Sol-Gel Microspheres Doped with Glycerol: A Structural Insight in Light of Forthcoming Applications in the Polyurethane Foam Industry

Porous silica-based microspheres encapsulating aqueous glycerol can be potential curing agents for one-component foams (OCFs). Such agents have the advantage of an enhanced sustainability profile on top of being environmentally friendly materials. A synthetically convenient and scalable sol-gel process was used to make silica and organosilica microspheres doped with aqueous glycerol. These methyl-modified silica microspheres, named “GreenCaps”, exhibit remarkable physical and chemical stability. The microspheres were characterized by scanning electron microscopy, transmission electron microscopy at reduced pressure, and cryogenic nitrogen adsorption—desorption analysis. The structure of the materials was also analyzed at the molecular level by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. As expected, the degree of methylation affects the degree of encapsulation and pore structure. Microspheres similarly methylated, however, can differ considerably in surface area and pore size due to the templating effect of glycerol on the organosilica structure. The results of the structure analysis reveal that glycerol is efficiently encapsulated, acts as a template, barely leaches over time, but is released by depressurization. A proper application of these microspheres can later on enhance both the environmental and health profile, as well as the technical performance (curing speed, foam quality, and froth thixotropy) of spray polyurethane foams.     

Liquid Phase Hydrogenolysis of Biomass‐derived Lactate to 1,2‐Propanediol over Silica Supported Cobalt Nanocatalyst

Liquid phase hydrogenolysis of ethyl lactate to 1,2‐propanediol was performed over silica supporting cobalt catalysts prepared by two different methods: precipitation‐gel (PG) technique and deposition‐precipitation (DP) procedure. The cobalt species (Co₃O₄/cobalt phyllosilicate) present in the corresponding calcined PG and DP catalysts were different as a consequence of the preparation methods, and Co OH Co olation and Si O Co oxolation molecular mechanisms were employed to elucidate the chemical phenomena during the different preparation procedures. In addition, the texture (BET), reduction behavior (TPR and in‐situ XRD), surface dispersion and state of cobalt species (XPS), and catalytic performance differ greatly between the samples. Because of small particle size, high dispersion of cobalt species and facile reducibility, the Co/SiO₂ catalyst prepared by precipitation‐gel method presented a much higher activity than the catalyst prepared by deposition‐precipitation method. Metallic cobalt is assumed to be the catalytically active site for the hydrogenolysis reaction according to the catalytic results of both cobalt samples reduced at different temperatures and the structure changes after reaction.     

Cyclohexane transformations over metal oxide catalysts. 2. Selective cyclohexane ring opening to form n-hexane over mono- and bimetallic rhodium catalysts

The activity of monometallic Rh and Pt catalysts and bimetallic Pt—Rh catalysts on oxide supports in cyclohexane ring opening to form n-hexane was studied. The Rh-containing catalysts are highly active and selective in this reaction. Cyclohexane dehydrogenation predominates in the case of the Pt catalysts. The use of the bimetallic alumina-supported Pt—Rh catalysts allows one to minimize the contribution of cyclohexane cracking and to enhance the selectivity for n-hexane with the yield of the latter slightly depending on the metal ratio in the bimetallic system under the experimental conditions.     

乙二醇／水与丙三醇／水体系的焓浓图与浓图

本文基于乙二醇／水与丙三醇／水两组二元体系在不同温度下的实验数据,对超额焓数据应用局部作用模型拟合,并分析拟合效果与拟合参数变化情况,发现Wilson模型拟合效果较好。通过Wilson方程的活度系数表达形式,推算了两组体系的气液平衡,并进而计算了两组体系的焓浓图与(火用)浓图。     

Hydro-de-halogenation and consecutive deprotection of chlorinated N-amido-pyrrolidin-2-ones with Raney-Ni: an effective approach to gabapentin

The benzoylamino group was identified as a useful radical cyclization auxiliary that can be smoothly removed on hydro-de-halogenation of chlorinated N-substituted-pyrrolidin-2-ones with Raney-Ni. This methodology was successfully implemented in a new and appealing route to the anti-epileptic drug gabapentin.     

A system with non-aqueous birefringent microemulsions

Non-aqueous birefringent microemulsions were found in a system ofp-xylene, glycerol, triethanolammonium oleate and oleic acid. The microemulsions showed long term stability once formed, but failed to form spontaneously when the components were contacted. After partial separation by centrifugation, no signs of spontaneous reformation were found.     

短孔道Pt/W-s-SBA-15催化剂的合成及甘油催化氢解制1,3-丙二醇性能的研究

合成了孔道平行于短轴方向的W原位掺杂的介孔SBA-15分子筛(W-s-SBA-15), 以其为载体制备了Pt/W-s-SBA-15催化剂, 考察了催化剂中Pt、W负载量变化对甘油氢解制1,3-丙二醇(1,3-PDO)性能的影响. 采用多种手段对催化剂的形貌、活性组分Pt和W的存在状态、催化剂的酸性等性质进行了系统的表征. 催化剂评价结果表明, 随着Pt、W负载量的增加, 甘油的总转化率和液相转化率(CTL)提高, 而1,3-PDO选择性呈先升高后降低的火山型变化趋势. 在Pt负载量为4.0 wt%、W/Si物质的量比为1/480的4Pt/W-s-SBA-15(1/480)催化剂上, 在433 K、H₂压力4.0 MPa、反应时间24 h的条件下, 甘油氢解制1,3-PDO的得率可达49.0%. 根据表征结果, 我们发现在Pt/W-s-SBA-15催化剂上的甘油转化率与Pt活性比表面积直接相关, 而小的Pt粒径、Pt与单分散WO₄之间密切的协同作用, 则有助于提高1,3-PDO的选择性.