Double-resonance Raman(DRR)scattering in two-di-mensional(2D)materials describes the intravalley or intervalley scattering of an electron or a hole excited by incident photons.Although the presence of defects can prov...Double-resonance Raman(DRR)scattering in two-di-mensional(2D)materials describes the intravalley or intervalley scattering of an electron or a hole excited by incident photons.Although the presence of defects can provide additional momentum and influence the scat-tering process involving one or two phonons,only the idealized defects without any structural details are considered in tra-ditional DRR theory.Here,the second-order DRR spectra of WSe_(2) monolayer with different types of defects are calculated involving the combinations of acoustic and optical phonons in the vicinity of K(K')and M points of the Brillouin zone.The electronic band structures are modified due to the presence of defects,and the band unfolding method is adopted to show the bending of valence and conduction bands for the defective WSe_(2) monolayers.The associ-ated phononic band structures also exhibit different changes in phonon dispersion curves,re-sulting in different DRR spectra corresponding to the different types of defects in the WSe_(2) monolayers.For example,the existence of W vacancy in the WSe_(2) monolayer would result in downshifts in vibrational frequencies and asymmetrical broadenings in linewidths for most combination modes due to the dramatic changes in contour shape of electronic valleys at K and K'.Moreover,the scattering from K to Q is found to be forbidden for the two Se vacan-cies because of the elevation of conduction band at the Q point.Our work highlights the role of defect structures in the intervalley scattering and may provide better understanding in the underlying physics of DRR process in 2D materials.展开更多
ZnO-based catalysts have been widely used in hydrogenation reactions,but less attention has been paid to the electrocatalytic hydrogenation process on ZnO electrodes.In this work,the preparation of hydrogen species an...ZnO-based catalysts have been widely used in hydrogenation reactions,but less attention has been paid to the electrocatalytic hydrogenation process on ZnO electrodes.In this work,the preparation of hydrogen species and the associ-ated reduction properties under electrochemi-cal processes in aqueous solutions have been in-vestigated on ZnO and Au/ZnO electrodes.The measurements of cyclic voltammetry(CV),X-ray diffraction,and electron paramagnetic resonance(EPR)confirm the formation of hydro-gen species on the interstitial sites(Hi)or on the oxygen vacancy sites(H_(O)).The hydrogena-tion reaction of p-nitrophenol(pNP)at 40μmol/L occurs on both ZnO and Au/ZnO elec-trodes,and the hydrogenation reduction performance of Au/ZnO electrode is better than that of ZnO electrode.CVs show H_(O)species is much more reactive with pNP than Hi species.Compared with the ZnO electrode,the presence of Au on ZnO promotes the formation of H_(O)species and improves the electro-reduction performance to pNP.These results help us to un-derstand the reaction processes related to the electrochemical hydrogenation on ZnO and Au/ZnO surfaces and shed new light on the design of new catalytic hydrogenation systems.展开更多
Molecular constructs define the elementary units in porous materials for efficient CO_(2)capture.The design of appro-priate interpore and intermolecular space is crucial to stabilize CO_(2)molecules and maximize the c...Molecular constructs define the elementary units in porous materials for efficient CO_(2)capture.The design of appro-priate interpore and intermolecular space is crucial to stabilize CO_(2)molecules and maximize the capacity.While the molecular construct usually has a fixed dimension,whether its inter-molecular space could be self-adjustable during CO_(2)capture and release,behaving as a balloon,has captured imagination.Here we report a flexible intermolecular space of the double chain structure of self-assembled 1,4-pheny-lene diisocyanide(PDI)molecules on Ag(110)surface,which dynamically broadens and recovers during the CO_(2)capture and release.The incipient PDI double chains organize along the[001]direction of Ag(110),in which individual PDI molecules stand up in a zigzag order with the interchain width defined by twice the Ag lattice distance along_([110])direction(2α_([110])).When CO_(2)molecules are introduced,they assemble to occupy the interchain spaces,expanding the interchain width to 3α_([110]),4α_([110])and 5α_([110]):Warming up the sample leads to the thermally-driven CO_(2)desorption that recovers the original interchain space.High-resolution scanning tunneling microscopy(STM)jointly with density functional theory(DFT)calculations determine the structural and electronic interactions of CO_(2)molecules with the dynamical PDI structures,providing a molecular-level perspective for the design of a self-adjustable metal-organic construct for reversible gas capture and release.展开更多
Acetobacteraceae has garnered significant attention because of its unique properties and the broad applications of the bacterial cellulose it produces.However,unlike model strains,Acetobacteraceae have few synthetic b...Acetobacteraceae has garnered significant attention because of its unique properties and the broad applications of the bacterial cellulose it produces.However,unlike model strains,Acetobacteraceae have few synthetic biology applications because they are difficult to manipulate genetically and have insufficient genetic regulatory elements,among other factors.To address this limitation,this study characterized the fundamental properties and synthetic biology elements of three commonly used bacterial cellulose-producing strains.First,the basic characteristics of the three strains,including their cellulose film production ability,division time,antibiotic susceptibility,and plasmid features,were analyzed.Two inducible promoters(pTrc and pLux101)were subsequently characterized within the three strains.The inducibility of the pTrc promoter was relatively low across the three strains(induction ratio:1.98–6.39),whereas the pLux101 promoter demonstrated a significantly greater level of inducibility within the three strains(induction ratio:87.28–216.71).Finally,through gene knockout experiments,this study identified four genes essential for bacterial cellulose film production in the genome of the Gluconacetobacter hansenii ATCC 5358 strain.This study not only enriches the library of synthetic biology elements in nonmodel strains,but also lays the foundation for the synthetic biology applications of Acetobacteraceae.展开更多
