Facile synthesis of hybrid porous composites and its porous carbon for enhanced H2 and CH4 storage

The anticipated energy crisis due to the extensive use of limited stock fossil fuels forces the scientific society for find prompt solution for commercialization of hydrogen as a clean source of energy. Hence, convenient and efficient solid-state hydrogen storage adsorbents are required. Additionally, the safe commercialization of huge reservoir natural gas (CH₄) as an on-board vehicle fuel and alternative to gasoline due to its environmentally friendly combustion is also a vital issue. To this end, in this study we report facile synthesis of polymer-based composites for H₂ and CH₄ uptake. The cross-linked polymer and its porous composites with activated carbon were developed through in-situ synthesis method. The mass loadings of activated carbon were varied from 7 to 20 wt%. The developed hybrid porous composites achieved high specific surface area (SSA) of 1420 m²/g and total pore volume (TPV) of 0.932 cm³/g as compared to 695 m²/g and 0.857 cm³/g for pristine porous polymer. Additionally, the porous composite was activated converted to a highly porous carbon material achieving SSA and TPV of 2679 m²/g and 1.335 cm³/g, respectively. The H₂ adsorption for all developed porous materials was studied at 77 and 298 K and 20 bar achieving excess uptake of 4.4 wt% and 0.17 wt% respectively, which is comparable to the highest reported value for porous carbon. Furthermore, the developed porous materials achieved CH₄ uptake of 8.15 mmol/g at 298 K and 20 bar which is also among the top reported values for porous carbon.     

煤化工烟道气毒性成分对Chlorella pyrenoidosa生长和细胞成分的影响

探究煤化工烟道气中毒性成分对微藻的影响是利用微藻固定煤化工烟道气CO₂实现减排的关键。本文利用不同浓度的NaHS、Na₂SO₃和NH₃·H₂O培养Chlorella pyrenoidosa（C. pyrenoidosa），以探究煤化工烟道气主要毒性成分H₂S、SO₂和NH₃气体水溶物的毒性。实验结果表明：NaHS、Na₂SO₃和NH₃·H₂O浓度分别低于1mmol/(L·d)、40mmol/(L·d)和7mmol/(L·d)时对C. pyrenoidosa生长无抑制作用，而且Na₂SO₃[＜40mmol/(L·d)]会显著促进 C. pyrenoidosa的生长；NaHS 添加4mmol/(L·d)时会在生长初期抑制C. pyrenoidosa的生长，NH₃·H₂O添加35mmol/(L·d)则会直接造成藻细胞的破碎死亡。与对照组相比，NaHS和Na₂SO₃浓度分别低于1mmol/(L·d)、10mmol/(L·d)时对C. pyrenoidosa的细胞成分无影响；NaHS添加4mmol/(L·d)使藻蛋白含量提高7.13%；Na₂SO₃添加40mmol/(L·d)使藻蛋白降低13.45%，总糖含量提高42.90%；NH₃·H₂O的添加会使藻蛋白含量降低，总糖含量提高。微藻生物质整体蛋白质含量较高，可作为蛋白饲料来源。研究结果表明，C. pyrenoidosa对煤化工烟道气中的主要毒性气体有较好的耐受性，利用煤化工烟道气培养微藻具有可行性。     

二氧化碳联合核桃壳提取液促进单针藻Monoraphidium sp. QLZ-3的生长和油脂积累

以单针藻Monoraphidium sp. QLZ-3为对象，研究了CO₂对微藻在核桃壳提取液（walnut shell extracts，WSE）中生长及油脂积累的影响。结果显示，在12%的CO₂条件下，微藻在WSE中的生物量产率及油脂产率达到196.85mg/(L·d)和97.52mg/(L·d)，分别是对照组的1.33倍和1.57倍。WSE培养下，外源CO₂上调了微藻中核酮糖1,5-二磷酸羧化酶基因（ribulose 1,5-bisphosphate carboxylase/oxygenase，rbcL）的表达量，从而促进了CO₂的固定。此外，12% 的CO₂提高了微藻对WSE中多酚的利用，同时上调了乙酰辅酶A羧化酶（acetyl coenzyme A carboxylase，ACCase）和苹果酸酶（malic enzyme，ME）活性，下调了磷酸烯醇式丙酮酸羧化酶（phosphoenolpyruvate carboxylase，PEPC）活性。研究表明，CO₂可以提高WSE中微藻的生物量产率和油脂产率，降低培养成本，为核桃壳的资源化利用及微藻的工业化生产提供了新的理论基础。     

