CuO-SiO2气凝胶@TiO2纳米纤维无牺牲剂光催化还原CO2

采用溶胶-凝胶法制备CuO-SiO2复合气凝胶,通过在气凝胶孔道内填充TiCl4,然后将其气相水解,得到了在CuO-SiO2气凝胶表面生长了高结晶度的TiO2纳米纤维(CuO-SiO2@TiO2),纤维直径～16 nm.通过XPS、UPS、UV-Vis DRS、荧光光谱(PL)等表征了材料的结构及光电性能.结果表明,制备的CuO-SiO2@TiO2对可见光有明显吸收,且荧光强度较商用TiO2(P25)大幅降低,光生电子-空穴对更加稳定.再在纳米纤维上负载CuO,所得CuO-SiO2@TiO2/CuO在可见光区的荧光强度进一步增强.以300 W氙灯为光源,分别以CuO-SiO2@TiO2及CuO-SiO2@TiO2/CuO为催化剂,无牺牲剂条件下光催化还原CO2,4 h后甲醇产率分别为1304.0及1589.0μmol/g-cat,转换频率(TOF)分别为0.038及0.046 h–1.循环实验表明,纳米纤维具有较好的光催化稳定性,经过4次光催化循环实验后,CuO-SiO2@TiO2/CuO的保留率～94％,甲醇产率可达1472.0μmol/g-cat,TOF为0.042 h–1.     

Prediction of Flooding in Packed Liquid-Liquid and High-Pressure Extraction Columns Using a Gaussian Process

Reliable prediction of flooding conditions is needed for sizing and operating packed extraction columns. Due to the complex interplay of physicochemical properties, operational parameters and the packing-specific properties, it is challenging to develop accurate semi-empirical or rigorous models with a high validity range. State of the art models may therefore fail to predict flooding accurately. To overcome this problem, a data-driven model based on Gaussian processes is developed to predict flooding for packed liquid-liquid and high-pressure extraction columns. The optimized Gaussian process for the liquid-liquid extraction column results in an average absolute relative error (AARE) of 15.23 %, whereas the algorithm for the high-pressure extraction column results in an AARE of 13.68 %. Both algorithms can predict flooding curves for different packing geometries and chemical systems precisely.     

致密砂岩油藏能量补充方式评价及优化

针对致密砂岩油藏大规模体积压裂开发后能量补充困难的问题,利用自主设计制作的大型人造三维岩心物理模型和物理模拟实验舱,开展致密砂岩油藏能量补充方式优化研究。实验结果表明:致密砂岩油藏压裂开发过程中,地层能量损耗严重,采取注水或注气的方式可有效进行能量补充;地层中裂缝规模越大,越有利于原油渗流,后续补充能量的传播范围越广,有助于进一步提高原油采收率;从提高驱油效率和扩大波及系数方面优选吞吐渗吸介质,CO₂均优于活性水,CO₂吞吐开发在矿场试验中取得了显著的增油效果,因此,CO₂吞吐作为一种有效的能量补充方式在致密油开发中展现了良好的应用前景。该文分析了致密砂岩储层水平井压裂开发的渗流规律,优选出致密砂岩储层大规模压裂开发后最佳渗吸介质,可为致密砂岩油藏开发设计提供重要的理论依据。     

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。     

翅果油超临界CO2流体萃取工艺优化及其不同提取方法的比较

对翅果油的超临界CO_2流体萃取工艺条件进行研究。在单因素试验的基础上,以萃取压力、萃取温度、萃取时间和原料粒度为影响因素,以翅果油得率为指标,采用正交试验优化工艺条件。比较了浸出法、超临界CO_2流体萃取法、冷榨法和热榨法4种不同提取方法对翅果油得率和微量活性成分的影响。结果表明:超临界CO_2流体萃取翅果油最优工艺条件为萃取压力30 MPa、萃取温度50℃、萃取时间150 min、原料粒度80目,此条件下翅果油得率为(28. 32±1. 15)%; 4种提取方法中,浸出法的翅果油得率、VE及甾醇含量最高,其次是超临界CO_2流体萃取法,除热榨法的翅果油角鲨烯含量最高外,压榨法的其他指标均最低。     

Human responses to high levels of carbon dioxide and air temperature

In this study, 30 subjects were exposed to different combinations of air temperature (T_a: 24, 27, and 30°C) and CO₂ level (8000, 10 000, and 12 000 ppm) in a high-humidity (RH: 85%) underground climate chamber. Subjective assessments, physiological responses, and cognitive performance were investigated. The results showed that as compared with exposure to T_a = 24°C, exposure to 30°C at all CO₂ levels caused subjects to feel uncomfortably warm and experience stronger odor intensity, while increased mental effort and greater intensity of acute health symptoms were reported. However, no significant effects of T_a on task performance or physiological responses were found. This indicated that subjects had to exert more effort to maintain their performance in an uncomfortably warm environment. Increasing CO₂ from 8000 to 12 000 ppm at all T_a caused subjects to report higher rates of headache, fatigue, agitation, and feeling depressed, although the results were statistically significant only at 24 and 27°C. The text typing performance and systolic blood pressure (SBP) decreased significantly at this exposure, whereas diastolic blood pressure (DBP) and thermal discomfort increased significantly. These effects suggest higher arousal/stress. No significant interaction effect of T_a and CO₂ concentration on human responses was identified.     

