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
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),N2/NOx,organics,and O_(2))into high-value...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),N2/NOx,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
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
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 elec-trolytes,their efficie...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 elec-trolytes,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)elec-trolysis,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
To provide a scientific basis for controlling mulberry bacterial blight in Bazhong,Sichuan,China(BSC),this study aimed to isolate and purify pathogenic bacteria from diseased branches of mulberry trees in the region a...To provide a scientific basis for controlling mulberry bacterial blight in Bazhong,Sichuan,China(BSC),this study aimed to isolate and purify pathogenic bacteria from diseased branches of mulberry trees in the region and to clarify their taxonomic status using morphological observation,physiological and biochemical detection,molecular-level identification,and the construction of a phylogenetic tree.A total of 218 bacterial strains were isolated from samples of diseased mulberry branches.Of these,7 strains were identified as pathogenic bacteria based on pathogenicity tests conducted in accordance with Koch’s postulates.Preliminary findings from the analysis of the 16S rRNA sequence indicated that the 7 pathogenic bacteria are members of Klebsiella spp.Morphological observation revealed that the pathogenic bacteria were oval-shaped and had capsules but no spores.They could secrete pectinase,cellulase,and protease and were able to utilize D-glucose,D-mannose,D-maltose,and D-Cellobiose.The 7 strains of pathogenic bacteria exhibited the highest homology with Klebsiella oxytoca.This study identifies Klebsiella oxytoca as the causative agent of mulberry bacterial blight in BSC,laying the foundation for the prevention and control of this pathogen and further investigation into its pathogenic mechanism.展开更多
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
Perennial grasses have developed intricate mechanisms to adapt to diverse environments,enabling their resistance to various biotic and abiotic stressors.These mechanisms arise from strong natural selection that contri...Perennial grasses have developed intricate mechanisms to adapt to diverse environments,enabling their resistance to various biotic and abiotic stressors.These mechanisms arise from strong natural selection that contributes to enhancing the adaptation of forage plants to various stress conditions.Methods such as antisense RNA technology,CRISPR/Cas9 screening,virus-induced gene silencing,and transgenic technology,are commonly utilized for investigating the stress response functionalities of grass genes in both warm-season and cool-season varieties.This review focuses on the functional identification of stress-resistance genes and regulatory elements in grasses.It synthesizes recent studies on mining functional genes,regulatory genes,and protein kinase-like signaling factors involved in stress responses in grasses.Additionally,the review outlines future research directions,providing theoretical support and references for further exploration of(i)molecular mechanisms underlying grass stress responses,(ii)cultivation and domestication of herbage,(iii)development of high-yield varieties resistant to stress,and(iv)mechanisms and breeding strategies for stress resistance in grasses.展开更多
As a pioneer leguminous shrub species for vegetation re-establishment, Caragana microphylla is widely distributed in the semi-fixed and fixed sandy lands of the Horqin region, North China. C. microphylla planta- tions...As a pioneer leguminous shrub species for vegetation re-establishment, Caragana microphylla is widely distributed in the semi-fixed and fixed sandy lands of the Horqin region, North China. C. microphylla planta- tions modify organic carbon (SOC), nitrogen (N) and phosphorus dynamics, bulk density and water-holding capacity and biological activities in soils, but little is known with regard to soil exchange properties. Variation in soil ex- changeable base cations was examined under C. microphylla plantations with an age sequence of 0, 5, 10, and 22 years in the Horqin Sandy Land, and at the depth of 0-10, 10-20, and 20-30 cm, respectively. C. microphylla has been planted on the non-vegetated sand dunes with similar physical-chemical soil properties. The results showed that exchangeable calcium (Ca), magnesium (Mg), and potassium (K), and cation exchange capacity (CEC) were significantly