using epoxy as the matrix for a CF-reinforced plastic (CFRP) device with sensing and detection functions produces a voltage varying from 0.27 to 3.53 V when impacted at acceleration from 0.1 to 0.4 m s⁻², with a lower output compared to the PDMS-coated device attributed to the greater stiffness of the matrix. Finally, spatially sensitive detection is demonstrated by positioning two piezoelectric structures at different locations, which can identify the location as well as the level of the impacting force from the fabricated device.     

A Polymer Defect Passivator for Efficient Hole-Conductor-Free Printable Mesoscopic Perovskite Solar Cells

Due to the low cost and excellent potential for mass production, printable mesoscopic perovskite solar cells (p-MPSCs) have drawn a lot of attention among other device structures. However, the low open-circuit voltage (V_OC) of such devices restricts their power conversion efficiency (PCE). This limitation is brought by the high defect density at perovskite grain boundaries in the mesoporous scaffold, which results in severe nonradiative recombination and is detrimental to the V_OC. To improve the perovskite crystallization process, passivate the perovskite defects, and enhance the PCE, additive engineering is an effective way. Herein, a polymeric Lewis base polysuccinimide (PSI) is added to the perovskite precursor solution as an additive. It improves the perovskite crystallinity and its carbonyl groups strongly coordinate with Pb²⁺, which can effectively passivate defects. Additionally, compared with its monomer, succinimide (SI), PSI serves as a better defect passivator because the long-chained macromolecule can be firmly anchored on those defect sites and form a stronger interaction with perovskite grains. As a result, the champion device has a PCE of 18.84%, and the V_OC rises from 973 to 1030 mV. This study offers a new strategy for fabricating efficient p-MPSCs.     

3D Printable One-Part Carbon Nanotube-Elastomer Ink for Health Monitoring Applications

3D printing of conductive elastomers is a promising route to personalized health monitoring applications due to its flexibility and biocompatibility. Here, a one-part, highly conductive, flexible, stretchable, 3D printable carbon nanotube (CNT)-silicone composite is developed and thoroughly characterized. The one-part nature of the inks: i) enables printing without prior mixing and cures under ambient conditions; ii) allows direct dispensing at ≈100 µm resolution printability on nonpolar and polar substrates; iii) forms both self-supporting and high-aspect-ratio structures, key aspects in additive biomanufacturing that eliminate the need for sacrificial layers; and iv) lends efficient, reproducible, and highly sensitive responses to various tensile and compressive stimuli. The high electrical and thermal conductivity of the CNT-silicone composite is further extended to facilitate use as a flexible and stretchable heating element, with applications in body temperature regulation, water distillation, and dual temperature sensing and Joule heating. Overall, the facile fabrication of this composite points to excellent synergy with direct ink writing and can be used to prepare patient-specific wearable electronics for motion detection and cardiac and respiratory monitoring devices and toward advanced personal health tracking and bionic skin applications.