To identify the species in liquid surface using mass spectrometry,we must eliminate or reduce interferences during the vaporization or desorption of the species from the liquid surface.It is much more challenging to i...To identify the species in liquid surface using mass spectrometry,we must eliminate or reduce interferences during the vaporization or desorption of the species from the liquid surface.It is much more challenging to isolate the ionic,larger species from the liquid surface,because of the frangible structures and the higher solvation energies of those species.Here we demonstrate a new mass spectrometry in which the ionic species at the liquid surface can be desorbed with ultrasoft infrared picosecond laser pulses while the liquid surface is not breached.This laser desorption assisted mass spectrometry is not only a powerful tool to detect the fragile species but also promising to investigate vibrational energy transfer dynamics in the liquid surface.展开更多
As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular...As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular force fields or ab initio molecular dynamics with semilocal density functionals.Inspired by recent studies on bulk water using increasingly accurate machine learning force fields,we report a new machine learning force field for liquid methanol with a hybrid functional revPBE0 plus dispersion correction.Molecular dynamics simulations on this machine learning force field are orders of magnitude faster than ab initio molecular dynamics simulations,yielding the radial distribution functions,selfdiffusion coefficients,and hydrogen bond network properties with very small statistical errors.The resulting structural and dynamical properties are compared well with the experimental data,demonstrating the superior accuracy of this machine learning force field.This work represents a successful step toward a first-principles description of this benchmark system and showcases the general applicability of the machine learning force field in studying liquid systems.展开更多
α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were ...α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.展开更多
The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nick...The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nickel-based catalysts have great application prospects in the industrialization process of olefin coordination polymerization.In this work,various N-aryl substituents with different electronic effects were synthesized and introduced intoα-diimine ligands.The aspreparedα-diimine nickel catalysts showed high polymerization activity(0.9×10^(7)–3.0×10^(7)g·mol^(−1)·h^(−1))in ethylene polymerization,generating polyethylene products with adjustable molecular weights(Mn values:7.4×10^(4)–146.9×10^(4)g·mol^(−1))and branching densities(31/1000 C–68/1000 C).The resulting polyethylene products showed excellent mechanical properties,with high tensile strength(up to 25.0 MPa)and high strain at break values(up to 3890%).The copolymerization of ethylene and polar monomers can also be achieved by these nicekel complexes,ultimately preparing functionalized polyolefins.展开更多
Deposition-precipitation(DP)method is commonly used to prepare the supported metal catalysts.In this study,the modification effect of the mild DP method on the photocatalytic performance of TiO_(2)was investigated.The...Deposition-precipitation(DP)method is commonly used to prepare the supported metal catalysts.In this study,the modification effect of the mild DP method on the photocatalytic performance of TiO_(2)was investigated.The TiO_(2)samples with DP treatment,as well as Au/TiO_(2)prepared under the same conditions,showed enhanced photocatalytic performance of the degradation of methylene blue(MB).·OH generated by photoexcited holes is identified as the main intermediate reactive species during the degradation reaction.X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)show that TiO_(2)(A)-17 after DP treatment has the most amount of surface OH^(-)_(ad)species.The presence of surface OH^(-)_(ad)species not only changes the surface zeta potential,favoring the attraction of cationic MB;but also depresses the electron-hole recombination,favoring photodegradation of MB by hole-produced·OH.An implication of these findings is that the modification of support properties should be taken into account while preparing supported metal catalysts using DP methods.展开更多
Materials with low thermal conductivity are applied extensively in energy management,and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists.Doping is a c...Materials with low thermal conductivity are applied extensively in energy management,and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists.Doping is a common strategy for achieving low thermal conductivity that can offer abundant scattering centers in which heavier dopants always result in lower phonon group velocities and lower thermal conductivities.However,the amount of equivalent heavyatom single dopant available is limited.Unfortunately,nonequivalent heavy dopants have finite solubility because of charge imbalance.Here,we propose a charge balance strategy for SnS by substituting Sn2+with Ag^(+)and heavy Bi^(3+),improving the doping limit of Ag from 2%to 3%.Ag and Bi codoping increases the point defect concentration and introduces abundant boundaries simultaneously,scattering the phonons at both the atomic scale and nanoscale.The thermal conductivity of Ag0.03Bi0.03Sn0.94S decreased to 0.535 W·m^(−1)·K^(−1)at room temperature and 0.388 W·m^(−1)·K^(−1)at 275°C,which is below the amorphous limit of 0.450 W·m^(−1)·K^(−1)for SnS.This strategy offers a simple way to enhance the doping limit and achieve ultralow thermal conductivity in solids below the amorphous limit without precise structural modification.展开更多
