环醚直接双羰基化合成α,ω-二元羧酸

二元羧酸是制备聚酰胺、聚酯和聚氨酯的重要中间体,其传统合成途径具有一定的局限性.以己二酸为例,其主要工业生产工艺是利用硝酸氧化KA油,该方法存在KA油产量低和产生大量温室气体N2O等问题.因此,探索工艺绿色、原子有效和采用可再生原料的二元羧酸制备方法具有重要意义.环醚和多元醇很容易从生物质原料中得到,以它们为原料,通过双羰基化直接制备二元羧酸,是一种非常有潜力的反应途径.但目前大多数文献报道由环醚或多元醇通过羰基化反应生成的产物主要是C+1单羧酸.本课题组一直致力于碘催化生物质衍生的多元醇的加氢脱氧,研究发现,在特定的反应条件下,多元醇可以选择性地形成多碘取代化合物的中间体.受此启发,本文报道了一种由环醚或多元醇形成二碘代物中间体,然后直接通过双羰基化反应生成对应的C+2二羧酸的新策略.由于己二酸是最重要的二元羧酸之一,且四氢呋喃(THF)可以从丰富的生物质衍生的糠醛中获得,本文重点研究了通过双羰基化反应直接利用THF合成己二酸.在优化的反应条件下,以铑盐为催化剂,碘为促进剂,乙酸和水为混合溶剂,在170℃,CO和H_(2)条件下,THF可以84%的产率转化为己二酸.循环实验结果表明,该催化体系在5次循环后仍能够稳定运行.该催化体系不仅适用于各种环醚,也适用于不同的伯二醇合成对应的C+2α,ω-二元羧酸.通过对反应中间体进行检测以及控制实验研究发现,选择性生成1,4-二碘丁烷中间体是进一步双羰基化制备己二酸的关键,而生成烯烃中间体和单碘代物中间体是形成副产物戊酸的主要原因.在实验结果和文献研究基础上,提出了THF转化为己二酸的反应机理.在反应中,活性铑常以Rh(I)的形式存在,并且从质谱中观察到了[Rh(CO)_(2)I_(2)]−阴离子,它可以在羰基化条件下由不同的铑前体(例如RhCl_(3))经过CO和碘还原后衍生.具体反应步骤为,首先铑催化剂催化H2和I2生成HI,然后THF与HI反应生成1,4-二碘丁烷中间体,此中间体经过铑催化活化在两端分别进行羰基化反应,最终生成产物己二酸.通过质谱检测到两个推测的中间体,进一步证实该反应机理.综上,本文为己二酸、戊二酸和其他重要的二羧酸(如1,7-庚二酸和1,8-辛二酸)的有效合成提供了一种新策略,为二元羧酸的高效、绿色合成提供参考.

相转移催化法合成邻苯二酚二(ω-氯代多甘醇)醚

在相转移催化剂存在下 ,由邻苯二酚和ω ,ω′- 二氯代多甘醇醚一步合成邻苯二酚二 (ω- 氯代多甘醇 )醚 ,探讨了催化剂、氢氧化钠浓度对产率的影响。此法较Kopolow法更简便、有效。

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.

Interfacial engineering through lead binding using crown ethers in perovskite solar cells

