A new type of rubidium ion-imprinted polymer has been synthesized by the surface-imprinting technique using methacrylic acid as the functional monomer,the rubidium ion as the template,methanol as the solvent,and silic...A new type of rubidium ion-imprinted polymer has been synthesized by the surface-imprinting technique using methacrylic acid as the functional monomer,the rubidium ion as the template,methanol as the solvent,and silica as a carrier.Ethylene glycol dimethacrylate and 2,2-azobisisobutyronitrile were used as acrosslinker and an initiator,respectively.In addition,based on the macrocyclic effect of crown ethers,the 18-crown-6 ligand was introduced as a ligand to fix the template ions better.Scanning electron microscopy,zeta-potential analysis,Fourier transform infrared spectroscopy,thermogravimetric analysis,and X-ray photoelectron spectroscopy were performed to characterize the ion-imprinted polymer.The effects of the preparation and adsorption conditions on the adsorption performance of the rubidium ion-imprinted polymer were investigated.The results indicated that the rubidium ion-imprinted polymer has high selectivity and faster kinetics than other adsorbents,with an equilibrium adsorption capacity of 200.19 mg·g^(-1)at 298 K within 25 min.The sorption isotherm was well described by the Freundlich isotherm model,while the adsorption kinetics fitted the pseudo-second-order kinetic model.Consecutive adsorption-desorption experiments showed that the ion-imprinted polymer had good chemical stability and reusability.展开更多
Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or a...Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.展开更多
Ozone(O_(3)) generated by a dielectric barrier discharge(DBD) is widely used in various industrial processes. In this study, NaCl aqueous solution was used as a novel electric power transmission electrode in a DBD rea...Ozone(O_(3)) generated by a dielectric barrier discharge(DBD) is widely used in various industrial processes. In this study, NaCl aqueous solution was used as a novel electric power transmission electrode in a DBD reactor(instead of a traditional metal electrode) for highly efficient ozone generation. The results demonstrated that a high O_(3) yield of 242 g k Wh^(-1) with a concentration of 14.6 g m^(-3)O_(3) was achieved. The power transmission mechanism works because NaCl aqueous solution behaves as a capacitor when an alternating pulse voltage below 8 k Hz is used.Compared with the resistance of the discharge barrier and discharge space, the resistance of NaCl aqueous solution can be ignored, which ensures that O_(3) is generated efficiently. It is expected that O_(3) generation using NaCl aqueous solution as a novel electrode in a DBD reactor could be an alternative technology with good application prospects.展开更多
1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combi...1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combining 25 cations and 8 anions,in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model.The extraction mechanism was investigated with the help ofσ-profile and interaction energy analyses.Both the cation and anion have impacts on the extraction efficiency,where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL.The IL composed of long alkyl-chain in cation and the anion of[PF6]-or[TF2 N]-,which has theσ-profile more likely distributed in the nonpolar region but less distributed in the polar region,is favorable for extraction.The experimental liquid-liquid equilibrium demonstrated the effects of cation and anion on extraction performance,which validated the reliability of COSMO-RS model in IL screening for PDA extraction.The IL[IM-1,8][PF6]could serve as a promising extractant for the downstream separation process of the biological production of PDA.展开更多
Kinetic processes of α naphthaleneacetic acid (NAA) photolysis were studied under different conditions. The results showed that the ultraviolet light was more effective than fluorescent light in promoting degradation...Kinetic processes of α naphthaleneacetic acid (NAA) photolysis were studied under different conditions. The results showed that the ultraviolet light was more effective than fluorescent light in promoting degradation, and the degradation of NAA under ultraviolet light followed the first order kinetics with the photolysis rate constant of 1 15×10 -2 min -1 and half life time (t 1/2 ) of 60 min. Further, it was proved that the photolysis rate was higher in the presence of oxygen, titanium dioxide (TiO 2), and low pH (acidic solution). At last, two photolysis intermediates were identified by GC MS and possible photolysis pathways were proposed.展开更多
Coal fly ash(CFA)is composed of minerals containing some oxides in crystalline phase(i.e.,quartz and mullite),as well as unburned carbon as mesoporous material,thus enabling CFA to act as a dual-sites adsorbent with u...Coal fly ash(CFA)is composed of minerals containing some oxides in crystalline phase(i.e.,quartz and mullite),as well as unburned carbon as mesoporous material,thus enabling CFA to act as a dual-sites adsorbent with unique properties.This work focused on the adsorption of Pb(Ⅱ)and Zn(Ⅱ)from binary system,a mixture containing two metal ion solutions present simultaneously,onto NaOH-modified CFA(MCFA).Several adsorption tests were conducted to evaluate the effect of several parameters,including pH and contact times.The experiment results indicated that chemical treatment of CFA with NaOH increased pore volume from 0.021 to 0.223 cm^3·g^(-1).In addition,it could also enhance the availability of functional groups on both minerals and unburned carbon,resulting in almost 100%Pb(Ⅱ)and 97%Zn(Ⅱ)adsorbed.The optimum pH for adsorption system was pH=3 and quasi-equilibrium occurred in 240 minutes.Equilibrium data from the experimental results were analyzed using Modified Extended Langmuir(MEL)and Competitive Adsorption Langmuir-Langmuir(CALL)isotherm models.The analysis results showed that the CALL isotherm model could better describe the Pb(Ⅱ)and Zn(Ⅱ)adsorption process onto MCFA in binary system compared with MEL isotherm model.展开更多
Chemical effects in different aqueous solutions induced by plasma with glow discharge electrolysis (GDE) and contact glow discharge electrolysis (CGDE) are described in this paper. The experimental and discharge chara...Chemical effects in different aqueous solutions induced by plasma with glow discharge electrolysis (GDE) and contact glow discharge electrolysis (CGDE) are described in this paper. The experimental and discharge characteristics are also reviewed. These are followed by a discussion of their mechanisms of both anodic and cathodic CGDE..展开更多
