Taking advantage of the effects on DNA secondary structure of two DNA-intercalators,ethidium bromide and chloroquine,we used each of them to treat nuclei from both mature erythrocytes and reticulocytes of chicken,as a...Taking advantage of the effects on DNA secondary structure of two DNA-intercalators,ethidium bromide and chloroquine,we used each of them to treat nuclei from both mature erythrocytes and reticulocytes of chicken,as an alternative approach to study the relationships between DNA secondary structure,nuclear proteins and chromatin structure.We presented results of differential extraction of nuclear proteins from nuclei with DNA-intercalators,as well as preliminary characterization of these proteins.A 45kd protein is the major component in fractions extracted by both intercalators from nuclei from either mature erythrocytes or reticulocytes and seems to be a DNA-binding protein.Furthermore,from current concepts of functional aspects of DNA conformation and structural heterogeneity in chromatin and nuclear proteins,we have discussed both the significance of our results as well as technical aspects of this approach.展开更多
By means of circular dichroism（CD） spectrum coupled with UV-Vis and fluorescence spectra,the binding model of DNA intercalator A1{4-（2-diethylamino-ethylamino）-8-oxo-8H-acenaphtho[1,2-b]pyrrole-9-carbonitrile} to ...By means of circular dichroism（CD） spectrum coupled with UV-Vis and fluorescence spectra,the binding model of DNA intercalator A1{4-（2-diethylamino-ethylamino）-8-oxo-8H-acenaphtho[1,2-b]pyrrole-9-carbonitrile} to calf thymus（CT） DNA was investigated,depending on the values of R（R is defined as the ratio of the concentration of A1 to CT DNA base pairs） and different outer factors.Molecules A1 were intercalated into the CT DNA base pairs in different orientations in the intercalation pocket at a lower R value（R≤0.20）,while A1 molecules aggregated on the surface of the helix of the CT DNA as the R value increased.The influence of NaCl on the binding was smaller because the electrostatic interaction only provided approximately 16% of the overall free energy of binding.The protonated diethylamine substitution would influence the binding geometry greatly at a low pH value via forming hydrogen bonds with the exposed C=O group on DNA surface.展开更多
Sodium-ion batteries(SIBs)have attracted significant attention in large-scale energy storage system because of their abundant sodium resource and cost-effectiveness.Layered oxide materials are particularly promising a...Sodium-ion batteries(SIBs)have attracted significant attention in large-scale energy storage system because of their abundant sodium resource and cost-effectiveness.Layered oxide materials are particularly promising as SIBs cathodes due to their high theoretical capacities and facile synthesis.However,their practical applications are hindered by the limitations in energy density and cycling stability.The comprehensive understanding of failure mechanisms within bulk structure and at the cathode/electrolyte interface of cathodes is still lacking.In this review,the issues related to bulk phase degradation and surface degradation,such as irreversible phase transitions,cation migration,transition metal dissolution,air/moisture instability,intergranular cracking,interfacial reactions,and reactive oxygen loss,are discussed.The latest advances and strategies to improve the stability of layered oxide cathodes and full cells are provided,as well as our perspectives on the future development of SIBs.展开更多
The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNT...The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).展开更多
V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve th...V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve the stability,organic small molecule choline chloride intercalation is used to expand the spacing of the vanadium pentoxide layers and increase the cycling stability.Therefore,we consider the introduction of Sr^(2+)to cointercalate with choline chloride.Here,we synthes-ized vanadium pentoxide cointercalated with Sr^(2+)and choline ions(Ch^(+))via a simple hydrothermal method.The electro-chemical performance shows an enhanced cathode capacitance contribution of Sr&Ch-V_(2)O_(5),with a discharge capacity of 526 mAh·g^(-1)at 0.1 A·g^(-1)and a retention rate of 78.9%after 2000 cycles at 5 A·g^(-1).This work offers a novel strategy for the design of organic‒inorganic hybrid materials for use as cathodes in aqueous zinc-ion batteries.展开更多
Targeting protein kinases(PKs) has been a promising strategy in treating cancer, as PKs are key regulators of cell survival and proliferation. Here in this study, we studied the ability of pyrimido[4',5':4,5]t...Targeting protein kinases(PKs) has been a promising strategy in treating cancer, as PKs are key regulators of cell survival and proliferation. Here in this study, we studied the ability of pyrimido[4',5':4,5]thieno(2,3-b)quinolines(PTQ) to inhibit different PKs by performing computational docking and in vitro screening. Docking studies revealed that 4-butylaminopyrimido[4',5':4,5]thieno(2,3-b)quinoline(BPTQ) has a higher order of interaction with the kinase receptors than other PTQ derivatives.In vitro screening confirms that BPTQ inhibits VEGFR1 and CHK2, with the IC_(50) values of 0.54 and1.70 mmol/L, respectively. Further, cytotoxicity of BPTQ was measured by trypan blue assay. Treatment with BPTQ decreased the proliferation of HL-60 cells with an IC_(50) value of 12 mmol/L and induces apoptosis, as explicated by the fall in the mitochondrial membrane potential, annexin V labeling and increased expression of caspase-3. Taken together, these data suggest that BPTQ possess ability to inhibit PKs and to induce cell death in human promyelocytic leukemia cells.展开更多
Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalyti...Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalytic reaction efficiency and selectivity[1–3].This technique has achieved significant progress in areas such as electrocatalysis,catalytic cracking,and energy conversion,especially in reactions like hydrogen generation,oxygen reduction,nitrogen reduction,and carbon dioxide reduction[4–6].Intercalation catalysis can enhance catalyst activity and selectivity,but challenges remain regarding stability,reusability,and industrial application.Future research will focus on developing new intercalation materials,optimizing catalyst design,and exploring their potential applications in complex environments[7].展开更多
Two-dimensional MXenes are renowned for their remarkable electrical conductivity and electrochemical activity making them highly promising for electrode applications.However,the restacking of MXene nanosheets impairs ...Two-dimensional MXenes are renowned for their remarkable electrical conductivity and electrochemical activity making them highly promising for electrode applications.However,the restacking of MXene nanosheets impairs their functionality by reducing active sites and obstructing ionic transport.This study presents a facile synthesis approach for nickel-intercalated MXene,designed to enhance surface reactivity,avoid restacking,and achieve improved electrochemical performance.Electrochemical studies revealed that the nickel-MXene hybrid showed better cycling stability,retaining 83.7%of its capacity after 10000 cycles and attaining an energy density of 26 Wh kg^(-1) at a power density of 1872Wkg^(-1).It also exhibited overpotentials of 109 and 482 mV at 10 and 100 mA cm^(-2),respectively,in the hydrogen evolution reaction.To predict the structural and electrical alterations caused by nickel inclusion,as well as to understand the intercalation mechanism,spin-polarized density functional theory calculations were carried out.The theoretical results showed an improved carrier concentration for nickel-MXene.Nickel-MXene possessed superior electronic characteristics and surplus active sites with hexagonal closed-packed(hcp)edge sites,which enhanced electrochemical properties.Our results demonstrate that nickel intercalation prevents the restacking of MXene but also significantly improves their electrochemical characteristics,making them ideal for energy storage and catalytic applications.展开更多
Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chlori...Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chloride oxidation reactions make oxygen evolution reaction(OER)in seawater extremely challenging.Herein,the low-cost and scalable CoFe layered double hydroxides with Cl^(-)intercalation and decorated with Ce(OH)_(3)(named as CoFe-Cl^(-)/Ce(OH)_(3))catalyst is synthesized via rapid electrodeposition under ambient conditions,which is quickly reconstructed into a CeO_(2)decorated and Cl^(-)intercalated CoFeOOH(CoFeOOH-Cl^(-)/CeO_(2))during OER.Theoretical investigation reveals that Cl^(-)intercalation weakens the adsorption ability of Cl^(-)on Co/Fe atoms and hinders unfavorable coupling with chloride,thereby preventing the chlorine corrosion process and enhancing catalytic stability and activity.The CeO_(2)with hard Lewis acidity preferentially binds to OH-with harder Lewis base to ensure the OH-rich microenvironment around catalyst even under high current operating conditions,thus further enhancing stability and improving OER activity.The functionalized CoFe-Cl^(-)/Ce(OH)_(3)delivers 1000 mA cm^(-2)current density at only 329 mV overpotential with excellent stability for 1000 h under alkaline seawater.Electrochemical experiments elucidate the OER catalytic mechanism in which CeO_(2)serves as a co-catalyst for enriching OH-and CoFeOOH-Cl^(-)is the active species.Our work is a substantial step towards achieving massive and sustainable production of hydrogen fuel from immense seawater.展开更多
Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an imp...Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.展开更多
Aqueous zinc-ion batteries(AZBs)are considered safer and potential substitutes for large-scale energy storage and conversion devices.The conventional vanadium pentoxide(V_(2)O_(5))cathode material has attracted widesp...Aqueous zinc-ion batteries(AZBs)are considered safer and potential substitutes for large-scale energy storage and conversion devices.The conventional vanadium pentoxide(V_(2)O_(5))cathode material has attracted widespread attention duo to its typical layered structure and high theoretical capacity.Unfortunately,it still suffers from severe structural collapse,sluggish diffusion dynamics,and fast capacity fading.Herein,we rationally designed and prepared trivalent Al^(3+)and H_(2)O co-intercalated V_(2)O_(5)(AlVO),in which Al^(3+)plays a“pillar”role and forms strong Al−O bonds,while H_(2)O acts as the“lubricant”,synergistically maintaining the structural stability and accelerating the diffusion of zinc ions.The Zn//AlVO battery is found to possess not only an impressive reversible capacity of 390.7 mAh·g^(−1) at 0.5 A·g^(−1),5.13 times that of Zn//c-V_(2)O_(5),but also excellent rate capability and long-term cycling performance(with the residual capacity of 138.2 mAh·g^(−1) over 10000 cycles at 10 A·g^(−1)).展开更多
The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of ...The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of cathode materials,which reduces the cycle stability and specific capacity,consequently limiting the practical application of zinc-ion batteries.In this work,hydroxypropylβ-cyclodextrin(HP-β-CD),a special stereo cyclic organic molecule with hydrophobic inner cavity and hydrophilic outer cavity,is used as the intercalator for hydrated vanadium oxide(VOH)to enlarge the layer spacing and enhance the hydrophobicity of the cathode material.The larger interlayer spacing(13.9Å)of HP-β-CD-VOH is beneficial for improving ion mobility and the intrinsic electrochemical reaction kinetics.HP-β-CD-VOH delivers a discharge capacity of 336.7 mAh g^(-1)at 0.2 A g^(-1)and high-rate capability(242 mAh g^(-1)at 5 A g^(-1)).Due to the hydrophobic property of HP-β-CD in the interlayer pillar,the vanadium dissolution effect of polar water molecules can be reduced during charge and discharge;HP-β-CDVOH demonstrates sustained high efficiency and extended cycle longevity,maintaining a remarkable durability of 6000 cycles at a current density of 10 A g^(-1).This study presents an effective strategy for developing high-performance aqueous zinc-ion battery cathode materials.展开更多
