Developing rapid charging and robust electrode materials for Na-ion batteries is of considerable significance in large-scale power electricity fields.Herein,the authors have proposed a multivalenceion intercalation st...Developing rapid charging and robust electrode materials for Na-ion batteries is of considerable significance in large-scale power electricity fields.Herein,the authors have proposed a multivalenceion intercalation strategy to construct threedimensional(3D)Co-MoS2 nanoflowers with tailorable 1T/2H phase and interlayer distance.The as-formed S-Co-S covalent bonds serve as“electric bridges”to accelerate interlayer charge transfer without 1T phase degeneration during sodiation and desodiation.Quantum density functional theory(QDFT)calculations further confirm that the optimal Co-MoS2 nanoflowers possess the highest Na adsorption energy with reduced ionic diffusion barrier.Consequently,they deliver a superior sodiumstorage capacity of 351 mAh g−1 in 0.4-3.0 V even at 20 A g−1 without capacity fading at 5 A g−1 for 2000 cycles.The high electrochemical reversibility of the 1T phase in Co-MoS2,which accounts for such excellent performance,has been unveiled for the first time by in situ Raman spectra.This finding demonstrates important insights onto promoting two-dimensional(2D)nanomaterials toward rapid charging alkali-ion batteries.展开更多
Metallic 1T-phase molybdenum disulfide(1T-MoS_(2))shows more excellent electrocatalytic performance for hydrogen evolution reaction(HER)than semiconducting 2H-phase MoS_(2)(2H-MoS_(2)).Therefore,the facile controllabl...Metallic 1T-phase molybdenum disulfide(1T-MoS_(2))shows more excellent electrocatalytic performance for hydrogen evolution reaction(HER)than semiconducting 2H-phase MoS_(2)(2H-MoS_(2)).Therefore,the facile controllable synthesis of hierarchical structure with rich 1T-MoS_(2)is desired for highly efficient electrocatalytic performance.In this work,a simple solvothermal method is proposed to fabricate hol-low NiCoP/MoS_(2)-V heterostructure with 63.2%1T-MoS_(2),in which the abundant catalytic active sites are exposed,the mass transfer properties are improved,and the electronic states are optimized.Moreover,the low energy difference between 2H and 1T phases and near zero free energy of hydrogen adsorption(△G H∗)result in fast kinetics and excellent catalytic performances.Specifically,the NiCoP/MoS_(2)-V com-posite exhibits enhanced HER activity with a low overpotential of 74.6 mV at 10 mA cm^(-2)and superior stability in alkaline electrolytes.This efficient design opens up new vistas for developing high-activity electrocatalysts.展开更多
1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great e...1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great efforts have been made to synthesize 1T-MoS_(2) and enhance its stability,it remains a big challenge to realize the phase control and stabilization of 1T-MoS_(2).Herein,based on crystal field theory analysis,we propose a new solution by designing an electrocatalyst of 1T-MoS_(2) nanosheets anchoring on black TiO2-xnanotube arrays in-situ grown on Ti plate(1T-MoS_(2)/TiO_(2-x)@Ti).The black TiO_(2-x)substrate is expected to play as electron donors to increase the charge in Mo 4 d orbits of 1T-MoS_(2) and thus weaken the asymmetric occupation of electrons in the Mo 4 d orbits.Experimental results demonstrate that black TiO_(2-x)nanotubes shift electrons to MoS_(2) and induce MoS_(2) to generate more 1 T phase due to stabilizing the 1T-MoS_(2) nanosheets compared with a Ti substrate.Thus 1T-MoS_(2/)TiO_(2-x)@Ti shows much improved HER performance with a small Tafel slope of 42 m V dec^(-1) and excellent catalytic stability with negligible degradation for 24 h.Theoretical calculations confirm that the black TiO_(2-x)substrate can effectively stabilize metastable 1T-MoS_(2) due to electrons transferring from black TiO_(2-x)to Mo 4 d orbits.This work sheds light on the instability of 1T-MoS_(2) and provides an essential method to stabilize and efficiently utilize 1T-MoS_(2) for HER.展开更多
Selective hydrogenation of biomass-derived maleic anhydride(MAH)to succinic anhydride(SA)is valuable but remains a challenge due to the complicated reaction network.We here report that single Pt atoms decorated onto t...Selective hydrogenation of biomass-derived maleic anhydride(MAH)to succinic anhydride(SA)is valuable but remains a challenge due to the complicated reaction network.We here report that single Pt atoms decorated onto the edges of two-dimensional(2D)1Tphase MoS_(2)(Pt1/1T-MOS_(2)SAC)as a proof-of-concept catalyst can efficiently convert biomass-derived MAH to SA with 100%conversion and 100%selectivity under mild conditions.The kinetic data and characterization results suggest that the catalytic performance of the edge-anchored Pt1/1T-MoS_(2)SAC originates from the facile H_(2)dissociation induced by the electron-deficient Pt1atoms and the pocket-like configuration of Pt1active site confines the adsorption configuration of MAH by the steric effect.The strategy of fabricating edge-confined catalysts offers a new direction to design novel SACs for biomass-derived transformations.展开更多
