An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium brom...An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.展开更多
Electrocatalytic reduction reactions,powered by clean energy sources such as solar energy and wind,offer a sustainable method for converting inexpensive feedstocks(e.g.,CO_(2),N_(2)/NO_(x),organics,and O_(2))into high...Electrocatalytic reduction reactions,powered by clean energy sources such as solar energy and wind,offer a sustainable method for converting inexpensive feedstocks(e.g.,CO_(2),N_(2)/NO_(x),organics,and O_(2))into high-value-added chemicals or fuels.The design and modification of electrocatalysts have been widely implemented to improve their performance in these reactions.However,bottle-necks are encountered,making it challenging to further improve performance through catalyst development alone.Recently,cations in the electrolyte have emerged as critical factors for tuning both the activity and product selectivity of reduction reactions.This review summarizes recent advances in understanding the role of cation effects in electrocatalytic reduction reactions.First,we introduce the mechanisms underlying cation effects.We then provide a comprehensive overview of their application in electroreduction reactions.Characterization techniques and theoretical calcula-tion methods for studying cation effects are also discussed.Finally,we address remaining challeng-es and future perspectives in this field.We hope that this review offers fundamental insights and design guidance for utilizing cation effects,thereby advancing their development.展开更多
Selective electrodialysis(SED)has surfaced as a highly promising membrane separation technique in the realm of acid recovery owing to its ability to effectively separate monovalent ions through the utilization of a po...Selective electrodialysis(SED)has surfaced as a highly promising membrane separation technique in the realm of acid recovery owing to its ability to effectively separate monovalent ions through the utilization of a potential difference.However,the current SED process is limited by conventional commercial monovalent cation permselective membranes(MCPMs).This study systematically investigates the use of an independently developed MCPM in the SED process for acid recovery.Various factors such as current density,volume ratio,initial ion concentration,and waste acid systems are considered.The independently developed MCPM offers several advantages over the commercial monovalent selective cation-exchange membrane(CIMS),including higher recovered acid concentration,better ion flux ratio,improved acid recovery efficiency,increased recovered acid purity,and higher current efficiency.The SED process with the MCPM achieves a recovered acid of 95.9%and a concentration of 2.3 mol·L^(–1) in the HCl/FeCl_(2) system,when a current density of 20 mA·cm^(-2) and a volume ratio of 1:2 are applied.Similarly,in the H_(2)SO_(4)/FeSO_(4) system,a purity of over 99%and a concentration of 2.1 mol·L^(–1) can be achieved in the recovered acid.This study thoroughly examines the impact of operation conditions on acid recovery performance in the SED process.The independently developed MCPM demonstrates outstanding acid recovery performance,highlighting its potential for future commercial utilization.展开更多
The reactive diluent prepared by siloxane modified Trimethylene oxide can improve the performance of the UV curing system.Therefore,1,7-bis[(3-ethyl-3-methoxyoxacylobutane)propyl]octadecylosiloxane(BEMOPOMTS)was synth...The reactive diluent prepared by siloxane modified Trimethylene oxide can improve the performance of the UV curing system.Therefore,1,7-bis[(3-ethyl-3-methoxyoxacylobutane)propyl]octadecylosiloxane(BEMOPOMTS)was synthesized from diethyl carbonate,trimethylopropanes,allyl bromide,and 1,1,3,3,5,5,7,7-octadecylosiloxane as the main raw materials.BEMOPOMTS can be used as reactive diluents in the field of cationic UV curing.It has good thermal stability,and the addition of BEMOPOMTS significantly improves the tensile strength and elongation at break of epoxy resin.Compared with the pure epoxy resin,adding 20%BEMOPOMTS increased the elastic modulus by 25%to 677 MPa.展开更多
Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.U...Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.展开更多
Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na...Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.展开更多
The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficien...The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2) conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2) electrolysis.It commences with an overview of the latest advancements in acidic CO_(2) electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2) electrolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2) electrolysis are suggested.展开更多
Rh has been widely studied as a catalyst for the promising hydrazine oxidation reaction that can replace oxygen evolution reactions for boosting hydrogen production from hydrazine-containing wastewater.Despite Rh bein...Rh has been widely studied as a catalyst for the promising hydrazine oxidation reaction that can replace oxygen evolution reactions for boosting hydrogen production from hydrazine-containing wastewater.Despite Rh being expensive,only a few studies have examined its electrocatalytic mass activity.Herein,surface-limited cation exchange and electrochemical activation processes are designed to remarkably enhance the mass activity of Rh.Rh atoms were readily replaced at the Ni sites on the surface of NiOOH electrodes by cation exchange,and the resulting RhOOH compounds were activated by the electrochemical reduction process.The cation exchange-derived Rh catalysts exhibited particle sizes not exceeding 2 nm without agglomeration,indicating a decrease in the number of inactive inner Rh atoms.Consequently,an improved mass activity of 30 A mg_(Rh)^(-1)was achieved at 0.4 V versus reversible hydrogen electrode.Furthermore,the two-electrode system employing the same CE-derived Rh electrodes achieved overall hydrazine splitting over 36 h at a stable low voltage.The proposed surface-limited CE process is an effective method for reducing inactive atoms of expensive noble metal catalysts.展开更多