DNA imaging and visualization techniques are crucial in biological experiments and have also emerged as a powerful method for single-molecule studies.Traditional intercalating dyes(e.g.,SYTOX,EtBr,GelRed)can stain DNA...DNA imaging and visualization techniques are crucial in biological experiments and have also emerged as a powerful method for single-molecule studies.Traditional intercalating dyes(e.g.,SYTOX,EtBr,GelRed)can stain DNA but may alter its structure and mechanical properties,and cause photocleavage.Recently,a novel fluorescent DNA-binding protein(FP-DBP)was introduced,which can stain DNA without sequence preference and without inducing photocleavage.In this study,using a custom-built magnetic tweezers system,we performed DNA stretching,twisting and unzipping experiments to compare the mechanical properties of DNA with and without two kinds of intercalating dyes(SYTOX Orange and GelRed)and mCherry FP-DBP.Our results show that mCherry FP-DBP does not affect DNA structure or mechanics,unlike SYTOX Orange and GelRed,making FP-DBP a promising tool for DNA visualization in single-molecule experiments.展开更多
Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performa...Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performance Mg cathode materials.Utilizing the common characteristics of various ionic intercalation-type electrodes,we design and train a Crystal Graph Convolutional Neural Network model that can accurately predict electrode voltages for various ions with mean absolute errors(MAE)between0.25 and 0.33 V.By deploying the trained model to stable Mg compounds from Materials Project and GNoME AI dataset,we identify 160 high voltage structures out of 15,308 candidates with voltages above3.0 V and volumetric capacity over 800 mA h/cm^(3).We further train a precise NequIP model to facilitate accurate and rapid simulations of Mg ionic conductivity.From the 160 high voltage structures,the machine learning molecular dynamics simulations have selected 23 cathode materials with both high energy density and high ionic conductivity.This Al-driven workflow dramatically boosts the efficiency and precision of material discovery for multivalent ion batteries,paving the way for advanced Mg battery development.展开更多
Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existen...Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existence form of leached oxygen anions are still controversial.Herein,we selected iron selenite-wrapped hydrated nickel molybdate(denoted as NiMoO/FeSeO)as a pre-catalyst to study the oxyanion effect.It is surprising to find that SeO_(2)-exists in the catalyst in the form of intercalation,which is different from previous studies that suggest that anions are doped with residual elements after electrochemical activation,or adsorbed on the catalyst surface.The experiment and theoretical calculations show that the existence of SeO_(4)^(2-)intercalation effectively adjusts the electronic structure of NiFeOOH,promotes intramolecular electron transfer and O-O release,and thus lowers the reaction energy barrier.As expected,the synthesized NiFeOOH-SeO only needs 202 and 285 mV to attain 100 and 1000 mA cm^(-2)in 1 M KOH.Further,the anion exchange membrane water electrolyzer(AEMWE)consisting of NiFeOOHSeO anode and Pt/C cathode can reach 1 A cm^(-2)at 1.70 V and no significant attenuation within 300 h.Our findings provide insights into the mechanism,by which the intercalated oxyanions enhance the OER performance of NiFeOOH,thereby facilitating large-scale hydrogen production through AEMWE.展开更多
MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties en...MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties enables the observation of exotic quantum phenomena such as the quantum anomalous Hall effect,axion insulator states,and Majorana fermions.While the intercalation of Bi_(2)Te_(3)can tune its magnetism,synthesizing pure-phase MnBi_(2)Te_(4)with uniform Bi_(2)Te_(3)intercalation remains challenging,and the fixed interlayer spacing of Bi_(2)Te_(3)limits magnetic coupling tunability.Here,we utilize electrochemical organic molecule intercalation to expand the van der Waals gap of MnBi_(2)Te_(4)and modulate its magnetic properties.Through x-ray diffraction(XRD)characterizations,we confirm that the interlayer spacing of MnBi_(2)Te_(4)is expanded from 13.6°A to 30.5°A and 61.0°A by intercalating quaternary ammonium cations(THA^(+)and CTA^(+)),respectively.The THA-MnBi_(2)Te_(4)exhibits dual complex magnetic behavior,combining AFM ordering with a Neel temperature(T_(N))of 12 K and a small ferromagnetic hysteresis loop at 2 K.The CTA-MnBi_(2)Te_(4)shows robust ferromagnetism,with a Curie point(T_(C))of 15 K,similar to that of the MnBi_(2)Te_(4)monolayer.These results demonstrate that remarkable changes in the magnetic properties of MnBi_(2)Te_(4)can be achieved via electrochemical intercalation,providing new insights into manipulating magnetism in layered magnetic materials.展开更多