increased, and Ca saturation tended to decrease, while Mg and K saturations were increased with the plantation years. No difference was observed for exchangeable sodium (Na) neither with plantation years nor at soil depths. Of all the base cations and soil layers, exchangeable K at the depth of 0-10 cm accumulated most quickly, and it increased by 1.76, 3.16, and 4.25 times, respectively after C. microphylla was planted for 5, 10, and 22 years. Exchangeable Ca, Mg, and K, and CEC were significantly (P〈0.001) and positively correlated with SOC, total N, pH and electrical conductivity (EC). Soil pH and SOC are regarded as the main factors influencing the variation in ex- changeable cations, and the preferential absorption of cations by plants and different leaching rates of base cations that modify cation saturations under C. microphylla plantation. It is concluded that as a nitrogen-fixation species, C. microphylla plantation is beneficial to increasing exchangeable base cations and CEC in soils, and therefore can improve soil fertility and create favorable microenvironments for plants and creatures in the semi-arid sandy land ecosystems.展开更多
The effects of alkaline cations (M^+ = Li^+, Na^+, K^+, Cs^+)on the electrochemical synthesis of polyaniline were carfled out under cyclovoltammetric conditions using nitrates of Li^+, Na^+, K^+, and Cs^+ a...The effects of alkaline cations (M^+ = Li^+, Na^+, K^+, Cs^+)on the electrochemical synthesis of polyaniline were carfled out under cyclovoltammetric conditions using nitrates of Li^+, Na^+, K^+, and Cs^+ as the supporting electrolytes. The results show that the oxidation potentials of aniline in the electrolytes decrease as the protonation extent of aniline decreases from the fast scan, which is caused by the decrease of the ionic radius of alkaline metal ions at the same concentration of alkaline cations. With the scan number increasing, the deposit charge Q as the characteristic growth function also depends on the protonation of aniline, and it increases with the ionic radius of alkaline cations increasing. SEM images show the effect of alkaline cations on the morphology of polyaniline. It is clear that the ionic mobility of alkaline cations is further lower than that of W. Alkaline cations and counter-ions were the species responsible for the enhancement of Pani electrosynthesis. Therefore, this is exactly what SEM images show: a relatively rough fibrous structure in the case of Pani-H^+ suggesting a sponge-like structure and a highly orderly fiber-like structure in the case of Pani-M^+.展开更多
The effects of simulated nitrogen(N)deposition on soil exchangeable cations were studied in three forest types of subtropical China.Four N treatments with three replications were designed for the monsoon evergreen bro...The effects of simulated nitrogen(N)deposition on soil exchangeable cations were studied in three forest types of subtropical China.Four N treatments with three replications were designed for the monsoon evergreen broadleaf forest (mature forest):control(0 kg N ha-1 year-1),low N(50 kg N ha-1 year-1),medium N(100 kg N ha-1 year-1)and high N(150 kg N ha-1 year-1),and only three treatments(i.e.,control,low N,medium N)were established for the pine and mixed forests.Nitrogen had been applied continuously for 26 months before the measurement.The mature forest responded more rapidly and intensively to N additions than the pine and mixed forests,and exhibited some significant negative symptoms,e.g.,soil acidification,Al mobilization and leaching of base cations from soil.The pine and mixed forests responded slowly to N additions and exhibited no significant response of soil cations.Response of soil exchangeable cations to N deposition varied in the forests of subtropical China,depending on soil N status and land-use history.展开更多
As one of the most important soil components, montmorillonite plays a vital role in transport and retention of organic pollutants in soils. Ciprofloxacin (CIP), an antibiotic of fluoroquiolones, has been frequently ...As one of the most important soil components, montmorillonite plays a vital role in transport and retention of organic pollutants in soils. Ciprofloxacin (CIP), an antibiotic of fluoroquiolones, has been frequently detected in water and soil environments due to its wide use in human and veterinary medicine. In this study, the adsorption of CIP onto different homoionic montmorillonite such as Na-, Ca- and Al-MMT was investigated, and the influence of types and charges of exchangeable cations in the interlayer of montmorillonite on CIP adsorption was evaluated. The results showed that different homoionic montmorillonite exhibited different sorption