Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challe...Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challenging.Herein,a support electron inductive effect of Pd-Mn/Ni foam catalyst was proposed via in-situ Mn doping to optimize the electronic structure of the Ni foam(NF),which can inductive regulation of Pd for improving the EHDC performance.The mass activity and current efficiency of Pd-Mn/NF catalyst are 2.91 and 1.34 times superior to that of Pd/NF with 2,4-dichlorophenol as model compound,respectively.The Mn-doped interlayer optimized the electronic structure of Pd by bringing the d-state closer to the Fermi level than Pd on the NF surface,which optimizied the binding of EHDC intermediates.Additionally,the Mn-doped interlayer acted as a promoter for generating H∗and accelerating the EHDC reaction.This work presents a simple and effective regulation strategy for constructing high-efficient cathode catalyst for the EHDC of chlorinated organic compounds.展开更多
Electrocatalytic conversion of nitrate to ammonia(NITRR)can simultaneously achieve the removal of nitrate and the synthesis of value-added ammonia,a promising candidate to replace Haber-Bosch process with low carbon d...Electrocatalytic conversion of nitrate to ammonia(NITRR)can simultaneously achieve the removal of nitrate and the synthesis of value-added ammonia,a promising candidate to replace Haber-Bosch process with low carbon dioxide emissions.However,high hydrogenation energy barrier for*NO intermediates and insufficient supply of active hydrogen cause slow hydrogenation process,and further result in low efficiency of nitrate conversion and ammonia synthesis.Herein,a series of tandem catalysts,one-dimensional coordination polymers(1D CCPs)with dual sites are synthesized and obtained 190.4 mg h^(-1)mgcat^(-1)ammonia production rate with Faradaic efficiency of 97.16%,outperforming to the most of recent reported catalysts.The catalytic performances are well-maintained even after a long-term stability test of 1200 h,laying the foundation for practical applications.Density functional theory results reveal that the stationary adsorbed*NO on Ni site induced proximity electronic effect could reduce the energy barrier for hydrogenation of*NO intermediates over Cu site.In addition,the Ni site in the dual sites 1D CCPs is conducive to generating active hydrogen,providing rich proton source to boost the hydrogenation of*NO,and further enhancing the compatibility of deoxygenation and hydrogenation process.Our work paves a new insight into the mechanism of NITRR process and will inspire more research interests in exploring the proximity electronic effect in catalytic process.展开更多
Multi-electron and multi-orbital effects play a crucial role in the interaction of strong laser fields with complex molecules.Here,multi-electron effects encompass not only electron-electron Coulomb interactions and e...Multi-electron and multi-orbital effects play a crucial role in the interaction of strong laser fields with complex molecules.Here,multi-electron effects encompass not only electron-electron Coulomb interactions and exchangecorrelation effects but also the interference between the dynamics of different electron wave packets.展开更多
A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings...A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings.The weak noncovalentπ-πinteraction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations.The roles of weakπ-πinteraction,steric bulk,and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail.The combination ofπ-πinteraction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130°C.展开更多
Organic compounds are promising electrode materials for aqueous zinc-ion batteries(AZIBs) but largely suffer from poor rate and cycling performance.This work reports that the push-pull electron effect of organic compo...Organic compounds are promising electrode materials for aqueous zinc-ion batteries(AZIBs) but largely suffer from poor rate and cycling performance.This work reports that the push-pull electron effect of organic compounds could be used to tune the electrochemical performance of AZIB s.Hexaazatriphenylene-based(HATN) small molecules with different withdrawing or donating groups were synthesized and used as electrodes for AZIBs.Compared to the hydrogen atoms and electrondonating methyl groups,the electron-withdrawing fluorine atoms endow HATN-based small molecule(HATN-6F)with a much-improved redox platform,rate performance and cycling stability.The fluorinated electrode HATN-6F potently amplifies and stabilizes the kinetics of cation co-(de)insertion reactions,concurrently enhancing the conductivity and electron affinity,resulting in improved rate performance and enhanced cycling stability.The combination of theoretical calculations and experimental characterization confirms that the fluorine-rich peripheral environment effectively modifies the distribution of conjugated electrons in HATN,enhancing its affinity for zinc ions and improving its capacity for cations zinc storage.This work demonstrates a new avenue for the design and synthesis of organic electrode with excellent electrochemical performance for ZIBs.展开更多
Earth-abundant and nontoxic Sn-based materials have been regarded as promising catalysts for the electrochemical conversion of CO_(2)to C1 products,e.g.,CO and formate.However,it is still difficult for Snbased materia...Earth-abundant and nontoxic Sn-based materials have been regarded as promising catalysts for the electrochemical conversion of CO_(2)to C1 products,e.g.,CO and formate.However,it is still difficult for Snbased materials to obtain satisfactory performance at low-to-moderate overpotentials.Herein,a simple and facile electrospinning technique is utilized to prepare a composite of a bimetallic Sn-Co oxide/carbon matrix with a hollow nanotube structure(Sn Co-HNT).Sn Co-HNT can maintain>90%faradaic efficiencies for C1 products within a wide potential range from-0.6 VRHE to-1.2 VRHE,and a highest 94.1%selectivity towards CO in an H-type cell.Moreover,a 91.2%faradaic efficiency with a 241.3 m A cm^(-2)partial current density for C1 products could be achieved using a flow cell.According to theoretical calculations,the fusing of Sn/Co oxides on the carbon matrix accelerates electron transfer at the atomic level,causing electron deficiency of Sn centers and reversible variation between Co^(2+)and Co^(3+)centers.The synergistic effect of the Sn/Co composition improves the electron affinity of the catalyst surface,which is conducive to the adsorption and stabilization of key intermediates and eventually increases the catalytic activity in CO_(2)electroreduction.This study could provide a new strategy for the construction of oxide-derived catalysts for CO_(2)electroreduction.展开更多