Preparation of molecularly imprinted fluorescence sensor based on carbon quantum dots via precipitation polymerization for fluorescence detection of tetracycline

A facile and effective method was proposed to prepare the molecularly imprinted fluorescence sensor with carbon quantum dots, which were modified vinyl groups by acrylic acid on the surface. The obtained fluorescence composite material was investigated by transmission electron microscope and Fourier transform infrared spectra. After the experimental conditions were optimized, a linear range of 1.0–60 μmol L⁻¹ was obtained and the detection limit was 0.17 μmol L⁻¹. The novel fluorescence sensor can be successfully used to detect tetracycline in real samples. This study provides a convenient strategy for selective recognition and rapid detection of tetracycline in the complex environment.     

Cobalt doping of α-Fe/Al2O3 catalysts for the production of hydrogen and high-quality carbon nanotubes by thermal decomposition of methane

Fe–Co/Al₂O₃ catalysts were developed and tested in the catalytic decomposition of methane (CDM) for the synthesis of multi-wall carbon nanotubes (MWCNT) and the CO₂-free hydrogen production. While Fe (54.5–66.7 mol.%) is the main active phase for the carbon formation on the catalyst, Co acts as dopant aiming to improve its overall catalytic behaviour. Catalysts with Co contents of up to 18.2 M% showed the presence of α-Fe and Fe–Co crystallites with different size and lattice parameter. Fe_1-xCo_x alloy with bcc crystal system was identified only for Co contents of 14.0% and above, and presented a lattice constant lower than α-Fe, which would modify the carbon diffusion of the metal particle during the MWCNT growth. Co inhibited the Fe₃C formation during CDM resulting in higher carbon formations and longer activity times. This phase, shown in undoped catalysts, favored the presence of bamboo-type carbon nanotubes.     

基于CFD-DEM方法的净化器流场模拟与结构优化

针对空气净化器能耗高的问题，使用离散元方法(DEM)在吸附滤网中建立随机堆积柱形活性炭模型，采用计算流体力学(CFD)方法对空气净化器内部流场进行数值模拟，在模拟与实验验证的基础上，考察了压降最小、流场最均匀的吸附滤网结构。结果表明，空气净化器压降主要发生在轴向，活性炭吸附滤网中回流、沟流现象严重，流体阻力是其他两种滤网的3倍。边数对多边形填充孔结构吸附滤网内压降与流场均匀性无影响，当孔结构改为圆形时，压降减小约52 Pa，节能18.4%(49 W)；当孔直径由8 mm增至12 mm，压降减小约48 Pa，节能19.4%(45 W)；滤网间距对空气净化器压降无影响，圆形、小孔径的吸附滤网内流场最均匀。     

改性氧化钛对羟乙基乙二胺水溶液解吸CO2的强化

羟乙基乙二胺（AEE）水溶液的CO₂循环吸收量高（1.2molCO₂/molAEE），吸收速度快，稳定性好，但解吸速度慢、解吸量少（0.8mol CO₂/mol AEE）是限制该技术广泛应用的主要原因。本文通过向AEE水溶液中添加质量分数为0.05%～0.20%的改性氧化钛（TiO₂-MWCNT和TiO₂-OH）强化AEE的解吸能力。CO₂循环吸收（40℃）-解吸（120℃）实验结果表明改性氧化钛的添加比氧化钛强化CO₂解吸效果更好，强化顺序为TiO₂-MWCNT＞TiO₂-OH；其对应的最大解吸速率分别为0.093L/min（质量分数0.15%）和0.083L/min（质量分数0.20%），相对于AEE水溶液，分别提高了32.9%和18.6%；其对应的最大解吸量分别为0.92molCO₂/molAEE（质量分数0.15%）和0.88molCO₂/molAEE（质量分数0.20%），分别提高了12.2%和9.7%；其对应的CO₂循环吸收量分别是0.95molCO₂/molAEE（质量分数0.15%）和0.89molCO₂/molAEE（质量分数0.15%），分别提高了18.75%和11.25%；5次循环吸收解吸实验结果表明改性氧化钛强化CO₂解吸效果稳定，具有较强的化学稳定性。对反应后的改性氧化钛进行XRD、BET、FTIR和SEM表征，结果表明改性氧化钛具有较强的结构稳定性。TiO₂-MWCNT和TiO₂-OH在促进有机胺溶液解吸CO₂方面具有一定的工业应用潜力。     

