查看更多>>摘要：Recently,the continuous tube-in-tube reactor based on the Teflon AF membrane is emerging as a powerful toolkit for accelerating gas-liquid mass transfer and reaction rate.Because of its large gas-liquid interfacial area and short mass transfer distance,the reactor can allow a fast gas-liquid mass transfer without direct contact between gas and liquid phases,offering an efficient and safe platform for implementing gas-liquid reaction and rapid determination of gas-liquid parameters.In this review,a detailed description and construction method of this reactor are pro-vided.Then,the recent advancements of the tube-in-tube reactor in fundamental studies and practical applica-tions in gas-involved chemical reactions and biosynthetic processes are discussed.Finally,a perspective on future potential applications of such flow reactors is provided.
查看更多>>摘要：Researchers prefer mild aqueous static zinc-ion batteries(ASZIBs)for their distinct benefits of excellent safety,abundant zinc resources,low cost,and high energy density.However,at the moment there are some issues with the cathode materials of mild ASZIBs,including dissolution,by-products,poor conductivity,and a contentious energy storage system.Consequently,there are numerous difficulties in the development of high-performance mild ASZIBs cathode materials.This overview examines the mechanisms for storing energy and the de-velopments in inorganic,organic,and other novel cathode materials that have emerged in recent years.At the same time,three solutions—structural engineering,interface engineering,and reaction pathway engineering—as well as the difficulties now faced by the cathode materials of mild ASZIBs are forcefully introduced.Finally,a prospect is made regarding the evolution of cathode materials in the future.
查看更多>>摘要：The coupling reaction of carbon dioxide(CO2)and epoxides is one of the most efficient pathways to achieve the carbon balance.However,to accomplish it under the mild conditions,especially under the atmospheric pressure,is still a perplexing problem.Three novel ionic liquids(ILs),[DMAPBrPC][TMGH],[DMAPBrPC][DBUH],and[DMAPBrPC][BTMA],are designed and synthesized.All of them display the excellent catalytic activity for the title reaction achieving the yield over 96.6％under the atmospheric CO2 pressure at 60 ℃.Interestingly,[DMAPBrPC][BTMA]with the inert hydrogen atom in cation exhibits the superior catalytic activity as compared to other two ILs with the protic hydrogen atom in cation along with the same anion.The active hydrogen atom in[DMAPBrPC][TMGH]and[DMAPBrPC][DBUH]would impede the-COO-group to absorb CO2,which is an unfavorable item for the reaction.Moreover,the strong hydrogen bond in[DMAPBrPC][TMGH]and[DMAPBrPC][DBUH]would lessen the nucleophilic ability of Br-anion resulting in the inferior catalytic performance,which is further confirmed by the density functional theory(DFT)calculations.The cation without the active hydrogen atom could also be employed to design the ILs with the excellent catalytic feature when it is combined with the suitable anion.
查看更多>>摘要：Lignin utilization is a potential approach for replacing fossil energy and releasing the environment pressure.Herein,we synthesized a series of novel Cu-based catalysts,Cu@NS-SiO2(NS=nano sphere)and alkali metals(Na,K,Rb,and Cs)doped Cu@NS-SiO2,and applied them in hydrodeoxygenation reaction of anisole.High Cu dispersion was presented on all catalysts.The modification of alkali metals on Cu@NS-SiO2 significantly enhanced the electron density of Cu sites in the following order:Cs＞Rb＞K＞Na,among which Cs decreased the Cu 2p3/2 binding energy most(by 0.7 eV).Moreover,the modification did not substantially affect the geometric structure of Cu species.This regulable electronic environment of Cu sites was crucial for selective deoxygenation and inhibiting the hydrogenation of aromatic rings in anisole,and thus promoted the selectivity of benzene.Compared with Cu@NS-SiO2(～59％),the highest benzene selectivity was obtained on Cs/10Cu@NS-SiO2 at～83％.
查看更多>>摘要：Dissolution of lithium cobalt oxide(LCO)is the key step for the recovery of valuable metals(e.g.,Co and Li)from spent LCO-based lithium-ion batteries(LIBs).However,the dissolution process of LCO either needs toxic solvents,and high temperature,or shows low efficiency.Deep eutectic solvents(DESs)are potential green solvents to dissolve LCO.Here,DESs with polyethylene glycol(PEG)as hydrogen bond acceptor and ascorbic acid(AA)as hydrogen bond donor are found to dissolve LCO with 84.2％Co leaching efficiency at 80 ℃ and 72 h,which is higher than that from the reported references by common DESs.Furthermore,both DESs components(i-e.,PEG and AA)are cheap,biodegradable,and biocompatible.AA could be easily and abundantly extracted from natural fruits or vegetables.It provides a new guide for the green,mild,and efficient dissolution of LCO aiming at sus-tainable recovery of spent LIBs.