We analyzed a novel cationic collector using chemical plant byproducts,such as cetyltrimethylammonium bromide(CTAB)and dibutyl phthalate(DBP).Our aim is to establish a highly effective and economical process for the r...We analyzed a novel cationic collector using chemical plant byproducts,such as cetyltrimethylammonium bromide(CTAB)and dibutyl phthalate(DBP).Our aim is to establish a highly effective and economical process for the removal of quartz from collophane.A microflotation test with a 25 mg·L^(−1)collector at pH value of 6-10 demonstrates a considerable difference in the floatability of pure quartz and fluorapatite.Flotation tests for a collophane sample subjected to the first reverse flotation for magnesium removal demonstrates that a rough flotation process(using a 0.4 kg·t−1 new collector at pH=6)results in a collophane concentrate with 29.33wt%P_(2)O_(5)grade and 12.66wt%SiO2 at a 79.69wt%P_(2)O_(5)recovery,providing desirable results.Mechanism studies using Fourier transform infrared spectroscopy,zeta potential,and contact angle measurements show that the adsorption capacity of the new collector for quartz is higher than that for fluorapatite.The synergistic effect of DBP increases the difference in hydrophobicity between quartz and fluorapatite.The maximum defoaming rate of the novel cationic collector reaches 142.8 mL·min−1.This is considerably higher than that of a conventional cationic collector.展开更多
Researchers and scientists need rapid access to text documents such as research papers,source code and dissertations.Many research documents are available on the Internet and need more time to retrieve exact documents...Researchers and scientists need rapid access to text documents such as research papers,source code and dissertations.Many research documents are available on the Internet and need more time to retrieve exact documents based on keywords.An efficient classification algorithm for retrieving documents based on keyword words is required.The traditional algorithm performs less because it never considers words’polysemy and the relationship between bag-of-words in keywords.To solve the above problem,Semantic Featured Convolution Neural Networks(SF-CNN)is proposed to obtain the key relationships among the searching keywords and build a structure for matching the words for retrieving correct text documents.The proposed SF-CNN is based on deep semantic-based bag-of-word representation for document retrieval.Traditional deep learning methods such as Convolutional Neural Network and Recurrent Neural Network never use semantic representation for bag-of-words.The experiment is performed with different document datasets for evaluating the performance of the proposed SF-CNN method.SF-CNN classifies the documents with an accuracy of 94%than the traditional algorithms.展开更多
High-performance lithium-ion batteries(LIB)are important in powering emerging technologies.Cathodes are regarded as the bottleneck of increasing battery energy density,among which layered oxides are the most promising...High-performance lithium-ion batteries(LIB)are important in powering emerging technologies.Cathodes are regarded as the bottleneck of increasing battery energy density,among which layered oxides are the most promising candidates for LIB.However,a limitation with layered oxides cathodes is the transition metal and Li site mixing,which significantly impacts battery capacity and cycling stability.Despite recent research on Li/Ni mixing,there is a lack of comprehensive understanding of the origin of cation mixing between the transition metal and Li;therefore,practical means to address it.Here,a critical review of cation mixing in layered cathodes has been provided,emphasising the understanding of cation mixing mechanisms and their impact on cathode material design.We list and compare advanced characterisation techniques to detect cation mixing in the material structure;examine methods to regulate the degree of cation mixing in layered oxides to boost battery capacity and cycling performance,and critically assess how these can be applied practically.An appraisal of future research directions,including superexchange interaction to stabilise structures and boost capacity retention has also been concluded.Findings will be of immediate benefit in the design of layered cathodes for high-performance rechargeable LIB and,therefore,of interest to researchers and manufacturers.展开更多
The analysis of remote sensing image areas is needed for climate detec-tion and management,especially for monitoringflood disasters in critical environ-ments and applications.Satellites are mostly used to detect disast...The analysis of remote sensing image areas is needed for climate detec-tion and management,especially for monitoringflood disasters in critical environ-ments and applications.Satellites are mostly used to detect disasters on Earth,and they have advantages in capturing Earth images.Using the control technique,Earth images can be used to obtain detailed terrain information.Since the acquisi-tion of satellite and aerial imagery,this system has been able to detectfloods,and with increasing convenience,flood detection has become more desirable in the last few years.In this paper,a Big Data Set-based Progressive Image Classification Algorithm(PICA)system is introduced to implement an image processing tech-nique,detect disasters,and determine results with the help of the PICA,which allows disaster analysis to be extracted more effectively.The PICA is essential to overcoming strong shadows,for proper access to disaster characteristics to false positives by operators,and to false predictions that affect the impact of the disas-ter.The PICA creates tailoring and adjustments obtained from satellite images before training and post-disaster aerial image data patches.Two types of proposed PICA systems detect disasters faster and more accurately(95.6%).展开更多
