SnO_(2),with its high theoretical capacity,abundant resources,and environmental friendliness,is widely regarded as a potential anode material for lithium-ion batteries(LIBs).Nevertheless,the coarsening of the Sn nanop...SnO_(2),with its high theoretical capacity,abundant resources,and environmental friendliness,is widely regarded as a potential anode material for lithium-ion batteries(LIBs).Nevertheless,the coarsening of the Sn nanoparticles impedes the reconversion back to SnO_(2),resulting in low coulombic efficiency and rapid capacity decay.In this study,we fabricated a heterostructure by combining SnO_(2)nanoparticles with MoS_(2)nanosheets via plasma-assisted milling.The heterostructure consists of in-situ exfoliated MoS_(2)nanosheets predominantly in 1 T phase,which tightly encase the SnO_(2)nanoparticles through strong bonding.This configuration effectively mitigates the volume change and particle aggregation upon cycling.Moreover,the strong affinity of Mo,which is the lithiation product of MoS_(2),toward Sn plays a pivotal role in inhibiting the coarsening of Sn nanograins,thus enhancing the reversibility of Sn to SnO_(2)upon cycling.Consequently,the SnO_(2)/MoS_(2)heterostructure exhibits superb performance as an anode material for LIBs,demonstrating high capacity,rapid rate capability,and extended lifespan.Specifically,discharged/charged at a rate of 0.2 A g^(-1)for 300 cycles,it achieves a remarkable reversible capacity of 1173.4 mAh g^(-1).Even cycled at high rates of 1.0 and 5.0 A g^(-1)for 800 cycles,it still retains high reversible capacities of 1005.3 and 768.8 mAh g^(-1),respectively.Moreover,the heterostructure exhibits outstanding electrochemical performance in both full LIBs and sodium-ion batteries.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
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
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
基金the financial support from the National Key Research and Development Program of China(2018YFA0209402,2022YFB2502003)Guangdong Basic and Applied Basic Research Foundation(2023B1515040011)Jiangxi Provincial Natural Science Foundation(20212BAB214028)
文摘SnO_(2),with its high theoretical capacity,abundant resources,and environmental friendliness,is widely regarded as a potential anode material for lithium-ion batteries(LIBs).Nevertheless,the coarsening of the Sn nanoparticles impedes the reconversion back to SnO_(2),resulting in low coulombic efficiency and rapid capacity decay.In this study,we fabricated a heterostructure by combining SnO_(2)nanoparticles with MoS_(2)nanosheets via plasma-assisted milling.The heterostructure consists of in-situ exfoliated MoS_(2)nanosheets predominantly in 1 T phase,which tightly encase the SnO_(2)nanoparticles through strong bonding.This configuration effectively mitigates the volume change and particle aggregation upon cycling.Moreover,the strong affinity of Mo,which is the lithiation product of MoS_(2),toward Sn plays a pivotal role in inhibiting the coarsening of Sn nanograins,thus enhancing the reversibility of Sn to SnO_(2)upon cycling.Consequently,the SnO_(2)/MoS_(2)heterostructure exhibits superb performance as an anode material for LIBs,demonstrating high capacity,rapid rate capability,and extended lifespan.Specifically,discharged/charged at a rate of 0.2 A g^(-1)for 300 cycles,it achieves a remarkable reversible capacity of 1173.4 mAh g^(-1).Even cycled at high rates of 1.0 and 5.0 A g^(-1)for 800 cycles,it still retains high reversible capacities of 1005.3 and 768.8 mAh g^(-1),respectively.Moreover,the heterostructure exhibits outstanding electrochemical performance in both full LIBs and sodium-ion batteries.
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.