The study of oxide heteroepitaxy has been hindered by the issues of misfit strain and substrate clamping,which impede both the optimization of performance and the acquisition of a fundamental understanding of oxide sy...The study of oxide heteroepitaxy has been hindered by the issues of misfit strain and substrate clamping,which impede both the optimization of performance and the acquisition of a fundamental understanding of oxide systems.Recently,however,the development of freestanding oxide membranes has provided a plausible solution to these substrate limitations.Single-crystalline functional oxide films can be released from their substrates without incurring significant damage and can subsequently be transferred to any substrate of choice.This paper discusses recent advancements in the fabrication,adjustable physical properties,and various applications of freestanding oxide perovskite films.First,we present the primary strategies employed for the synthesis and transfer of these freestanding perovskite thin films.Second,we explore the main functionalities observed in freestanding perovskite oxide thin films,with special attention to the tunable functionalities and physical properties of these freestanding perovskite membranes under varying strain states.Next,we encapsulate three representative devices based on freestanding oxide films.Overall,this review highlights the potential of freestanding oxide films for the study of novel functionalities and flexible electronics.展开更多
The preparation of large crystals is highly important for the characterization and application of a newly found structure but remains a challenge for one-dimensional(1D)C_(60) polymers.In this work,we successfully fab...The preparation of large crystals is highly important for the characterization and application of a newly found structure but remains a challenge for one-dimensional(1D)C_(60) polymers.In this work,we successfully fabricated a 1D C_(60) polymer crystal via on-site annealing of a millimeter-sized C_(60) molecular crystal withα-Li_(3)N at 500°C and ambient pres�sure.Characterizations show that the C_(60) cages in the crystal have been efficiently connected,forming 1D chains along the<110>direction in an orthorhombic 3D structure.At the same time,the crystal maintains a morphology similar to that of the pristine C_(60)crystal,providing opportunities for characterization of all the facets of the crystal via Raman spectroscopy and thus suggesting the formation mechanism of such crystals.展开更多
The achievement of electrical spin control is highly desirable.One promising strategy involves electrically mod-ulating the Rashba spin orbital coupling effect in materials.A semiconductor with high sensitivity in its...The achievement of electrical spin control is highly desirable.One promising strategy involves electrically mod-ulating the Rashba spin orbital coupling effect in materials.A semiconductor with high sensitivity in its Rashba constant to external electric fields holds great potential for short channel lengths in spin field-effect transistors,which is crucial for preserving spin coherence and enhancing integration density.Hence,two-dimensional(2D)Rashba semiconductors with large Rashba constants and significant electric field responses are highly desirable.Herein,by employing first-principles calculations,we design a thermodynamically stable 2D Rashba semiconductor,YSbTe_(3),which possesses an indirect band gap of 1.04 eV,a large Rashba constant of 1.54 eV·Åand a strong electric field response of up to 4.80 e·Å^(2).In particular,the Rashba constant dependence on the electric field shows an unusual nonlinear relationship.At the same time,YSbTe_(3)has been identified as a 2D ferroelectric material with a moderate polarization switching energy barrier(~0.33 eV per formula).By changing the electric polarization direction,the Rashba spin texture of YSbTe_(3)can be reversed.These out-standing properties make the ferroelectric Rashba semiconductor YSbTe_(3)quite promising for spintronic applications.展开更多
Electrocatalytic water splitting provides an efficient method for the production of hydrogen.In electrocatalytic water splitting,the oxygen evolution reaction(OER)involves a kinetically sluggish four-electron transfer...Electrocatalytic water splitting provides an efficient method for the production of hydrogen.In electrocatalytic water splitting,the oxygen evolution reaction(OER)involves a kinetically sluggish four-electron transfer process,which limits the efficiency of electrocatalytic water splitting.Therefore,it is urgent to develop highly active OER catalysts to accelerate reaction kinetics.Coupling single atoms and clusters in one system is an innovative approach for developing efficient catalysts that can synergistically optimize the adsorption and configuration of intermediates and improve catalytic activity.However,research in this area is still scarce.Herein,we constructed a heterogeneous single-atom cluster system by anchoring Ir single atoms and Co clusters on the surface of Ni(OH)_(2)nanosheets.Ir single atoms and Co clusters synergistically improved the catalytic activity toward the OER.Specifically,Co_(n)Ir_(1)/Ni(OH)_(2)required an overpotential of 255 mV at a current density of 10 mA·cm^(−2),which was 60 mV and 67 mV lower than those of Co_(n)/Ni(OH)_(2)and Ir1/Ni(OH)_(2),respectively.The turnover frequency of Co_(n)Ir_(1)/Ni(OH)_(2)was 0.49 s^(−1),which was 4.9 times greater than that of Co_(n)/Ni(OH)_(2)at an overpotential of 300 mV.展开更多
We report a mechanistic study of excitonic photoluminescence in predesigned hybrid organic-inorganic perovskite(HOIP)systems,i.e.,(DMAEA)Pb_(2)I_(6),(DMAPA)PbI_(4),(DEAEA)Pb_(2)I_(6),and(DEAPA)_(4)Pb_(5)I_(18),featuri...We report a mechanistic study of excitonic photoluminescence in predesigned hybrid organic-inorganic perovskite(HOIP)systems,i.e.,(DMAEA)Pb_(2)I_(6),(DMAPA)PbI_(4),(DEAEA)Pb_(2)I_(6),and(DEAPA)_(4)Pb_(5)I_(18),featuring targeted regulation of organic cations.Starting from the prototype DMAEA(i.e.,2-N,N-dimethylamino-l-ethylamine)for(DMAEA)Pb_(2)I_(6),the other three HOIPs differ only in the extensions with CH_(2)group(s)at the“head”or/and“tail”of DMAEA that is an“alkylated ammonia”.Their crystal structures are constructed and structural distortions are evaluated.The steady-state/transient absorption and emission spectroscopic characterizations,combined with the band-structure calculations,are conducted.The two different photoluminescence(PL)mechanisms are identified,i.e.,PL emissions dominated by free excitons for(DMAPA)PbI_(4)and by self-trapped excitons for(DMAEA)Pb_(2)I_(6),(DEAEA)Pb_(2)I_(6),and(DEAPA)_(4)Pb_(5)I_(18).The self-trapped excitonic effect involved in the latter three HOIPs is quantitatively analyzed.This work would be of guiding value for the design of HOIP systems based on organic-cation engineering,beneficial for the pertinent performance optimization in light-emitting applications.展开更多