Trivalent rare-earth ions （La3＋,Pr3＋,Nd3＋,Sm3＋,Gd3＋,Tb3＋,Dy3＋,Ho3＋,Er3＋,Tm3＋,and Yb3＋） were investigated as the codoped auxiliary sensitizer for the electron trapping materials SrS：Eu2＋ in order to enha...Trivalent rare-earth ions （La3＋,Pr3＋,Nd3＋,Sm3＋,Gd3＋,Tb3＋,Dy3＋,Ho3＋,Er3＋,Tm3＋,and Yb3＋） were investigated as the codoped auxiliary sensitizer for the electron trapping materials SrS：Eu2＋ in order to enhance the fluorescence properties.It was found that Sm3＋ and Tb3＋ had the best photoluminescence stimulated luminescence （PSL） effect among the selected trivalent rare-earth ions.All the SrS：Eu2＋ samples doped by different trivalent rare-earth ions could be stimulated by 980 nm laser after being exposed to the conventional sunlight,and they emitted PSL with the peak located at 615 nm.The result also indicated that some co-doped rare earth ions could increase fluorescence intensities of the traditional electron trapping materials SrS：Eu2＋.展开更多
Attaining a highly efficient and inexpensive electrocatalyst is significant for the hydrogen evolution reaction(HER)but still challenging nowadays.The transition-metal phosphides(TMPs)catalysts with platinum-like elec...Attaining a highly efficient and inexpensive electrocatalyst is significant for the hydrogen evolution reaction(HER)but still challenging nowadays.The transition-metal phosphides(TMPs)catalysts with platinum-like electronic structures are a potential candidate for the HER,but those are prone to be strongly bound with hydrogen intermediates(H∗),resulting in sluggish HER kinetics.Herein we report a unique hybrid structure of CoP anchored on graphene nanoscrolls@carbon nano tubes(CNTs)scaffold(Ni M@C-CoP)encapsulating various Ni M(M=Zn,Mo,Ni,Co)bimetal nanoalloy via chemical vapor deposi-tion(CVD)growth of CNT on graphene nanoscrolls followed by the impregnation of cobalt precursors and phosphorization for efficiently electrocatalytic hydrogen evolution.CoP nanoparticles mainly scattered at the tip of CNT branches which exhibited the analogical“Three-layer core-shell”structures.Experiments and density functional theory(DFT)calculations consistently disclose that the encapsulated various NiMs can offer different numbers of electrons to weaken the interactions of outmost CoP with H∗and push the downshift of the d-band center to different degrees as well as stabilize the outmost CoP nanopar-ticles to gain catalytic stability via the electron traversing effect.The electrocatalytic HER activity can be maximumly enhanced with low overpotentials of 78 mV(alkaline)and 89 mV(acidic)at a current density of 10 mA/cm^(2) and sustained at least 24 h especially for NiZn@C-CoP catalyst.This novel system is distinct from conventional three-layer heterostructure,providing a specially thought of d-band center control engineering strategy for the design of heterogeneous catalysts and expanding to other electrocat-alysts,energy storage,sensing,and other applications.展开更多
The development of bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N‐heterocycles is a challenge.In this study,Ru_(2)P/AC effectively promoted reversible transformations bet...The development of bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N‐heterocycles is a challenge.In this study,Ru_(2)P/AC effectively promoted reversible transformations between unsaturated and saturated N‐heterocycles affording yields of 98%and 99%,respectively.Moreover,a remarkable enhancement in the reusability of Ru_(2)P/AC was observed compared with other Ru‐based catalysts.According to density functional theory calculations,the superior performance of Ru_(2)P/AC was ascribed to specific synergistic factors,namely geometric and electronic effects induced by P.P greatly reduced the large Ru‐Ru ensembles and finely modified the electronic structures,leading to a low reaction barrier and high desorption ability of the catalyst,further boosting the hydrogenation and acceptorless dehydrogenation processes.展开更多
The objective of this work is to contribute an understanding of the effects of electrons in the plasmas on the mass transfer of plasma species in aqueous solution by means of the numerical simulation based on a one-di...The objective of this work is to contribute an understanding of the effects of electrons in the plasmas on the mass transfer of plasma species in aqueous solution by means of the numerical simulation based on a one-dimensional diffusion-reaction model.The plasma species are divided into two groups,i.e.electrons and the other species,and the mass transfer in the three scenarios has been simulated,including the systematic calculations of the depth distributions of five major reactive species,OH,O3,HO2,O2^-,and H2O2.In the three scenarios,the particles considered to enter into aqueous solution are all the plasma species(the scenario Ⅰ,where the mass transfer of plasma species is a result due to the synergy of the electrons and the other plasma species),the other species(the scenario Ⅱ),and only electrons in plasma species(the scenario Ⅲ),respectively.The detailed analyses on the difference between the depth distributions of each reactive species in these three scenarios show the following conclusions.The electrons play an important role in the mass transfer of plasma species in aqueous solution and the synergy of the electrons and the other plasma species(the electron-species synergy)presents its different effects on the mass transfer.The vast majority of H2O2 are generated from a series of the electronrelated reactions in aqueous solution,which is hardly affected by the electron-species synergy.Compared to the results when only the electrons enter into the liquid region,the electron-species synergy evidently weakens the generation of O2^-,O3,and OH,but promotes to produce HO2.展开更多
