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.

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.

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.

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.

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.

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].

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.

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.

Concentrated ternary ether electrolyte allows for stable cycling of a lithium metal battery with commercial mass loading high-nickel NMC and thin anodes

A new concentrated ternary salt ether-based electrolyte enables stable cycling of lithium metal battery(LMB)cells with high-mass-loading(13.8 mg cm^(−2),2.5 mAh cm^(−2))NMC622(LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2))cathodes and 50μm Li anodes.Termed“CETHER-3,”this electrolyte is based on LiTFSI,LiDFOB,and LiBF4 with 5 vol%fluorinated ethylene carbonate in 1,2-dimethoxyethane.Commer-cial carbonate and state-of-the-art binary salt ether electrolytes were also tested as baselines.With CETHER-3,the electrochemical performance of the full-cell battery is among the most favorably reported in terms of high-voltage cycling stability.For example,LiNi_(x)Mn_(y)Co_(1-x-y)O_(2)(NMC)-Li metal cells retain 80%capacity at 430 cycles with a 4.4 V cut-off and 83%capacity at 100 cycles with a 4.5 V cut-off(charge at C/5,discharge at C/2).According to simulation by density functional theory and molecular dynamics,this favorable performance is an outcome of enhanced coordination between Li^(+)and the solvent/salt molecules.Combining advanced microscopy(high-resolution transmission electron microscopy,scanning electron microscopy)and surface science(X-ray photoelectron spectroscopy,time-of-fight secondary ion mass spectroscopy,Fourier-transform infrared spectroscopy,Raman spectroscopy),it is demonstrated that a thinner and more stable cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)are formed.The CEI is rich in lithium sulfide(Li_(2)SO_(3)),while the SEI is rich in Li_(3)N and LiF.During cycling,the CEI/SEI suppresses both the deleterious transformation of the cathode R-3m layered near-surface structure into disordered rock salt and the growth of lithium metal dendrites.

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.

2,4-Dinitrophenyl Ether of Polyvinyl Alcohol and Polymer Bound Anionic SIGMA Complexes

A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP polymer was characterized by NMR, IR, and UV-visible spectroscopy. The reaction of PVA-DNP with sodium methoxide was followed by NMR and UV-visible spectroscopy. Evidence of polymer bound spirocyclic SIGMA complex, C-1 and C-3 polymer bound DNP-methoxy SIGMA complexes and the formation and C-1 methoxy complex of 2,4-dinitroanisole was observed.

Ether as the Fundamental Substance of the Creation of the Universe

The paper analyzes the concept of Ether and substantiates the necessity of its existence as a physical reality, which arises within the framework of the concept developed by the authors of the work. The authors come to the conclusion that the existence of Ether in two different forms, plays an exceptional role in the formation of Dark Matter and Dark Energy and leads to the emergence of exotic cosmological structures and their hierarchy in energy, temporal, and spatial scale. The mechanism of the formation of physical structures before the Big Bang and their further evolution, up to the formation of worlds of galaxies and stars, is considered. The necessity of the emergence of exotic structures, such as 3 spheres of the Primary Relict, is shown, its structure and dynamic properties leading to the formation of Order from Chaos are considered. The role of the 1st and 2nd type Ether in the formation of the mechanism of transformation of cosmic energies and quantum phase transitions, in the process of the birth and evolution of the Universe is discussed. The conclusion is made about the existence of universal properties of matter, at the level of Macro and Microcosms, and a multidimensional cosmological model with an isothermal temperature distribution is constructed, leading to a discrete distribution of matter separated by transitions, by analogy with Black-and-White Holes. It is shown that the postulate of the constancy of the speed of light in any inertial system is a consequence of the principle of covariance.

The Quantum Chromodynamics Gas Density Drop and the General Theory of Relativity Ether

β decay is one of the most fundamental and thoroughly studied nuclear decay. Surprisingly, the β decay rates were found to have a periodic time variability [1]. However, others argued that there is no evidence for such cyclic deviation from the exponential first order kinetics decay law [2]. Here we propose that the β decay is a pseudo-first order exchange reaction triggered by udd&utilde;exotic mesons and propose a QCD gas theory. In analogy to the atmospheric gas density, the proposed QCD gas density drops with elevation from the sun. Accordingly, we propose that the β decay rate periodic variability is due to the pseudo-first order exchange reaction kinetics and the QCD gas atmospheric density drop. The proposed QCD gas may be a possible candidate for Einstein’s general theory of relativity ether [3]. Our main results are the derived formulas for calculating the effective mass of the QCD gas and the cosmology perfect fluid equation of state dimensionless parameter, based on the measured ratio of the β decay rates at the earth trajectory aphelion and perihelion dates. .