Degradation of α-naphthol induced by plasma in aqueous solution was investigated in different initial concentration with contact glow discharge electrolysis(CGDE). The results showed that the degradation of α-naphth...Degradation of α-naphthol induced by plasma in aqueous solution was investigated in different initial concentration with contact glow discharge electrolysis(CGDE). The results showed that the degradation of α-naphthol obeyed the first-rate law. Some of predominant products were analyzed by a high performance liquid chromatography (HPLC). A path of α-naphthol disappearance caused by plasma was proposed according to the detected intermediate products.展开更多
The objective of this work is to contribute an understanding of the effects of electrons in the plasmas on the mass transfer of plasma species in aqueous solution by means of the numerical simulation based on a one-di...The objective of this work is to contribute an understanding of the effects of electrons in the plasmas on the mass transfer of plasma species in aqueous solution by means of the numerical simulation based on a one-dimensional diffusion-reaction model.The plasma species are divided into two groups,i.e.electrons and the other species,and the mass transfer in the three scenarios has been simulated,including the systematic calculations of the depth distributions of five major reactive species,OH,O3,HO2,O2^-,and H2O2.In the three scenarios,the particles considered to enter into aqueous solution are all the plasma species(the scenario Ⅰ,where the mass transfer of plasma species is a result due to the synergy of the electrons and the other plasma species),the other species(the scenario Ⅱ),and only electrons in plasma species(the scenario Ⅲ),respectively.The detailed analyses on the difference between the depth distributions of each reactive species in these three scenarios show the following conclusions.The electrons play an important role in the mass transfer of plasma species in aqueous solution and the synergy of the electrons and the other plasma species(the electron-species synergy)presents its different effects on the mass transfer.The vast majority of H2O2 are generated from a series of the electronrelated reactions in aqueous solution,which is hardly affected by the electron-species synergy.Compared to the results when only the electrons enter into the liquid region,the electron-species synergy evidently weakens the generation of O2^-,O3,and OH,but promotes to produce HO2.展开更多
Carbonate-bearing fluids widely exist in different geological settings,and play important roles in transporting some elements such as the rare earth elements.They may be trapped as large or small fluid inclusions(with...Carbonate-bearing fluids widely exist in different geological settings,and play important roles in transporting some elements such as the rare earth elements.They may be trapped as large or small fluid inclusions(with the size down to<1μm sometimes),and record critical physical-chemical signals for the formations of their host minerals.Spectroscopic methods like Raman spectroscopy and infrared spectroscopy have been proposed as effective methods to quantify the carbonate concentrations of these fluid inclusions.Although they have some great technical advantages over the conventional microthermometry method,there are still some technical difficulties to overcome before they can be routinely used to solve relevant geological problems.The typical limitations include their interlaboratory difference and poor performance on micro fluid inclusions.This study prepared standard ion-distilled water and K_(2)CO_(3)aqueous solutions at different molarities(from 0.5 to 5.5 mol/L),measured densities,collected Raman and infrared spectra,and explored correlations between the K_(2)CO_(3)molarity and the spectroscopic features at ambient P-T conditions.The result confirms that the Raman O-H stretching mode can be used as an internal standard to determine the carbonate concentrations despite some significant differences among the correlations,established in different laboratories,between the relative Raman intensity of the C-O symmetric stretching mode and that of the O-H stretching mode.It further reveals that the interlaboratory difference can be readily removed by performing one high-quality calibration experiment,provided that later quantifying analyses are conducted using the same Raman spectrometer with the same analytical conditions.Our infrared absorption data were collected from thin fluid films(thickness less than~2μm)formed by pressing the prepared solutions in a Microcompression Cell with two diamond-II plates.The data show that both the O-H stretching mode and the O-H bending mode can be used as internal standards to determine the carbonate concentrations.Since the IR signals of the C-O antisymmetric stretching vibration of the CO32ion,and the O-H stretching and bending vibrations from our thin films are very strong,their relative IR absorbance intensity,if well calibrated,can be used to investigate the micron-sized carbonate-bearing aqueous fluid inclusions.This study establishes the first calibration of this kind,which may have some applications.Additionally,our spectroscopic data suggest that as the K_(2)CO_(3)concentration increases the aqueous solution forms more large water molecule clusters via more intense hydrogen-bonding.This process may significantly alter the physical and chemical behavior of the fluids.展开更多
Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physic...Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physical properties of the obtained QC derivatives were characterized using nitrogen content analysis,Fourier transform infrared spectroscopy( FT-IR),~1H-nuclear magnetic resonance(1H-NMR),X-ray diffraction( XRD),and thermal gravity analysis( TGA). The FT-IR and ~1H-NMR results confirmed the successful introduction of cationic quaternary ammonium groups into the main chain of cellulose. A series of QC derivatives with the degree of substitution( DS) values ranging from 0. 33 to 0. 80 were derived by adjusting the molar ratio of CHPTAC to anhydroglucose unit( AGU) of cellulose,concentration of cellulose in the Na OH-urea solution,as well as reaction temperature and time. According to the DS values of the QC derivatives,the optimized synthetic conditions were as follows: 25℃ reaction temperature,3% cellulose in Na OH-urea solution,the molar ratio of etherification agent to glycosidic cellulose of 15∶ 1,and 12 h reaction time. The TGA and XRD results revealed that the crystalline structure was destroyed during etherification,and the thermal stability of the QC derivatives was lower than that of cellulose.展开更多