Interlayer engineering of two-dimensional structural materials provides unique advantages for tuning the electromagnetic properties of metal oxides,injecting unlimited energy into the design of advanced two-dimensiona...Interlayer engineering of two-dimensional structural materials provides unique advantages for tuning the electromagnetic properties of metal oxides,injecting unlimited energy into the design of advanced two-dimensional metal oxide electromagnetic wave absorbers.In this study,Manganese dioxide intercalated with alkali metal ions was prepared by a simple molten salt method.The pre-intercalation of ions not only enhances the polarization loss at the heterogeneous interface between cations(point sites)and man-ganese dioxide(face sites)but also alters the energy band structure of manganese oxide and enhances its electrical conductivity,which in turn enhances the conductive loss of the manganese dioxide.Due to the synergistic effect of multiple polarizations and conductive losses,NaMO exhibits superb electromag-netic wave absorption properties and an effective absorption bandwidth of 5.36 GHz at thinner matched thicknesses.In addition,the RCS simulation result further verifies the excellent electromagnetic wave ab-sorption capability of NaMO.Under the positive incidence of electromagnetic waves,the electromagnetic wave reflection intensity of the metal plate coated with NaMO is effectively reduced.Finally,this work establishes a new way to modulate the electromagnetic properties.展开更多
The interaction between charge and spin degrees of freedom has always been the central issue of condensed matter physics,and transition metal dichalcogenides(TMDs)provide an ideal platform to study it benefiting from ...The interaction between charge and spin degrees of freedom has always been the central issue of condensed matter physics,and transition metal dichalcogenides(TMDs)provide an ideal platform to study it benefiting from their highly tunable properties.In this article,the influence of Fe intercalation in NbSe_(2)was elaborately investigated using a combination of techniques.Magnetic studies have shown that the insertion of Fe atoms induces an antiferromagnetic state in which the easy axis aligns out of the plane.The sign reversal of the magnetoresistance across the Neel temperature can be satisfactorily explained by the moderate interaction between electrons and local spins.The Hall and Seebeck measurements reveal a multi-band nature,and the contribution of various phonon scattering processes is discussed based on the thermal conductivity and specific heat data.展开更多
We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an...We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an expansion along the c-axis and intralayer distortions within the Ta-Se coordination network.The superconducting transition temperature(T_(c))is increased to 2.95 K at x=0.1 driven by the synergistic enhancement of the electronic density of states at the Fermi level,N(EF),and strengthened electron-phonon coupling.With further Li doping,although N(EF)continues to increase,lattice stiffening and pronounced distortions in the Ta-Se coordination polyhedra weaken the electron-phonon interaction,ultimately suppressing superconductivity.These findings highlight the critical role of intralayer structural modulation in governing structure-tunable superconductivity in layered materials.展开更多
The sandwich heterostructures(SHSs)are novel two-dimensional materials that hold great potential as efficient electro-catalysts.In this work,we computationally designed the BC_(3)/TM/Gr SHSs by intercalating transitio...The sandwich heterostructures(SHSs)are novel two-dimensional materials that hold great potential as efficient electro-catalysts.In this work,we computationally designed the BC_(3)/TM/Gr SHSs by intercalating transition metal atoms into the BC_(3)/graphene heterostructure.After the computational screening,only BC_(3)/Sc/Gr,BC_(3)/Ti/Gr,BC_(3)/Y/Gr and BC_(3)/Zr/Gr are validated as stable SHSs.The electron donation from the intercalated TM atom results in the formation of the negatively charged boron atom(B^(δ)-)and activation of the BC_(3)surface,making the BC_(3)/TM/Gr SHSs highly promising as single-atom catalysts(SACs).The BC_(3)/Sc/Gr and BC_(3)/Y/Gr SHSs exhibit potential in carbon dioxide reduction reaction(CO_(2)RR)and carbon monoxide reduction reaction(CORR)electro-catalysis.Particularly,when BC_(3)/Y/Gr SHS serves as CORR electro-catalyst,the step(∗CHO→∗CHOH)is a potential determining step,with an extremely low limiting potential(UL=-0.10 V).The BC_(3)/Ti/Gr and BC_(3)/Zr/Gr SHSs are suitable as hydrogen evolution reaction(HER)electro-catalysts.Specially,the BC_(3)/Ti/Gr SHS serves as an ideal HER electro-catalyst in acid condition,with close-to-zero adsorption free energy(△GH=0.006 eV)and fairly low overall activation barrier(0.20 eV).By analyzing the electronic properties,the unique adsorption activity of the B^(δ)-on H atom and unsaturated CO_(2)RR intermediates is elucidated as the origin of excellent catalytic activity of BC_(3)/TM/Gr SHSs,which is modulated by the intercalated TM atom.Our work is instructive to rational design of SACs towards energy conversion based on non-metal elements.展开更多
文摘Taking advantage of the effects on DNA secondary structure of two DNA-intercalators,ethidium bromide and chloroquine,we used each of them to treat nuclei from both mature erythrocytes and reticulocytes of chicken,as an alternative approach to study the relationships between DNA secondary structure,nuclear proteins and chromatin structure.We presented results of differential extraction of nuclear proteins from nuclei with DNA-intercalators,as well as preliminary characterization of these proteins.A 45kd protein is the major component in fractions extracted by both intercalators from nuclei from either mature erythrocytes or reticulocytes and seems to be a DNA-binding protein.Furthermore,from current concepts of functional aspects of DNA conformation and structural heterogeneity in chromatin and nuclear proteins,we have discussed both the significance of our results as well as technical aspects of this approach.