ABPBI/SPEEK高温质子交换复合膜的制备与表征

采用溶剂蒸发法制备聚(2,5-苯并咪唑)/磺化聚醚醚酮(ABPBI/SPEEK)高温质子交换复合膜。考察了SPEEK的掺入对ABPBI/SPEEK质子交换复合膜的结构及性能的影响。结果表明,ABPBI膜和ABPBI/SPEEK复合膜在高温下的热稳定性能良好;随着SPEEK的掺入,ABPBI/SPEEK复合膜有更好的氧化稳定性和机械性能,ABPBI/SPEEK(20%)复合膜在芬顿试剂中96 h后的质量损失为0.84%,其拉伸强度为120.51 MPa,相较于Nafion 117膜明显提高;ABPBI/SPEEK(20%)复合膜的酸掺杂率为186.68%,该膜在160℃、0%RH时的质子电导率为3.4 mS/cm,约为ABPBI膜的1.78倍。

HFBAPP/6FDA/BPADA含氟苯醚型聚酰亚胺薄膜的制备与性能研究

以2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(HFBAPP)为二胺单体,2,2′-双(3,4-二羧酸)六氟丙烷二酐(6FDA)和双酚A型二醚二酐(BPADA)为二酐单体制备了一系列HFBAPP/6FDA/BPADA含氟苯醚型PI薄膜。通过改变二酐单体比例,分析比较醚键与三氟甲基对PI薄膜综合性能的影响。结果表明:随着三氟甲基含量的升高和醚键含量的降低,HFBAPP/6FDA/BPADA含氟苯醚型PI薄膜的光学性能和热学性能提高,而力学性能下降,玻璃化转变温度最高可达247.3℃,800℃时的残炭率最高可达56.3%,可见光范围内的透光率最高可达88.2%,拉伸强度最高可达84.7 MPa。

蒸压轻质混凝土板专用粘结砂浆的制备与性能研究

采用P·O42.5水泥、粉煤灰、石灰石超细粉、矿粉以及外加剂为原料制备水泥基粘结砂浆。采用正交试验确定水泥基胶凝材料的最优配合比,研究淀粉醚对纤维素醚取代率和膨胀剂对水泥基粘结砂浆的性能影响,并利用XRD和SEM分析水化产物和微观形貌,研究外加剂的作用机理。结果表明,m(水泥)∶m(粉煤灰)∶m(矿粉)∶m(石灰石超细粉)=22∶4∶4∶5时,水泥基胶凝材料的性能最优;淀粉醚适量取代纤维素醚可以增强砂浆保水性,提高砂浆强度,减少收缩;少量膨胀剂可以提高砂浆的早期强度,增加掺量则降低早期强度,提高砂浆后期强度。制备的水泥基粘结砂浆符合JC/T 890—2017《蒸压加气混凝土墙体专用砂浆》的要求。

热休克蛋白90对hERG-A561V通道蛋白转运及通道功能影响的研究

目的探讨热休克蛋白90(Hsp90)对人类ether-a-go-go相关基因(hERG)-A561V通道蛋白转运及通道功能影响的研究。方法构建野生型(WT)、突变型(A561V)、杂合型(WT/A561V)细胞模型,采用蛋白质印迹法检测各组细胞hERG及Hsp90蛋白表达差异。转染减表达空载(Itf NC)、Hsp90减表达(Hsp90-)、过表达空载(Ovp NC)或Hsp90过表达(Hsp90+)质粒至各细胞模型(即Itf NC组、Hsp90-组、Ovp NC组、Hsp90+组),另设不加载体的对照(Ctl)组,采用蛋白质印迹法检测各组细胞调控Hsp90前后hERG及Hsp90蛋白表达差异。采用免疫荧光法检测Hsp90调控前后杂合型细胞模型hERG及Hsp90蛋白定位表达情况。采用全细胞膜片钳技术检测调控Hsp90前后杂合型细胞模型hERG通道激活电流及尾电流密度。结果突变型、杂合型细胞模型Hsp90及hERG(135 kDa)蛋白表达水平均较野生型明显升高(均P<0.05)。野生型细胞模型Hsp90+组hERG(135 kDa)、hERG(155 kDa)蛋白表达水平较Ctl组、Ovp NC组均明显升高(均P<0.05),突变型细胞模型Hsp90+组hERG(135 kDa)蛋白表达水平较Ctl组、Ovp NC组均明显升高(均P<0.05),杂合型细胞模型Hsp90+组hERG(155 kDa)蛋白表达水平较Ctl组、Ovp NC组均明显升高(均P<0.05)。融合Hsp90和hERG蛋白后,Ctl组hERG表达于细胞膜、细胞质,Hsp90-组细胞膜上hERG蛋白表达减少,Hsp90+组细胞膜上hERG蛋白表达增多。与Ctl组比较,Hsp90+组Ikr曲线左移14.709,斜率因子k值未见明显变化。杂合型细胞模型Ctl组、Hsp90-组、Hsp90+组激活电流及尾电流密度均在50 mV处达到最高;杂合型细胞模型Hsp90+组在20、30 mV处的激活电流密度均明显高于Ctl组、Hsp90-组(均P<0.05),在30、40 mV处的尾电流密度均明显高于Ctl组、Hsp90-组(均P<0.05)。结论Hsp90在hERG-A561V通道蛋白折叠转运中起作用,而上调Hsp90可促进WT/A561V hERG的折叠转运,进而影响通道功能。