Methane is the second most important greenhouse gas after carbon dioxide,and the reduction of methane emissions is a key focus in IPCC reports.At present,atmospheric methane is monitored through ground-based observati...Methane is the second most important greenhouse gas after carbon dioxide,and the reduction of methane emissions is a key focus in IPCC reports.At present,atmospheric methane is monitored through ground-based observations and satellite remote sensing that depend on spectral characteristics.However,the positions of the methane lines provided by the widely utilized HITRAN database lack the precision required for accurate retrievals.In this work,we used cavity-enhanced absorption spectroscopy to record the absorption spectrum near the atmospheric detection window of methane at 1.66µm.From the saturated absorption peaks(“Lamb dips”)observed on top of Doppler-broadened methane absorption lines,we determined the line positions with an absolute frequency accuracy of better than 2 MHz.The results also indicate the incompetence of the HITRAN database and theoretical models based onαb initio calculations of methane lines in this region.展开更多
Time-sliced velocity map ion imaging(VMI)experiments were performed to investigate the photodissociation of H_(2)S^(+)X^(2)B_(1),via the excitation to the A^(2)A_(1)(0,11,0)state.Experimental images of the S^(+)(^(4)S...Time-sliced velocity map ion imaging(VMI)experiments were performed to investigate the photodissociation of H_(2)S^(+)X^(2)B_(1),via the excitation to the A^(2)A_(1)(0,11,0)state.Experimental images of the S^(+)(^(4)Su)products were recorded near 349.60 nm for the K=1 band,and near 344.30 nm for the K=2 band.The derived product total kinetic energy release(TKER)spectra exhibit partially rotationally resolved structures corresponding to the H_(2)(X^(1)∑_(g)^(+))co-products.The observed product state and angular distributions both exhibit sensitive dependence on the photolysis wavelength at near 349.60 nm and 344.30 nm.These phenomena indicate the underlying rich dynamic details and the role of the rotational excitation of H_(2)S^(+).展开更多
Spin-crossover （SCO） magnets can act as one of the most possible building blocks in molec- ular spintronics due to their magnetic bistability between the high-spin （HS） and low-spin （LS） states. Here, the electr...Spin-crossover （SCO） magnets can act as one of the most possible building blocks in molec- ular spintronics due to their magnetic bistability between the high-spin （HS） and low-spin （LS） states. Here, the electronic structures and transport properties through SCO magnet Fe（II）-N4S2 complexes sandwiched between gold electrodes are explored by performing exten- sive density functional theory calculations combined with non-equilibrium Green＇s function formalism. The optimized Fe-N and Fe-S distances and predicted magnetic moment of the SCO magnet Fe（II）-N4S2 complexes agree well with the experimental results. The reversed spin transition between the HS and LS states can be realized by visible light irradiation according to the estimated SCO energy barriers. Based on the obtained transport results, we observe nearly perfect spin-filtering effect in this SCO magnet Fe（II）-N4S2 junction with the HS state, and the corresponding current under small bias voltage is mainly contributed by the spin-down electrons, which is obviously larger than that of the LS case. Clearly, these theoretical findings suggest that SCO magnet Fe（II）-N4S2 complexes hold potential applications in molecular spintronies.展开更多
Residues of tetracycline antibiotics(TCs) in environments may be harmful to human.Due to their high polarities,it is extremely challenging to efficiently enrich TCs with low concentrations in natural waters for analys...Residues of tetracycline antibiotics(TCs) in environments may be harmful to human.Due to their high polarities,it is extremely challenging to efficiently enrich TCs with low concentrations in natural waters for analysis.In this work,a magnetic metal-organic framework Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]was synthesized and applied as a dispersive micro-solid phase extraction adsorbent for TCs enrichment.Effects of dispersive micro-solid phase extraction conditions including extraction time,solution p H,and elution solvent on the extraction efficiencies of TCs were investigated.Results show that TCs could be enriched efficiently by Fe_(3)O_(4)@[Cu_(3)(btc)_(2)],and electrostatic interaction between TCs and Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]dominated this process.Combined with liquid chromatography-tandem mass spectrometry,four TCs residues (oxytetracycline,tetracycline,chlortetracycline,and doxycycline) in natural waters were determined.The detection limits (LOD,S/N=3) of the four antibiotics were 0.01-0.02μg/L,and the limits of quantitation (LOQ,S/N=10)were 0.04-0.07μg/L.The recoveries obtained from river water and aquaculture water spiked with three TCs concentration levels ranged from 70.3%to 96.5%with relative standard deviations of 3.8%-12.8%.Results indicate that the magnetic metal-organic framework based dispersive micro-solid phase extraction is simple,rapid and high-loading for antibiotics enrichment from water,which further expand the practical application of metal-organic frameworks in sample pretreatment for environmental pollutant analysis.展开更多
基金supported by the National Natural Sci-ence Foundation of China(No.22174135,No.21790352)the National Key R&D Program of China(No.2021YFA1500500,No.2016YFA0200600)+4 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000)Anhui Initiative in Quantum Information Technologies(No.AHY090100)CAS Project for Young Scientists in Basic Research(No.YSBR-054)Innovation Program for Quantum Science and Technology(No.2021ZD0303301)the Fundamental Research Funds for the Central Universities.