capacity of CIP. At pH 3, the sorption capacity of CIP decreased in the order Na-MMT Ca-MMT Al-MMT, following the lyotropic series. When solution pH increased to 11, the sorption capacity of CIP followed the order Ca-MMT Al-MMT Na-MMT. Accompanying CIP adsorption on Ca-MMT, a certain amount of Ca2+ was released into solution. Compared to pH 3, the lower Ca concentration in solution at pH 11 indicated that the adsorption of CIP on Ca-MMT at strong alkaline pH was no longer via cation exchange, and surface complexation or cation bridging might contribute to CIP adsorption. The adsorption of CIP on Na- and Ca-MMT at pH 3 and 11 resulted in the expansion of d-spacing, indicative of intercalation of CIP into the interlayer space of the montmorillonite. However, a decrease of d-spacing was observed when CIP adsorbed on Al-MMT at pH 11, which might be attributed to the dissolution of Al-CIP complex formed between CIP and Al3+ in the interlayer of montmorillonite. The results suggest that the types and charges of exchangeable cations in the interlayer of montmorillonite play an important role in CIP adsorption on montmorillonite.展开更多
This paper determined cations and anions concentrations, Total Kjeldahl Nitrogen (TKN), and heavy metals content in sewage sludge collected from the drying beds of wastewater treatment plant in Gaza. The aim was to te...This paper determined cations and anions concentrations, Total Kjeldahl Nitrogen (TKN), and heavy metals content in sewage sludge collected from the drying beds of wastewater treatment plant in Gaza. The aim was to test the possibility of using this sewage sludge as an alternative source of mineral fertilizers. Many instruments were used in this work: flame photometry (K, Na), EDTA titration (Ca, Mg), the turbidity method () , spectrophotometer (turbidity), ascorbic acid method (orthophosphate), titrimetric method (Cl﹣), inductive coupled plasma analyzer (ICP, heavy metals). All the processes of experiments and analyses were described clearly for reference. Results showed that concentrations of Na﹢, K﹢, Ca2﹢ and Mg2﹢ were 28.93, 2.53, 271 and 177 mg/kg respectively whereas? were 0.434, 18.59, 0.87 and 0.026 g/kg respectively. The concentrations of Fe, Cu, Pb, Zn and Mn were 125.12, 172.56, 76.88, 218.73 and 157.56 mg/kg respectively. These results indicate that sewage sludge from Gaza contained high fractions of most plant nutrients accordingly, and it may be advantageous to use the sludge as a natural source of plant fertilizers.展开更多
The effects of different structures of 2:1 layer minerals, layer charge location, and changes of structure and charge during the weathering process on the fixation and release of interlayer cations are reviewed. It co...The effects of different structures of 2:1 layer minerals, layer charge location, and changes of structure and charge during the weathering process on the fixation and release of interlayer cations are reviewed. It could be concluded that the fixation capacity is determined by the total amount of interlayer charge originating from both octahedral and tetrahedral sheets. The relationship between interlayer cation fixation and octahedral structure of the secondary minerals may be different from that of the primary minerals. The oxidation and reduction of cations with variable valence can greatly influence the cation-fixation capacity.展开更多
The electrical conductivities (ECs) of suspensions containing 25 and 30 gkg^(-1) solids prepared from the electrodialyzed clay fraction (< 2μm in diameter) of latosol,yellow-brown soil, and black soil, dispersed i...The electrical conductivities (ECs) of suspensions containing 25 and 30 gkg^(-1) solids prepared from the electrodialyzed clay fraction (< 2μm in diameter) of latosol,yellow-brown soil, and black soil, dispersed in various nitrate solutions having concentrations of 1X 10^(-4)/z mol L^(-1), where z is the valence, and in distilled water, were measured at fieldstrengths ranging from 14 kV cm^(-1) to 210 kV cm^(-1). On the basis of analyses of the chargedensity and exchangeable ion composition on the surfaces of soil particles in the suspensions, andof the characters of the EC-field strength curves of the various suspensions, it was inferred thatthe increment of EC (ΔEC) and/or relative electrical conductivity (REC) can indicate the bondingstrength between cations and soil particles. The bonding strengths of various cations with the soilsdiminished in the order: K^+ > Zn^(2+) > Mg^(2+) = Ca^(2+) > Na^+ for latosol, Ca^(2+) > Zn^(2+) >Mg^(2+) = K^+ > Na^+ for yellow-brown soil, and Zn^(2+) ≥ Ca^(2+) ≥ Mg^(2+) > K^+ > Na^+ for blacksoil.展开更多
