Synthesis of mordenite by solvent-free method and its application in the dimethyl ether carbonylation reaction

Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.

Highly dispersed MgInCe-mixed metal oxides catalyzed direct carbonylation of glycerol and CO_(2)into glycerol carbonate

Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.

Controlling Reactivity of Palladium Amides for Selective Carbonylation towards Urea and Oxamide Derivatives

Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways.Herein,our study introduces a strategy employing palladium amides,harnessing their unique reactivity control,to direct the selective carbonylation of amines for the targeted synthesis of urea and oxamide derivatives.The palladium amide structure was elucidated using single-crystal X-ray diffraction.Controlled experiments and cyclic voltammetry studies further elucidate that the oxidation of palladium amide or its insertion into a carbonyl group diverges into distinct pathways.By employing sodium percarbonate as an eco-friendly oxidant and base,we have successfully constructed a switchable carbonylation system co-catalyzed by palladium and iodide under room temperature.The utilizing strategy in this study not only facilitates effective control over reaction selectivity but also mitigates the risk of explosions,a critical safety concern in traditional carbonylation methods.

Mechanism of CO_(2)reduction in carbonylation reaction promoted by ionic liquid additives:A computational and experimental study

The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).

Effect of polytetrafluoroethylene hollow fiber microstructure on formaldehyde carbonylation performance in membrane contactor

Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene(PTFE)membrane contactor has been proved in our previous study. In this paper, the effect of membrane microstructure on process performance was further investigated. Three porous PTFE hollow fibers with different pore sizes and one polydimethylsiloxane(PDMS)/PTFE composite membrane with dense layer were fabricated for comparison. The physical and chemical properties of four membranes, including chemical composition, morphology, contact angle, liquid entry pressure, thermodynamic analysis and gas permeability, were systemically characterized. Experiments of formaldehyde carbonylation under different reaction conditions were conducted. The results indicated that the yield of glycolic acid increased with decreasing pore size for porous membranes, which was due to the improvement of wetting behavior. The dense layer of PDMS in composite hollow fiber could effectively prevent the solvent from entering membrane pores, thus the membrane exhibited the best performance. At reaction temperature of 120℃ and operation pressure of 3.0 MPa, the yield of glycolic acid was always higher than 90% as the mass ratio of trioxane and phosphotungstic acid increased from 0.2:1 to 0.8:1. The highest turnover frequency was up to 26.37 mol·g^(-1)·h^(-1). This study provided a reference for the understanding and optimization of membrane contactors for the synthesis of glycolic acid using solvent with low surface tension.

离子漏斗聚焦光致化学电离质谱法在线同时测定7种大气羰基化合物

建立离子漏斗聚焦光致化学电离质谱在线同时测定7种大气羰基化合物的方法。基于飞行时间质量分析器,发展了离子漏斗聚焦光致化学电离源,通过光电子产生的H3O+试剂离子对羰基化合物分子进行化学电离,获得羰基化合物[M+H]+或[M-H2O+H]+的特征离子峰,利用特征峰面积外标法定量。甲醛、乙醛、丙酮、正丁醛、正戊醛、正己醛和苯甲醛7种羰基化合物在气体体积分数为5×10^(-9)~250×10^(-9)范围内与各目标物的质谱特征峰面积线性关系良好,相关系数均大于0.998,检出限为0.010×10^(-9)~0.087×10^(-9)。样品加标回收率为93.5%~107.7%,测定结果的相对标准偏差为1.2%~5.4%(n=5)。该方法适用于环境研究领域中大气羰基化合物的在线监测。

《有机化学》课程知识模块重构探究——以金属有机化合物和羰基化合物反应为例

《有机化学》课程知识内容庞杂,章节之间知识点内在关联多,易混淆,本文以金属有机化合物和羰基化合物反应为例介绍“知识模块重构”教学方法。该方法内容上不仅将跨章节具有联系的知识点进行深层次分析总结,重构成新的教学内容,还将实验、科研新成果和思政元素融入重构内容的基础教学中;教学上采用多维度启发、多种教学方法相结合,充分发挥学生的主动性;形成“新思维、多手段、全方位”的教学模式,达到全面提升学生专业素养和综合能力的目的。