基金Supported by National Natural Science Foundation of China(No.30772622)
文摘By means of circular dichroism（CD） spectrum coupled with UV-Vis and fluorescence spectra,the binding model of DNA intercalator A1{4-（2-diethylamino-ethylamino）-8-oxo-8H-acenaphtho[1,2-b]pyrrole-9-carbonitrile} to calf thymus（CT） DNA was investigated,depending on the values of R（R is defined as the ratio of the concentration of A1 to CT DNA base pairs） and different outer factors.Molecules A1 were intercalated into the CT DNA base pairs in different orientations in the intercalation pocket at a lower R value（R≤0.20）,while A1 molecules aggregated on the surface of the helix of the CT DNA as the R value increased.The influence of NaCl on the binding was smaller because the electrostatic interaction only provided approximately 16% of the overall free energy of binding.The protonated diethylamine substitution would influence the binding geometry greatly at a low pH value via forming hydrogen bonds with the exposed C=O group on DNA surface.
基金supported by the National Natural Science Foundation of China(Grant No.W2412060,22325902 and 52171215)the State Key Laboratory of Clean Energy Utilization(Open Fund Project No.ZJUCEU2023002)。
文摘Sodium-ion batteries(SIBs)have attracted significant attention in large-scale energy storage system because of their abundant sodium resource and cost-effectiveness.Layered oxide materials are particularly promising as SIBs cathodes due to their high theoretical capacities and facile synthesis.However,their practical applications are hindered by the limitations in energy density and cycling stability.The comprehensive understanding of failure mechanisms within bulk structure and at the cathode/electrolyte interface of cathodes is still lacking.In this review,the issues related to bulk phase degradation and surface degradation,such as irreversible phase transitions,cation migration,transition metal dissolution,air/moisture instability,intergranular cracking,interfacial reactions,and reactive oxygen loss,are discussed.The latest advances and strategies to improve the stability of layered oxide cathodes and full cells are provided,as well as our perspectives on the future development of SIBs.
基金the financial support from the National Natural Science Foundation of China(No.22178307)China Southern Power Grid(Grant Nos.0470002022030103HX00002-01).
文摘The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).
文摘V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve the stability,organic small molecule choline chloride intercalation is used to expand the spacing of the vanadium pentoxide layers and increase the cycling stability.Therefore,we consider the introduction of Sr^(2+)to cointercalate with choline chloride.Here,we synthes-ized vanadium pentoxide cointercalated with Sr^(2+)and choline ions(Ch^(+))via a simple hydrothermal method.The electro-chemical performance shows an enhanced cathode capacitance contribution of Sr&Ch-V_(2)O_(5),with a discharge capacity of 526 mAh·g^(-1)at 0.1 A·g^(-1)and a retention rate of 78.9%after 2000 cycles at 5 A·g^(-1).This work offers a novel strategy for the design of organic‒inorganic hybrid materials for use as cathodes in aqueous zinc-ion batteries.
基金supported by grant BT/PR10513/BRB/10/618/2008 to GMA from Department of Biotechnology(DBT),Ministry of Science and Technology,Government of India(New Delhi)HGR was supported by DBT(India)
文摘Targeting protein kinases(PKs) has been a promising strategy in treating cancer, as PKs are key regulators of cell survival and proliferation. Here in this study, we studied the ability of pyrimido[4',5':4,5]thieno(2,3-b)quinolines(PTQ) to inhibit different PKs by performing computational docking and in vitro screening. Docking studies revealed that 4-butylaminopyrimido[4',5':4,5]thieno(2,3-b)quinoline(BPTQ) has a higher order of interaction with the kinase receptors than other PTQ derivatives.In vitro screening confirms that BPTQ inhibits VEGFR1 and CHK2, with the IC_(50) values of 0.54 and1.70 mmol/L, respectively. Further, cytotoxicity of BPTQ was measured by trypan blue assay. Treatment with BPTQ decreased the proliferation of HL-60 cells with an IC_(50) value of 12 mmol/L and induces apoptosis, as explicated by the fall in the mitochondrial membrane potential, annexin V labeling and increased expression of caspase-3. Taken together, these data suggest that BPTQ possess ability to inhibit PKs and to induce cell death in human promyelocytic leukemia cells.
文摘Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalytic reaction efficiency and selectivity[1–3].This technique has achieved significant progress in areas such as electrocatalysis,catalytic cracking,and energy conversion,especially in reactions like hydrogen generation,oxygen reduction,nitrogen reduction,and carbon dioxide reduction[4–6].Intercalation catalysis can enhance catalyst activity and selectivity,but challenges remain regarding stability,reusability,and industrial application.Future research will focus on developing new intercalation materials,optimizing catalyst design,and exploring their potential applications in complex environments[7].
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF-2020R1A6A1A03043435 and NRF-2021R1A2C1008798).
文摘Two-dimensional MXenes are renowned for their remarkable electrical conductivity and electrochemical activity making them highly promising for electrode applications.However,the restacking of MXene nanosheets impairs their functionality by reducing active sites and obstructing ionic transport.This study presents a facile synthesis approach for nickel-intercalated MXene,designed to enhance surface reactivity,avoid restacking,and achieve improved electrochemical performance.Electrochemical studies revealed that the nickel-MXene hybrid showed better cycling stability,retaining 83.7%of its capacity after 10000 cycles and attaining an energy density of 26 Wh kg^(-1) at a power density of 1872Wkg^(-1).It also exhibited overpotentials of 109 and 482 mV at 10 and 100 mA cm^(-2),respectively,in the hydrogen evolution reaction.To predict the structural and electrical alterations caused by nickel inclusion,as well as to understand the intercalation mechanism,spin-polarized density functional theory calculations were carried out.The theoretical results showed an improved carrier concentration for nickel-MXene.Nickel-MXene possessed superior electronic characteristics and surplus active sites with hexagonal closed-packed(hcp)edge sites,which enhanced electrochemical properties.Our results demonstrate that nickel intercalation prevents the restacking of MXene but also significantly improves their electrochemical characteristics,making them ideal for energy storage and catalytic applications.