文摘Double-resonance Raman(DRR)scattering in two-di-mensional(2D)materials describes the intravalley or intervalley scattering of an electron or a hole excited by incident photons.Although the presence of defects can provide additional momentum and influence the scat-tering process involving one or two phonons,only the idealized defects without any structural details are considered in tra-ditional DRR theory.Here,the second-order DRR spectra of WSe_(2) monolayer with different types of defects are calculated involving the combinations of acoustic and optical phonons in the vicinity of K(K')and M points of the Brillouin zone.The electronic band structures are modified due to the presence of defects,and the band unfolding method is adopted to show the bending of valence and conduction bands for the defective WSe_(2) monolayers.The associ-ated phononic band structures also exhibit different changes in phonon dispersion curves,re-sulting in different DRR spectra corresponding to the different types of defects in the WSe_(2) monolayers.For example,the existence of W vacancy in the WSe_(2) monolayer would result in downshifts in vibrational frequencies and asymmetrical broadenings in linewidths for most combination modes due to the dramatic changes in contour shape of electronic valleys at K and K'.Moreover,the scattering from K to Q is found to be forbidden for the two Se vacan-cies because of the elevation of conduction band at the Q point.Our work highlights the role of defect structures in the intervalley scattering and may provide better understanding in the underlying physics of DRR process in 2D materials.
基金supported by the National Key Re-search and Development Program of China(No.2021YFA1500403)the National Natural Science Foundation of China(No.21773047 and No.U1832180)partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication.
文摘ZnO-based catalysts have been widely used in hydrogenation reactions,but less attention has been paid to the electrocatalytic hydrogenation process on ZnO electrodes.In this work,the preparation of hydrogen species and the associ-ated reduction properties under electrochemi-cal processes in aqueous solutions have been in-vestigated on ZnO and Au/ZnO electrodes.The measurements of cyclic voltammetry(CV),X-ray diffraction,and electron paramagnetic resonance(EPR)confirm the formation of hydro-gen species on the interstitial sites(Hi)or on the oxygen vacancy sites(H_(O)).The hydrogena-tion reaction of p-nitrophenol(pNP)at 40μmol/L occurs on both ZnO and Au/ZnO elec-trodes,and the hydrogenation reduction performance of Au/ZnO electrode is better than that of ZnO electrode.CVs show H_(O)species is much more reactive with pNP than Hi species.Compared with the ZnO electrode,the presence of Au on ZnO promotes the formation of H_(O)species and improves the electro-reduction performance to pNP.These results help us to un-derstand the reaction processes related to the electrochemical hydrogenation on ZnO and Au/ZnO surfaces and shed new light on the design of new catalytic hydrogenation systems.
基金supported by the Innovation Program for Quantum Science and Technology(2021ZD0303302)the CAS Project for Young Scientists in Basic Research(YSBR-054)+2 种基金the National Natural Science Foundation of China(Nos.22425206,21972129)NSF grant CHE-2303197the New Cornerstone Science Foundation.
文摘Molecular constructs define the elementary units in porous materials for efficient CO_(2)capture.The design of appro-priate interpore and intermolecular space is crucial to stabilize CO_(2)molecules and maximize the capacity.While the molecular construct usually has a fixed dimension,whether its inter-molecular space could be self-adjustable during CO_(2)capture and release,behaving as a balloon,has captured imagination.Here we report a flexible intermolecular space of the double chain structure of self-assembled 1,4-pheny-lene diisocyanide(PDI)molecules on Ag(110)surface,which dynamically broadens and recovers during the CO_(2)capture and release.The incipient PDI double chains organize along the[001]direction of Ag(110),in which individual PDI molecules stand up in a zigzag order with the interchain width defined by twice the Ag lattice distance along_([110])direction(2α_([110])).When CO_(2)molecules are introduced,they assemble to occupy the interchain spaces,expanding the interchain width to 3α_([110]),4α_([110])and 5α_([110]):Warming up the sample leads to the thermally-driven CO_(2)desorption that recovers the original interchain space.High-resolution scanning tunneling microscopy(STM)jointly with density functional theory(DFT)calculations determine the structural and electronic interactions of CO_(2)molecules with the dynamical PDI structures,providing a molecular-level perspective for the design of a self-adjustable metal-organic construct for reversible gas capture and release.
文摘Acetobacteraceae has garnered significant attention because of its unique properties and the broad applications of the bacterial cellulose it produces.However,unlike model strains,Acetobacteraceae have few synthetic biology applications because they are difficult to manipulate genetically and have insufficient genetic regulatory elements,among other factors.To address this limitation,this study characterized the fundamental properties and synthetic biology elements of three commonly used bacterial cellulose-producing strains.First,the basic characteristics of the three strains,including their cellulose film production ability,division time,antibiotic susceptibility,and plasmid features,were analyzed.Two inducible promoters(pTrc and pLux101)were subsequently characterized within the three strains.The inducibility of the pTrc promoter was relatively low across the three strains(induction ratio:1.98–6.39),whereas the pLux101 promoter demonstrated a significantly greater level of inducibility within the three strains(induction ratio:87.28–216.71).Finally,through gene knockout experiments,this study identified four genes essential for bacterial cellulose film production in the genome of the Gluconacetobacter hansenii ATCC 5358 strain.This study not only enriches the library of synthetic biology elements in nonmodel strains,but also lays the foundation for the synthetic biology applications of Acetobacteraceae.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0450202).
文摘To identify the species in liquid surface using mass spectrometry,we must eliminate or reduce interferences during the vaporization or desorption of the species from the liquid surface.It is much more challenging to isolate the ionic,larger species from the liquid surface,because of the frangible structures and the higher solvation energies of those species.Here we demonstrate a new mass spectrometry in which the ionic species at the liquid surface can be desorbed with ultrasoft infrared picosecond laser pulses while the liquid surface is not breached.This laser desorption assisted mass spectrometry is not only a powerful tool to detect the fragile species but also promising to investigate vibrational energy transfer dynamics in the liquid surface.