In the domain of perovskite solar cells(PSCs),the imperative to reconcile impressive photovoltaic performance with lead-related issue and environmental stability has driven innovative solutions.This study pioneers an approach that not only rectifies lead leakage but also places paramount importance on the attainment of rigorous interfacial passivation.Crown ethers,notably benzo-18-crown-6-ether(B18C6),were strategically integrated at the perovskite-hole transport material interface.Crown ethers exhibit a dual role:efficiently sequestering and immobilizing Pb^(2+)ions through host-guest complexation and simultaneously establishing a robust interfacial passivation layer.Selected crown ether candidates,guided by density functional theory(DFT)calculations,demonstrated proficiency in binding Pb2+ions and optimizing interfacial energetics.Photovoltaic devices incorporating these materials achieved exceptional power conversion efficiency(PCE),notably 21.7%for B18C6,underscoring their efficacy in lead binding and interfacial passivation.Analytical techniques,including time-of-flight secondary ion mass spectrometry(ToF-SIMS),ultraviolet photoelectron spectroscopy(UPS),time-resolved photoluminescence(TRPL),and transient absorption spectroscopy(TAS),unequivocally affirmed Pb^(2+)ion capture and suppression of non-radiative recombination.Notably,these PSCs maintained efficiency even after enduring 300 h of exposure to 85%relative humidity.This research underscores the transformative potential of crown ethers,simultaneously addressing lead binding and stringent interfacial passivation for sustainable PSCs poised to commercialize and advance renewable energy applications.

The effect of salt anion in ether‐based electrolyte for electrochemical performance of sodium‐ion batteries:A case study of hard carbon

Compared with the extensively used ester‐based electrolyte,the hard carbon(HC)electrode is more compatible with the ether‐based counterpart in sodium‐ion batteries,which can lead to improved cycling stability and robust rate capability.However,the impact of salt anion on the electrochemical performance of HC electrodes has yet to be fully understood.In this study,the anionic chemistry in regulating the stability of electrolytes and the performance of sodium‐ion batteries have been systematically investigated.This work shows discrepancies in the reductive stability of the anionic group,redox kinetics,and component/structure of solid electrolyte interface(SEI)with different salts(NaBF_(4),NaPF_(6),and NaSO_(3)CF_(3))in the typical ether solvent(diglyme).Particularly,the density functional theory calculation manifests the preferred decomposition of PF_(6)−due to the reduced reductive stability of anions in the solvation structure,thus leading to the formation of NaF‐rich SEI.Further investigation on redox kinetics reveals that the NaPF_(6)/diglyme can induce the fast ionic diffusion dynamic and low charge transfer barrier for HC electrode,thus resulting in superior sodium storage performance in terms of rate capability and cycling life,which outperforms those of NaBF_(4)/diglyme and NaSO_(3)CF_(3)/diglyme.Importantly,this work offers valuable insights for optimizing the electrochemical behaviors of electrode materials by regulating the anionic group in the electrolyte.

TLC Identification and Extraction Process of Rubiasin-1-methyl Ether from Yao Medicine Chuanlianzhu

[Objectives]To establish a thin-layer chromatography(TLC)method for the determination of rubiadin-1-methyl ether in Yao Medicine Chuanlianzhu(Damnacanthus giganteus).[Methods]A silica gel G thin-layer plate was adopted for TLC.Petroleum ether(60-90℃)-chloroform-methanol-water(7:15:3:1)was used as the developing solvent and inspected under ultraviolet lamp(365 nm).The content was determined by Inertsil ODS-3 C 18 column(4.60 mm×250 mm,5μm),mobile phase:acetonitrile-0.2%phosphoric acid gradient elution,detection wavelength 277 nm,flow rate 1.0 mL/min,column temperature 30℃,injection volume 10μL.[Results]The spots of 10 Chuanlianzhu samples from different origins showed the same color at the same position as the control,and the spots were clear and specific.The injection volume of rubiadin-1-methyl ether showed a good linear relationship in the range of 2.90-145μg(R=0.9996).The average recovery rate of rubiadin-1-methyl ether in the low,medium and high dose groups of Yao Medicine Chuanlianzhu was 98.72%,and RSD=1.78%.[Conclusions]This method can effectively identify Yao Medicine Chuanlianzhu medicinal materials and accurately determine the content of rubiadin-1-methyl ether in the medicinal materials.It provides a scientific basis for the development and utilization of Yao Medicine Chuanlianzhu medicinal resources.