基金financial support from the National Natural Science Foundation of China(52372173,52072034)。
文摘Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chloride oxidation reactions make oxygen evolution reaction(OER)in seawater extremely challenging.Herein,the low-cost and scalable CoFe layered double hydroxides with Cl^(-)intercalation and decorated with Ce(OH)_(3)(named as CoFe-Cl^(-)/Ce(OH)_(3))catalyst is synthesized via rapid electrodeposition under ambient conditions,which is quickly reconstructed into a CeO_(2)decorated and Cl^(-)intercalated CoFeOOH(CoFeOOH-Cl^(-)/CeO_(2))during OER.Theoretical investigation reveals that Cl^(-)intercalation weakens the adsorption ability of Cl^(-)on Co/Fe atoms and hinders unfavorable coupling with chloride,thereby preventing the chlorine corrosion process and enhancing catalytic stability and activity.The CeO_(2)with hard Lewis acidity preferentially binds to OH-with harder Lewis base to ensure the OH-rich microenvironment around catalyst even under high current operating conditions,thus further enhancing stability and improving OER activity.The functionalized CoFe-Cl^(-)/Ce(OH)_(3)delivers 1000 mA cm^(-2)current density at only 329 mV overpotential with excellent stability for 1000 h under alkaline seawater.Electrochemical experiments elucidate the OER catalytic mechanism in which CeO_(2)serves as a co-catalyst for enriching OH-and CoFeOOH-Cl^(-)is the active species.Our work is a substantial step towards achieving massive and sustainable production of hydrogen fuel from immense seawater.
基金financially supported by the National Natural Science Foundation of China(Nos.22435005,22193042,21921001,52202194,22305105,22201284)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBSLY-SLH024)。
文摘Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.
基金supported by National Natural Science Foundation of China(Grant No.22369006)Key Talent Projects in Gansu Province(2025RCXM011)+2 种基金College Students’Innovation and Entrepreneurship Training Program Project(S202310740033)Science and Technology Innovation Project for College Students(Grant Nos.Z10 and 146)Open Research Fund of the State Key Laboratory of Molecular Engineering of Polymers(K2025-21,Fudan University).
文摘Aqueous zinc-ion batteries(AZBs)are considered safer and potential substitutes for large-scale energy storage and conversion devices.The conventional vanadium pentoxide(V_(2)O_(5))cathode material has attracted widespread attention duo to its typical layered structure and high theoretical capacity.Unfortunately,it still suffers from severe structural collapse,sluggish diffusion dynamics,and fast capacity fading.Herein,we rationally designed and prepared trivalent Al^(3+)and H_(2)O co-intercalated V_(2)O_(5)(AlVO),in which Al^(3+)plays a“pillar”role and forms strong Al−O bonds,while H_(2)O acts as the“lubricant”,synergistically maintaining the structural stability and accelerating the diffusion of zinc ions.The Zn//AlVO battery is found to possess not only an impressive reversible capacity of 390.7 mAh·g^(−1) at 0.5 A·g^(−1),5.13 times that of Zn//c-V_(2)O_(5),but also excellent rate capability and long-term cycling performance(with the residual capacity of 138.2 mAh·g^(−1) over 10000 cycles at 10 A·g^(−1)).
基金financially supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJQN202300759)the Vanadium Titanium Materials Engineering Technology Research Center Foundation Project of Sichuan(No.2022FTGC07)+5 种基金the National Key R&D Program of China(No.2023YFC3009500)the National Natural Science Foundation of China(No.22379103)the Science and Technology Projects of Suzhou City(No.SYC2022043)the Campus Science Fund Project of Chongqing Jiaotong University(Nos.2020020086 and 2020023032)the Graduate Tutor Team Construction Project of Chongqing(No.JDDSTD2022006)the Graduate Student Research Innovation Project of Chongqing(No.2024S0110)
文摘The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of cathode materials,which reduces the cycle stability and specific capacity,consequently limiting the practical application of zinc-ion batteries.In this work,hydroxypropylβ-cyclodextrin(HP-β-CD),a special stereo cyclic organic molecule with hydrophobic inner cavity and hydrophilic outer cavity,is used as the intercalator for hydrated vanadium oxide(VOH)to enlarge the layer spacing and enhance the hydrophobicity of the cathode material.The larger interlayer spacing(13.9Å)of HP-β-CD-VOH is beneficial for improving ion mobility and the intrinsic electrochemical reaction kinetics.HP-β-CD-VOH delivers a discharge capacity of 336.7 mAh g^(-1)at 0.2 A g^(-1)and high-rate capability(242 mAh g^(-1)at 5 A g^(-1)).Due to the hydrophobic property of HP-β-CD in the interlayer pillar,the vanadium dissolution effect of polar water molecules can be reduced during charge and discharge;HP-β-CDVOH demonstrates sustained high efficiency and extended cycle longevity,maintaining a remarkable durability of 6000 cycles at a current density of 10 A g^(-1).This study presents an effective strategy for developing high-performance aqueous zinc-ion battery cathode materials.