A group of five bis(arylimino)pyridine-cobalt(Ⅱ)chloride complexes,[2-{(2,6-(Ph_(2)CH)_(2)-4-MeOC_(6)H_(2))N=CMe}-6-(ArN=CMe)C_5 H_(3)N]CoCl_(2)(Ar=2,6-Me_(2)C_(6)H_(3)Co1,2,6-Et_(2)C_(6)H_(3)Co2,2,6-iPr_(2)C_(6)H_(3...A group of five bis(arylimino)pyridine-cobalt(Ⅱ)chloride complexes,[2-{(2,6-(Ph_(2)CH)_(2)-4-MeOC_(6)H_(2))N=CMe}-6-(ArN=CMe)C_5 H_(3)N]CoCl_(2)(Ar=2,6-Me_(2)C_(6)H_(3)Co1,2,6-Et_(2)C_(6)H_(3)Co2,2,6-iPr_(2)C_(6)H_(3)Co3,2,4,6-Me_(3)C_(6)H_(2)Co4,2,6-Et_(2)-4-MeC_(6)H_(2)Co5),each containing one N-4-methoxy-2,6-dibenzhydrylphenyl group and one smaller sterically/electronically variable N-aryl group,have been synthesized in good yield(>71%)from the corresponding neutral terdentate nitrogen-donor precursor,L1-L5.All complexes have been characterized by^(1)H-NMR and FTIR spectroscopy with the former highlighting the paramagnetic nature of these cobaltous species and the unsymmetrical nature of the chelating ligand.The molecular structures of Co3 and Co4 emphasize the steric differences of the two inequivalent N-aryl groups and the distorted square pyramidal geometry about the metal centers.In the presence of MAO or MMAO,Co1-Co5 collectively displayed high activities for ethylene polymerization producing high molecular weight polyethylenes that,in general,exhibited narrow dispersities(M_w/M_n values:2.12-4.07).Notably,the least sterically hindered Co1 when activated with MAO was the most productive(6.92×10^(6)g_(PE)·mol^(-1)_((Co))·h^(-1))at an operating temperature of60℃.Conversely,the most sterically hindered Co3/MMAO produced the highest molecular weight polyethylene(M_w=6.29×10^(5)g·mol^(-1)).All the polymers displayed high linearity as demonstrated by their melting temperatures(>130℃)and their~1 H-and^(13)C-NMR spectra.By comparison of Co1 with its para-methyl,-chloro and-nitro counterparts,the presence of the para-methoxy substituent showed the most noticeable effect of enhancing the thermal stability of the catalyst.展开更多
In this study,the support effects on the Pd-catalyzed semi-hydrogenation of acetylene have been investigated from the structural and kinetic perspectives.According to the results of kinetic analysis and X-ray photoele...In this study,the support effects on the Pd-catalyzed semi-hydrogenation of acetylene have been investigated from the structural and kinetic perspectives.According to the results of kinetic analysis and X-ray photoelectron spectroscopy,hydrogen temperature-programmed reduction,temperature-programmed hydride decomposition,and in situ X-ray diffraction measurements,using carbon nanotubes as support for Pd nanocatalysts with various sizes instead of a-Al_(2)O_(3) decreases the Pd^(0)3d binding energy and suppresses the formation of undesirable palladium hydride species,thus increasing the ethylene yield.Furthermore,X-ray absorption spectroscopy,high-resolution transmission electron microscopy,and C_(2)H_(4) temperature-programmed desorption studies combined with density-functional theory calculations reveal the existence of a unique Pd local environment,containing subsurface carbon atoms,that produces positive geometric effects on the acetylene conversion reaction.Therefore,tailoring the Pd local environment and electronic properties represents an effective strategy for the fabrication and design of highly active and selective Pd semi-hydrogenation catalysts.展开更多
In order to improve the catalytic performance of the nitrobenzene hydrogenation rearrangement to prepare p-aminophenol,a bimetallic Pt-Ni/C(PNC)catalyst was synthesized.Taking advantage of the synergistic effect of Ni...In order to improve the catalytic performance of the nitrobenzene hydrogenation rearrangement to prepare p-aminophenol,a bimetallic Pt-Ni/C(PNC)catalyst was synthesized.Taking advantage of the synergistic effect of Ni and Pt to enhance product selectivity and catalytic performance stability,the electrons in Ni are moved to Pt by the electron effect,which affects the catalyst’s ability to activate H_(2)as well as the amount of hydrogen activated.Furthermore,due to the strong Pt(5d)-Ni(3d)coupling effect,Ni can effectively maintain Pt stability in the acidic system and reduce Pt dissolution.The stability of the PNC can be found to be greatly enhanced compared to the Pt/C(PC)catalyst,and p-aminophenol selectivity is greatly enhanced,showing excellent catalytic performance.展开更多
As the channel length of metal-oxide-semiconductor field-effect transistors （MOSFETs） scales into the nanometer regime, quantum mechanical effects are becoming more and more significant. In this work, a model for th...As the channel length of metal-oxide-semiconductor field-effect transistors （MOSFETs） scales into the nanometer regime, quantum mechanical effects are becoming more and more significant. In this work, a model for the surrounding-gate （SG） nMOSFET is developed. The SchrSdinger equation is solved analytically. Some of the solutions are verified via results obtained from simulations. It is found that the percentage of the electrons with lighter conductivity mass increases as the silicon body radius decreases, or as the gate voltage reduces, or as the temperature decreases. The eentroid of inversion-layer is driven away from the silicon-oxide interface towards the silicon body, therefore the carriers will suffer less scattering from the interface and the electrons effective mobility of the SG nMOSFETs will be enhanced.展开更多
The important features of the rescattering trajectories in strong field ionization process such as the cutoff of the return energy at 3.17Up and that of the final energy at 10Up are obtained, based on the adiabatic ap...The important features of the rescattering trajectories in strong field ionization process such as the cutoff of the return energy at 3.17Up and that of the final energy at 10Up are obtained, based on the adiabatic approximation in which the initial momentum of the electron is assumed to be zero. We theoretically study the nonadiabatic effect by assuming a nonzero initial momentum on the rescattering trajectories based on the semiclassical simpleman model. We show that the nonzero initial momentum will modify both the maximal return energy at collision and the final energy after backward scattering, but in different ways for odd and even number of return trajectories. The energies are increased for even number of returns but are decreased for odd number of returns when the nonzero （positive or negative） initial momentum is applied.展开更多