First-row(3 d)transition metal oxyhydroxides have attracted increasing attention due to their various advantages.Although investigating the oxidation mechanism and processing such materials into hierarchical architect...First-row(3 d)transition metal oxyhydroxides have attracted increasing attention due to their various advantages.Although investigating the oxidation mechanism and processing such materials into hierarchical architectures are greatly desired for their further development,it remains unclear how the oxidation state change occurs,and efforts to produce hierarchical oxyhydroxides in compliance with high ecological and economic standards have progressed slowly.Here,we describe a facile one-step coprecipitation route for the preparation of hierarchical CoOOH,NiOOH and MnOOH,which involves the diffusion of NH_(3)originating from ammonium hydroxide solution into an aqueous solution containing metal ion salts and K_(2)S_(2)O_(8).Comprehensive characterizations by scanning electron microscope,transmission electron microscopy,X-ray diffraction analysis,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy and in situ p H measurement demonstrated that K_(2)S_(2)O_(8)induces the oxidation state change of metal ion species after the start of hydrolysis.Meanwhile,it was found that,benefiting from the OH–concentration gradient created by the NH_(3)diffusion method and the suitable growth environment provided by the presence of K_(2)S_(2)O_(8)(high nucleation rate and secondary nucleation),the formation of hierarchical oxyhydroxide structures can be realized in aqueous solution at ambient temperature without the use of heat energy and additional structure-directing agents.The hierarchical CoOOH structures are performed as the electrocatalysts for the oxygen evolution reaction in alkaline media,which exhibit good activity with an overpotential of 320 m V at 10 m A cm^(-2)and a low Tafel slope of 59.6 m V dec^(–1),outperforming many congeneric electrocatalysts.Overall,our study not only provides important insights to understand the formation mechanism of hierarchical oxyhydroxides,but also opens up new opportunities for the preparation of hierarchical oxyhydroxides via a facile,green and low-cost method.展开更多
The quartz crystal microbalance(QCM) is an important tool that can sense nanogram changes in mass. The hybrid temperature effect on a QCM resonator in aqueous solutions leads to unconvincing detection results. Control...The quartz crystal microbalance(QCM) is an important tool that can sense nanogram changes in mass. The hybrid temperature effect on a QCM resonator in aqueous solutions leads to unconvincing detection results. Control of the temperature effect is one of the keys when using the QCM for high precision measurements. Based on the Sauerbrey's and Kanazawa's theories, we proposed a method for enhancing the accuracy of the QCM measurement, which takes into account not only the thermal variations of viscosity and density but also the thermal behavior of the QCM resonator. We presented an improved Sauerbrey equation that can be used to effectively compensate the drift of the QCM resonator. These results will play a significant role when applying the QCM at the room temperature.展开更多
The membranes were prepared by the incorporation of highly hydrophobic silicalite and carbon molecular sieves (CMS) from different precursors into the PDMS casting solutions. The pervaporative removal of VOCs, such as...The membranes were prepared by the incorporation of highly hydrophobic silicalite and carbon molecular sieves (CMS) from different precursors into the PDMS casting solutions. The pervaporative removal of VOCs, such as benzene, from aqueous solutions was carried out using the separation factor and permeation flux as the evaluating parameters. The effects of the CMS types and structures, feed concentrations on the pervaporation performance were preliminarily investigated.展开更多
Hydroxypropyl celluloses(HPC) were homogenously synthesized by the reaction of cellulose with propylene oxide in NaOH/urea aqueous solution.Water-soluble HPC with molar degree of substitution(MSNMR) in the range of 0....Hydroxypropyl celluloses(HPC) were homogenously synthesized by the reaction of cellulose with propylene oxide in NaOH/urea aqueous solution.Water-soluble HPC with molar degree of substitution(MSNMR) in the range of 0.52~0.78 was prepared from microcrystalline cellulose,cotton linters,and spruce sulfite pulp.The structure of the HPC samples was characterized by means of FT-IR,NMR,gas chromatography(GC),and size exclusion chromatography(SEC) analyses.Three types of cellulose samples with different molecular weights were found to dissolve well in the NaOH/urea solvent with no obvious differences in reactivity and regioselectivity.The relative reactivity of hydroxyl groups in the glycosyl unit was in the following order:O-6>O-2>O-3.In addition,the results of the study indicated that the tandem reaction during hydroxypropylation could be ignored.展开更多
Covalent organic framework(COF)nanocrystals are useful in biological applications;however,their hydrophobic nature makes them aggregate into clusters in aqueous media.In this work,we show that by modifying the crystal...Covalent organic framework(COF)nanocrystals are useful in biological applications;however,their hydrophobic nature makes them aggregate into clusters in aqueous media.In this work,we show that by modifying the crystal surface with hydrophilic functional groups,these nanocrystals can maintain in the monodispersed form in aqueous solution.Specifically,three COFs,TPB-DMTP COF,TAPB-PDA COF and TAPB-BPDA COF were synthesized using organic Lewis acid as the catalyst,to generate nanoparticles with the size ranging from 180 nm to 1μm.2-Aminoethanesulfonic acid(AESA)was applied to react with the terminal aldehyde functional groups exposed at the surface of COF nanocrystals.The resulting negatively charged surface keeps these nanocrystals apart from each other in aqueous solution for at least 48 h.The mesopore of these COF nanocrystals allows the entering of single-strand DNA molecules and the release in the presence of complementary DNA.展开更多
Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is...Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is proposed by using molecular dynamics simulation,and the relationship between ion-to-ion interaction and salt solubility in a simulated seawater water-salt system is investigated.By analyzing the variation of distance and contact time between ions in an electrolyte solution,from both spatial and temporal perspectives,new parameters were proposed to describe the interaction between ions:interaction distance(ID),and interaction time ratio(ITR).The best correlation between characteristic time ratio and solubility was found for a molar ratio of salt-to-water of 10:100 with a correlation coefficient of 0.96.For the same salt,a positive correlation was found between CTR and the molar ratio of salt and water.For type 1-1,type 2-1,type 1-2,and type 2-2 salts,the correlation coefficients between CTR and solubility were 0.93,0.96,0.92,and 0.98 for a salt-to-water molar ratio of 10:100,respectively.The solubility of multiple salts was predicted by simulations and compared with experimental values,yielding an average relative deviation of 12.4%.The new ion-interaction parameters offer significant advantages in describing strongly correlated and strongly hydrated electrolyte solutions.展开更多
The behavior of room temperature phosphorescence quenching and fluorescence enhancing of gadolinium labeled sinoporphyrin sodium(Gd-DVDMS) in the aqueous solution were studied.Gd-DVDMS was characterized by various tec...The behavior of room temperature phosphorescence quenching and fluorescence enhancing of gadolinium labeled sinoporphyrin sodium(Gd-DVDMS) in the aqueous solution were studied.Gd-DVDMS was characterized by various techniques including mass spectra,Fourier transform infrared spectra and transmission electron microscopy.The optical behavior was monitored through UV-vis absorption spectra and photoluminescence spectra.The result shows that the phosphorescence intensity gradually quenches,almost disappears after dissolved 120 min,meanwhile the fluorescence intensity enhances 5 times.The above behavior is attributed to the decreased population of Gd-DVDMS as first excited triplet state(T1),Based on the time-invariant of both absorption spectra and phosphorescence decay curves at710 nm of Gd-DVDMS in different dissolution time,the reason for the decreased population of GdDVDMS in T1 state is that the intersystem crossing from first excited state(S1) to T1 is prevented.In addition,the fluorescent decay curves of Gd-DVDMS initially dissolved in the aqueous solution and dissolved for 120 min were also measured for comparison.The big change in fluorescent lifetime further proves the conclusion that intersystem crossing is prevented,meanwhile,the increase in fluorescence intensity is demonstrated.In this work,the possibility of decomposition of Gd-DVDMS is excluded because the phosphorescence decay curve in Gd-DVDMS aqueous solution is sensible to DVDMS.展开更多
A process for extraction of artemisinin(Ars)from Artemisia annua L.based on aqueous solution of cyclodextrin derivative under ultrasonic irradiation was proposed.Among the test additives,the system containing edible h...A process for extraction of artemisinin(Ars)from Artemisia annua L.based on aqueous solution of cyclodextrin derivative under ultrasonic irradiation was proposed.Among the test additives,the system containing edible hydroxypropyl-β-cyclodextrin(HPBCD)was shown to be efficient for this extraction.The optimal extraction conditions were predicted by artificial neural network,under which the extraction amount of Ars could reach 8.66 mg per gram of the leaves,much higher than the value in water(1.70 mg g-1).Kinetics study indicated that HPBCD enhanced the equilibrium amount of Ars in water,and ultrasonic irradiation accelerated extraction rate and reduced the activation energy.Mechanism study showed that the formation of Ars-HPBCD complex during extraction enhanced the water solubility of Ars and facilitated the extraction,and the configuration of Ars-HPBCD complex was modeled by molecular docking,which was further verified by characterizations.This work provides a convenient way to fabricate the traditional tea-based medicament of natural drugs to make production of this famous antimalarial medicine cheaper.展开更多
To solve the environmental pollution and low yield during the sythesis of zeolitic imidazolate frameworks(ZIFs)and their derived materials,a KOH-assisted aqueous strategy is proposed to synthesize cobalt zeolitic imid...To solve the environmental pollution and low yield during the sythesis of zeolitic imidazolate frameworks(ZIFs)and their derived materials,a KOH-assisted aqueous strategy is proposed to synthesize cobalt zeolitic imidazolate framework(ZIF-67)polyhedrons,which are used as precursors to prepare cobalt selenide/carbon composites with different crystal phases(Co_(0.85)Se,CoSe_2).When evaluated as anode material for lithium ion batteries,Co_(0.85)Se/C composites deliver a reversible capacity of 758.7 m A·h·g^(-1)with a capacity retention rate of 90.5%at 1.0 A·g^(-1)after 500 cycles,and the superior rate capability is 620 m A·h·g^(-1)at 2.0 A·g^(-1).The addition of KOH accelerates the production of ZIF-67 crystals by boosting deprotonation of dimethylimidazole,resulting in rapid growth and structures transition from two-dimensional to three-dimensional of ZIF-67 in aqueous solution,which greatly promotes the application of MOFs in the field of energy storage and conversion.展开更多
基金supported by the National Natural Science Foundation of China(22125802 and 22078010)Beijing Natural Science Foundation(2222017)Big Science Project from BUCT(XK180301)。
文摘A new type of rubidium ion-imprinted polymer has been synthesized by the surface-imprinting technique using methacrylic acid as the functional monomer,the rubidium ion as the template,methanol as the solvent,and silica as a carrier.Ethylene glycol dimethacrylate and 2,2-azobisisobutyronitrile were used as acrosslinker and an initiator,respectively.In addition,based on the macrocyclic effect of crown ethers,the 18-crown-6 ligand was introduced as a ligand to fix the template ions better.Scanning electron microscopy,zeta-potential analysis,Fourier transform infrared spectroscopy,thermogravimetric analysis,and X-ray photoelectron spectroscopy were performed to characterize the ion-imprinted polymer.The effects of the preparation and adsorption conditions on the adsorption performance of the rubidium ion-imprinted polymer were investigated.The results indicated that the rubidium ion-imprinted polymer has high selectivity and faster kinetics than other adsorbents,with an equilibrium adsorption capacity of 200.19 mg·g^(-1)at 298 K within 25 min.The sorption isotherm was well described by the Freundlich isotherm model,while the adsorption kinetics fitted the pseudo-second-order kinetic model.Consecutive adsorption-desorption experiments showed that the ion-imprinted polymer had good chemical stability and reusability.