Graphene-based polymer composites with ultra-high in-plane thermal conductivity: A comparison study between optothermal Raman spectroscopy and laser flash method

We developed a simple solution mixing and molding process for the incorporation of graphene nano-flakes (GNFs) in polymer films. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(ethylene-co-methacrylic acid) (PEMAA) were used for preparation of the samples. The orientation and stacking of GNFs were confirmed using a scanning electron microscope. The thermal conductivity values for these composites were obtained using (1) laser flash method (commercially available) and (2) an optothermal Raman (OTR) technique (homemade device). The former measures the thermal diffusivity (α) and one needs to measure the density (ρ) and the heat capacity (C_p) of the composites in order to measure the in-plane thermal conductivity (κ = α.ρ.C_p), while the latter measures the in-plane thermal conductivity directly from the relation between the excitation power and the position of the Raman resonance. The data obtained from Raman spectroscopy were analyzed, assuming heat propagation in three and two dimensions. The Raman results obtained based on the two-dimensional model were very close to the results obtained using the laser flash method with less than 10% difference. The OTRspectroscopy was found to be a promising technique for measuring the in-plane thermal conductivity of carbon-based polymer composites. PVDF-HFP and PEMAA composite films with very high in-plane thermal conductivity (25 W m⁻¹ K⁻¹) were obtained through the incorporation of GNFs (20 wt % concentration). Considering a very low thermal conductivity of these polymers (<0.2 W m⁻¹ K⁻¹), this corresponds to a large enhancement of roughly 12 400%. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48927.     

Microwave pyrolysis of polystyrene and polypropylene mixtures using different activated carbon from biomass

In this study, microwave pyrolysis was experimented with mixed types of plastic waste. Two different plastic wastes polystyrene waste (PSW) and polypropylene waste (PPW) were used as feedstock. Carbon and activated carbon were synthesized from different biomass; rice husk (RH), corn husk (CH) and coconut sheath (CS) respectively which are used as microwave susceptors. The effect of impregnation on product yields was studied. Microwave pyrolysis at 900 W and with a polymer to an absorbent ratio of 10:1, produced the highest oil yield of 84.30 wt% when coconut sheath activated carbon (CSAC) was used as an absorbent. The reaction time was 10 min for the complete decomposition of polymer mixtures. Oil properties were determined and a high calorific value of 46.87 MJ kg⁻¹ was obtained. These properties were compared to conventional fuel properties and the product oil has a density of 0.76 g ml⁻¹ and viscosity of 2.4 cSt which is an equivalent fraction obtained to that of gasoline. Product oil has a styrene recovery of 67.58% from microwave pyrolysis. The results demonstrate that, microwave pyrolysis has a great potential for energy recovery from mixed plastic waste and the use of agricultural residues as absorbents enhanced the production efficiency of the process.     

High-performance sodium polyacrylate nanocomposites developed by using ionic liquid covalently modified multiwalled carbon nanotubes

Ionic liquids grafted with multiwalled-nanotubes (CNT Br/NTf₂), involving hydrophilic bromide salt and hydrophobic bis(trifluoromethanesulphonyl)imide salt, were prepared by amidation, followed by an easy solution-casting method of blending CNT Br/NTf₂ with sodium polyacrylate (PAA) as well as crosslinking agent (XR-100) to form PAA hybrid nanocomposites. The uniform dispersion of CNT Br/NTf₂ were analyzed by TEM. The defects and physical properties of fillers were characterized by Raman spectroscopy, Contact angle test, and TGA. Furthermore, microstructures of hybrid nanocomposites were characterized by SEM, from which it can be found that fillers were homogeneously distributed in the PAA matrix. CNT Br/NTf₂ significantly improved the mechanical properties and tensile fatigue resistance, as well as offered tunable swelling behavior of PAA nanocomposites without wasting too much of thermal stability. This study offers a simple approach to develop multifunctional materials based on ionic liquids covalently modified MWCNTs PAA nanocomposites.