相转移催化法合成对苯二酚二(ω-氯代二甘醇)醚

在相转移催化剂存在下 ,由对苯二酚和 2 氯乙醚一步合成对苯二酚二 (ω 氯代二甘醇 )醚 ,收率 81 %。

六-(ω-羟基丙基)肌醇醚及其衍生物的合成

本文报道六-(ω-羟基丙基)肌醇醚及其相应的四个新衍牛物的合成。它们可用于新型多分枝大分子—Cascade分子的合成研究。

相转移催化法合成邻苯二酚二(ω-氯代二甘醇)醚

在相转移催化剂存在下,由邻苯二酚和2-氯乙醚一步合成邻苯二酚二(ω-氯代二甘醇)醚,探讨了催化剂、氢氧化钠浓度对产率的影响。本法较Koplow法更简便、有效。

液晶冠醚4-(ω-十一烯基氧)-4′-(4′-羧基苯并-15-冠-5)联苯的变温红外光谱研究

研究了液晶冠醚４＿（ω＿十一烯基氧）＿４′＿（４′＿羧基苯并＿１５＿冠＿５）联苯在升温时从晶态到液晶态再到液态的相转变过程中，其红外特征频率、相对强度及峰形所发生的变化。初步归属了该化合物的红外特征频率。

四-(ω-羟基聚乙氧基)-季戊四醇醚及其磺酸酯化合物的合成

报道了Cascade(树状分枝化合物)分子四方向核心四-(ω-羟基聚乙氧基)-季戊四醇醚及四-(ω-对甲苯磺酰氧聚乙氧基)-季戊四醇醚的合成,其结构经元素分析、IR、NMR和MS图谱确证。

Economy, environmental assessment and energy conservation for separation of isopropanol/diisopropyl ether/water multi-azeotropes via extractive distillation coupled pervaporation process

This wok proposed the extraction distillation coupled pervaporation(ED+PV) technology process using two different solvents to separate isopropanol(IPA) and diisopropyl ether(DIPE) from DIPE/IPA/H_(2)O ternary heterogeneous azeotropes in industrial wastewater from the synthesis of isopropanol in this study.Based on strict design specifications, simulation and sequential iteration methods are used for process design and optimization. Compared to the ethylene glycol(EG)-EG+H_(2)O process and the 1,3-propanediol(PDO)-IPA+H_(2)O process, the total annual cost(TAC) of the EG-IPA+H_(2)O process decreased by 20.76% and 7.86%(PDO). Compared to the EG-EG+H_(2)O process, the TAC of the PDO-IPA+H_(2)O process reduced 14%, but the global warming potential(GWP) and human toxicity of the PDO-IPA+H_(2)O process increased 11.3% and 4.07% respectively. Compared to the PDO-IPA+H_(2)O process, the EG-IPA+H_(2)O process saves 7.86%(TAC), 9.78%(GWP) and 9.85%(human toxicity). The ED+PV process with EG is superior to PDO in factors of TAC, energy consumption, human toxicity and environment. The EG-IPA+H_(2)O process changed the separation order of the products of the multi-azeotropic system, reduced the cost and energy conservation of the system, and enhanced the environmental protection evaluation of the process, is the best process through life cycle assessment for analyzing the economy, energy conservation, environmental assessment and human toxicity, designing cleaner products, controlling waste discharge, and promoting the chemical purification industry. This work provides a new process design and optimized separation ideas, will have a good guiding significance for the research and application separation of multi-azeotropic mixture with mixed solvents in organic wastewater from the cleaner chemical production, has been up to standard wastewater discharge process, and realized the development goal of carbon peak and carbon neutrality in the sustainable development of chemical clean industry.