基金supported by the Key Area Research&Development Program of Guangdong Province(2020B0101070001)the National Natural Science Foundation of China(21978053,51508547)。
文摘Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.
基金supported by National Natural Science Foundation of China (Nos. 12075037 and 22206013)the Natural Science Foundation of Jiangsu Province (No. BK20210857)the Leading Innovative Talents Cultivation Project of Changzhou City (No. CQ20210083)。
文摘Ozone(O_(3)) generated by a dielectric barrier discharge(DBD) is widely used in various industrial processes. In this study, NaCl aqueous solution was used as a novel electric power transmission electrode in a DBD reactor(instead of a traditional metal electrode) for highly efficient ozone generation. The results demonstrated that a high O_(3) yield of 242 g k Wh^(-1) with a concentration of 14.6 g m^(-3)O_(3) was achieved. The power transmission mechanism works because NaCl aqueous solution behaves as a capacitor when an alternating pulse voltage below 8 k Hz is used.Compared with the resistance of the discharge barrier and discharge space, the resistance of NaCl aqueous solution can be ignored, which ensures that O_(3) is generated efficiently. It is expected that O_(3) generation using NaCl aqueous solution as a novel electrode in a DBD reactor could be an alternative technology with good application prospects.
基金The financial support from National Natural Science Foundation of China(21978096,21861132019,and 21776074)Natural Science Foundation of Shanghai(19ZR1412600)is greatly acknowledged
文摘1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combining 25 cations and 8 anions,in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model.The extraction mechanism was investigated with the help ofσ-profile and interaction energy analyses.Both the cation and anion have impacts on the extraction efficiency,where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL.The IL composed of long alkyl-chain in cation and the anion of[PF6]-or[TF2 N]-,which has theσ-profile more likely distributed in the nonpolar region but less distributed in the polar region,is favorable for extraction.The experimental liquid-liquid equilibrium demonstrated the effects of cation and anion on extraction performance,which validated the reliability of COSMO-RS model in IL screening for PDA extraction.The IL[IM-1,8][PF6]could serve as a promising extractant for the downstream separation process of the biological production of PDA.
基金TheNationalNaturalScienceFoundationofChina (No .396 70 42 0 )
文摘Kinetic processes of α naphthaleneacetic acid (NAA) photolysis were studied under different conditions. The results showed that the ultraviolet light was more effective than fluorescent light in promoting degradation, and the degradation of NAA under ultraviolet light followed the first order kinetics with the photolysis rate constant of 1 15×10 -2 min -1 and half life time (t 1/2 ) of 60 min. Further, it was proved that the photolysis rate was higher in the presence of oxygen, titanium dioxide (TiO 2), and low pH (acidic solution). At last, two photolysis intermediates were identified by GC MS and possible photolysis pathways were proposed.
基金Deanship of Scientific Research(DSR)at King Saud University(KSU),Saudi Arabia for financially supporting this research project(No.RG-1435-078)。
文摘Coal fly ash(CFA)is composed of minerals containing some oxides in crystalline phase(i.e.,quartz and mullite),as well as unburned carbon as mesoporous material,thus enabling CFA to act as a dual-sites adsorbent with unique properties.This work focused on the adsorption of Pb(Ⅱ)and Zn(Ⅱ)from binary system,a mixture containing two metal ion solutions present simultaneously,onto NaOH-modified CFA(MCFA).Several adsorption tests were conducted to evaluate the effect of several parameters,including pH and contact times.The experiment results indicated that chemical treatment of CFA with NaOH increased pore volume from 0.021 to 0.223 cm^3·g^(-1).In addition,it could also enhance the availability of functional groups on both minerals and unburned carbon,resulting in almost 100%Pb(Ⅱ)and 97%Zn(Ⅱ)adsorbed.The optimum pH for adsorption system was pH=3 and quasi-equilibrium occurred in 240 minutes.Equilibrium data from the experimental results were analyzed using Modified Extended Langmuir(MEL)and Competitive Adsorption Langmuir-Langmuir(CALL)isotherm models.The analysis results showed that the CALL isotherm model could better describe the Pb(Ⅱ)and Zn(Ⅱ)adsorption process onto MCFA in binary system compared with MEL isotherm model.