This paper extends the criterion of the misclassification ratio of discriminant model and presents a new selection method of discriminant model.For selecting the discriminant model,this method establishes the rule of ...This paper extends the criterion of the misclassification ratio of discriminant model and presents a new selection method of discriminant model.For selecting the discriminant model,this method establishes the rule of misclassification degree ratio through misclassification ratio of the discriminant model and misclassification degree of the samples.To test the effect of this method,this work uses seven UCI data sets.Numerical experiments on these examples indicate that this method has certain rationality and has a better effect to select a discriminant model.展开更多
Bis(15-crown-5)-stilbenes containing crown ether parts have been widely used in a variety of chemical applications,such as cation detectors,because of their ability to selectively bind to alkali metal cations,Bis(15-c...Bis(15-crown-5)-stilbenes containing crown ether parts have been widely used in a variety of chemical applications,such as cation detectors,because of their ability to selectively bind to alkali metal cations,Bis(15-crown-5)-stilbenes and its derivatives with complexation of one-or two-alkali metal cation(Li^(+),Na^(+)and K^(+))have been theoretically investigat-ed by quantum chemistry methods.The coordination of alkali cations results in partial shrinkage of crown ethers,which directly affected natural distribution analysis charges and molecular orbital energy levels.The number of alkali metal ions has significant effects on absorption spectra and mean second hyperpolarizability.When one alkali metal ion was added to the anticonformer of bis(15-crown-5)-stilbene,the absorption spectra were obvious-ly redshifted and the mean second hyperpolarizability values were slightly increased;while two alkali metal ions were added to bis(15-crown-5)-stilbene,the absorption spectra were ob-viously blue shifted and the mean second hyperpolarizability values decreased.On the other hand,as the radius of the alkali ions increased,the mean second hyperpolarizability values of the compounds increased gradually.It is indicated that the mean second hyperpolarizability value is sensitive to the number and radius of the alkali metal cations,thus the third order nonlinear optical response can be used as a signal to detect the number and type of alkali met-al ions.展开更多
Predictive Maintenance is a type of condition-based maintenance that assesses the equipment's states and estimates its failure probability and when maintenance should be performed.Although machine learning techniq...Predictive Maintenance is a type of condition-based maintenance that assesses the equipment's states and estimates its failure probability and when maintenance should be performed.Although machine learning techniques have been frequently implemented in this area,the existing studies disregard to the nat-ural order between the target attribute values of the historical sensor data.Thus,these methods cause losing the inherent order of the data that positively affects the prediction performances.To deal with this problem,a novel approach,named Ordinal Multi-dimensional Classification(OMDC),is proposed for estimating the conditions of a hydraulic system's four components by taking into the natural order of class values.To demonstrate the prediction ability of the proposed approach,eleven different multi-dimensional classification algorithms(traditional Binary Relevance(BR),Classifier Chain(CC),Bayesian Classifier Chain(BCC),Monte Carlo Classifier Chain(MCC),Probabilistic Classifier Chain(PCC),Clas-sifier Dependency Network(CDN),Classifier Trellis(CT),Classifier Dependency Trellis(CDT),Label Powerset(LP),Pruned Sets(PS),and Random k-Labelsets(RAKEL))were implemented using the Ordinal Class Classifier(OCC)algorithm.Besides,seven different classification algorithms(Multilayer Perceptron(MLP),Support Vector Machine(SVM),k-Nearest Neighbour(kNN),Decision Tree(C4.5),Bagging,Random Forest(RF),and Adaptive Boosting(AdaBoost))were chosen as base learners for the OCC algorithm.The experimental results present that the proposed OMDC approach using binary relevance multi-dimensional classification methods predicts the conditions of a hydraulic system's multiple components with high accuracy.Also,it is clearly seen from the results that the OMDC models that utilize ensemble-based classification algorithms give more reliable prediction performances with an average Hamming score of 0.853 than the others that use traditional algorithms as base learners.展开更多
In this study,a new tannic acid adsorbent(ethylene glycol diglycidyl ether crosslinked tannic acid,TAEGDE)for adsorptive removal of dyes from water was prepared using EGDE as a cross-linking agent.The resultant TA-EGD...In this study,a new tannic acid adsorbent(ethylene glycol diglycidyl ether crosslinked tannic acid,TAEGDE)for adsorptive removal of dyes from water was prepared using EGDE as a cross-linking agent.The resultant TA-EGDE was in particulate form with rough surface morphology and a diameter ranging from 10 to 30μm.The adsorption performance of the TA-EGDE was evaluated in a flow-through mode using water samples contaminated with methylene blue(MB)and two-component mixed dyes,respectively.The TA-EGDE provided adsorption capacity up to 721.8 mg·g^(-1)at 65°C for MB.It showed a high removal efficiency(99%)of MB(50 mg·L^(-1))from the water sample and could recovery 90%of the adsorbed MB by eluting with acidic ethanol aqueous solution.The excellent adsorption of MB and neutral red on the TA-EGDE may be the result of the synergy of electrostatic interaction andπ-πinteraction.Furthermore,the TA-EGDE could separate dyes from water samples contaminated with twocomponent mixed dyes with a separation coefficient ranging from 1.8 to 36.5.The anionic TA-EGDE would be an effective adsorbent to remove and recycle dyes from the contaminated water.展开更多
