Maskless Preparation of Spatially-Resolved Plasmonic Nanoparticles on Polydimethylsiloxane via In Situ Fluoride-Assisted Synthesis

Here, a fluoride-assisted route for the controlled in-situ synthesis of metal nanoparticles (NPs) (i.e., AgNPs, AuNPs) on polydimethylsiloxane (PDMS) is reported. The size and coverage of the NPs on the PDMS surface are modulated with time and over space during the synthetic process, leveraging the improved yield (10×) and faster kinetics (100×) of NP formation in the presence of F⁻ ions, compared to fluoride-free approaches. This enables the maskless preparation of both linear and step gradients and patterns of NPs in 1D and 2D on the PDMS surface. As an application in flexible plasmonics/photonics, continuous and step-wise spatial modulations of the plasmonic features of PDMS slabs with 1D and 2D AgNP gradients on the surface are demonstrated. An excellent spatially resolved tuning of key optical parameters, namely, optical density from zero to 5 and extinction ratio up to 100 dB, is achieved with AgNP gradients prepared in AgF solution for 12 minutes; the performance are comparable to those of commercial dielectric/interference filters. When used as a rejection filter in optical fluorescence microscopy, the AgNP-PDMS slabs are able to reject the excitation laser at 405 nm and retain the green fluorescence of microbeads (100 µm) used as test cases.     

Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Investigation the correlation between chemical structure and swelling,thermal and flocculation properties of carboxymethylcellulose hydrogels

Hydrophilic polymer networks (hydrogels) based on sodium carboxymethylcellulose (NaCMC) and polycarboxylic acids (oxalic, succinic, citric and adipic) as cross-linking agents are synthesized by esterification reaction; one series of NaCMC hydrogels cross-linked with citric acid is prepared with acrylamide and acrylic acid (Aam/Aac) copolymers using the design of semi-interpenetrating polymer networks (semi-IPN), in order to increase their potential application for flocculation purposes. The Infrared spectroscopy (FTIR) of hydrogels confirms the esterification reaction between NaCMC and cross-linking agents. Results of swelling measurements show that citric acid in the amount of 15 wt% gives the hydrogels with the best absorption capacity. The results of Differential scanning calorimetry (DSC) and Thermal gravimetric analysis (TGA) show no significant difference in thermal properties of neat and semi-interpenetrating NaCMC hydrogels. The amorphous nature of hydrogels is confirmed by X-ray diffraction analysis (XRD). The results of flocculation study show that combination of NaCMC network and Aam/Aac copolymer with initial mass ratio of 10/90 creates a theoretical platform for the production of flocculant which could show high efficacy in purifying of water dominated by positively charged particles.     

Synthesis of Light Hydrocarbons from Biogas and Hydrogen: Investigation of a Fe-Mn-K/MgO Catalyst

Fischer-Tropsch synthesis of the CO₂ in biogas aims at producing light hydrocarbons and increasing its calorific value for feeding into the grid. Fe catalysts with Mn and K as promoters are supposed to yield high amounts of light hydrocarbons. Using a Fe-Mn-K/MgO catalyst, a parameter screening and long-term experiments were carried out. The catalyst shows, within the examined range, the highest selectivity to C₂–C₄ hydrocarbons at 450 °C, 8 bar(a), and a gas hourly space velocity of 350 h⁻¹. Calcination of the catalyst resulted in a significant drop of activity and an almost complete loss of selectivity to hydrocarbons. Admixture of steam to the reactant gas lowers the tendency to carbon deposition but also promotes the water-gas shift reaction and results in lower yields of hydrocarbons.     