The intramolecular electronic communication and multilevel ion-pairing effect of triferrocenylmethane（TriFcM） in organic phase was studied with the ＂thin-layer electrochemistry＂ approach.Three pairs of symmetric p...The intramolecular electronic communication and multilevel ion-pairing effect of triferrocenylmethane（TriFcM） in organic phase was studied with the ＂thin-layer electrochemistry＂ approach.Three pairs of symmetric peaks in cyclic voltammetry of TriFcM correspond to three one-electron electrochemical reaction processes and indicate strong intramolecular electronic communication,which could be used to study the multilevel ion-pairing effect.Three different formation constants of ion-pairs between the three ferroceniums of TriFcM and perchlorate in thin organic film were obtained and compared.展开更多
A first-order itinerant electron metamagnetic (IEM) transition above the Curie temperature Tc for ferromagnetic La(Fe_xSi_1-x)13 compounds has been confirmed by applying magnetic field. The volume change just above T_...A first-order itinerant electron metamagnetic (IEM) transition above the Curie temperature Tc for ferromagnetic La(Fe_xSi_1-x)13 compounds has been confirmed by applying magnetic field. The volume change just above T_C for x=0.88 is huge of about 1.5%, which is caused by a large magnetic moment induced by the IEM transition. These compounds have a possibility for practical applications as giant magnetostrictive materials. Pronounced Invar effects bring about a negative thermal expansion below TC, closely correlated with the negative mode-mode coupling among spin fluctuations.展开更多
This study investigated the enhancement effects of dissolved carbonates on the peroxymonosulfate-based advanced oxidation process with CuS as a catalyst.It was found that the added CO_(3)^(2−)increased both the cataly...This study investigated the enhancement effects of dissolved carbonates on the peroxymonosulfate-based advanced oxidation process with CuS as a catalyst.It was found that the added CO_(3)^(2−)increased both the catalytic activity and the stability of the catalyst.Under optimized reaction conditions in the presence of CO_(3)^(2−),the degradation removal of 4-methylphenol(4-MP)within 2 min reached 100%,and this was maintained in consecutivemulti-cycle experiments.The degradation rate constant of 4-MP was 2.159 min^(−1),being 685%greater than that in the absence of CO_(3)^(2−)(0.315 min−1).The comparison of dominated active species and 4-MP degradation pathways in both CO_(3)^(2−)-free and CO_(3)^(2−)-containing systems suggested thatmore CO_(3)·^(−)/^(1)O_(2) was produced in the case of CO_(3)^(2−)deducing an electron transfer medium,which tending to react with electron-richmoieties.Meanwhile,Characterization by X-ray photoelectron spectroscopic and cyclic voltammetrymeasurement verified CO_(3)^(2−)enabled the effective reduction of Cu^(2+)to Cu^(+).By investigating the degradation of 11 phenolics with different substituents,the dependence of degradation kinetic rate constant of the phenolics on their chemical structures indicated that there was a good linear relationship between the Hammett constantsσp of the aromatic phenolics and the logarithm of k in the CO_(3)^(2−)-containing system.This work provides a new strategy for efficient removal of electron-rich moieties under the driving of carbonate being widely present in actual water bodies.展开更多
Graphite intercalation compounds（GIC） were tested as an experimental model for studying the electronic effect of carbon support on the catalytic activity and poisoning tolerance of Pt catalyst for direct methanol fu...Graphite intercalation compounds（GIC） were tested as an experimental model for studying the electronic effect of carbon support on the catalytic activity and poisoning tolerance of Pt catalyst for direct methanol fuel cells. The GIC samples with different intercalation degrees were prepared by electrolyzing graphite flake in H2SO4 for varying the periods of time. The GIC-supported Pt catalyst was deposited electrochemically. The catalytic activity and poisoning tolerance of the GIC-supported Pt catalysts were evaluated. It was found that GIC with sulfate anion as intercalate was able to catalyze methanol electrooxidation, which could be related to the positive charges generated on the graphite layer upon intercalation. As intercalation degree increased, the catalytic activity of the GIC-supported Pt catalyst decreased while the poisoning tolerance improved. This suggests that electron donation from support to catalyst had great effect on both catalytic activity and poisoning tolerance of Pt catalyst. And intercalation can be adopted as another important way to make modification on carboneous catalyst support.展开更多
Iron(Fe)-based alloys,which have been widely used as structural materials in nuclear reactors,can significantly change their microstructure properties and macroscopic properties under high flux neutron irradiation dur...Iron(Fe)-based alloys,which have been widely used as structural materials in nuclear reactors,can significantly change their microstructure properties and macroscopic properties under high flux neutron irradiation during operation,thus,the problems associated with the safe operation of nuclear reactors have been put forward naturally.In this work,a molecular dynamics simulation approach combined with electronic effects is developed for investigating the primary radiation damage process inα-Fe.Specifically,the influence of electronic effects on the collision cascade in Fe is systematically evaluated based on two commonly used interatomic potentials for Fe.The simulation results reveal that both electronic stopping(ES)and electron-phonon coupling(EPC)can contribute to the decrease of the number of defects in the thermal spike phase.The application of ES reduces the number of residual defects after the cascade evolution,whereas EPC has a reverse effect.The introduction of electronic effects promotes the formation of the dispersive subcascade:ES significantly changes the geometry of the damaged region in the thermal spike phase,whereas EPC mainly reduces the extent of the damaged region.Furthermore,the incorporation of electronic effects effectively mitigates discrepancies in simulation outcomes when using different interatomic potentials.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22178388 and 22108306)Taishan Scholars Program of Shandong Province(No.tsqn201909065)Chongqing Science and Technology Bureau(No.cstc2019jscx-gksb X0032).