文摘Chemical effects in different aqueous solutions induced by plasma with glow discharge electrolysis (GDE) and contact glow discharge electrolysis (CGDE) are described in this paper. The experimental and discharge characteristics are also reviewed. These are followed by a discussion of their mechanisms of both anodic and cathodic CGDE..
基金a grant from the Science and Technology Key Project of Education Ministry, China and KJCX-01 of Northwest Normal University, Chi
文摘Degradation of α-naphthol induced by plasma in aqueous solution was investigated in different initial concentration with contact glow discharge electrolysis(CGDE). The results showed that the degradation of α-naphthol obeyed the first-rate law. Some of predominant products were analyzed by a high performance liquid chromatography (HPLC). A path of α-naphthol disappearance caused by plasma was proposed according to the detected intermediate products.
基金supported by the Fundamental Research Funds of Shandong University(2018TB037)。
文摘The objective of this work is to contribute an understanding of the effects of electrons in the plasmas on the mass transfer of plasma species in aqueous solution by means of the numerical simulation based on a one-dimensional diffusion-reaction model.The plasma species are divided into two groups,i.e.electrons and the other species,and the mass transfer in the three scenarios has been simulated,including the systematic calculations of the depth distributions of five major reactive species,OH,O3,HO2,O2^-,and H2O2.In the three scenarios,the particles considered to enter into aqueous solution are all the plasma species(the scenario Ⅰ,where the mass transfer of plasma species is a result due to the synergy of the electrons and the other plasma species),the other species(the scenario Ⅱ),and only electrons in plasma species(the scenario Ⅲ),respectively.The detailed analyses on the difference between the depth distributions of each reactive species in these three scenarios show the following conclusions.The electrons play an important role in the mass transfer of plasma species in aqueous solution and the synergy of the electrons and the other plasma species(the electron-species synergy)presents its different effects on the mass transfer.The vast majority of H2O2 are generated from a series of the electronrelated reactions in aqueous solution,which is hardly affected by the electron-species synergy.Compared to the results when only the electrons enter into the liquid region,the electron-species synergy evidently weakens the generation of O2^-,O3,and OH,but promotes to produce HO2.
基金the DREAM project of MOST,China(Grant No.2016YFC0600408)the Strategic Priority Research Program(B)of Chinese Academy of Sciences(Grant No.XDB18000000)the Program of the National Mineral Rock and Fossil Specimens Resource Center from MOST,China.
文摘Carbonate-bearing fluids widely exist in different geological settings,and play important roles in transporting some elements such as the rare earth elements.They may be trapped as large or small fluid inclusions(with the size down to<1μm sometimes),and record critical physical-chemical signals for the formations of their host minerals.Spectroscopic methods like Raman spectroscopy and infrared spectroscopy have been proposed as effective methods to quantify the carbonate concentrations of these fluid inclusions.Although they have some great technical advantages over the conventional microthermometry method,there are still some technical difficulties to overcome before they can be routinely used to solve relevant geological problems.The typical limitations include their interlaboratory difference and poor performance on micro fluid inclusions.This study prepared standard ion-distilled water and K_(2)CO_(3)aqueous solutions at different molarities(from 0.5 to 5.5 mol/L),measured densities,collected Raman and infrared spectra,and explored correlations between the K_(2)CO_(3)molarity and the spectroscopic features at ambient P-T conditions.The result confirms that the Raman O-H stretching mode can be used as an internal standard to determine the carbonate concentrations despite some significant differences among the correlations,established in different laboratories,between the relative Raman intensity of the C-O symmetric stretching mode and that of the O-H stretching mode.It further reveals that the interlaboratory difference can be readily removed by performing one high-quality calibration experiment,provided that later quantifying analyses are conducted using the same Raman spectrometer with the same analytical conditions.Our infrared absorption data were collected from thin fluid films(thickness less than~2μm)formed by pressing the prepared solutions in a Microcompression Cell with two diamond-II plates.The data show that both the O-H stretching mode and the O-H bending mode can be used as internal standards to determine the carbonate concentrations.Since the IR signals of the C-O antisymmetric stretching vibration of the CO32ion,and the O-H stretching and bending vibrations from our thin films are very strong,their relative IR absorbance intensity,if well calibrated,can be used to investigate the micron-sized carbonate-bearing aqueous fluid inclusions.This study establishes the first calibration of this kind,which may have some applications.Additionally,our spectroscopic data suggest that as the K_(2)CO_(3)concentration increases the aqueous solution forms more large water molecule clusters via more intense hydrogen-bonding.This process may significantly alter the physical and chemical behavior of the fluids.
基金financially supported by grants from the National Natural Science Foundation of China(No.31500493)the Liaoning Educational Common Scientific Research Project(No.L2015044)+1 种基金the Liaoning Natural Science Foundation(No.2015020576)the Open Foundation of the Key Lab of Pulp and Paper Science & Technology,and Ministry of Education(Shandong Province),Qilu University of Technology(No.08031338)
文摘Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physical properties of the obtained QC derivatives were characterized using nitrogen content analysis,Fourier transform infrared spectroscopy( FT-IR),~1H-nuclear magnetic resonance(1H-NMR),X-ray diffraction( XRD),and thermal gravity analysis( TGA). The FT-IR and ~1H-NMR results confirmed the successful introduction of cationic quaternary ammonium groups into the main chain of cellulose. A series of QC derivatives with the degree of substitution( DS) values ranging from 0. 33 to 0. 80 were derived by adjusting the molar ratio of CHPTAC to anhydroglucose unit( AGU) of cellulose,concentration of cellulose in the Na OH-urea solution,as well as reaction temperature and time. According to the DS values of the QC derivatives,the optimized synthetic conditions were as follows: 25℃ reaction temperature,3% cellulose in Na OH-urea solution,the molar ratio of etherification agent to glycosidic cellulose of 15∶ 1,and 12 h reaction time. The TGA and XRD results revealed that the crystalline structure was destroyed during etherification,and the thermal stability of the QC derivatives was lower than that of cellulose.
