二氧化硅负载支链有机膦的合成及其在二氧化碳催化氢化反应中的催化性能

以改性二氧化硅为核,利用发散法合成出二氧化硅负载的1～6代端胺基树枝状高分子(SiO2-PAMAM),样品经FT-IR,TG和端胺基分析表征.利用功能化载体表面的氨基与[Ph2P(CH2OH)2]+Cl-发生反应,合成出SiO2-PAMAM负载的有机膦(SiO2-PAMAM-PPh2),与三氯化钌复配成催化体系,考察了其对吗啉存在下的二氧化碳催化氢化反应的催化性能,该催化体系的催化活性(TOF)可达4 195.     

Isosteric heat of sorption of CO2 in poly(ethylene terephthalate)

Sorption isotherms for carbon dioxide in poly(ethylene terephthalate) have been measured at 35–55°C. The isotherms were measured gravimetrically on a Mettler Thermoanalyzer-1 from vacuum to 1 atmosphere. The sorption data were used to generate sorption isotherms from which the isosteric heat of sorption of CO₂ in PET was determined. At 45°C the isosteric heat of sorption increases from −10 kcal/mole at a concentration of 0.5 cm³ (STP)/cm³ (polymer) to −8 kcal mole⁻¹ at a concentration of 1.5 cm³ (STP)/cm³ (polymer). It has been reported in the literature that the isosteric heat of sorption for this system decreased through a minimum before increasing with increasing concentration. Our measurement of the low-pressure sorption isotherms shows that this is not the case.     

Intergranular oxidation of silicon in 20Cr-25Ni niobium-stabilized stainless steel at 1140–1230 K

The kinetics of intergranular oxidation of silicon in a 20Cr-25Ni Nb-stabilized stainless steel are reported, at temperatures in the range 1140–1230 K, in CO₂ at 40 bar pressure. The depth of attack increased parabolically with respect to time, with an activation energy of 335±30 kJ/mol. The mechanism of growth is discussed in terms of classical internal-oxidation theories, and an alternative explanation based on an available-space theory is developed. The internal oxidation rates in a number of different alloys are compared with diffusivities of metals in the base alloy. It is proposed that intergranular oxidation in the 20–25 Nb steel is controlled by the rate of outward diffusion of iron or chromium in the alloy.     

Application of optical transmission interferometry for in-situ structural investigations of titanium dioxide sputter-deposited coatings

Titanium dioxide coatings (from 0.1 to 1.5 μm thick) have been dc sputter-deposited on glass slides from titanium targets in various Ar-O₂ reactive gas mixtures. Deposition rate and optical properties were controlled in-situ by optical transmission interferometry (OTI) with an optical fibre located behind the glass substrate in order to perform a real-time control of transmittance of the growing film. Thus, it is possible to determine in-situ the optical indices (n, k) and the thickness of the as-deposited film by using a simple simulation, developed on Matlab software. The optical properties of the films were investigated in relation to their structure, which depends on the sputtering conditions adopted. In particular, the effects of the sputtering pressure (working pressure and oxygen partial pressure), the discharge power and the substrate location into the reactor are investigated in detail. Films structure is assessed by standard grazing incidence X-ray diffraction (XRD).     

石墨烯气体传感解吸附特性研究

分析探讨了石墨烯气体解吸附特性与解吸附方法。通过实验分析石墨烯对NO2气体分子的响应时间、气体分子解吸附时间,分析探讨石墨烯的气敏特性。实验表明,石墨烯对NO2气体传感灵敏度高,响应快,但恢复过程缓慢,气体解吸附时间长。分析表明,通过加热的方法、光照的方法可有效减少石墨烯气体解吸附时间,改善解吸附特性。     

RBF神经网络在红外CO_2传感器压力补偿中的应用研究

在红外CO2传感器的测量过程中,环境总压是一个重要的影响因素。在环境总压变化的情况下做好压力补偿得出正确的CO2气体分压值,对提高传感器的测量精度有重要意义。提出一种基于聚类和梯度法的径向基函数(RBF)神经网络方法,利用它的局部逼近特性,建立起其在红外CO2传感器的非线性压力补偿中的网络模型。实验结果表明:该应用收到了良好的效果。     

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.     

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.     

Hydrothermal Synthesis of VO2 Polymorphs: Advantages,Challenges and Prospects for the Application of Energy Efficient Smart Windows

Vanadium dioxide (VO₂) is a widely studied inorganic phase change material, which has a reversible phase transition from semiconducting monoclinic to metallic rutile phase at a critical temperature of τ_c ≈ 68 °C. The abrupt decrease of infrared transmittance in the metallic phase makes VO₂ a potential candidate for thermochromic energy efficient windows to cut down building energy consumption. However, there are three long‐standing issues that hindered its application in energy efficient windows: high τ_c, low luminous transmittance (T_lum), and undesirable solar modulation ability (ΔT_sol). Many approaches, including nano‐thermochromism, porous films, biomimetic surface reconstruction, gridded structures, antireflective overcoatings, etc, have been proposed to tackle these issues. The first approach—nano‐thermochromism—which is to integrate VO₂ nanoparticles in a transparent matrix, outperforms the rest; while the thermochromic performance is determined by particle size, stoichiometry, and crystallinity. A hydrothermal method is the most common method to fabricate high‐quality VO₂ nanoparticles, and has its own advantages of large‐scale synthesis and precise phase control of VO₂. This Review focuses on hydrothermal synthesis, physical properties of VO₂ polymorphs, and their transformation to thermochromic VO₂(M), and discusses the advantages, challenges, and prospects of VO₂(M) in energy‐efficient smart windows application.