Alkali and alkaline‐earth metals from fly ash have a significant deactivation effect on catalysts used for selective catalytic reduction of NOx by NH3(NH3‐SCR).Bromides are considered effective additives to improve ...Alkali and alkaline‐earth metals from fly ash have a significant deactivation effect on catalysts used for selective catalytic reduction of NOx by NH3(NH3‐SCR).Bromides are considered effective additives to improve Hg0 oxidation on SCR catalysts.In this work,the effects of different bromides(NH4Br,NaBr,KBr,and CaBr2)on a commercial V2O5‐WO3/TiO2 catalyst were studied.NOx conversion decreased significantly over the KBr‐poisoned catalyst(denoted as L‐KBr),while that over NaBr‐and CaBr2‐poisoned catalysts(denoted as L‐NaBr and L‐CaBr,respectivity)decreased to a lesser extent compared with the fresh sample.Poor N2 selectivity was observed over L‐NaBr,L‐KBr and L‐CaBr catalysts.The decrease in the ratio of chemisorbed oxygen to total surface oxygen(Oα/(Oα+Oβ+Ow)),reducibility and surface acidity might contribute to the poor activity and N2 selectivity over L‐KBr catalyst.The increased Oαratio was conducive to the enhanced reducibility of L‐CaBr.Combined with enhanced surface acidity,this might offset the negative effect of the loss of active sites by CaBr2 covering.The overoxidation of NH3 and poor N2 selectivity in NH3 oxidation should retard the SCR activity at high temperatures over L‐CaBr catalyst.The increased basicity might contribute to increased NOx adsorption on L‐KBr and L‐CaBr catalysts.A correlation between the acid‐basic and redox properties of bromide‐poisoned catalysts and their catalytic properties is established.展开更多
An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C_2H_4 on MX(M=Ag, Cu; X=F, Cl). The calculated results show the following order of adsorptio...An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C_2H_4 on MX(M=Ag, Cu; X=F, Cl). The calculated results show the following order of adsorption strength: F ->Cl - for anions; Cu +>Ag + for cations. The results can be explained by the detailed analysis of atomic charge, orbital energy and orbital population by using the natural bond orbital(NBO) theory: (1) anions with stronger electronegativity can attract more electrons from the s orbital of M, while at the same time it does not obviously weaken the d orbital occupation of M, thus the nearly vacant s orbital and the sufficiently filled d orbitals of M help with forming σ-donation and d-π * backdonation with the π orbital and the π * orbital of olefin, respectively; (2) a smaller energy gap of symmetry-adapted orbitals between olefin and a cation can favor the electron transfer, that is why Cu + forms stronger adsorption with olefin than Ag + does.展开更多
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.
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),N2/NOx,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.
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.
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 elec-trolytes,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)elec-trolysis,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 Key Scientific and Technological Grant of Zhejiang for Breeding New Agricultural Varieties(2021C02072-6)the Natural Science Foundation of Anhui Provincial Education Department(KJ2019A0574).
文摘To provide a scientific basis for controlling mulberry bacterial blight in Bazhong,Sichuan,China(BSC),this study aimed to isolate and purify pathogenic bacteria from diseased branches of mulberry trees in the region and to clarify their taxonomic status using morphological observation,physiological and biochemical detection,molecular-level identification,and the construction of a phylogenetic tree.A total of 218 bacterial strains were isolated from samples of diseased mulberry branches.Of these,7 strains were identified as pathogenic bacteria based on pathogenicity tests conducted in accordance with Koch’s postulates.Preliminary findings from the analysis of the 16S rRNA sequence indicated that the 7 pathogenic bacteria are members of Klebsiella spp.Morphological observation revealed that the pathogenic bacteria were oval-shaped and had capsules but no spores.They could secrete pectinase,cellulase,and protease and were able to utilize D-glucose,D-mannose,D-maltose,and D-Cellobiose.The 7 strains of pathogenic bacteria exhibited the highest homology with Klebsiella oxytoca.This study identifies Klebsiella oxytoca as the causative agent of mulberry bacterial blight in BSC,laying the foundation for the prevention and control of this pathogen and further investigation into its pathogenic mechanism.
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.
基金supported by the Chief Scientist Program of Qinghai Province(2024-SF-101).