Monocyclic nitrogen-rich 3-(aminomethyl)-4,5-diamine-1,2,4-triazole(1)and fused cyclic 3,7-diamine-6-(aminomethyl)-[1,2,4]triazolo[4,3-b][1,2,4]triazole(9)were synthesized through the convenient cyclization reaction f...Monocyclic nitrogen-rich 3-(aminomethyl)-4,5-diamine-1,2,4-triazole(1)and fused cyclic 3,7-diamine-6-(aminomethyl)-[1,2,4]triazolo[4,3-b][1,2,4]triazole(9)were synthesized through the convenient cyclization reaction from the readily available reactant.Their energetic salts with high nitrogen content were proved to be rare examples of divalent monocyclic/fused cyclic cationic salts according to the single crystal analyses.The structure of intermediate B was also identified and verified by its trivalent cation crystal 17.5H_2O indirectly.Energetic compounds 2-8 and 10-17 were fully characterized by NMR spectroscopy,infrared spectroscopy,differential scanning calorimetry,elemental analysis.These energetic salts exhibit good thermal stability with decomposition temperatures ranged from 182℃to 245℃.The sensitivity of compounds 2,6,10 and 14 is similar or superior to that of RDX while the others were much more insensitive to mechanical stimulate.Furthermore,detonation velocity of 10(8843 m/s)surpass that of RDX(D=8795 m/s).Considering the high gas production volume(≥808 L/kg)of 2,4,10and 12,constant-volume combustion experiments were conduct to evaluate their gas production capacities specifically.These compounds possess much higher maximum gas-production pressures(P_(max):7.88-10.08 MPa)than the commonly used reagent guanidine nitrate(GN:P_(max)=4.20 MPa),which indicate their strong gas production capacity.展开更多
Individuals with special needs learn more slowly than their peers and they need repetitions to be permanent.However,in crowded classrooms,it is dif-ficult for a teacher to deal with each student individually.This probl...Individuals with special needs learn more slowly than their peers and they need repetitions to be permanent.However,in crowded classrooms,it is dif-ficult for a teacher to deal with each student individually.This problem can be overcome by using supportive education applications.However,the majority of such applications are not designed for special education and therefore they are not efficient as expected.Special education students differ from their peers in terms of their development,characteristics,and educational qualifications.The handwriting skills of individuals with special needs are lower than their peers.This makes the task of Handwriting Recognition(HWR)more difficult.To over-come this problem,we propose a new personalized handwriting verification sys-tem that validates digits from the handwriting of special education students.The system uses a Convolutional Neural Network(CNN)created and trained from scratch.The data set used is obtained by collecting the handwriting of the students with the help of a tablet.A special education center is visited and the handwrittenfigures of the students are collected under the supervision of special education tea-chers.The system is designed as a person-dependent system as every student has their writing style.Overall,the system achieves promising results,reaching a recognition accuracy of about 94%.Overall,the system can verify special educa-tion students’handwriting digits with high accuracy and is ready to integrate with a mobile application that is designed to teach digits to special education students.展开更多
Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quater...Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quaternary ammoniums bearing different cationic sizes,i.e.MTOA+(methyltrioctylammonium,[(C_(8)H_(17))_(3)CH_(3)N]+),HTMA+(hexadecyltrimethylammonium,[(C_(16)H_(33))(CH_(3))_(3)N]+) and DMDOA+(dimethyldioctadecylammonium,[(C_(18)H_(37))_(2)(CH_(3))_(2)N]+) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs),which were used in the styrene epoxidations.Among them,(MTOA)_(3)PW_(4)O_(24)exhibits the best catalytic performance judged from the highest styrene conversion rate(52%) and styrene oxide selectivity (93%),during which the styrene epoxidation conditions were optimized.Meanwhile,the deactivation mechanism of this kind of PTCs was proposed firstly,i.e.in the case of low H_(2)O_(2) content,the oxidant can only be used in the styrene epoxidation,in which the catalyst can transform into stable Keggin-type POM.But when the content of H_(2)O_(2) is higher,the excess H_(2)O_(2) can reactivate the Keggin-type POM into active (PW_(4)O_(24))_(3)-anions,which can trigger the ring-opening polymerization of styrene oxide.Consequently,the catalyst is deactivated by adhered poly(styrene oxide)irreversibly,which was determined by NMR spectra.In this situation,the active moiety{PO_(4)[WO(O_(2))_(2)]_(4)}_(3)-in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides.This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.展开更多
Study of physisorbed and chemisorbed carbon dioxide (CO<sub>2</sub>) species was carried out on the NaX zeolite modified by cationic exchanges with bivalent cations (Ca<sup>2+</sup> and Ba<s...Study of physisorbed and chemisorbed carbon dioxide (CO<sub>2</sub>) species was carried out on the NaX zeolite modified by cationic exchanges with bivalent cations (Ca<sup>2+</sup> and Ba<sup>2+</sup>) by temperature-programmed desorption of CO<sub>2</sub> (CO<sub>2</sub>-TPD). Others results were obtained by infrared to complete the study. The results of this research showed, in the physisorption region (213 - 473 K), that the cationic exchanges on NaX zeolite with bivalent cations increase slightly the interactions of CO<sub>2</sub> molecule with adsorbents and/or cationic site. Indeed, the desorption energies of physisorbed CO<sub>2</sub> obtained on the reference zeolite NaX (13.5 kJ·mol<sup>-1</sup>) are lower than that of exchanged zeolites E-CaX and E-BaX (15.77 and 15.17 kJ·mol<sup>-1</sup> respectively). In the chemisorbed CO<sub>2</sub> region (573 - 873 K), the desorption energies related to desorbed species (bidentate carbonates: CO<sub>3</sub>2-</sup>) on the exchanged zeolites E-CaX and E-BaX are about 81 kJ·mol<sup>-1</sup>, higher than the desorbed species (bicarbonates: HCO<sub>3</sub>2-</sup>) on the reference R-NaX (62 kJ·mol<sup>-1</sup>). In addition, the exchanged E-BaX zeolite develops the secondary adsorption sites corresponding to bicarbonates species with desorption energies of 35 kJ·mol<sup>-1</sup> lower to desorption energies of bicarbonates noted on the reference zeolite NaX.展开更多
基金financial support from Singapore Ministry of Education under its AcRF Tier 2 Grant No MOE-T2EP10123-0001Singapore National Research Foundation Investigatorship under Grant No NRF-NRFI08-2022-0009Academic Excellence Foundation of BUAA for PhD Students(applicant:Hongfei Xu).