基金supported by the CAS Project for Young Scientists in Basic Research(YSBR-005)the National Natural Science Foundation of China(22325304,22221003 and 22033007)We acknowledge the Supercomputing Center of USTC,Hefei Advanced Computing Center,Beijing PARATERA Tech Co.,Ltd.,for providing high-performance computing services。
文摘As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular force fields or ab initio molecular dynamics with semilocal density functionals.Inspired by recent studies on bulk water using increasingly accurate machine learning force fields,we report a new machine learning force field for liquid methanol with a hybrid functional revPBE0 plus dispersion correction.Molecular dynamics simulations on this machine learning force field are orders of magnitude faster than ab initio molecular dynamics simulations,yielding the radial distribution functions,selfdiffusion coefficients,and hydrogen bond network properties with very small statistical errors.The resulting structural and dynamical properties are compared well with the experimental data,demonstrating the superior accuracy of this machine learning force field.This work represents a successful step toward a first-principles description of this benchmark system and showcases the general applicability of the machine learning force field in studying liquid systems.
基金supported by the National Natural Science Foundation of China(52203016)the USTC Research Funds of the Double First-Class Initiative(YD9990002018)+3 种基金the Overseas Students Innovation and Entrepreneurship Support Program Project of Anhui Province(2021LCX022)the Key R&D Projects in Anhui Province(2022i01020012)the Natural Science Foundation of Hefei(2022039)the Excellent Research and Innovation Team Project of Anhui Province(2022AH010001).
文摘α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.
基金supported by the National Key R&D Program of China(2021YFA1501700)Fundamental Research Funds for the Central Universities(WK9990000142).
文摘The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nickel-based catalysts have great application prospects in the industrialization process of olefin coordination polymerization.In this work,various N-aryl substituents with different electronic effects were synthesized and introduced intoα-diimine ligands.The aspreparedα-diimine nickel catalysts showed high polymerization activity(0.9×10^(7)–3.0×10^(7)g·mol^(−1)·h^(−1))in ethylene polymerization,generating polyethylene products with adjustable molecular weights(Mn values:7.4×10^(4)–146.9×10^(4)g·mol^(−1))and branching densities(31/1000 C–68/1000 C).The resulting polyethylene products showed excellent mechanical properties,with high tensile strength(up to 25.0 MPa)and high strain at break values(up to 3890%).The copolymerization of ethylene and polar monomers can also be achieved by these nicekel complexes,ultimately preparing functionalized polyolefins.
基金supported by the National Key Research and Development Program of China(No.2021YFA1500403)the National Natural Science Foundation of China(No.21773047 and No.U1832180)partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication.
文摘Deposition-precipitation(DP)method is commonly used to prepare the supported metal catalysts.In this study,the modification effect of the mild DP method on the photocatalytic performance of TiO_(2)was investigated.The TiO_(2)samples with DP treatment,as well as Au/TiO_(2)prepared under the same conditions,showed enhanced photocatalytic performance of the degradation of methylene blue(MB).·OH generated by photoexcited holes is identified as the main intermediate reactive species during the degradation reaction.X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)show that TiO_(2)(A)-17 after DP treatment has the most amount of surface OH^(-)_(ad)species.The presence of surface OH^(-)_(ad)species not only changes the surface zeta potential,favoring the attraction of cationic MB;but also depresses the electron-hole recombination,favoring photodegradation of MB by hole-produced·OH.An implication of these findings is that the modification of support properties should be taken into account while preparing supported metal catalysts using DP methods.
基金supported by the CAS Project for Young Scientists in Basic Research(YSBR-070)the National Natural Science Foundation of China(21925110,21890750,U2032161,12147105)+8 种基金the USTC Research Funds of the Double First-Class Initiative(YD2060002004)the National Key Research and Development Program of China(2022YFA1203600,2022YFA1203601,2022YFA1203602)the Natural Science Foundation of China-Anhui Joint Fund(U23A20121)the Outstanding Youth Foundation of Anhui Province(2208085J14)the Anhui Provincial Key Research and Development Project(202004a050200760)the Key R&D Program of Shandong Province(2021CXGC010302)the Users with Excellence Project of Hefei Science Center CAS(2021HSC-UE004)the Fellowship of the China Postdoctoral Science Foundation(2022M710141)the open foundation of the Key Laboratory of the Engineering Research Center of Building Energy Efficiency Control and Evaluation,Ministry of Education(AHJZNX-2023-04).
文摘Materials with low thermal conductivity are applied extensively in energy management,and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists.Doping is a common strategy for achieving low thermal conductivity that can offer abundant scattering centers in which heavier dopants always result in lower phonon group velocities and lower thermal conductivities.However,the amount of equivalent heavyatom single dopant available is limited.Unfortunately,nonequivalent heavy dopants have finite solubility because of charge imbalance.Here,we propose a charge balance strategy for SnS by substituting Sn2+with Ag^(+)and heavy Bi^(3+),improving the doping limit of Ag from 2%to 3%.Ag and Bi codoping increases the point defect concentration and introduces abundant boundaries simultaneously,scattering the phonons at both the atomic scale and nanoscale.The thermal conductivity of Ag0.03Bi0.03Sn0.94S decreased to 0.535 W·m^(−1)·K^(−1)at room temperature and 0.388 W·m^(−1)·K^(−1)at 275°C,which is below the amorphous limit of 0.450 W·m^(−1)·K^(−1)for SnS.This strategy offers a simple way to enhance the doping limit and achieve ultralow thermal conductivity in solids below the amorphous limit without precise structural modification.
基金supported by the Fundamental Research Funds for the Central Universities(WK9990000102,WK2030000035).