文摘Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challenging.Herein,a support electron inductive effect of Pd-Mn/Ni foam catalyst was proposed via in-situ Mn doping to optimize the electronic structure of the Ni foam(NF),which can inductive regulation of Pd for improving the EHDC performance.The mass activity and current efficiency of Pd-Mn/NF catalyst are 2.91 and 1.34 times superior to that of Pd/NF with 2,4-dichlorophenol as model compound,respectively.The Mn-doped interlayer optimized the electronic structure of Pd by bringing the d-state closer to the Fermi level than Pd on the NF surface,which optimizied the binding of EHDC intermediates.Additionally,the Mn-doped interlayer acted as a promoter for generating H∗and accelerating the EHDC reaction.This work presents a simple and effective regulation strategy for constructing high-efficient cathode catalyst for the EHDC of chlorinated organic compounds.
文摘Electrocatalytic conversion of nitrate to ammonia(NITRR)can simultaneously achieve the removal of nitrate and the synthesis of value-added ammonia,a promising candidate to replace Haber-Bosch process with low carbon dioxide emissions.However,high hydrogenation energy barrier for*NO intermediates and insufficient supply of active hydrogen cause slow hydrogenation process,and further result in low efficiency of nitrate conversion and ammonia synthesis.Herein,a series of tandem catalysts,one-dimensional coordination polymers(1D CCPs)with dual sites are synthesized and obtained 190.4 mg h^(-1)mgcat^(-1)ammonia production rate with Faradaic efficiency of 97.16%,outperforming to the most of recent reported catalysts.The catalytic performances are well-maintained even after a long-term stability test of 1200 h,laying the foundation for practical applications.Density functional theory results reveal that the stationary adsorbed*NO on Ni site induced proximity electronic effect could reduce the energy barrier for hydrogenation of*NO intermediates over Cu site.In addition,the Ni site in the dual sites 1D CCPs is conducive to generating active hydrogen,providing rich proton source to boost the hydrogenation of*NO,and further enhancing the compatibility of deoxygenation and hydrogenation process.Our work paves a new insight into the mechanism of NITRR process and will inspire more research interests in exploring the proximity electronic effect in catalytic process.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFE0134200)the National Natural Science Foundation of China(Grant No.12204214)+1 种基金the Fundamental Research Funds for the Central Universities(Grant No.GK202207012)QCYRCXM-2022-241。
文摘Multi-electron and multi-orbital effects play a crucial role in the interaction of strong laser fields with complex molecules.Here,multi-electron effects encompass not only electron-electron Coulomb interactions and exchangecorrelation effects but also the interference between the dynamics of different electron wave packets.
基金supported by the State Key Research Development Program of China(No.2021YFB3800701)National Natural Science Foundation of China(NSFC,No.52173016)+2 种基金Guangdong Basic and Applied Basic Research Foundation(Nos.2024A1515012784,2024A1515011102,and 2023A1515110549)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.24qnpy047)PetroChina Scientific and Technological Projects(No.2022DJ6308).
文摘A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings.The weak noncovalentπ-πinteraction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations.The roles of weakπ-πinteraction,steric bulk,and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail.The combination ofπ-πinteraction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130°C.
基金financially supported by the Guangdong-Hong Kong-Macao Joint Innovation Fund(No.2024A0505040001)Basic Research Project of the Science and Technology Innovation Commission of Shenzhen(No.JCYJ20220818100418040)+2 种基金the National Natural Science Foundation of China(Nos.92372114,21875097 and 22409216)the Guangdong Basic and Applied Basic Research(No.2023A1515010035)the Jiangyin-SUSTech Innovation Fund(No.OR2404014)
文摘Organic compounds are promising electrode materials for aqueous zinc-ion batteries(AZIBs) but largely suffer from poor rate and cycling performance.This work reports that the push-pull electron effect of organic compounds could be used to tune the electrochemical performance of AZIB s.Hexaazatriphenylene-based(HATN) small molecules with different withdrawing or donating groups were synthesized and used as electrodes for AZIBs.Compared to the hydrogen atoms and electrondonating methyl groups,the electron-withdrawing fluorine atoms endow HATN-based small molecule(HATN-6F)with a much-improved redox platform,rate performance and cycling stability.The fluorinated electrode HATN-6F potently amplifies and stabilizes the kinetics of cation co-(de)insertion reactions,concurrently enhancing the conductivity and electron affinity,resulting in improved rate performance and enhanced cycling stability.The combination of theoretical calculations and experimental characterization confirms that the fluorine-rich peripheral environment effectively modifies the distribution of conjugated electrons in HATN,enhancing its affinity for zinc ions and improving its capacity for cations zinc storage.This work demonstrates a new avenue for the design and synthesis of organic electrode with excellent electrochemical performance for ZIBs.
基金supported by the National Natural Science Foundation of China(U21A20312,22172099,21975162,51902209)the Natural Science Foundation of Guangdong(2020A1515010840)the Shenzhen Science and Technology Program(SGDX20201103095802006,RCBS20200714114819161,JCYJ20190808111801674,JCYJ20200109105803806,RCYX20200714114535052)。
文摘Earth-abundant and nontoxic Sn-based materials have been regarded as promising catalysts for the electrochemical conversion of CO_(2)to C1 products,e.g.,CO and formate.However,it is still difficult for Snbased materials to obtain satisfactory performance at low-to-moderate overpotentials.Herein,a simple and facile electrospinning technique is utilized to prepare a composite of a bimetallic Sn-Co oxide/carbon matrix with a hollow nanotube structure(Sn Co-HNT).Sn Co-HNT can maintain>90%faradaic efficiencies for C1 products within a wide potential range from-0.6 VRHE to-1.2 VRHE,and a highest 94.1%selectivity towards CO in an H-type cell.Moreover,a 91.2%faradaic efficiency with a 241.3 m A cm^(-2)partial current density for C1 products could be achieved using a flow cell.According to theoretical calculations,the fusing of Sn/Co oxides on the carbon matrix accelerates electron transfer at the atomic level,causing electron deficiency of Sn centers and reversible variation between Co^(2+)and Co^(3+)centers.The synergistic effect of the Sn/Co composition improves the electron affinity of the catalyst surface,which is conducive to the adsorption and stabilization of key intermediates and eventually increases the catalytic activity in CO_(2)electroreduction.This study could provide a new strategy for the construction of oxide-derived catalysts for CO_(2)electroreduction.