CIPs@Mn_(0.8)Zn_(0.2)Fe_(2)O_(4)-CNTs复合材料低频吸波性能研究

随着5G无线通信与低频雷达侦察技术的飞速发展,低频电磁波辐射已成为当代的严重问题。目前,中高频段吸波材料的研究已趋于成熟,而设计低频段吸波材料仍面临巨大的挑战,亟待研究者们解决。基于四分之一波长相消机制,本研究设计了0.5~3 GHz低频段复合吸波材料。采用简单的一步水热法,诱导铁氧体在羰基铁粉与碳纳米管表面生长,制备出CIPs@Mn_(0.8)Zn_(0.2)Fe_(2)O_(4)-CNTs三元复合材料,对比研究了碳纳米管含量对材料吸收峰频率的影响。实验结果表明,引入碳纳米管,一方面为材料带来了界面极化、偶极极化等额外的损耗机制,增加了材料的衰减系数;另一方面基于四分之一波长相消机制,高介电与高磁导率的耦合,使材料在低频段获得良好的阻抗匹配。最终,在4 mm厚度下,样品分别在2.11与1.75 GHz处,获得了–40.8与–32.1 dB的反射损耗,–10 dB带宽分别为1.70~2.70 GHz和1.40~2.20 GHz。该复合材料制备工艺简单,低频吸收性能良好,具有很大的应用潜力,为开发更有效的低频吸波材料提供了新的思路和方法。

羰基铁粉生产工艺及用途概述

通过回顾全球羰基铁粉的发展史,简述了羰基铁粉主要生产流程、全球生产企业情况、产能情况以及羰基铁粉主要用途。随着羰基铁粉产业的发展,羰基铁粉也得到了广泛应用,主要用于注射成形、软磁一体化电感、吸波屏蔽、磁流变液、食品添加等行业。

脉冲磁场幅值对制备聚硅氧烷复合材料的电磁屏蔽性能影响规律

脉冲磁场已被证实通过诱导纳米粒子在基体中取向排列可以显著提高复合材料的电磁屏蔽性能,然而脉冲磁场幅值对复合材料电磁屏蔽性能的影响规律尚不明确。因此,采用脉宽为10μs、频率为50Hz的脉冲磁场诱导片状羰基铁(flaky carbonyl iron,FCI)在聚二甲基硅氧烷(polydimethylsiloxane,PDMS)中定向排列,研究磁场幅值(0~0.7T)对复合材料电磁屏蔽性能的影响规律。用扫描电子显微镜(scanning electron microscope,SEM)和X射线衍射(X-ray diffraction,XRD)对纳米粒子的取向和排列进行了表征。结果表明,脉冲磁场可以有效控制羰基铁的取向和排列,形成导电网络结构,提高复合材料的导电性,最终显著提高取向复合材料的电磁屏蔽性能。脉冲磁场对复合材料的屏蔽效能增强效果可达27%,达到的最高屏蔽效率为15.36dB。理论分析和实验结果的一致性证实了微秒级脉冲磁场在改善复合材料电磁屏蔽性能方面的有效性。该研究制备的高性能柔性电磁屏蔽复合材料具有应用于先进电子设备的潜力。

脲醛树脂包覆对片状羰基铁粉电磁吸波性能的影响

目的提高片状羰基铁粉(FCI)的吸波性能。方法采用原位聚合法制备脲醛树脂(UF)包覆片状羰基铁粉核壳复合粒子。通过透射电子显微镜(TEM)和X射线衍射仪(XRD)分别对试验前后样品的微观形貌和物相组分进行表征。采用矢量网络分析仪对处理前后片状羰基铁粉在0.5~18 GHz频率范围内的电磁参数进行测试,基于传输线理论对其反射损耗曲线进行拟合分析。结果微观形貌及X射线衍射谱结果表明,成功合成了脲醛树脂包覆片状羰基铁粉复合粒子(FCI@UF)。对测得的电磁参数进行分析,与原始片状羰基铁粉相比,包覆后铁粉介电常数和磁导率的实部、虚部均呈下降趋势,电磁波衰减能力减弱,与空气的阻抗匹配能力增强。反射损耗曲线图中,包覆后铁粉能有效吸收频带变宽(以反射损耗小于‒10 dB的带宽作为有效吸收频带),由3.15GHz变为4.38GHz,在13.84GHz时有最小反射损耗(‒20.64dB),最小反射损耗向高频移动,最小值降低率达41.38%。结论使用脲醛树脂对片状羰基铁粉进行包覆,制备了综合吸波性能更具优势的FCI@UF复合粒子,有效提高了片状羰基铁粉的吸波性能。

覆盖整个UHF频段的吸波结构

设计了一种覆盖整个特高频(Ultra-High Frequency,UHF)频段的超宽带吸波结构.利用了磁性材料的磁导率随频率减小而增大的特性,降低了吸波结构性能对频率的敏感性;结合等效电路方法,引入电损耗,进一步改善了吸波结构的低频性能.在整个UHF频段测量了羰基铁粉的介电常数和磁导率,采用遗传算法优化了等效电路参数,采用全波仿真软件优化了结构参数,在低频端对所加工的吸波结构的反射系数进行了测量.测量结果、仿真结果和等效电路结果吻合良好.所设计的吸波结构的相对带宽超过164%,厚度为最低工作频率波长的2.9%.