文摘The study of oxide heteroepitaxy has been hindered by the issues of misfit strain and substrate clamping,which impede both the optimization of performance and the acquisition of a fundamental understanding of oxide systems.Recently,however,the development of freestanding oxide membranes has provided a plausible solution to these substrate limitations.Single-crystalline functional oxide films can be released from their substrates without incurring significant damage and can subsequently be transferred to any substrate of choice.This paper discusses recent advancements in the fabrication,adjustable physical properties,and various applications of freestanding oxide perovskite films.First,we present the primary strategies employed for the synthesis and transfer of these freestanding perovskite thin films.Second,we explore the main functionalities observed in freestanding perovskite oxide thin films,with special attention to the tunable functionalities and physical properties of these freestanding perovskite membranes under varying strain states.Next,we encapsulate three representative devices based on freestanding oxide films.Overall,this review highlights the potential of freestanding oxide films for the study of novel functionalities and flexible electronics.
基金supported by the National Key R&D Program of China(2020YFA0711502)the National Natural Science Foundation of China(52325202,52202052,52373310)。
文摘The preparation of large crystals is highly important for the characterization and application of a newly found structure but remains a challenge for one-dimensional(1D)C_(60) polymers.In this work,we successfully fabricated a 1D C_(60) polymer crystal via on-site annealing of a millimeter-sized C_(60) molecular crystal withα-Li_(3)N at 500°C and ambient pres�sure.Characterizations show that the C_(60) cages in the crystal have been efficiently connected,forming 1D chains along the<110>direction in an orthorhombic 3D structure.At the same time,the crystal maintains a morphology similar to that of the pristine C_(60)crystal,providing opportunities for characterization of all the facets of the crystal via Raman spectroscopy and thus suggesting the formation mechanism of such crystals.
基金supported by the National Natural Science Foundation of China(22322304,22273092,22373095)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450101)+2 种基金the Innovation Program for Quantum Science and Technology(2021ZD0303306)the USTC Tang ScholarThe authors wish to acknowledge the Supercomputing Center of the USTC for providing computational resources.
文摘The achievement of electrical spin control is highly desirable.One promising strategy involves electrically mod-ulating the Rashba spin orbital coupling effect in materials.A semiconductor with high sensitivity in its Rashba constant to external electric fields holds great potential for short channel lengths in spin field-effect transistors,which is crucial for preserving spin coherence and enhancing integration density.Hence,two-dimensional(2D)Rashba semiconductors with large Rashba constants and significant electric field responses are highly desirable.Herein,by employing first-principles calculations,we design a thermodynamically stable 2D Rashba semiconductor,YSbTe_(3),which possesses an indirect band gap of 1.04 eV,a large Rashba constant of 1.54 eV·Åand a strong electric field response of up to 4.80 e·Å^(2).In particular,the Rashba constant dependence on the electric field shows an unusual nonlinear relationship.At the same time,YSbTe_(3)has been identified as a 2D ferroelectric material with a moderate polarization switching energy barrier(~0.33 eV per formula).By changing the electric polarization direction,the Rashba spin texture of YSbTe_(3)can be reversed.These out-standing properties make the ferroelectric Rashba semiconductor YSbTe_(3)quite promising for spintronic applications.
基金supported by the National Key Research and Development Program of China(2021YFA1500500,2019-YFA0405600)the CAS Project for Young Scientists in Basic Research(YSBR-051)+6 种基金the National Science Fund for Distinguished Young Scholars(21925204)the National Natural Science Foundation of China(22202192,U19A2015,22221003,22250007,22163002)the Collaborative Innovation Program of Hefei Science Center,CAS(2022HSCCIP004)the International Partnership,the DNL Cooperation Fund,CAS(DNL202003)the USTC Research Funds of the Double First-Class Initiative(YD9990002016,YD999000-2014)the Program of Chinese Academy of Sciences(123GJHZ2022101GC)the Fundamental Research Funds for the Central Universities(WK9990000095,WK999000-0124).
文摘Electrocatalytic water splitting provides an efficient method for the production of hydrogen.In electrocatalytic water splitting,the oxygen evolution reaction(OER)involves a kinetically sluggish four-electron transfer process,which limits the efficiency of electrocatalytic water splitting.Therefore,it is urgent to develop highly active OER catalysts to accelerate reaction kinetics.Coupling single atoms and clusters in one system is an innovative approach for developing efficient catalysts that can synergistically optimize the adsorption and configuration of intermediates and improve catalytic activity.However,research in this area is still scarce.Herein,we constructed a heterogeneous single-atom cluster system by anchoring Ir single atoms and Co clusters on the surface of Ni(OH)_(2)nanosheets.Ir single atoms and Co clusters synergistically improved the catalytic activity toward the OER.Specifically,Co_(n)Ir_(1)/Ni(OH)_(2)required an overpotential of 255 mV at a current density of 10 mA·cm^(−2),which was 60 mV and 67 mV lower than those of Co_(n)/Ni(OH)_(2)and Ir1/Ni(OH)_(2),respectively.The turnover frequency of Co_(n)Ir_(1)/Ni(OH)_(2)was 0.49 s^(−1),which was 4.9 times greater than that of Co_(n)/Ni(OH)_(2)at an overpotential of 300 mV.
基金supported by the National Natural Science Foundation of China(No.22173090 and No.91950207)the Innovation Program for Quantum Science and Technology(No.2021ZD0303303)+2 种基金the National Key Research and Development Program of China(No.2016YFA0200602 and No.2018YFA0208702)the Anhui Initiative in Quantum Information Technologies(No.AHY090200)the USTC Key Directions Project Incubation Fund(No.WK2340000106).