基金Project supported by the National Natural Science Foundations of China (20876002, 20976002)the Beijing Natural Science Foundation (2091002)Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality
文摘Trivalent rare-earth ions （La3＋,Pr3＋,Nd3＋,Sm3＋,Gd3＋,Tb3＋,Dy3＋,Ho3＋,Er3＋,Tm3＋,and Yb3＋） were investigated as the codoped auxiliary sensitizer for the electron trapping materials SrS：Eu2＋ in order to enhance the fluorescence properties.It was found that Sm3＋ and Tb3＋ had the best photoluminescence stimulated luminescence （PSL） effect among the selected trivalent rare-earth ions.All the SrS：Eu2＋ samples doped by different trivalent rare-earth ions could be stimulated by 980 nm laser after being exposed to the conventional sunlight,and they emitted PSL with the peak located at 615 nm.The result also indicated that some co-doped rare earth ions could increase fluorescence intensities of the traditional electron trapping materials SrS：Eu2＋.
基金This work was supported by the Science and Technology Pro-gram of Shaanxi Province(No.2019GY-200).Shengwu Guo and Wei Wang contributed to the material TEM and SEM characterizations in this work.
文摘Attaining a highly efficient and inexpensive electrocatalyst is significant for the hydrogen evolution reaction(HER)but still challenging nowadays.The transition-metal phosphides(TMPs)catalysts with platinum-like electronic structures are a potential candidate for the HER,but those are prone to be strongly bound with hydrogen intermediates(H∗),resulting in sluggish HER kinetics.Herein we report a unique hybrid structure of CoP anchored on graphene nanoscrolls@carbon nano tubes(CNTs)scaffold(Ni M@C-CoP)encapsulating various Ni M(M=Zn,Mo,Ni,Co)bimetal nanoalloy via chemical vapor deposi-tion(CVD)growth of CNT on graphene nanoscrolls followed by the impregnation of cobalt precursors and phosphorization for efficiently electrocatalytic hydrogen evolution.CoP nanoparticles mainly scattered at the tip of CNT branches which exhibited the analogical“Three-layer core-shell”structures.Experiments and density functional theory(DFT)calculations consistently disclose that the encapsulated various NiMs can offer different numbers of electrons to weaken the interactions of outmost CoP with H∗and push the downshift of the d-band center to different degrees as well as stabilize the outmost CoP nanopar-ticles to gain catalytic stability via the electron traversing effect.The electrocatalytic HER activity can be maximumly enhanced with low overpotentials of 78 mV(alkaline)and 89 mV(acidic)at a current density of 10 mA/cm^(2) and sustained at least 24 h especially for NiZn@C-CoP catalyst.This novel system is distinct from conventional three-layer heterostructure,providing a specially thought of d-band center control engineering strategy for the design of heterogeneous catalysts and expanding to other electrocat-alysts,energy storage,sensing,and other applications.
文摘The development of bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N‐heterocycles is a challenge.In this study,Ru_(2)P/AC effectively promoted reversible transformations between unsaturated and saturated N‐heterocycles affording yields of 98%and 99%,respectively.Moreover,a remarkable enhancement in the reusability of Ru_(2)P/AC was observed compared with other Ru‐based catalysts.According to density functional theory calculations,the superior performance of Ru_(2)P/AC was ascribed to specific synergistic factors,namely geometric and electronic effects induced by P.P greatly reduced the large Ru‐Ru ensembles and finely modified the electronic structures,leading to a low reaction barrier and high desorption ability of the catalyst,further boosting the hydrogenation and acceptorless dehydrogenation processes.
基金supported by the Fundamental Research Funds of Shandong University(2018TB037)。
文摘The objective of this work is to contribute an understanding of the effects of electrons in the plasmas on the mass transfer of plasma species in aqueous solution by means of the numerical simulation based on a one-dimensional diffusion-reaction model.The plasma species are divided into two groups,i.e.electrons and the other species,and the mass transfer in the three scenarios has been simulated,including the systematic calculations of the depth distributions of five major reactive species,OH,O3,HO2,O2^-,and H2O2.In the three scenarios,the particles considered to enter into aqueous solution are all the plasma species(the scenario Ⅰ,where the mass transfer of plasma species is a result due to the synergy of the electrons and the other plasma species),the other species(the scenario Ⅱ),and only electrons in plasma species(the scenario Ⅲ),respectively.The detailed analyses on the difference between the depth distributions of each reactive species in these three scenarios show the following conclusions.The electrons play an important role in the mass transfer of plasma species in aqueous solution and the synergy of the electrons and the other plasma species(the electron-species synergy)presents its different effects on the mass transfer.The vast majority of H2O2 are generated from a series of the electronrelated reactions in aqueous solution,which is hardly affected by the electron-species synergy.Compared to the results when only the electrons enter into the liquid region,the electron-species synergy evidently weakens the generation of O2^-,O3,and OH,but promotes to produce HO2.