相转移催化法合成邻苯二酚二(ω-氯代二甘醇)醚

报导了邻苯二酚二（ω-氯代二甘醇）醚的相转移催化合成，探讨了催化剂、氢氧化钠浓度对产率的影响。

A Comparative Study of the Hydroxyl Value and Iodine Value in Polyoxyl Stearyl Ether in United States Pharmacopeia Specifications

The iodine value (iodine number) and hydroxyl value are important analytical characteristics of fats and oils. The iodine (I2) required saturating the fatty acids present in 100 grams of the oil or fat. Iodine value is a measure of the total number of double bonds (-C=C-) present in fats and oils. Unsaturated compounds contain molecules with double and triple bonds which are very reactive towards iodine. The iodine value has been determined according to Hanus with iodine monobromide in glacial acetic acid, and then the amount of iodine remaining unreacted is determined by titration using sodium thiosulfate volumetric standard solution. The hydroxyl value is the amount of potassium hydroxide in milligrams that is equivalent to the hydroxyl amount of 1 gram of the sample (mg KOH/g sample). Poloxyl Stearyl Ether is a mixture of the monostearyl ethers of mixed polyethylene glycols. It may contain various amounts of free stearyl alcohol and some free polyethylene glycol. In this study, the iodine value and hydroxyl value have been determined by titration in polyoxyl stearyl ether. Iodine value 1.84 g of I2 absorbed/100g sample, and hydroxyl value 162.65 mg KOH/g sample have been found in poloxyl stearyl ether. The iodine value and hydroxyl value results met the United States Pharmacopeia specifications for Polyoxyl Stearyl Ether.

Butyl ether as Co-diluent in medium-concentrated electrolyte for Li-S battery

1. Introduction The Lithium-sulfur battery(LSB) shows promise as a highdensity energy source, with a theoretical energy density of approximately 2600 W h kg^(-1)[1]. However, practical application of the LSB has been hindered by the “shuttle effect” and Li anode corrosion [2,3]. Highly concentrated electrolytes(HCEs) have been proposed as a solution, as they can inhibit the dissolution of lithium polysulfide and promote homogeneous lithium deposition [4].

Harnessing dimethyl ether and methyl formate fuels for direct electrochemical energy conversion

In this work,the oxidation of a mixture of dimethyl ether(DME) and methyl formate(MF) was studied in both an aqueous electrochemical cell and a vapor-fed polymer electrolyte membrane fuel cell(PEMFC)utilizing a multi-metallic alloy catalyst,Pt_(3)Pd_(3)Sn_(2)/C,discovered earlier by us.The current obtained during the bulk oxidation of a DME-saturated 1 M MF was higher than the summation of the currents provided by the two fuels separately,suggesting the cooperative effect of mixing these fuels.A significant increase in the anodic charge was realized during oxidative stripping of a pre-adsorbed DME+MF mixture as compared to DME or MF individually.This is ascribed to greater utilization of specific catalytic sites on account of the relatively lower adsorption energy of the dual-molecules than of the sum of the individual molecules as confirmed by the density fu nctional theory(DFT) calculations.Fuel cell polarization was also conducted using a Pt_(3)Pd_(3)Sn_(2)/C(anode) and Pt/C(cathode) catalysts-coated membrane(CCM).The enhanced surface coverage and active site utilization resulted in providing a higher peak power density by the DME+MF mixture-fed fuel cell(123 mW cm^(-2)at 0.45 V) than with DME(84mW cm^(-2)at 0.35 V) or MF(28 mW cm^(-2)at 0.2 V) at the same total anode hydrocarbon flow rate,temperature,and ambient pressure.

Durable semi-crystalline interphase engineering to stabilize high voltage Ni-rich cathode in dilute ether electrolyte

Ethers are promising electrolyte solvents for secondary Li metal batteries because of their excellent reduction stability.However,their oxidation stability has been mostly relying on the high concentration approach,and limited progress has been made on building effective interphase to protect the cathode from the corrosion of the electrolyte.In this work,we construct a semi-crystalline interfacial layer on the surface of Li(Ni_(0.8)Co_(0.1)Mn_(0.1))O_(2)cathode that can achieve improved electrochemical stability in the highly corrosive chemical environment formed by the decomposition of ether molecules.Different from traditional brittle crystalline interphases,the optimized semi-crystalline layer with low modulus and high ionic conductivity can effectively relieve electrode strain and maintain the integrity of the interface layer.Due to this design,the continuous oxidation decomposition of ether-based electrolytes could be significantly suppressed and the battery shows outstanding cycling stability(84%capacity retention after 300 cycles).This article provides a solution to address the oxidation instability issue of ether-based electrolytes.