文摘Perennial grasses have developed intricate mechanisms to adapt to diverse environments,enabling their resistance to various biotic and abiotic stressors.These mechanisms arise from strong natural selection that contributes to enhancing the adaptation of forage plants to various stress conditions.Methods such as antisense RNA technology,CRISPR/Cas9 screening,virus-induced gene silencing,and transgenic technology,are commonly utilized for investigating the stress response functionalities of grass genes in both warm-season and cool-season varieties.This review focuses on the functional identification of stress-resistance genes and regulatory elements in grasses.It synthesizes recent studies on mining functional genes,regulatory genes,and protein kinase-like signaling factors involved in stress responses in grasses.Additionally,the review outlines future research directions,providing theoretical support and references for further exploration of(i)molecular mechanisms underlying grass stress responses,(ii)cultivation and domestication of herbage,(iii)development of high-yield varieties resistant to stress,and(iv)mechanisms and breeding strategies for stress resistance in grasses.
基金supported by the National Key Basic Research Program of China (2011CB403204)the Natural Science Foundation of China (31000200)
文摘As a pioneer leguminous shrub species for vegetation re-establishment, Caragana microphylla is widely distributed in the semi-fixed and fixed sandy lands of the Horqin region, North China. C. microphylla planta- tions modify organic carbon (SOC), nitrogen (N) and phosphorus dynamics, bulk density and water-holding capacity and biological activities in soils, but little is known with regard to soil exchange properties. Variation in soil ex- changeable base cations was examined under C. microphylla plantations with an age sequence of 0, 5, 10, and 22 years in the Horqin Sandy Land, and at the depth of 0-10, 10-20, and 20-30 cm, respectively. C. microphylla has been planted on the non-vegetated sand dunes with similar physical-chemical soil properties. The results showed that exchangeable calcium (Ca), magnesium (Mg), and potassium (K), and cation exchange capacity (CEC) were significantly increased, and Ca saturation tended to decrease, while Mg and K saturations were increased with the plantation years. No difference was observed for exchangeable sodium (Na) neither with plantation years nor at soil depths. Of all the base cations and soil layers, exchangeable K at the depth of 0-10 cm accumulated most quickly, and it increased by 1.76, 3.16, and 4.25 times, respectively after C. microphylla was planted for 5, 10, and 22 years. Exchangeable Ca, Mg, and K, and CEC were significantly (P〈0.001) and positively correlated with SOC, total N, pH and electrical conductivity (EC). Soil pH and SOC are regarded as the main factors influencing the variation in ex- changeable cations, and the preferential absorption of cations by plants and different leaching rates of base cations that modify cation saturations under C. microphylla plantation. It is concluded that as a nitrogen-fixation species, C. microphylla plantation is beneficial to increasing exchangeable base cations and CEC in soils, and therefore can improve soil fertility and create favorable microenvironments for plants and creatures in the semi-arid sandy land ecosystems.
基金This project was financially supported by the National Natural Science Foundation of China (No. 50274010)the National High-Tech Research and Development Program of China ("863" Program, No. 2002AA-302404).
文摘The effects of alkaline cations (M^+ = Li^+, Na^+, K^+, Cs^+)on the electrochemical synthesis of polyaniline were carfled out under cyclovoltammetric conditions using nitrates of Li^+, Na^+, K^+, and Cs^+ as the supporting electrolytes. The results show that the oxidation potentials of aniline in the electrolytes decrease as the protonation extent of aniline decreases from the fast scan, which is caused by the decrease of the ionic radius of alkaline metal ions at the same concentration of alkaline cations. With the scan number increasing, the deposit charge Q as the characteristic growth function also depends on the protonation of aniline, and it increases with the ionic radius of alkaline cations increasing. SEM images show the effect of alkaline cations on the morphology of polyaniline. It is clear that the ionic mobility of alkaline cations is further lower than that of W. Alkaline cations and counter-ions were the species responsible for the enhancement of Pani electrosynthesis. Therefore, this is exactly what SEM images show: a relatively rough fibrous structure in the case of Pani-H^+ suggesting a sponge-like structure and a highly orderly fiber-like structure in the case of Pani-M^+.