查看更多>>摘要：Benzene(BEN)and cyclohexane(CYH),which have very close boiling points and a binary azeotrope,are the most difficult binary components in the separation of aromatic and non-aromatic hydrocarbons.This study further explored the separation mechanism and industrial application prospects of BEN+CYH mixtures separated by a dicationic ionic liquid(DIL)[C5(MIM)2][NTf2]2 based on experimental research.The calculation results of the Conductor-like Screening model Segment Activity Coefficient(COSMO-SAC)model show that selectivity and solvent capacity of the DIL are significantly improved.The effects of different anions and cations on the micro-structure distribution and diffusion behavior of BEN+CYH system were investigated by quantum chemistry(QC)calculations and molecular dynamics(MD)simulations.The results indicate that the anion[NTf2]-has low polarity,uniform charge distribution,and a dual role of hydrogen bonding and π-π bonding,and the cation[Cs(MIM)2]2+has stronger interaction with BEN and higher selectivity than conventional cations.The liquid-liquid extraction and extractive distillation(LLE-ED)process using an optimized 65 mol/mol DIL+35 mol/mol H2O mixed solution as the extractant was proposed,which solved the problem of low product purity in the LLE process and high energy consumption in the ED process.Under the best operating conditions,the purity of CYH product was 99.9％,the purity of BEN product was 99.6％,the recovery rate of BEN reached 99.9％,and the recovery rate of DIL reached 99.9％.The heat-integrated LLE-ED process reduced total annual cost by 21.6％,and reduced CO2 emissions by 48.0％,which has broad industrial application prospects.
查看更多>>摘要：Image guided photodynamic therapy(PDT)combines fluorescence tracing and phototherapy,which can achieve a more accurate and effective treatment effect.However,traditional photosensitizers are limited by the aggregation-caused fluorescence quenching(ACQ)effect and low reactive oxygen species(ROS)generation in a hypoxic environment,resulting in poor imaging and treatment effect.Herein,we report a tricyano-methylene-pyridine(TCM)-based Type Ⅰ aggregation-induced emission(AIE)photosensitizer(TCM-MBP),the strong elec-tron acceptance(D-A)effect extends the wavelength to near-infrared(NIR)region to reduce the autofluorescence interference,and oxygen atoms provide lone pair electrons to enhance the inter system crossing(ISC)rate,thereby promoting the generation of more triplet states to produce ROS.The AIE photosensitizer TCM-MBP exhibited low oxygen dependence,NIR emission,and higher ROS production compared to commercially avail-able Ce 6 and RB.After encapsulation with DSPE-PEG2000,TCM-MBP nanoparticles(TCM-MBP NPs)could penetrate to visualize cells and efficiently kill cancer cells upon light irradiation.This study provides an oxygen-independent AIE photosensitizer,which has great potential to replace the commercial ACQ photosensitizers.
查看更多>>摘要：Electrochemical CO2 reduction driven by renewable electricity is one of the promising strategies to store sus-tainable energy as fuels.However,the selectivity of value-added multi-carbon products remains poor for further application of this process.Here,we regulate CO adsorption by forming a Nafion layer on the copper(Cu)electrode that is repulsive to OH-,contributing to enhanced selectivity of CO2 reduction to C2+products with the suppression of C1 products.The operando Raman spectroscopy indicates that the local OH-would adsorb on part of active sites and decrease the adsorption of CO.Therefore,the electrode with repulsive to OH-can adjust the concentration of OH-,leading to the increased adsorption of CO and enhanced C-C coupling.This work shows that electrode design could be an effective strategy for improving the selectivity of CO2 reduction to multi-carbon products.
查看更多>>摘要：Benzene alkylation catalyzed by immobilized ionic liquids(ILs)on solid carriers is considered as a heterogeneous reaction,in which the interfacial properties play an important role.Hence,the interfacial characteristics between benzene/1-dodecene mixture and immobilized chloroaluminate ILs with different alkyl chain length on the silica substrate were investigated by molecular dynamics simulation.The grafted ILs can obviously promote the enrichment of benzene near the interface,leading to a higher ratio of benzene to dodecene,and the interfacial width increases slightly with increased alkyl chain of grafted cations.At the same time,the grafted cations can also enhance the benzene diffusion and suppress the dodecene diffusion at the interface,which probably helps to inhibit the inactivation of catalysts.This work provides deeply insights into the rational design of novel immo-bilized ILs catalysts for the benzene alkylation.
查看更多>>摘要：A new ultra-long chain monounsaturated 4-(N-nervonicamidopropyl-N,N-dimethylammonium)butane sulfonate(NDAS)zwitterionic surfactant with ultralow interfacial tensions was developed through the modification of nervonic acid derived from renewable non-edible seed oils by a simple and effective method.Its structure was characterized by ESI-HRMS,1H NMR,and 13C NMR.NDAS surfactant exhibited a strong interfacial activity(～10-4 mN/m)between the crude oil and the formation brine at a very low surfactant dosage(0.05 g/L)and at high salinity conditions,which is equivalent to 2％(w/w)of dosage of the most traditional surfactants used in the enhanced oil recovery field.Meanwhile,at a very low concentration(0.05 g/L),NDAS demonstrated strong NaCl compatibility up to 100 g/L,Ca2+ions compatibility up to 200 mg/L,and temperature stability up to 90 ℃.The surface tension,emulsification,and biodegradability parameters were also evaluated.This work consolidates our hypothesis that increasing the hydrophobic chain length of a surfactant certainly contributes to the high inter-facial activity and good compatibility of salts and temperatures.Hence,it will facilitate the design of a sustainable alternative to petroleum-based chemicals to develop bio-based surfactants and extend the domain of bio-based surfactants to new applications such as in enhanced oil recovery(EOR).
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