基金funded by the Deutsche Forschungsgemeinschaft DFG and the Sino-German Center for Research Promotion(Grants GZ 1351 and CO 194/19-1)funded by a Chinese Scholarship Council stipend。
文摘First-row(3 d)transition metal oxyhydroxides have attracted increasing attention due to their various advantages.Although investigating the oxidation mechanism and processing such materials into hierarchical architectures are greatly desired for their further development,it remains unclear how the oxidation state change occurs,and efforts to produce hierarchical oxyhydroxides in compliance with high ecological and economic standards have progressed slowly.Here,we describe a facile one-step coprecipitation route for the preparation of hierarchical CoOOH,NiOOH and MnOOH,which involves the diffusion of NH_(3)originating from ammonium hydroxide solution into an aqueous solution containing metal ion salts and K_(2)S_(2)O_(8).Comprehensive characterizations by scanning electron microscope,transmission electron microscopy,X-ray diffraction analysis,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy and in situ p H measurement demonstrated that K_(2)S_(2)O_(8)induces the oxidation state change of metal ion species after the start of hydrolysis.Meanwhile,it was found that,benefiting from the OH–concentration gradient created by the NH_(3)diffusion method and the suitable growth environment provided by the presence of K_(2)S_(2)O_(8)(high nucleation rate and secondary nucleation),the formation of hierarchical oxyhydroxide structures can be realized in aqueous solution at ambient temperature without the use of heat energy and additional structure-directing agents.The hierarchical CoOOH structures are performed as the electrocatalysts for the oxygen evolution reaction in alkaline media,which exhibit good activity with an overpotential of 320 m V at 10 m A cm^(-2)and a low Tafel slope of 59.6 m V dec^(–1),outperforming many congeneric electrocatalysts.Overall,our study not only provides important insights to understand the formation mechanism of hierarchical oxyhydroxides,but also opens up new opportunities for the preparation of hierarchical oxyhydroxides via a facile,green and low-cost method.
基金supported by the National Natural Science Foundation of China(Grant No.61672094)
文摘The quartz crystal microbalance(QCM) is an important tool that can sense nanogram changes in mass. The hybrid temperature effect on a QCM resonator in aqueous solutions leads to unconvincing detection results. Control of the temperature effect is one of the keys when using the QCM for high precision measurements. Based on the Sauerbrey's and Kanazawa's theories, we proposed a method for enhancing the accuracy of the QCM measurement, which takes into account not only the thermal variations of viscosity and density but also the thermal behavior of the QCM resonator. We presented an improved Sauerbrey equation that can be used to effectively compensate the drift of the QCM resonator. These results will play a significant role when applying the QCM at the room temperature.
文摘The membranes were prepared by the incorporation of highly hydrophobic silicalite and carbon molecular sieves (CMS) from different precursors into the PDMS casting solutions. The pervaporative removal of VOCs, such as benzene, from aqueous solutions was carried out using the separation factor and permeation flux as the evaluating parameters. The effects of the CMS types and structures, feed concentrations on the pervaporation performance were preliminarily investigated.
文摘Hydroxypropyl celluloses(HPC) were homogenously synthesized by the reaction of cellulose with propylene oxide in NaOH/urea aqueous solution.Water-soluble HPC with molar degree of substitution(MSNMR) in the range of 0.52~0.78 was prepared from microcrystalline cellulose,cotton linters,and spruce sulfite pulp.The structure of the HPC samples was characterized by means of FT-IR,NMR,gas chromatography(GC),and size exclusion chromatography(SEC) analyses.Three types of cellulose samples with different molecular weights were found to dissolve well in the NaOH/urea solvent with no obvious differences in reactivity and regioselectivity.The relative reactivity of hydroxyl groups in the glycosyl unit was in the following order:O-6>O-2>O-3.In addition,the results of the study indicated that the tandem reaction during hydroxypropylation could be ignored.
基金supported by the National Natural Science Foundation of China(NSFC)(22025106 and 21971199)the National Key Research and Development Program of China(2022YFA1502902)。
文摘Covalent organic framework(COF)nanocrystals are useful in biological applications;however,their hydrophobic nature makes them aggregate into clusters in aqueous media.In this work,we show that by modifying the crystal surface with hydrophilic functional groups,these nanocrystals can maintain in the monodispersed form in aqueous solution.Specifically,three COFs,TPB-DMTP COF,TAPB-PDA COF and TAPB-BPDA COF were synthesized using organic Lewis acid as the catalyst,to generate nanoparticles with the size ranging from 180 nm to 1μm.2-Aminoethanesulfonic acid(AESA)was applied to react with the terminal aldehyde functional groups exposed at the surface of COF nanocrystals.The resulting negatively charged surface keeps these nanocrystals apart from each other in aqueous solution for at least 48 h.The mesopore of these COF nanocrystals allows the entering of single-strand DNA molecules and the release in the presence of complementary DNA.