Ka频段羰基铁材料电磁性能测试

本文首先介绍了羰基铁材料及其电磁特性的参数表征,然后研究适合羰基铁材料电磁特性测试的方法,制备适合的羰基铁材料测试样本,实现羰基铁材料多种微波频段下的电磁特性测试。

Synthesis of Methyl Acetate by Dimethyl Ether Carbonylation over Cu/HMOR： Effect of Catalyst Preparation Method

Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor- denite supported copper （Cu/HMOR） catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The results showed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210℃, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption centers, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.

Effect of Calcination Temperature on Catalytic Activity and Textual Property of Cu/HMOR Catalysts in Dimethyl Ether Carbonylation Reaction

The effect of calcination temperature on the catalytic activity for the dimethyl ether （DME） carbonylation into methyl acetate （MA） was investigated over mordenite supported copper （Cu/HMOR） prepared by ion-exchange process. The results showed that the catalytic activity was obviously affected by the calcination temperature. The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 ℃ under conditions of 210 ℃, 1.5 MPa, and GSHV of 4883 h^-1. The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction, N2 absorption, NH3 temperature program desorption, CO temperature program desorption, and Raman techniques. Proper calcination temperature was effective to promote copper ions migration and diffusion, and led the support HMOR to possess more acid activity sites, which exhibited the complete decomposing of copper nitrate, large surface area and optimum micropore structure, more amount of CO adsorption site and proper amount of weak acid centers.

Effect of NH_4^+ exchange on CuY catalyst for oxidative carbonylation of methanol

NaY and ion exchanged NaNH4Y zeolite with NH4NO3 were used as the support to prepare CuY cata‐lysts by a high temperature anhydrous interaction between the support and copper （II） acety‐lacetonate Cu（acac）2. The catalysts were used for the oxidative carbonylation of methanol to dime‐thyl carbonate （DMC） at atmospheric pressure. The textural and acidic properties of NaNH4Y zeolite and the CuY catalysts were investigated by X‐ray diffraction, scanning electron microscopy, N2 ad‐sorption‐desorption, temperature programmed reduction of H2, X‐ray photoelectron spectroscopy and temperature programmed desorption of NH3. With increasing NH4NO3 concentration, the NH4＋exchange degree increased while the crystallinity of the zeolite remained intact. Crystalline CuO was formed when the NH4＋exchange degree of NaNH4Y was low, and the corresponding CuY catalyst showed low catalytic activity. With increasing of the NH4＋exchange degree of NaNH4Y, the content of surface bound Cu＋active centers increased and the catalytic activity of the corresponding CuY catalyst also increased. The surface bound Cu＋content reached its maximum when the NH4＋ex‐change degree of NaNH4Y reached towards saturation. The CuY exhibited optimal catalytic activity with 267.3 mg/（g·h） space time yield of DMC, 6.9%conversion of methanol, 68.5%selectivity of DMC.

构筑开放锡位点实现酸性增强的二甲醚羰基化丝光沸石催化剂设计

Due to their tunable acidity,shape selectivity,and excellent stability,zeolites are of great importance as solid acid materials in industrial catalysis.Tuning the properties of the acid sites in zeolites allows for the rational design and fabrication of catalysts for target reactions.Dimethyl ether(DME)carbonylation,a critical chain-growth reaction for C1 resource utilization,is selectively catalyzed by the Brønsted acid sites within the eight-membered rings(8-MRs)of mordenite(MOR).It is anticipated that strengthening the Brønsted acidity—particularly in 8-MRs—will improve the catalytic performance of MOR.In this work,density functional theory(DFT)calculations are first employed and the results used to design a modified MOR with stannum(Sn)and to predict the corresponding changes in acidity.Guided by the theoretical studies,a series of Sn-modified MOR are synthesized via a defect-engineering and subsequent heteroatom-substitution strategy.After partial desilication,isolated tetrahedral Sn species in an open configuration are successfully synthesized for the first time,within which tetrahedrally coordinated Al sites are preserved.An acidic characterization is used to confirm that the acidity of the Brønsted acid sites is enhanced by the introduction of the Sn species;as a result,the sample exhibits excellent activity in DME carbonylation reaction.Kinetic and DFT studies reveal that this strengthened acidity facilitates the adsorption of DME and reduces the activation barriers of DME dissociation and acetyl formation,accounting for the improved activity.The work demonstrates mechanistic insights into the promoting effects of strong acidity on DME carbonylation and offers a promising strategy to precisely control the acidic strength of zeolites.