文摘An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.
文摘Electrocatalytic reduction reactions,powered by clean energy sources such as solar energy and wind,offer a sustainable method for converting inexpensive feedstocks(e.g.,CO_(2),N_(2)/NO_(x),organics,and O_(2))into high-value-added chemicals or fuels.The design and modification of electrocatalysts have been widely implemented to improve their performance in these reactions.However,bottle-necks are encountered,making it challenging to further improve performance through catalyst development alone.Recently,cations in the electrolyte have emerged as critical factors for tuning both the activity and product selectivity of reduction reactions.This review summarizes recent advances in understanding the role of cation effects in electrocatalytic reduction reactions.First,we introduce the mechanisms underlying cation effects.We then provide a comprehensive overview of their application in electroreduction reactions.Characterization techniques and theoretical calcula-tion methods for studying cation effects are also discussed.Finally,we address remaining challeng-es and future perspectives in this field.We hope that this review offers fundamental insights and design guidance for utilizing cation effects,thereby advancing their development.
基金supported by the National Key Research and Development Program of China(2022YFB3805100)National Natural Science Foundation of China(22222812 and 22178330)+1 种基金Anhui Provincial Key Research and Development Plan(202104b11020030)Major Science and Technology Innovation Projects in Shandong Province(2022CXGC020415).
文摘Selective electrodialysis(SED)has surfaced as a highly promising membrane separation technique in the realm of acid recovery owing to its ability to effectively separate monovalent ions through the utilization of a potential difference.However,the current SED process is limited by conventional commercial monovalent cation permselective membranes(MCPMs).This study systematically investigates the use of an independently developed MCPM in the SED process for acid recovery.Various factors such as current density,volume ratio,initial ion concentration,and waste acid systems are considered.The independently developed MCPM offers several advantages over the commercial monovalent selective cation-exchange membrane(CIMS),including higher recovered acid concentration,better ion flux ratio,improved acid recovery efficiency,increased recovered acid purity,and higher current efficiency.The SED process with the MCPM achieves a recovered acid of 95.9%and a concentration of 2.3 mol·L^(–1) in the HCl/FeCl_(2) system,when a current density of 20 mA·cm^(-2) and a volume ratio of 1:2 are applied.Similarly,in the H_(2)SO_(4)/FeSO_(4) system,a purity of over 99%and a concentration of 2.1 mol·L^(–1) can be achieved in the recovered acid.This study thoroughly examines the impact of operation conditions on acid recovery performance in the SED process.The independently developed MCPM demonstrates outstanding acid recovery performance,highlighting its potential for future commercial utilization.
基金Funded by the National Natural Science Foundation of China(No.21865017)。
文摘The reactive diluent prepared by siloxane modified Trimethylene oxide can improve the performance of the UV curing system.Therefore,1,7-bis[(3-ethyl-3-methoxyoxacylobutane)propyl]octadecylosiloxane(BEMOPOMTS)was synthesized from diethyl carbonate,trimethylopropanes,allyl bromide,and 1,1,3,3,5,5,7,7-octadecylosiloxane as the main raw materials.BEMOPOMTS can be used as reactive diluents in the field of cationic UV curing.It has good thermal stability,and the addition of BEMOPOMTS significantly improves the tensile strength and elongation at break of epoxy resin.Compared with the pure epoxy resin,adding 20%BEMOPOMTS increased the elastic modulus by 25%to 677 MPa.
基金the National Key Research and Development Program of China(2019YFA0705400)the National Natural Science Foundation of China(T2293692,21925404,22021001,21991151,and 22002036)+1 种基金the Natural Science Foundation of Fujian Province of China(2021J06001)the National Natural Science Foundation of Henan province(232300421081).
文摘Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.
基金funding supports from the National Key R&D Program of China(Grant Nos.2022YFB2404400 and 2019YFA0308500)Beijing Natural Science Foundation(Z190010)National Natural Science Foundation of China(Grant Nos.51991344,52025025,52072400,and 52002394)。
文摘Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.
文摘The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2) conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2) electrolysis.It commences with an overview of the latest advancements in acidic CO_(2) electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2) electrolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2) electrolysis are suggested.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry ofEducation(2021R1A2C3011870 and 2019R1A6A1A03033215)the Korea Research Fellowship Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(2020H1D3A1A04081323)
文摘Rh has been widely studied as a catalyst for the promising hydrazine oxidation reaction that can replace oxygen evolution reactions for boosting hydrogen production from hydrazine-containing wastewater.Despite Rh being expensive,only a few studies have examined its electrocatalytic mass activity.Herein,surface-limited cation exchange and electrochemical activation processes are designed to remarkably enhance the mass activity of Rh.Rh atoms were readily replaced at the Ni sites on the surface of NiOOH electrodes by cation exchange,and the resulting RhOOH compounds were activated by the electrochemical reduction process.The cation exchange-derived Rh catalysts exhibited particle sizes not exceeding 2 nm without agglomeration,indicating a decrease in the number of inactive inner Rh atoms.Consequently,an improved mass activity of 30 A mg_(Rh)^(-1)was achieved at 0.4 V versus reversible hydrogen electrode.Furthermore,the two-electrode system employing the same CE-derived Rh electrodes achieved overall hydrazine splitting over 36 h at a stable low voltage.The proposed surface-limited CE process is an effective method for reducing inactive atoms of expensive noble metal catalysts.