文摘We report a mechanistic study of excitonic photoluminescence in predesigned hybrid organic-inorganic perovskite(HOIP)systems,i.e.,(DMAEA)Pb_(2)I_(6),(DMAPA)PbI_(4),(DEAEA)Pb_(2)I_(6),and(DEAPA)_(4)Pb_(5)I_(18),featuring targeted regulation of organic cations.Starting from the prototype DMAEA(i.e.,2-N,N-dimethylamino-l-ethylamine)for(DMAEA)Pb_(2)I_(6),the other three HOIPs differ only in the extensions with CH_(2)group(s)at the“head”or/and“tail”of DMAEA that is an“alkylated ammonia”.Their crystal structures are constructed and structural distortions are evaluated.The steady-state/transient absorption and emission spectroscopic characterizations,combined with the band-structure calculations,are conducted.The two different photoluminescence(PL)mechanisms are identified,i.e.,PL emissions dominated by free excitons for(DMAPA)PbI_(4)and by self-trapped excitons for(DMAEA)Pb_(2)I_(6),(DEAEA)Pb_(2)I_(6),and(DEAPA)_(4)Pb_(5)I_(18).The self-trapped excitonic effect involved in the latter three HOIPs is quantitatively analyzed.This work would be of guiding value for the design of HOIP systems based on organic-cation engineering,beneficial for the pertinent performance optimization in light-emitting applications.
基金supported by the Ministry of Science and Technology of China(No.2022YFF0606500)the National Natural Science Foundation of China(No.22273096).
文摘Methane is the second most important greenhouse gas after carbon dioxide,and the reduction of methane emissions is a key focus in IPCC reports.At present,atmospheric methane is monitored through ground-based observations and satellite remote sensing that depend on spectral characteristics.However,the positions of the methane lines provided by the widely utilized HITRAN database lack the precision required for accurate retrievals.In this work,we used cavity-enhanced absorption spectroscopy to record the absorption spectrum near the atmospheric detection window of methane at 1.66µm.From the saturated absorption peaks(“Lamb dips”)observed on top of Doppler-broadened methane absorption lines,we determined the line positions with an absolute frequency accuracy of better than 2 MHz.The results also indicate the incompetence of the HITRAN database and theoretical models based onαb initio calculations of methane lines in this region.
基金supported by the National Natural Science Foundation of China(No.22125302 and No.22327801)the Innovation Program for Quantum Science and Technology(No.2021ZD0303304)the University of Science and Technology of China.
文摘Time-sliced velocity map ion imaging(VMI)experiments were performed to investigate the photodissociation of H_(2)S^(+)X^(2)B_(1),via the excitation to the A^(2)A_(1)(0,11,0)state.Experimental images of the S^(+)(^(4)Su)products were recorded near 349.60 nm for the K=1 band,and near 344.30 nm for the K=2 band.The derived product total kinetic energy release(TKER)spectra exhibit partially rotationally resolved structures corresponding to the H_(2)(X^(1)∑_(g)^(+))co-products.The observed product state and angular distributions both exhibit sensitive dependence on the photolysis wavelength at near 349.60 nm and 344.30 nm.These phenomena indicate the underlying rich dynamic details and the role of the rotational excitation of H_(2)S^(+).
基金supported by the National Natural Science Foundation of China(No.21473168 and No.11634011)the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology
文摘Spin-crossover （SCO） magnets can act as one of the most possible building blocks in molec- ular spintronics due to their magnetic bistability between the high-spin （HS） and low-spin （LS） states. Here, the electronic structures and transport properties through SCO magnet Fe（II）-N4S2 complexes sandwiched between gold electrodes are explored by performing exten- sive density functional theory calculations combined with non-equilibrium Green＇s function formalism. The optimized Fe-N and Fe-S distances and predicted magnetic moment of the SCO magnet Fe（II）-N4S2 complexes agree well with the experimental results. The reversed spin transition between the HS and LS states can be realized by visible light irradiation according to the estimated SCO energy barriers. Based on the obtained transport results, we observe nearly perfect spin-filtering effect in this SCO magnet Fe（II）-N4S2 junction with the HS state, and the corresponding current under small bias voltage is mainly contributed by the spin-down electrons, which is obviously larger than that of the LS case. Clearly, these theoretical findings suggest that SCO magnet Fe（II）-N4S2 complexes hold potential applications in molecular spintronies.
基金supported by the National Natural Science Foundation of China(No.21607003).
文摘Residues of tetracycline antibiotics(TCs) in environments may be harmful to human.Due to their high polarities,it is extremely challenging to efficiently enrich TCs with low concentrations in natural waters for analysis.In this work,a magnetic metal-organic framework Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]was synthesized and applied as a dispersive micro-solid phase extraction adsorbent for TCs enrichment.Effects of dispersive micro-solid phase extraction conditions including extraction time,solution p H,and elution solvent on the extraction efficiencies of TCs were investigated.Results show that TCs could be enriched efficiently by Fe_(3)O_(4)@[Cu_(3)(btc)_(2)],and electrostatic interaction between TCs and Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]dominated this process.Combined with liquid chromatography-tandem mass spectrometry,four TCs residues (oxytetracycline,tetracycline,chlortetracycline,and doxycycline) in natural waters were determined.The detection limits (LOD,S/N=3) of the four antibiotics were 0.01-0.02μg/L,and the limits of quantitation (LOQ,S/N=10)were 0.04-0.07μg/L.The recoveries obtained from river water and aquaculture water spiked with three TCs concentration levels ranged from 70.3%to 96.5%with relative standard deviations of 3.8%-12.8%.Results indicate that the magnetic metal-organic framework based dispersive micro-solid phase extraction is simple,rapid and high-loading for antibiotics enrichment from water,which further expand the practical application of metal-organic frameworks in sample pretreatment for environmental pollutant analysis.