基金supported by the National Natural Science Foundation of China(Grant No.32371284)the Open Fund of the State Key Laboratory of Optoelectronic Materials and Technologies,Sun Yatsen University(Grant No.OEMT-2024-ZTS-04)support from the Physical Research Platform in the School of Physics,Sun Yatsen University(Grant No.PRPSP,SYSU).
文摘DNA imaging and visualization techniques are crucial in biological experiments and have also emerged as a powerful method for single-molecule studies.Traditional intercalating dyes(e.g.,SYTOX,EtBr,GelRed)can stain DNA but may alter its structure and mechanical properties,and cause photocleavage.Recently,a novel fluorescent DNA-binding protein(FP-DBP)was introduced,which can stain DNA without sequence preference and without inducing photocleavage.In this study,using a custom-built magnetic tweezers system,we performed DNA stretching,twisting and unzipping experiments to compare the mechanical properties of DNA with and without two kinds of intercalating dyes(SYTOX Orange and GelRed)and mCherry FP-DBP.Our results show that mCherry FP-DBP does not affect DNA structure or mechanics,unlike SYTOX Orange and GelRed,making FP-DBP a promising tool for DNA visualization in single-molecule experiments.
基金supported by the National Key R&D Program of China(2022YFA1203400)the National Natural Science Foundation of China(W2441009)。
文摘Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performance Mg cathode materials.Utilizing the common characteristics of various ionic intercalation-type electrodes,we design and train a Crystal Graph Convolutional Neural Network model that can accurately predict electrode voltages for various ions with mean absolute errors(MAE)between0.25 and 0.33 V.By deploying the trained model to stable Mg compounds from Materials Project and GNoME AI dataset,we identify 160 high voltage structures out of 15,308 candidates with voltages above3.0 V and volumetric capacity over 800 mA h/cm^(3).We further train a precise NequIP model to facilitate accurate and rapid simulations of Mg ionic conductivity.From the 160 high voltage structures,the machine learning molecular dynamics simulations have selected 23 cathode materials with both high energy density and high ionic conductivity.This Al-driven workflow dramatically boosts the efficiency and precision of material discovery for multivalent ion batteries,paving the way for advanced Mg battery development.
基金supported by the National Natural Science Foundation of China(22075196,U22A20418,21878204)the Research Project Supported by Shanxi Scholarship Council of China(2022-050).
文摘Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existence form of leached oxygen anions are still controversial.Herein,we selected iron selenite-wrapped hydrated nickel molybdate(denoted as NiMoO/FeSeO)as a pre-catalyst to study the oxyanion effect.It is surprising to find that SeO_(2)-exists in the catalyst in the form of intercalation,which is different from previous studies that suggest that anions are doped with residual elements after electrochemical activation,or adsorbed on the catalyst surface.The experiment and theoretical calculations show that the existence of SeO_(4)^(2-)intercalation effectively adjusts the electronic structure of NiFeOOH,promotes intramolecular electron transfer and O-O release,and thus lowers the reaction energy barrier.As expected,the synthesized NiFeOOH-SeO only needs 202 and 285 mV to attain 100 and 1000 mA cm^(-2)in 1 M KOH.Further,the anion exchange membrane water electrolyzer(AEMWE)consisting of NiFeOOHSeO anode and Pt/C cathode can reach 1 A cm^(-2)at 1.70 V and no significant attenuation within 300 h.Our findings provide insights into the mechanism,by which the intercalated oxyanions enhance the OER performance of NiFeOOH,thereby facilitating large-scale hydrogen production through AEMWE.
基金supported by the National Key Research and Development Program of China(Grant Nos.2022YFA1402404 and 2023YFA1406304)the National Natural Science Foundation of China(Grant Nos.92161201,T2221003,12104221,12104220,12274208,12025404,12004174,91961101,T2394473,62274085,12374043,and U2032208)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant Nos.BK20230079,BK20243013,and BK20233001)the Fundamental Research Funds for the Central Universities(Grant Nos.020414380192 and 2024300432).
文摘MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties enables the observation of exotic quantum phenomena such as the quantum anomalous Hall effect,axion insulator states,and Majorana fermions.While the intercalation of Bi_(2)Te_(3)can tune its magnetism,synthesizing pure-phase MnBi_(2)Te_(4)with uniform Bi_(2)Te_(3)intercalation remains challenging,and the fixed interlayer spacing of Bi_(2)Te_(3)limits magnetic coupling tunability.Here,we utilize electrochemical organic molecule intercalation to expand the van der Waals gap of MnBi_(2)Te_(4)and modulate its magnetic properties.Through x-ray diffraction(XRD)characterizations,we confirm that the interlayer spacing of MnBi_(2)Te_(4)is expanded from 13.6°A to 30.5°A and 61.0°A by intercalating quaternary ammonium cations(THA^(+)and CTA^(+)),respectively.The THA-MnBi_(2)Te_(4)exhibits dual complex magnetic behavior,combining AFM ordering with a Neel temperature(T_(N))of 12 K and a small ferromagnetic hysteresis loop at 2 K.The CTA-MnBi_(2)Te_(4)shows robust ferromagnetism,with a Curie point(T_(C))of 15 K,similar to that of the MnBi_(2)Te_(4)monolayer.These results demonstrate that remarkable changes in the magnetic properties of MnBi_(2)Te_(4)can be achieved via electrochemical intercalation,providing new insights into manipulating magnetism in layered magnetic materials.