Li^(+)-ion bound crown ether functionalization enables dual promotion of dynamics and thermodynamics for ambient ammonia synthesis

Electrosynthesis of ammonia from the reduction of nitrogen is still confronted with the limited supply of gas reactant in dynamics as well as high activation barrier in thermodynamics.Unfortunately,despite tremendous efforts devoted to electrocatalysts themselves,they still fail to tackle the above two challenges simultaneously.Herein,we employ a heterogeneous catalyst adlayer-composed of crown ethers associated with Li^(+)ions-to achieve the dual promotion of dynamics and thermodynamics for ambient ammonia synthesis.Dynamically,the bound Li^(+)ions interact with the strong quadrupole moment of nitrogen,and trigger considerable reactant flux toward the catalyst.Thermodynamically,Li^(+)associated with the oxygen of crown ether achieves a higher density of states at the Fermi level for the catalyst,enabling effortless electron transfer from the catalysts to nitrogen and thus greatly reducing the activation barrier.As expected,the proof-of-concept system achieves an ammonia yield rate of 168.5μg h^(-1)mg^(-1)and a Faradaic efficiency of 75.3%at-0.3 V vs.RHE.This system-level approach opens up pathways for tackling the two key challenges that have limited the field of ammonia synthesis.

Functional zirconium phosphate nanosheets enabled transfer hydrogenolysis of aromatic ether bonds over a low usage of Ru nanocatalysts

Catalytic hydrogenolysis of aromatic ether bonds is a highly promising strategy for upgrading lignin into small-molecule chemicals,which relies on developing innovative heterogeneous catalysts with high activity.Herein,we designed porous zirconium phosphate nanosheet-supported Ru nanocatalysts(Ru/ZrPsheet)as the heterogeneous catalyst by a process combining ball milling and molten-salt(KNO_(3)).Very interestingly,the fabricated Ru/ZrPsheetshowed good catalytic performance on the transfer hydrogenolysis of various types of aromatic ether bonds contained in lignin,i.e.,4-O-5,a-O-4,β-O-4,and aryl-O-CH3,over a low Ru usage(<0.5 mol%)without using any acidic/basic additive.Detailed investigations indicated that the properties of Ru and the support were indispensable.The excellent activity of Ru/ZZrPsheetoriginated from the strong acidity and basicity of ZrPsheetand the higher electron density of metallic Ru0as well as the nanosheet structure of ZrPsheet.

Density Functional Theory Study of Marine Polybrominated Diphenyl Ethers in Anaerobic Degradation

Polybrominated diphenyl ethers(PBDEs)are a kind of serious pollutants in the ocean.Biodegradation is considered as an economical and safe way for PBDEs removal and reductive debromination dominates the initial pathway of anaerobic degradation.On the basis of experimental study,Octa-BDE 197,Hepta-BDE 183,Hexa-BDE 153,Penta-BDE 99 and Tetra-BDE 47 were selected as the initial degradation objects,and their debromination degradation were studied using density functional theory.The structures were optimized by Gaussian 09 program.Furthermore,the molecular orbitals and charge distribution were analyzed.All C-Br bond dissociation energies at different positions including ortho,meta and para bromine atoms were calculated and the sequence of debromination was obtained.There is a close relationship between molecular structure,charge,molecular orbital and C-Br bond.All PBDEs exhibited similar debromination pathways with preferential removal of meta and para bromines.