基金the financial support from the National Natural Science Foundation of China(No.51804188)the support of the Yunnan Yuntianhua Co.,Ltd.,China,for providing the phosphate samples.
文摘We analyzed a novel cationic collector using chemical plant byproducts,such as cetyltrimethylammonium bromide(CTAB)and dibutyl phthalate(DBP).Our aim is to establish a highly effective and economical process for the removal of quartz from collophane.A microflotation test with a 25 mg·L^(−1)collector at pH value of 6-10 demonstrates a considerable difference in the floatability of pure quartz and fluorapatite.Flotation tests for a collophane sample subjected to the first reverse flotation for magnesium removal demonstrates that a rough flotation process(using a 0.4 kg·t−1 new collector at pH=6)results in a collophane concentrate with 29.33wt%P_(2)O_(5)grade and 12.66wt%SiO2 at a 79.69wt%P_(2)O_(5)recovery,providing desirable results.Mechanism studies using Fourier transform infrared spectroscopy,zeta potential,and contact angle measurements show that the adsorption capacity of the new collector for quartz is higher than that for fluorapatite.The synergistic effect of DBP increases the difference in hydrophobicity between quartz and fluorapatite.The maximum defoaming rate of the novel cationic collector reaches 142.8 mL·min−1.This is considerably higher than that of a conventional cationic collector.
文摘Researchers and scientists need rapid access to text documents such as research papers,source code and dissertations.Many research documents are available on the Internet and need more time to retrieve exact documents based on keywords.An efficient classification algorithm for retrieving documents based on keyword words is required.The traditional algorithm performs less because it never considers words’polysemy and the relationship between bag-of-words in keywords.To solve the above problem,Semantic Featured Convolution Neural Networks(SF-CNN)is proposed to obtain the key relationships among the searching keywords and build a structure for matching the words for retrieving correct text documents.The proposed SF-CNN is based on deep semantic-based bag-of-word representation for document retrieval.Traditional deep learning methods such as Convolutional Neural Network and Recurrent Neural Network never use semantic representation for bag-of-words.The experiment is performed with different document datasets for evaluating the performance of the proposed SF-CNN method.SF-CNN classifies the documents with an accuracy of 94%than the traditional algorithms.
基金the Australian Institute of Nuclear Science and Engineering (AINSE) Limited for providing financial assistance in the form of a Post Graduate Research Award (PGRA) to carry out this worksupported by the Australian Research Council under grants DP200101862, DP210101486, and FL210100050
文摘High-performance lithium-ion batteries(LIB)are important in powering emerging technologies.Cathodes are regarded as the bottleneck of increasing battery energy density,among which layered oxides are the most promising candidates for LIB.However,a limitation with layered oxides cathodes is the transition metal and Li site mixing,which significantly impacts battery capacity and cycling stability.Despite recent research on Li/Ni mixing,there is a lack of comprehensive understanding of the origin of cation mixing between the transition metal and Li;therefore,practical means to address it.Here,a critical review of cation mixing in layered cathodes has been provided,emphasising the understanding of cation mixing mechanisms and their impact on cathode material design.We list and compare advanced characterisation techniques to detect cation mixing in the material structure;examine methods to regulate the degree of cation mixing in layered oxides to boost battery capacity and cycling performance,and critically assess how these can be applied practically.An appraisal of future research directions,including superexchange interaction to stabilise structures and boost capacity retention has also been concluded.Findings will be of immediate benefit in the design of layered cathodes for high-performance rechargeable LIB and,therefore,of interest to researchers and manufacturers.
基金funded by Princess Nourah bint Abdulrahman University,Riyadh,Saudi Arabia,under grant No.(PNURSP2022R161).
文摘The analysis of remote sensing image areas is needed for climate detec-tion and management,especially for monitoringflood disasters in critical environ-ments and applications.Satellites are mostly used to detect disasters on Earth,and they have advantages in capturing Earth images.Using the control technique,Earth images can be used to obtain detailed terrain information.Since the acquisi-tion of satellite and aerial imagery,this system has been able to detectfloods,and with increasing convenience,flood detection has become more desirable in the last few years.In this paper,a Big Data Set-based Progressive Image Classification Algorithm(PICA)system is introduced to implement an image processing tech-nique,detect disasters,and determine results with the help of the PICA,which allows disaster analysis to be extracted more effectively.The PICA is essential to overcoming strong shadows,for proper access to disaster characteristics to false positives by operators,and to false predictions that affect the impact of the disas-ter.The PICA creates tailoring and adjustments obtained from satellite images before training and post-disaster aerial image data patches.Two types of proposed PICA systems detect disasters faster and more accurately(95.6%).
基金Supported by the National Natural Science Foundation of China(52070119)Key Laboratory of Financial Mathematics of Fujian Province University(Putian University)(JR201801).