济南市区典型污染时期大气中醛酮化合物的组分特征及生成机制

利用2,4-二硝基苯肼采样管采样-高效液相色谱仪分析的方法,在济南市夏季典型臭氧污染时期(2022年6月14~22日)对两个不同市区点位(建大和创业园)大气中醛酮化合物开展同步采样分析,利用基于观测的化学箱式模型(OBM)对主要醛酮化合物的光化学反应进行模拟,识别主要醛酮化合物的二次生成途径及重要前体物.采样期间醛酮化合物总浓度为(19.78±9.83)×10^(-9),甲醛、乙醛和丙酮贡献率分别为36.75%、21.39%、14.64%,是最主要的醛酮化合物.建大点位甲醛浓度存在午间与夜间双峰高值,创业园点位甲醛浓度存在早晚高峰变化特征,两点位乙醛浓度呈“夜高昼低”日变化特征.两点位甲醛和乙醛特征比值(C1/C2)分别为1.97、1.47,乙醛和丙醛特征比值(C2/C3)分别为9.27、8.76,建大点位C1/C2存在明显的午间峰值.OBM模拟结果显示,甲醛最大生成速率为6.17×10^(-9)h^(-1),乙醛最大生成速率为1.67×10^(-9)h^(-1),丙酮最大生成速率为0.66×10^(-9)h^(-1),烷氧自由基(RO)+O_(2)反应是二次生成的主要途径.结合相对增量反应活性(RIR)结果发现,烯烃对济南市大气中甲醛和乙醛的二次生成有重要影响,乙烯、异戊二烯和丙烯是甲醛的重要前体物,丙烯和2-丁烯是乙醛的重要前体物,对人为烯烃重点排放行业进行科学合理管控将有利于阻抑大气中主要醛酮化合物的二次生成.

Preparation of CIP@TiO_(2) composite with broadband electromagnetic wave absorption properties

Scholars aim for the improved impedance matching (Z) of materials while maintaining their excellent wave absorption properties. Based on the hydrolysis characteristics of isopropyl titanate, a simple preparation process for the coating of carbonyl iron powder(CIP) with TiO_(2) was designed. Given the TiO2coating, the Z of the CIP@TiO_(2) composite was adjusted well by decreasing the dielectric constant. Moreover, the interfacial polarization of CIP@TiO_(2) was enhanced. Ultimately, the electromagnetic-wave (EMW) absorption property of the CIP@TiO_(2)composite was improved substantially, the minimum reflection loss reached-46.07 dB, and the effective absorption bandwidth can reach 8 GHz at the composite thickness of 1.5 mm. Moreover, compared with CIP, the oxidation resistance of CIP@TiO_(2)showed remarkable improvement. The results revealed that the oxidation starting temperature of CIP@TiO_(2) as about 400℃,whereas the uncoated CIP had an oxidation starting temperature of approximately 250℃. Moreover, the largest oxidation rate temperature of CIP@TiO_(2) increased to around 550℃. This work opens up a novel strategy for the production of high-performance EMW absorbers via structural design.

Selenium-catalyzed oxidative carbonylation of 2-aminobenzyl alcohol to give 1,4-dihydro-2H-3,1-benzoxazin-2-one

An efficient,economical,and phosgene-free approach was developed for the preparation of l,4-dihydro-2H-3,l-benzoxazin-2-one from 2-aminobenzyl alcohol.In terms of its key features,this reaction uses the cheap and recyclable non-metal selenium as a catalyst instead of the noble metal palladium;carbon monoxide as a carbonylation agent instead of virulent phosgene or one of its derivatives;and oxygen as an oxidant.The selenium-catalyzed oxidative carbonylation reaction of2-aminobenzyl alcohol proceeded efficiently in a single pot in the presence of triethylamine to afford l,4-dihydro-2H-3,l-benzoxazin-2-one in 87%yield.Furthermore,the selenium catalyst was readily recovered and recycled,affording a product yield of 80%after five cycles.