基金Project supported by the National Natural Science Foundation of China(No.30670392)the Knowledge Innovation Program of the Chinese Academy of Sciences(Nos.KZCX2-YW-432 and KSCX2-SW-133)
文摘The effects of simulated nitrogen(N)deposition on soil exchangeable cations were studied in three forest types of subtropical China.Four N treatments with three replications were designed for the monsoon evergreen broadleaf forest (mature forest):control(0 kg N ha-1 year-1),low N(50 kg N ha-1 year-1),medium N(100 kg N ha-1 year-1)and high N(150 kg N ha-1 year-1),and only three treatments(i.e.,control,low N,medium N)were established for the pine and mixed forests.Nitrogen had been applied continuously for 26 months before the measurement.The mature forest responded more rapidly and intensively to N additions than the pine and mixed forests,and exhibited some significant negative symptoms,e.g.,soil acidification,Al mobilization and leaching of base cations from soil.The pine and mixed forests responded slowly to N additions and exhibited no significant response of soil cations.Response of soil exchangeable cations to N deposition varied in the forests of subtropical China,depending on soil N status and land-use history.
基金Funded by the Key Project of Chinese Ministry of Education (No. 107076)Wisconsin Groundwater Research Council to Z.Li
文摘As one of the most important soil components, montmorillonite plays a vital role in transport and retention of organic pollutants in soils. Ciprofloxacin (CIP), an antibiotic of fluoroquiolones, has been frequently detected in water and soil environments due to its wide use in human and veterinary medicine. In this study, the adsorption of CIP onto different homoionic montmorillonite such as Na-, Ca- and Al-MMT was investigated, and the influence of types and charges of exchangeable cations in the interlayer of montmorillonite on CIP adsorption was evaluated. The results showed that different homoionic montmorillonite exhibited different sorption capacity of CIP. At pH 3, the sorption capacity of CIP decreased in the order Na-MMT Ca-MMT Al-MMT, following the lyotropic series. When solution pH increased to 11, the sorption capacity of CIP followed the order Ca-MMT Al-MMT Na-MMT. Accompanying CIP adsorption on Ca-MMT, a certain amount of Ca2+ was released into solution. Compared to pH 3, the lower Ca concentration in solution at pH 11 indicated that the adsorption of CIP on Ca-MMT at strong alkaline pH was no longer via cation exchange, and surface complexation or cation bridging might contribute to CIP adsorption. The adsorption of CIP on Na- and Ca-MMT at pH 3 and 11 resulted in the expansion of d-spacing, indicative of intercalation of CIP into the interlayer space of the montmorillonite. However, a decrease of d-spacing was observed when CIP adsorbed on Al-MMT at pH 11, which might be attributed to the dissolution of Al-CIP complex formed between CIP and Al3+ in the interlayer of montmorillonite. The results suggest that the types and charges of exchangeable cations in the interlayer of montmorillonite play an important role in CIP adsorption on montmorillonite.
文摘This paper determined cations and anions concentrations, Total Kjeldahl Nitrogen (TKN), and heavy metals content in sewage sludge collected from the drying beds of wastewater treatment plant in Gaza. The aim was to test the possibility of using this sewage sludge as an alternative source of mineral fertilizers. Many instruments were used in this work: flame photometry (K, Na), EDTA titration (Ca, Mg), the turbidity method () , spectrophotometer (turbidity), ascorbic acid method (orthophosphate), titrimetric method (Cl﹣), inductive coupled plasma analyzer (ICP, heavy metals). All the processes of experiments and analyses were described clearly for reference. Results showed that concentrations of Na﹢, K﹢, Ca2﹢ and Mg2﹢ were 28.93, 2.53, 271 and 177 mg/kg respectively whereas? were 0.434, 18.59, 0.87 and 0.026 g/kg respectively. The concentrations of Fe, Cu, Pb, Zn and Mn were 125.12, 172.56, 76.88, 218.73 and 157.56 mg/kg respectively. These results indicate that sewage sludge from Gaza contained high fractions of most plant nutrients accordingly, and it may be advantageous to use the sludge as a natural source of plant fertilizers.
基金Project(No.39770427)supported by the National Natural Science Foundation of China.