甲基双酚类单体共聚-溴化-羧化法制备羧基化聚醚醚酮

针对2,5-二羟基甲苯、对苯二酚和4,4’-二氟二苯甲酮共聚反应进行研究。结果表明,随着固含量、反应温度以及碱金属碳酸盐中碳酸钾比例的增加,产物含甲基的聚醚醚酮(PEEK-CH_(3))的分子量分布先降低后增加,其最佳反应条件:固含量为25%,缩聚温度为200℃,碱金属碳酸盐与双酚单体物质的量比为1.05:1,碱金属碳酸盐中碳酸钠与碳酸钾的物质的量比为19:1,反应时间为3.5 h。PEEK-CH_(3)溴化反应中二溴取代产物(PEEK-CHBr_(2))最为重要,在液溴用量为—CH_(3)摩尔当量的20倍、反应温度为160℃、365 nm长波紫外线光照下反应2 h后,PEEK-CHBr_(2)占比达到95.8%。最后,通过次氯酸钠氧化PEEK-CHBr_(2),成功制备了数均分子量为4.6×10^(4)、特性黏度为1.5 dL/g的羧基化聚醚醚酮,其水接触角从未改性的PEEK的133.9°降至29.9°。

氯自由基介导的光催化芳基醚C(sp^(3))−H氧化生成酯

饱和的碳氢键氧化是合成化学和化学工业中一类重要的化学反应.然而,饱和C(sp^(3))−H键离解能(BDEs)较高、极性较弱,导致了底物难以活化和催化转化效率较低等问题.在过去的几十年,C(sp^(3))−H键的定向活化转化取得了重要的进展.其中,关于C(sp^(3))−H键催化氧化的研究主要涉及一些键能低的、预活化的C−H键,包括苄基型、亚甲基型、脂肪族X−CH_(2)(X=O,N)和甲苯等,含有未活化C(sp^(3))−H键的复杂化合物的选择性氧化仍具有挑战性.例如,芳基醚C(sp^(3))−H键功能化通常采用计量的过氧化物氧化剂,或者通过单电子氧化和碱促进的去质子化进一步构建C−C/C−N键,产物选择性较低,也带来了一些不利的环境影响.因此,有必要开发高效、温和的芳基醚C(sp^(3))−H键选择氧化方法,并将其应用于有机合成和药物开发.近年来,光催化C(sp^(3))−H键氧化因其操作简便、氧化还原中性等优点,已发展成为一种有用且多样的催化研究工具.本文发展了一种利用氧气作为氧化剂,在可见光驱动下选择性地将芳基醚C(sp^(3))−H键氧化成为甲酸苯酯类产物的新方法.使用Mes-10-phenyl-Acr^(+)−BF_(4)^(-)光催化剂,高效活化多种氯源(如盐酸、无机氯盐和有机氯化物)得到氯自由基,由于其具有较高的氧化能力(+2.03 V vs.SCE)和对氢原子的亲和力,能够通过氢原子转移过程活化芳基醚C(sp^(3))−键,攫取氢自由基得到相应的烷基碳自由基(•CH_(2)OPh)中间体,进一步被分子氧选择氧化得到酯类目标产物.研究结果表明,多种链状芳基醚和不同取代(如给电子基和吸电子基)芳基醚均可发生氧化反应,高收率地合成了一系列官能团丰富的甲酸苯酯类化合物.本文方法具有反应条件温和、操作简单、官能团耐受性好以及可规模化放大等优点,并且少量的水对反应没有明显影响.机理实验研究结果表明,芳基醚C(sp^(3))−H键的断裂是反应过程的决速步骤.紫外可见吸收光谱结果表明,氯离子与催化剂之间的相互作用强于底物,并且自由基捕获实验证实反应体系中存在氯自由基和烷基碳自由基物种,表明反应经历自由基路径.此外,电子顺磁共振测试结果表明,反应过程中存在单线态氧物种,可能是激发态的光催化剂直接与氧气发生能量转移得到;同位素实验(18O)揭示了甲酸苯酯类化合物氧的来源.综上,本文实现了温和条件下光催化芳基醚C(sp^(3))−H键选择氧化反应,高收率合成了一系列甲酸苯酯类化合物.该方法避免了化学计量的过氧化物和碱等添加剂的使用以及底物的过度氧化,阐明了催化反应机制,为其他醚类化合物的C(sp^(3))−H键氧化功能化提供了新思路,为后续化学合成和药物开发提供了参考和启示.