Effect of the ZIF‐8 Distribution in Mixed‐Matrix Membranes Based on Matrimid® 5218‐PEG on CO2 Separation

In theory, the combination of inorganic materials and polymers may provide a synergistic performance for mixed‐matrix membranes (MMMs); however, the filler dispersion into the MMMs is a crucial technical parameter for obtaining compelling MMMs. The effect of the filler distribution on the gas separation performance of the MMMs based on Matrimid®‐PEG 200 and ZIF‐8 nanoparticles is demonstrated. The MMMs were prepared by two different membrane preparation procedures, namely, the traditional method and non‐dried metal‐organic framework (MOF) method. In CO₂/CH₄ binary mixtures, the MMMs were tested under fixed conditions and characterized by various methods. Finally, regardless of the MMM preparation procedure, the incorporation of 30 wt % ZIF‐8 nanoparticles allowed to increase the CO₂ permeability in MMMs. The ZIF‐8 dispersion influenced significantly the separation factor.     

Plasma-assisted Co/Zr-metal organic framework catalysis of CO_2 hydrogenation:influence of Co precursors

In this study, Co/Zr-metal organic framework(MOF) precursors were obtained by a roomtemperature liquid-phase precipitation method and the equivalent-volume impregnation method,respectively, using a Zr-MOF as the support, and Co/Zr-MOF-M and Co/Zr-MOF-N catalysts were prepared after calcination in a hydrogen–argon mixture gases(V_(Ar):V_(H_2)= 9: 1) at 350 °C for 2 h. The catalytic activities of the prepared samples for CO_2 methanation under atmosphericpressure cold plasma were studied. The results showed that Co/Zr-MOF-M had a good synergistic effect with cold plasma. At a discharge power of 13.0 W, V_(H_2):V_(CO_2)= 4: 1 and a gas flow rate of 30 ml·min~(-1), the CO_2 conversion was 58.9% and the CH_4 selectivity reached 94.7%,which was higher than for Co/Zr-MOF-N under plasma(CO_2 conversion 24.8%, CH_4 selectivity 9.8%). X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N_2 adsorption and desorption(Brunauer–Emmett–Teller) and x-ray photoelectron spectroscopy analysis results showed that Co/Zr-MOF-M and Co/Zr-MOF-N retained a good Zr-MOF framework structure, and the Co oxide was uniformly dispersed on the surface of the Zr-MOF. Compared with Co/Zr-MOF-N, the Co/Zr-MOF-M catalyst has a larger specific surface area and higher Co~(2+)/Cototaland Co/Zr ratios. Additionally, the Co oxide in Co/ZrMOF-M is distributed on the surface of the Zr-MOF in the form of porous particles, which may be the main reason why the catalytic activity of Co/Zr-MOF-M is higher than that of Co/ZrMOF-N.     

Synthesis,structure, CO oxidation,and H2 production activities of CaCu3−xMnxTi4−xMnxO12 (x = 0, 0.5, and 1.0)

Synthesis of nanocrystalline pristine and Mn-doped calcium copper titanate quadruple perovskites, CaCu_3?xMn_xTi_4?xMn_xO₁₂ (x = 0, 0.5, and 1.0) by modified citrate solution combustion method has been reported. Powder X-ray diffraction patterns attest the phase purity of the perovskite materials. Average particle sizes of all the materials obtained from the Scherrer's formula are in the range of 55–70 nm. The specific surface areas for all the perovskites obtained from BET isotherms are found to be low as expected for the condensed oxide systems and fall in the range of 13–17 m² g^?1. Transmission electron microscopy studies show a reduction in particle size of CaCu₃Ti₄O₁₂ with increase in Mn doping. Ca and Ti are present in +2 and +4 oxidation states in all the materials as demonstrated by X-ray photoelectron spectroscopy analyses. Cu²⁺ gets reduced in CaCu₃Ti₄O₁₂ with higher Mn content. Mn is observed to be present only in +3 oxidation state. All the materials have been examined to be active in CO oxidation as well as H₂ production from methanol steam reforming. CaCu₃Ti₄O₁₂ with ~14 at.% Mn is found to show best catalytic activities among these materials. A comprehensive analysis of the catalytic activities of these perovskites toward CO oxidation and H₂ production from MSR reveal the cooperative activity of copper-manganese in the doped perovskites and it is more effective at lower manganese content.     

A triptycene derived hypercrosslinked polymer for gas capture and separation applications

This work describes facile synthesis of a porous polymeric material ( T-HCP ) using readily available reagents. Specifically, T-HCP is a thermally stable and hypercrosslinked polymer (HCP) that is essentially microporous with a high BET specific surface area (940 m² g^?1). Triptycene based polymers are known to feature internal free volume. Thus, the incorporation of triptycene units and extensive crosslinking by an external cross-linker in T-HCP makes it a promising adsorbent for small gas capture applications. Experimental results show that T-HCP demonstrated good CO₂ capture capacity of 132 mg g^?1 (273 K, 1 bar). Molecular hydrogen storage capacity of T-HCP is estimated to be 17.7 mg g^?1 (77 K, 1 bar). T-HCP revealed high CO₂/N₂ selectivity (up to 63) as well as promising CO₂/CH₄ (up to 9.1) selectivity suggesting its potential applicability for CO₂ separation from flue and natural gases.