基金supported by the Jiangxi Provincial Natural Science Foundation(No.20232BAB202036).
文摘Interlayer engineering of two-dimensional structural materials provides unique advantages for tuning the electromagnetic properties of metal oxides,injecting unlimited energy into the design of advanced two-dimensional metal oxide electromagnetic wave absorbers.In this study,Manganese dioxide intercalated with alkali metal ions was prepared by a simple molten salt method.The pre-intercalation of ions not only enhances the polarization loss at the heterogeneous interface between cations(point sites)and man-ganese dioxide(face sites)but also alters the energy band structure of manganese oxide and enhances its electrical conductivity,which in turn enhances the conductive loss of the manganese dioxide.Due to the synergistic effect of multiple polarizations and conductive losses,NaMO exhibits superb electromag-netic wave absorption properties and an effective absorption bandwidth of 5.36 GHz at thinner matched thicknesses.In addition,the RCS simulation result further verifies the excellent electromagnetic wave ab-sorption capability of NaMO.Under the positive incidence of electromagnetic waves,the electromagnetic wave reflection intensity of the metal plate coated with NaMO is effectively reduced.Finally,this work establishes a new way to modulate the electromagnetic properties.
基金Project supported by the National Natural Science Foundation of China(Grant No.12274440)the National Key R&D Program of China(Grant No.2022YFA1403903)+1 种基金the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(Grant No.XDB33010100)the Fund of the Synergetic Extreme Condition User Facility(SECUF)。
文摘The interaction between charge and spin degrees of freedom has always been the central issue of condensed matter physics,and transition metal dichalcogenides(TMDs)provide an ideal platform to study it benefiting from their highly tunable properties.In this article,the influence of Fe intercalation in NbSe_(2)was elaborately investigated using a combination of techniques.Magnetic studies have shown that the insertion of Fe atoms induces an antiferromagnetic state in which the easy axis aligns out of the plane.The sign reversal of the magnetoresistance across the Neel temperature can be satisfactorily explained by the moderate interaction between electrons and local spins.The Hall and Seebeck measurements reveal a multi-band nature,and the contribution of various phonon scattering processes is discussed based on the thermal conductivity and specific heat data.
基金supported by the National Natural Science Foundation of China(Grant Nos.22090042 and 22175018).
文摘We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an expansion along the c-axis and intralayer distortions within the Ta-Se coordination network.The superconducting transition temperature(T_(c))is increased to 2.95 K at x=0.1 driven by the synergistic enhancement of the electronic density of states at the Fermi level,N(EF),and strengthened electron-phonon coupling.With further Li doping,although N(EF)continues to increase,lattice stiffening and pronounced distortions in the Ta-Se coordination polyhedra weaken the electron-phonon interaction,ultimately suppressing superconductivity.These findings highlight the critical role of intralayer structural modulation in governing structure-tunable superconductivity in layered materials.
基金supported by the National Natural Science Foundation of China(No.51972150)the National Key Research Program of China(No.2022YFA1503101)+1 种基金Science and Technology Development Fund,Macao SAR(FDCT No.0024/2022/ITP)the Project of National Center for International Research on Intelligent Nano-Materials and Detection Technology in Environmental Protection,Soochow University(No.SDGH2303).
文摘The sandwich heterostructures(SHSs)are novel two-dimensional materials that hold great potential as efficient electro-catalysts.In this work,we computationally designed the BC_(3)/TM/Gr SHSs by intercalating transition metal atoms into the BC_(3)/graphene heterostructure.After the computational screening,only BC_(3)/Sc/Gr,BC_(3)/Ti/Gr,BC_(3)/Y/Gr and BC_(3)/Zr/Gr are validated as stable SHSs.The electron donation from the intercalated TM atom results in the formation of the negatively charged boron atom(B^(δ)-)and activation of the BC_(3)surface,making the BC_(3)/TM/Gr SHSs highly promising as single-atom catalysts(SACs).The BC_(3)/Sc/Gr and BC_(3)/Y/Gr SHSs exhibit potential in carbon dioxide reduction reaction(CO_(2)RR)and carbon monoxide reduction reaction(CORR)electro-catalysis.Particularly,when BC_(3)/Y/Gr SHS serves as CORR electro-catalyst,the step(∗CHO→∗CHOH)is a potential determining step,with an extremely low limiting potential(UL=-0.10 V).The BC_(3)/Ti/Gr and BC_(3)/Zr/Gr SHSs are suitable as hydrogen evolution reaction(HER)electro-catalysts.Specially,the BC_(3)/Ti/Gr SHS serves as an ideal HER electro-catalyst in acid condition,with close-to-zero adsorption free energy(△GH=0.006 eV)and fairly low overall activation barrier(0.20 eV).By analyzing the electronic properties,the unique adsorption activity of the B^(δ)-on H atom and unsaturated CO_(2)RR intermediates is elucidated as the origin of excellent catalytic activity of BC_(3)/TM/Gr SHSs,which is modulated by the intercalated TM atom.Our work is instructive to rational design of SACs towards energy conversion based on non-metal elements.