文摘The effects of different structures of 2:1 layer minerals, layer charge location, and changes of structure and charge during the weathering process on the fixation and release of interlayer cations are reviewed. It could be concluded that the fixation capacity is determined by the total amount of interlayer charge originating from both octahedral and tetrahedral sheets. The relationship between interlayer cation fixation and octahedral structure of the secondary minerals may be different from that of the primary minerals. The oxidation and reduction of cations with variable valence can greatly influence the cation-fixation capacity.
基金Project(Nos.49771046 and 49831005)supported by the National Natural Science Foundation of China and the Center for International Cooperation,Ministry of Foreign Affairs,State of Israel.
文摘The electrical conductivities (ECs) of suspensions containing 25 and 30 gkg^(-1) solids prepared from the electrodialyzed clay fraction (< 2μm in diameter) of latosol,yellow-brown soil, and black soil, dispersed in various nitrate solutions having concentrations of 1X 10^(-4)/z mol L^(-1), where z is the valence, and in distilled water, were measured at fieldstrengths ranging from 14 kV cm^(-1) to 210 kV cm^(-1). On the basis of analyses of the chargedensity and exchangeable ion composition on the surfaces of soil particles in the suspensions, andof the characters of the EC-field strength curves of the various suspensions, it was inferred thatthe increment of EC (ΔEC) and/or relative electrical conductivity (REC) can indicate the bondingstrength between cations and soil particles. The bonding strengths of various cations with the soilsdiminished in the order: K^+ > Zn^(2+) > Mg^(2+) = Ca^(2+) > Na^+ for latosol, Ca^(2+) > Zn^(2+) >Mg^(2+) = K^+ > Na^+ for yellow-brown soil, and Zn^(2+) ≥ Ca^(2+) ≥ Mg^(2+) > K^+ > Na^+ for blacksoil.
基金supported by the National Key R&D Program of China(2016YFC0203900,2016YFC0203901)National Natural Science Foundation of China(51778619,21577173)~~
文摘Alkali and alkaline‐earth metals from fly ash have a significant deactivation effect on catalysts used for selective catalytic reduction of NOx by NH3(NH3‐SCR).Bromides are considered effective additives to improve Hg0 oxidation on SCR catalysts.In this work,the effects of different bromides(NH4Br,NaBr,KBr,and CaBr2)on a commercial V2O5‐WO3/TiO2 catalyst were studied.NOx conversion decreased significantly over the KBr‐poisoned catalyst(denoted as L‐KBr),while that over NaBr‐and CaBr2‐poisoned catalysts(denoted as L‐NaBr and L‐CaBr,respectivity)decreased to a lesser extent compared with the fresh sample.Poor N2 selectivity was observed over L‐NaBr,L‐KBr and L‐CaBr catalysts.The decrease in the ratio of chemisorbed oxygen to total surface oxygen(Oα/(Oα+Oβ+Ow)),reducibility and surface acidity might contribute to the poor activity and N2 selectivity over L‐KBr catalyst.The increased Oαratio was conducive to the enhanced reducibility of L‐CaBr.Combined with enhanced surface acidity,this might offset the negative effect of the loss of active sites by CaBr2 covering.The overoxidation of NH3 and poor N2 selectivity in NH3 oxidation should retard the SCR activity at high temperatures over L‐CaBr catalyst.The increased basicity might contribute to increased NOx adsorption on L‐KBr and L‐CaBr catalysts.A correlation between the acid‐basic and redox properties of bromide‐poisoned catalysts and their catalytic properties is established.
文摘An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C_2H_4 on MX(M=Ag, Cu; X=F, Cl). The calculated results show the following order of adsorption strength: F ->Cl - for anions; Cu +>Ag + for cations. The results can be explained by the detailed analysis of atomic charge, orbital energy and orbital population by using the natural bond orbital(NBO) theory: (1) anions with stronger electronegativity can attract more electrons from the s orbital of M, while at the same time it does not obviously weaken the d orbital occupation of M, thus the nearly vacant s orbital and the sufficiently filled d orbitals of M help with forming σ-donation and d-π * backdonation with the π orbital and the π * orbital of olefin, respectively; (2) a smaller energy gap of symmetry-adapted orbitals between olefin and a cation can favor the electron transfer, that is why Cu + forms stronger adsorption with olefin than Ag + does.