文摘This paper extends the criterion of the misclassification ratio of discriminant model and presents a new selection method of discriminant model.For selecting the discriminant model,this method establishes the rule of misclassification degree ratio through misclassification ratio of the discriminant model and misclassification degree of the samples.To test the effect of this method,this work uses seven UCI data sets.Numerical experiments on these examples indicate that this method has certain rationality and has a better effect to select a discriminant model.
基金surported by the Jilin Province Science and Technology Development Project(No.20220203017SF)Industrialization Project of the 13th Five-Year"Education Department of Jilin Province(No.JJKH20200334KJ)the National Natural Sci-ence Foundation of China(No.11704143).
文摘Bis(15-crown-5)-stilbenes containing crown ether parts have been widely used in a variety of chemical applications,such as cation detectors,because of their ability to selectively bind to alkali metal cations,Bis(15-crown-5)-stilbenes and its derivatives with complexation of one-or two-alkali metal cation(Li^(+),Na^(+)and K^(+))have been theoretically investigat-ed by quantum chemistry methods.The coordination of alkali cations results in partial shrinkage of crown ethers,which directly affected natural distribution analysis charges and molecular orbital energy levels.The number of alkali metal ions has significant effects on absorption spectra and mean second hyperpolarizability.When one alkali metal ion was added to the anticonformer of bis(15-crown-5)-stilbene,the absorption spectra were obvious-ly redshifted and the mean second hyperpolarizability values were slightly increased;while two alkali metal ions were added to bis(15-crown-5)-stilbene,the absorption spectra were ob-viously blue shifted and the mean second hyperpolarizability values decreased.On the other hand,as the radius of the alkali ions increased,the mean second hyperpolarizability values of the compounds increased gradually.It is indicated that the mean second hyperpolarizability value is sensitive to the number and radius of the alkali metal cations,thus the third order nonlinear optical response can be used as a signal to detect the number and type of alkali met-al ions.
文摘Predictive Maintenance is a type of condition-based maintenance that assesses the equipment's states and estimates its failure probability and when maintenance should be performed.Although machine learning techniques have been frequently implemented in this area,the existing studies disregard to the nat-ural order between the target attribute values of the historical sensor data.Thus,these methods cause losing the inherent order of the data that positively affects the prediction performances.To deal with this problem,a novel approach,named Ordinal Multi-dimensional Classification(OMDC),is proposed for estimating the conditions of a hydraulic system's four components by taking into the natural order of class values.To demonstrate the prediction ability of the proposed approach,eleven different multi-dimensional classification algorithms(traditional Binary Relevance(BR),Classifier Chain(CC),Bayesian Classifier Chain(BCC),Monte Carlo Classifier Chain(MCC),Probabilistic Classifier Chain(PCC),Clas-sifier Dependency Network(CDN),Classifier Trellis(CT),Classifier Dependency Trellis(CDT),Label Powerset(LP),Pruned Sets(PS),and Random k-Labelsets(RAKEL))were implemented using the Ordinal Class Classifier(OCC)algorithm.Besides,seven different classification algorithms(Multilayer Perceptron(MLP),Support Vector Machine(SVM),k-Nearest Neighbour(kNN),Decision Tree(C4.5),Bagging,Random Forest(RF),and Adaptive Boosting(AdaBoost))were chosen as base learners for the OCC algorithm.The experimental results present that the proposed OMDC approach using binary relevance multi-dimensional classification methods predicts the conditions of a hydraulic system's multiple components with high accuracy.Also,it is clearly seen from the results that the OMDC models that utilize ensemble-based classification algorithms give more reliable prediction performances with an average Hamming score of 0.853 than the others that use traditional algorithms as base learners.
文摘In this study,a new tannic acid adsorbent(ethylene glycol diglycidyl ether crosslinked tannic acid,TAEGDE)for adsorptive removal of dyes from water was prepared using EGDE as a cross-linking agent.The resultant TA-EGDE was in particulate form with rough surface morphology and a diameter ranging from 10 to 30μm.The adsorption performance of the TA-EGDE was evaluated in a flow-through mode using water samples contaminated with methylene blue(MB)and two-component mixed dyes,respectively.The TA-EGDE provided adsorption capacity up to 721.8 mg·g^(-1)at 65°C for MB.It showed a high removal efficiency(99%)of MB(50 mg·L^(-1))from the water sample and could recovery 90%of the adsorbed MB by eluting with acidic ethanol aqueous solution.The excellent adsorption of MB and neutral red on the TA-EGDE may be the result of the synergy of electrostatic interaction andπ-πinteraction.Furthermore,the TA-EGDE could separate dyes from water samples contaminated with twocomponent mixed dyes with a separation coefficient ranging from 1.8 to 36.5.The anionic TA-EGDE would be an effective adsorbent to remove and recycle dyes from the contaminated water.