We investigate the transport properties of electron in a 1T'-MoS_(2)-based p–n junction.The anisotropic refraction of electron is found when the electron beam crosses the p–n junction,which brings the phenomenon...We investigate the transport properties of electron in a 1T'-MoS_(2)-based p–n junction.The anisotropic refraction of electron is found when the electron beam crosses the p–n junction,which brings the phenomenon of valley splitting without any external fields.Moreover,it is found that the valley-spin-dependent anomalous Klein tunneling,i.e.,the perfect transmission exists at a nonzero incident angle of valley-spin-dependent electron,happens when the vertical electric field is equal to the critical electric field.These two peculiar properties arise from the same reason that the tilted band structure makes the directions of wavevector and velocity different.Our work designs a special valley splitter without any external fields and finds a new type of Klein tunneling.展开更多
基金This study was supported by the National Natural Science Foundation of China(nos.51672082,21975074,and 91534202)the Basic Research Program of Shanghai(no.17JC1402300)+1 种基金the Shanghai Scientific and Technological Innovation Project(no.18JC1410500)the National Program for Support of Top-Notch Young Professionals,and the Fundamental Research Funds for the Central Universities(no.222201718002).
文摘Developing rapid charging and robust electrode materials for Na-ion batteries is of considerable significance in large-scale power electricity fields.Herein,the authors have proposed a multivalenceion intercalation strategy to construct threedimensional(3D)Co-MoS2 nanoflowers with tailorable 1T/2H phase and interlayer distance.The as-formed S-Co-S covalent bonds serve as“electric bridges”to accelerate interlayer charge transfer without 1T phase degeneration during sodiation and desodiation.Quantum density functional theory(QDFT)calculations further confirm that the optimal Co-MoS2 nanoflowers possess the highest Na adsorption energy with reduced ionic diffusion barrier.Consequently,they deliver a superior sodiumstorage capacity of 351 mAh g−1 in 0.4-3.0 V even at 20 A g−1 without capacity fading at 5 A g−1 for 2000 cycles.The high electrochemical reversibility of the 1T phase in Co-MoS2,which accounts for such excellent performance,has been unveiled for the first time by in situ Raman spectra.This finding demonstrates important insights onto promoting two-dimensional(2D)nanomaterials toward rapid charging alkali-ion batteries.
基金supported by the Ningbo Bureau of Science and Technology(No.2012B82011)the Ningbo Natural Science Foundation(No.2017A610060)+1 种基金the National Natural Science Foundation of China(No.51706114)the China Postdoctoral Science Foundation(No.2016M601942)
基金supported by the National Natural Science Foundation of China(21975110,22378219,22302106)the Technology Support Program for the Youth Innovation Team of Shandong Higher Education Institutions(2023KJ225)the support from Taishan Youth Scholar Program of Shandong Province。
基金This work was financially supported by the National Natural Science Foundation of China(No.52271136)the Natural Science Foundation of Shaanxi Province(Nos.2019TD-020 and 2021JC-06)the Fundamental Scientific Research Business Expenses of Xi’an Jiaotong University(No.xzy022020017).
文摘Metallic 1T-phase molybdenum disulfide(1T-MoS_(2))shows more excellent electrocatalytic performance for hydrogen evolution reaction(HER)than semiconducting 2H-phase MoS_(2)(2H-MoS_(2)).Therefore,the facile controllable synthesis of hierarchical structure with rich 1T-MoS_(2)is desired for highly efficient electrocatalytic performance.In this work,a simple solvothermal method is proposed to fabricate hol-low NiCoP/MoS_(2)-V heterostructure with 63.2%1T-MoS_(2),in which the abundant catalytic active sites are exposed,the mass transfer properties are improved,and the electronic states are optimized.Moreover,the low energy difference between 2H and 1T phases and near zero free energy of hydrogen adsorption(△G H∗)result in fast kinetics and excellent catalytic performances.Specifically,the NiCoP/MoS_(2)-V com-posite exhibits enhanced HER activity with a low overpotential of 74.6 mV at 10 mA cm^(-2)and superior stability in alkaline electrolytes.This efficient design opens up new vistas for developing high-activity electrocatalysts.