基金financially supported by the National Natural Science Foundation of China(No.21871275)。
文摘A group of five bis(arylimino)pyridine-cobalt(Ⅱ)chloride complexes,[2-{(2,6-(Ph_(2)CH)_(2)-4-MeOC_(6)H_(2))N=CMe}-6-(ArN=CMe)C_5 H_(3)N]CoCl_(2)(Ar=2,6-Me_(2)C_(6)H_(3)Co1,2,6-Et_(2)C_(6)H_(3)Co2,2,6-iPr_(2)C_(6)H_(3)Co3,2,4,6-Me_(3)C_(6)H_(2)Co4,2,6-Et_(2)-4-MeC_(6)H_(2)Co5),each containing one N-4-methoxy-2,6-dibenzhydrylphenyl group and one smaller sterically/electronically variable N-aryl group,have been synthesized in good yield(>71%)from the corresponding neutral terdentate nitrogen-donor precursor,L1-L5.All complexes have been characterized by^(1)H-NMR and FTIR spectroscopy with the former highlighting the paramagnetic nature of these cobaltous species and the unsymmetrical nature of the chelating ligand.The molecular structures of Co3 and Co4 emphasize the steric differences of the two inequivalent N-aryl groups and the distorted square pyramidal geometry about the metal centers.In the presence of MAO or MMAO,Co1-Co5 collectively displayed high activities for ethylene polymerization producing high molecular weight polyethylenes that,in general,exhibited narrow dispersities(M_w/M_n values:2.12-4.07).Notably,the least sterically hindered Co1 when activated with MAO was the most productive(6.92×10^(6)g_(PE)·mol^(-1)_((Co))·h^(-1))at an operating temperature of60℃.Conversely,the most sterically hindered Co3/MMAO produced the highest molecular weight polyethylene(M_w=6.29×10^(5)g·mol^(-1)).All the polymers displayed high linearity as demonstrated by their melting temperatures(>130℃)and their~1 H-and^(13)C-NMR spectra.By comparison of Co1 with its para-methyl,-chloro and-nitro counterparts,the presence of the para-methoxy substituent showed the most noticeable effect of enhancing the thermal stability of the catalyst.
基金This work was financially supported by the Natural Science Foundation of China(21922803,21776077,and 22008067)the Innovation Program of Shanghai Municipal Education Commission,the Shanghai Natural Science Foundation(17ZR1407300 and 17ZR1407500)+4 种基金the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning,the Shanghai Rising-Star Program(17QA1401200)the China Postdoctoral Science Foundation(2020M681202)the Open Project of State Key Laboratory of Chemical Engineering(SKLChe-15C03)the State Key Laboratory of Organic-Inorganic Composites(oic-201801007)the Fundamental Research Funds for the Central Universities(222201718003).
文摘In this study,the support effects on the Pd-catalyzed semi-hydrogenation of acetylene have been investigated from the structural and kinetic perspectives.According to the results of kinetic analysis and X-ray photoelectron spectroscopy,hydrogen temperature-programmed reduction,temperature-programmed hydride decomposition,and in situ X-ray diffraction measurements,using carbon nanotubes as support for Pd nanocatalysts with various sizes instead of a-Al_(2)O_(3) decreases the Pd^(0)3d binding energy and suppresses the formation of undesirable palladium hydride species,thus increasing the ethylene yield.Furthermore,X-ray absorption spectroscopy,high-resolution transmission electron microscopy,and C_(2)H_(4) temperature-programmed desorption studies combined with density-functional theory calculations reveal the existence of a unique Pd local environment,containing subsurface carbon atoms,that produces positive geometric effects on the acetylene conversion reaction.Therefore,tailoring the Pd local environment and electronic properties represents an effective strategy for the fabrication and design of highly active and selective Pd semi-hydrogenation catalysts.
基金funded by the National Natural Science Foundation of China(U20A20119,22078292 and 22008212)。
文摘In order to improve the catalytic performance of the nitrobenzene hydrogenation rearrangement to prepare p-aminophenol,a bimetallic Pt-Ni/C(PNC)catalyst was synthesized.Taking advantage of the synergistic effect of Ni and Pt to enhance product selectivity and catalytic performance stability,the electrons in Ni are moved to Pt by the electron effect,which affects the catalyst’s ability to activate H_(2)as well as the amount of hydrogen activated.Furthermore,due to the strong Pt(5d)-Ni(3d)coupling effect,Ni can effectively maintain Pt stability in the acidic system and reduce Pt dissolution.The stability of the PNC can be found to be greatly enhanced compared to the Pt/C(PC)catalyst,and p-aminophenol selectivity is greatly enhanced,showing excellent catalytic performance.
基金Support of Shanghai Science Foundation under Grant No.09ZR1402900 the National Science Foundation of China under Grant No.60676020 Supported in part by the Special Funds for Major State Basic Research (973 Project) under Grant No.2006CB302703
文摘As the channel length of metal-oxide-semiconductor field-effect transistors （MOSFETs） scales into the nanometer regime, quantum mechanical effects are becoming more and more significant. In this work, a model for the surrounding-gate （SG） nMOSFET is developed. The SchrSdinger equation is solved analytically. Some of the solutions are verified via results obtained from simulations. It is found that the percentage of the electrons with lighter conductivity mass increases as the silicon body radius decreases, or as the gate voltage reduces, or as the temperature decreases. The eentroid of inversion-layer is driven away from the silicon-oxide interface towards the silicon body, therefore the carriers will suffer less scattering from the interface and the electrons effective mobility of the SG nMOSFETs will be enhanced.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11425414 and 11504215the Scientific Research Training Program of Shanxi University
文摘The important features of the rescattering trajectories in strong field ionization process such as the cutoff of the return energy at 3.17Up and that of the final energy at 10Up are obtained, based on the adiabatic approximation in which the initial momentum of the electron is assumed to be zero. We theoretically study the nonadiabatic effect by assuming a nonzero initial momentum on the rescattering trajectories based on the semiclassical simpleman model. We show that the nonzero initial momentum will modify both the maximal return energy at collision and the final energy after backward scattering, but in different ways for odd and even number of return trajectories. The energies are increased for even number of returns but are decreased for odd number of returns when the nonzero （positive or negative） initial momentum is applied.