基金supported by the National Natural Science Foundation of China(No.21776264).
文摘Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is proposed by using molecular dynamics simulation,and the relationship between ion-to-ion interaction and salt solubility in a simulated seawater water-salt system is investigated.By analyzing the variation of distance and contact time between ions in an electrolyte solution,from both spatial and temporal perspectives,new parameters were proposed to describe the interaction between ions:interaction distance(ID),and interaction time ratio(ITR).The best correlation between characteristic time ratio and solubility was found for a molar ratio of salt-to-water of 10:100 with a correlation coefficient of 0.96.For the same salt,a positive correlation was found between CTR and the molar ratio of salt and water.For type 1-1,type 2-1,type 1-2,and type 2-2 salts,the correlation coefficients between CTR and solubility were 0.93,0.96,0.92,and 0.98 for a salt-to-water molar ratio of 10:100,respectively.The solubility of multiple salts was predicted by simulations and compared with experimental values,yielding an average relative deviation of 12.4%.The new ion-interaction parameters offer significant advantages in describing strongly correlated and strongly hydrated electrolyte solutions.
基金supported by the National Natural Science Foundation of China (81571720,81530052,81727809)。
文摘The behavior of room temperature phosphorescence quenching and fluorescence enhancing of gadolinium labeled sinoporphyrin sodium(Gd-DVDMS) in the aqueous solution were studied.Gd-DVDMS was characterized by various techniques including mass spectra,Fourier transform infrared spectra and transmission electron microscopy.The optical behavior was monitored through UV-vis absorption spectra and photoluminescence spectra.The result shows that the phosphorescence intensity gradually quenches,almost disappears after dissolved 120 min,meanwhile the fluorescence intensity enhances 5 times.The above behavior is attributed to the decreased population of Gd-DVDMS as first excited triplet state(T1),Based on the time-invariant of both absorption spectra and phosphorescence decay curves at710 nm of Gd-DVDMS in different dissolution time,the reason for the decreased population of GdDVDMS in T1 state is that the intersystem crossing from first excited state(S1) to T1 is prevented.In addition,the fluorescent decay curves of Gd-DVDMS initially dissolved in the aqueous solution and dissolved for 120 min were also measured for comparison.The big change in fluorescent lifetime further proves the conclusion that intersystem crossing is prevented,meanwhile,the increase in fluorescence intensity is demonstrated.In this work,the possibility of decomposition of Gd-DVDMS is excluded because the phosphorescence decay curve in Gd-DVDMS aqueous solution is sensible to DVDMS.
基金supported by Innovation Academy for Green Manufacture,Chinese Academy of Sciences(No.IAGM-2019-A12)National Natural Science Foundation of China(No.22078324)CAS Pioneer Hundred Talents Program,and K.C.Wong Education Foundation(No.GJTD-2018-04).
文摘A process for extraction of artemisinin(Ars)from Artemisia annua L.based on aqueous solution of cyclodextrin derivative under ultrasonic irradiation was proposed.Among the test additives,the system containing edible hydroxypropyl-β-cyclodextrin(HPBCD)was shown to be efficient for this extraction.The optimal extraction conditions were predicted by artificial neural network,under which the extraction amount of Ars could reach 8.66 mg per gram of the leaves,much higher than the value in water(1.70 mg g-1).Kinetics study indicated that HPBCD enhanced the equilibrium amount of Ars in water,and ultrasonic irradiation accelerated extraction rate and reduced the activation energy.Mechanism study showed that the formation of Ars-HPBCD complex during extraction enhanced the water solubility of Ars and facilitated the extraction,and the configuration of Ars-HPBCD complex was modeled by molecular docking,which was further verified by characterizations.This work provides a convenient way to fabricate the traditional tea-based medicament of natural drugs to make production of this famous antimalarial medicine cheaper.
基金financially supported by the National Key Research and Development Program of China (2017YFA0208200)the National Natural Science Foundation of China (52102100,22022505 and 21872069)+4 种基金the Natural Science Foundation of Jiangsu Province (BK20181469)Guangdong Basic and Applied Basic Research Foundation (2020A1515110035)the Fundamental Research Funds for the Central Universities (0205-14380266,0205-14380272)the Scientific and Technological Innovation Special Fund for Carbon Peak and Carbon Neutrality of Jiangsu Province (BK20220008)the 2021 Suzhou Gusu Leading Talents of Science and Technology Innovation and Entrepreneurship in Wujiang District。
文摘To solve the environmental pollution and low yield during the sythesis of zeolitic imidazolate frameworks(ZIFs)and their derived materials,a KOH-assisted aqueous strategy is proposed to synthesize cobalt zeolitic imidazolate framework(ZIF-67)polyhedrons,which are used as precursors to prepare cobalt selenide/carbon composites with different crystal phases(Co_(0.85)Se,CoSe_2).When evaluated as anode material for lithium ion batteries,Co_(0.85)Se/C composites deliver a reversible capacity of 758.7 m A·h·g^(-1)with a capacity retention rate of 90.5%at 1.0 A·g^(-1)after 500 cycles,and the superior rate capability is 620 m A·h·g^(-1)at 2.0 A·g^(-1).The addition of KOH accelerates the production of ZIF-67 crystals by boosting deprotonation of dimethylimidazole,resulting in rapid growth and structures transition from two-dimensional to three-dimensional of ZIF-67 in aqueous solution,which greatly promotes the application of MOFs in the field of energy storage and conversion.