基金supported by the National Natural Science Foundation of China(No.21875110,22075143)the Science Challenge Project(No.TZ2018004)the Qing Lan Project for the grant。
文摘Monocyclic nitrogen-rich 3-(aminomethyl)-4,5-diamine-1,2,4-triazole(1)and fused cyclic 3,7-diamine-6-(aminomethyl)-[1,2,4]triazolo[4,3-b][1,2,4]triazole(9)were synthesized through the convenient cyclization reaction from the readily available reactant.Their energetic salts with high nitrogen content were proved to be rare examples of divalent monocyclic/fused cyclic cationic salts according to the single crystal analyses.The structure of intermediate B was also identified and verified by its trivalent cation crystal 17.5H_2O indirectly.Energetic compounds 2-8 and 10-17 were fully characterized by NMR spectroscopy,infrared spectroscopy,differential scanning calorimetry,elemental analysis.These energetic salts exhibit good thermal stability with decomposition temperatures ranged from 182℃to 245℃.The sensitivity of compounds 2,6,10 and 14 is similar or superior to that of RDX while the others were much more insensitive to mechanical stimulate.Furthermore,detonation velocity of 10(8843 m/s)surpass that of RDX(D=8795 m/s).Considering the high gas production volume(≥808 L/kg)of 2,4,10and 12,constant-volume combustion experiments were conduct to evaluate their gas production capacities specifically.These compounds possess much higher maximum gas-production pressures(P_(max):7.88-10.08 MPa)than the commonly used reagent guanidine nitrate(GN:P_(max)=4.20 MPa),which indicate their strong gas production capacity.
文摘Individuals with special needs learn more slowly than their peers and they need repetitions to be permanent.However,in crowded classrooms,it is dif-ficult for a teacher to deal with each student individually.This problem can be overcome by using supportive education applications.However,the majority of such applications are not designed for special education and therefore they are not efficient as expected.Special education students differ from their peers in terms of their development,characteristics,and educational qualifications.The handwriting skills of individuals with special needs are lower than their peers.This makes the task of Handwriting Recognition(HWR)more difficult.To over-come this problem,we propose a new personalized handwriting verification sys-tem that validates digits from the handwriting of special education students.The system uses a Convolutional Neural Network(CNN)created and trained from scratch.The data set used is obtained by collecting the handwriting of the students with the help of a tablet.A special education center is visited and the handwrittenfigures of the students are collected under the supervision of special education tea-chers.The system is designed as a person-dependent system as every student has their writing style.Overall,the system achieves promising results,reaching a recognition accuracy of about 94%.Overall,the system can verify special educa-tion students’handwriting digits with high accuracy and is ready to integrate with a mobile application that is designed to teach digits to special education students.
基金financial supported by the National Natural Science Foundation of China (22078065)Key Program of Qingyuan Innovation Laboratory (00221001)Quanzhou City Science & Technology Program of China (2020C008R)。
文摘Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quaternary ammoniums bearing different cationic sizes,i.e.MTOA+(methyltrioctylammonium,[(C_(8)H_(17))_(3)CH_(3)N]+),HTMA+(hexadecyltrimethylammonium,[(C_(16)H_(33))(CH_(3))_(3)N]+) and DMDOA+(dimethyldioctadecylammonium,[(C_(18)H_(37))_(2)(CH_(3))_(2)N]+) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs),which were used in the styrene epoxidations.Among them,(MTOA)_(3)PW_(4)O_(24)exhibits the best catalytic performance judged from the highest styrene conversion rate(52%) and styrene oxide selectivity (93%),during which the styrene epoxidation conditions were optimized.Meanwhile,the deactivation mechanism of this kind of PTCs was proposed firstly,i.e.in the case of low H_(2)O_(2) content,the oxidant can only be used in the styrene epoxidation,in which the catalyst can transform into stable Keggin-type POM.But when the content of H_(2)O_(2) is higher,the excess H_(2)O_(2) can reactivate the Keggin-type POM into active (PW_(4)O_(24))_(3)-anions,which can trigger the ring-opening polymerization of styrene oxide.Consequently,the catalyst is deactivated by adhered poly(styrene oxide)irreversibly,which was determined by NMR spectra.In this situation,the active moiety{PO_(4)[WO(O_(2))_(2)]_(4)}_(3)-in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides.This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.
文摘Study of physisorbed and chemisorbed carbon dioxide (CO<sub>2</sub>) species was carried out on the NaX zeolite modified by cationic exchanges with bivalent cations (Ca<sup>2+</sup> and Ba<sup>2+</sup>) by temperature-programmed desorption of CO<sub>2</sub> (CO<sub>2</sub>-TPD). Others results were obtained by infrared to complete the study. The results of this research showed, in the physisorption region (213 - 473 K), that the cationic exchanges on NaX zeolite with bivalent cations increase slightly the interactions of CO<sub>2</sub> molecule with adsorbents and/or cationic site. Indeed, the desorption energies of physisorbed CO<sub>2</sub> obtained on the reference zeolite NaX (13.5 kJ·mol<sup>-1</sup>) are lower than that of exchanged zeolites E-CaX and E-BaX (15.77 and 15.17 kJ·mol<sup>-1</sup> respectively). In the chemisorbed CO<sub>2</sub> region (573 - 873 K), the desorption energies related to desorbed species (bidentate carbonates: CO<sub>3</sub>2-</sup>) on the exchanged zeolites E-CaX and E-BaX are about 81 kJ·mol<sup>-1</sup>, higher than the desorbed species (bicarbonates: HCO<sub>3</sub>2-</sup>) on the reference R-NaX (62 kJ·mol<sup>-1</sup>). In addition, the exchanged E-BaX zeolite develops the secondary adsorption sites corresponding to bicarbonates species with desorption energies of 35 kJ·mol<sup>-1</sup> lower to desorption energies of bicarbonates noted on the reference zeolite NaX.