基金the NSFC(No.21173023)the 111 Project(No.B07012) in China and the TriFcM provided from professor Hua-Zhong Yu at Simon Fraser University in Canada
文摘The intramolecular electronic communication and multilevel ion-pairing effect of triferrocenylmethane（TriFcM） in organic phase was studied with the ＂thin-layer electrochemistry＂ approach.Three pairs of symmetric peaks in cyclic voltammetry of TriFcM correspond to three one-electron electrochemical reaction processes and indicate strong intramolecular electronic communication,which could be used to study the multilevel ion-pairing effect.Three different formation constants of ion-pairs between the three ferroceniums of TriFcM and perchlorate in thin organic film were obtained and compared.
基金Japanese Ministry of Education, Science, Sports and Culture!Grantin-Aid for Scientific Research (B)(2) 08455287
文摘A first-order itinerant electron metamagnetic (IEM) transition above the Curie temperature Tc for ferromagnetic La(Fe_xSi_1-x)13 compounds has been confirmed by applying magnetic field. The volume change just above T_C for x=0.88 is huge of about 1.5%, which is caused by a large magnetic moment induced by the IEM transition. These compounds have a possibility for practical applications as giant magnetostrictive materials. Pronounced Invar effects bring about a negative thermal expansion below TC, closely correlated with the negative mode-mode coupling among spin fluctuations.
基金This work was supported by the National Science Foundation of Hubei Province of China(No.2019CFB432)the National Natural Science Foundation of China(Nos.22076052 and 21976063)the China Postdoctoral Science Foundation(No.2018M642850).
文摘This study investigated the enhancement effects of dissolved carbonates on the peroxymonosulfate-based advanced oxidation process with CuS as a catalyst.It was found that the added CO_(3)^(2−)increased both the catalytic activity and the stability of the catalyst.Under optimized reaction conditions in the presence of CO_(3)^(2−),the degradation removal of 4-methylphenol(4-MP)within 2 min reached 100%,and this was maintained in consecutivemulti-cycle experiments.The degradation rate constant of 4-MP was 2.159 min^(−1),being 685%greater than that in the absence of CO_(3)^(2−)(0.315 min−1).The comparison of dominated active species and 4-MP degradation pathways in both CO_(3)^(2−)-free and CO_(3)^(2−)-containing systems suggested thatmore CO_(3)·^(−)/^(1)O_(2) was produced in the case of CO_(3)^(2−)deducing an electron transfer medium,which tending to react with electron-richmoieties.Meanwhile,Characterization by X-ray photoelectron spectroscopic and cyclic voltammetrymeasurement verified CO_(3)^(2−)enabled the effective reduction of Cu^(2+)to Cu^(+).By investigating the degradation of 11 phenolics with different substituents,the dependence of degradation kinetic rate constant of the phenolics on their chemical structures indicated that there was a good linear relationship between the Hammett constantsσp of the aromatic phenolics and the logarithm of k in the CO_(3)^(2−)-containing system.This work provides a new strategy for efficient removal of electron-rich moieties under the driving of carbonate being widely present in actual water bodies.
基金Supported by the National Natural Science Foundation of China(No.20673068)
文摘Graphite intercalation compounds（GIC） were tested as an experimental model for studying the electronic effect of carbon support on the catalytic activity and poisoning tolerance of Pt catalyst for direct methanol fuel cells. The GIC samples with different intercalation degrees were prepared by electrolyzing graphite flake in H2SO4 for varying the periods of time. The GIC-supported Pt catalyst was deposited electrochemically. The catalytic activity and poisoning tolerance of the GIC-supported Pt catalysts were evaluated. It was found that GIC with sulfate anion as intercalate was able to catalyze methanol electrooxidation, which could be related to the positive charges generated on the graphite layer upon intercalation. As intercalation degree increased, the catalytic activity of the GIC-supported Pt catalyst decreased while the poisoning tolerance improved. This suggests that electron donation from support to catalyst had great effect on both catalytic activity and poisoning tolerance of Pt catalyst. And intercalation can be adopted as another important way to make modification on carboneous catalyst support.
基金Project supported by the National MCF Energy Research and Development Program of China(Grant Nos.2022YFE03200200 and 2018YFE0308101)the National Natural Science Foundation of China(Grant No.12105194)the Natural Science Foundation of Sichuan Province,China(Grant Nos.2022NSFSC1265 and 2022NSFSC1251).
文摘Iron(Fe)-based alloys,which have been widely used as structural materials in nuclear reactors,can significantly change their microstructure properties and macroscopic properties under high flux neutron irradiation during operation,thus,the problems associated with the safe operation of nuclear reactors have been put forward naturally.In this work,a molecular dynamics simulation approach combined with electronic effects is developed for investigating the primary radiation damage process inα-Fe.Specifically,the influence of electronic effects on the collision cascade in Fe is systematically evaluated based on two commonly used interatomic potentials for Fe.The simulation results reveal that both electronic stopping(ES)and electron-phonon coupling(EPC)can contribute to the decrease of the number of defects in the thermal spike phase.The application of ES reduces the number of residual defects after the cascade evolution,whereas EPC has a reverse effect.The introduction of electronic effects promotes the formation of the dispersive subcascade:ES significantly changes the geometry of the damaged region in the thermal spike phase,whereas EPC mainly reduces the extent of the damaged region.Furthermore,the incorporation of electronic effects effectively mitigates discrepancies in simulation outcomes when using different interatomic potentials.