模块化微反应系统内溴化间甲基苯甲醚连续合成

根据微化工技术发展的主要趋势，针对4-溴-3-甲基苯甲醚间歇非均相合成技术存在的问题，以微筛孔反应器与玻璃微珠填充床为核心功能微设备单元构建了模块化微反应系统，并在此模块化微反应系统内对液-液非均相连续溴化合成4-溴-3-甲基苯甲醚开展研究。通过优化操作条件，在溴浓度(x_{\mathrm{B}{\mathrm{r}}_{\mathrm{2}}})为17.5%（质量分数）、溴与间甲基苯甲醚摩尔比(n_{\mathrm{B}{\mathrm{r}}_{\mathrm{2}}}/n_M)为1.01、反应起始温度(T)为 0℃、停留时间为0.78 min条件下，4-溴-3-甲基苯甲醚的收率大于98%，多溴代副产物的含量仅为1%。与传统间歇溴化反应相比，模块化微反应系统内连续溴化反应具有十分明显的优势：可将间歇过程连续化，在保证安全的基础上极大地提升了反应的效率（时空收率为6.5×10⁴ kg/(m³·h)）；另外，该过程是由传质控制的，微反应器的传质性能优异，可极大地改善产品的选择性（多溴代副产物的量减少50%）。该研究为4-溴-3-甲基苯甲醚的连续高效安全合成提供了技术和设备依据。     

碳化二亚胺类抗水解稳定剂Bio-SW100的合成与应用

以硫脲法工艺路线合成了单体型碳化二亚胺抗水解稳定剂SW-100,通过红外光谱、元素分析以及液相色谱考察了产物的结构、纯度。红外光谱和元素分析确定了合成产物结构正确,液相色谱确定产物纯度达到99%以上。在结构和纯度确定的基础上,将合成产物添加到聚乳酸中进行水解性能测试。结果表明,在1%添加量下聚乳酸拉伸强度保持率较纯树脂提高了80%。     

Comparison of co-current and counter-current flow in a bifunctional reactor containing ammonia synthesis and 2-butanol dehydrogenation to MEK

In this study, a multi-tubular thermally coupled packed bed reactor in which simultaneous production of ammonia and methyl ethyl ketone (MEK) takes place is simulated. The simulation results are presented in two co-current and counter-current flow modes. Based on this new configuration, the released heat from the ammonia synthesis reaction as an extremely exothermic reaction in the inner tube is employed to supply the required heat for the endothermic 2-butanol dehydrogenation reaction in the outer tube. On the other hand, MEK and hydrogen are produced by the dehydrogenation reaction of 2-butanol in the endothermic side, and the produced hydrogen is used to supply a part of the ammonia synthesis feed in the exothermic side. Thus, 30.72% and 31.88% of the required hydrogen for the ammonia synthesis are provided by the dehydrogenation reaction in the co-current and counter-current configurations, respectively. Also, according to the thermal coupling, the required cooler and furnace for the ammonia synthesis and 2-butanol dehydrogenation conventional plants are eliminated, respectively. As a result, operational costs, energy consumption and furnace emissions are considerably decreased. Finally, a sensitivity analysis and optimization are applied to study the effect of the main process parameters variation on the system performance and obtain the minimum hydrogen make-up flow rate, respectively.     

Sustainable ammonia production through process synthesis and global optimization

Current ammonia production technologies have a significant carbon footprint. In this study, we present a process synthesis and global optimization framework to discover the efficient utilization of renewable resources in ammonia production. Competing technologies are incorporated in a process superstructure where biomass, wind, and solar routes are compared with the natural gas-based reference case. A deterministic global optimization-based branch-and-bound algorithm is used to solve the resulting large-scale nonconvex mixed-integer nonlinear programming problem (MINLP). Case studies for Texas, California, and Iowa are conducted to examine the effects of different feedstock prices and availabilities. Results indicate that profitability of ammonia production is highly sensitive to feedstock and electricity prices, as well as greenhouse gas (GHG) restrictions. Under strict 75% GHG reductions, biomass to ammonia route is found to be competitive with natural gas route, whereas wind and solar to ammonia routes require further improvement to compete with those two routes. © 2018 American Institute of Chemical Engineers AIChE J, 65: e16498 2019     

Structural and optical properties of CdTe-nanocrystals thin films grown by chemical synthesis

By mans of a chemical synthesis technique stoichiometric CdTe-nanocrystals thin films were prepared on glass substrates at 70 °C. First, Cd(OH)₂ films were deposited on glass substrates, then these films were immersed in a growing solution prepared by dissolution of Te in hydroxymethane sulfinic acid to obtain CdTe. The structural analysis indicates that CdTe thin films have a zinc-blende structure. The average nanocrystal size was 19.4 nm and the thickness of the films 170 nm. The Raman characterization shows the presence of the longitudinal optical mode and their second order mode, which indicates a good crystalline quality. The optical transmittance was less than 5% in the visible region (400–700 nm). The compositional characterization indicates that CdTe films grew with Te excess.