基金supported by the New Zealand China Doctoral Research Scholarship (Grant no. 201706080124)support from the China Scholarships Council (CSC) for his study at the University of Auckland
文摘1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great efforts have been made to synthesize 1T-MoS_(2) and enhance its stability,it remains a big challenge to realize the phase control and stabilization of 1T-MoS_(2).Herein,based on crystal field theory analysis,we propose a new solution by designing an electrocatalyst of 1T-MoS_(2) nanosheets anchoring on black TiO2-xnanotube arrays in-situ grown on Ti plate(1T-MoS_(2)/TiO_(2-x)@Ti).The black TiO_(2-x)substrate is expected to play as electron donors to increase the charge in Mo 4 d orbits of 1T-MoS_(2) and thus weaken the asymmetric occupation of electrons in the Mo 4 d orbits.Experimental results demonstrate that black TiO_(2-x)nanotubes shift electrons to MoS_(2) and induce MoS_(2) to generate more 1 T phase due to stabilizing the 1T-MoS_(2) nanosheets compared with a Ti substrate.Thus 1T-MoS_(2/)TiO_(2-x)@Ti shows much improved HER performance with a small Tafel slope of 42 m V dec^(-1) and excellent catalytic stability with negligible degradation for 24 h.Theoretical calculations confirm that the black TiO_(2-x)substrate can effectively stabilize metastable 1T-MoS_(2) due to electrons transferring from black TiO_(2-x)to Mo 4 d orbits.This work sheds light on the instability of 1T-MoS_(2) and provides an essential method to stabilize and efficiently utilize 1T-MoS_(2) for HER.
基金financially supported by the National Natural Science Foundation of China(Nos.21908079,21872145 and U21A20326)Jiangsu Specially-Appointed Professor Fund(No.1046010241211400)+4 种基金Natural Science Foundation of Jiangsu Province(Nos.BK20211239,BK20221541 and BK20201345)the State Key Laboratory of Fine ChemicalsDalian University of Technology(No.KF2005)Dalian Institute of Chemical Physics(No.DICP 1201943)the Central Laboratory,School of Chemical and Material Engineering,Jiangnan University。
文摘Selective hydrogenation of biomass-derived maleic anhydride(MAH)to succinic anhydride(SA)is valuable but remains a challenge due to the complicated reaction network.We here report that single Pt atoms decorated onto the edges of two-dimensional(2D)1Tphase MoS_(2)(Pt1/1T-MOS_(2)SAC)as a proof-of-concept catalyst can efficiently convert biomass-derived MAH to SA with 100%conversion and 100%selectivity under mild conditions.The kinetic data and characterization results suggest that the catalytic performance of the edge-anchored Pt1/1T-MoS_(2)SAC originates from the facile H_(2)dissociation induced by the electron-deficient Pt1atoms and the pocket-like configuration of Pt1active site confines the adsorption configuration of MAH by the steric effect.The strategy of fabricating edge-confined catalysts offers a new direction to design novel SACs for biomass-derived transformations.
基金the National Natural Science Foundation of China(Grant Nos.12104232,11805103,and 11804167)the Natural Science Foundation of Jiangsu Province(Grant Nos.BK20190137 and BK20180739)+1 种基金the Innovation Research Project of Jiangsu Province(Grant No.CZ0070619002)NJUPT-SF(Grant No.NY218128)。
文摘We investigate the transport properties of electron in a 1T'-MoS_(2)-based p–n junction.The anisotropic refraction of electron is found when the electron beam crosses the p–n junction,which brings the phenomenon of valley splitting without any external fields.Moreover,it is found that the valley-spin-dependent anomalous Klein tunneling,i.e.,the perfect transmission exists at a nonzero incident angle of valley-spin-dependent electron,happens when the vertical electric field is equal to the critical electric field.These two peculiar properties arise from the same reason that the tilted band structure makes the directions of wavevector and velocity different.Our work designs a special valley splitter without any external fields and finds a new type of Klein tunneling.
