It is highly important to develop ultrastable electrode materials for Li-ion batteries(LIBs),especially in the low temperature.Herein,we report Fe^(3+)-stabilized Ti_(3)C_(2)T_(x) MXene(donated as T/F-4:1)as the anode...It is highly important to develop ultrastable electrode materials for Li-ion batteries(LIBs),especially in the low temperature.Herein,we report Fe^(3+)-stabilized Ti_(3)C_(2)T_(x) MXene(donated as T/F-4:1)as the anode material,which exhibits an ultrastable low-temperature Li-ion storage property(135.2 m A h g^(-1)after300 cycles under the current density of 200 m A g^(-1)at-10℃),compared with the negligible capacity for the pure Ti_(3)C_(2)T_(x) MXene(26 m A h g^(-1)at 200 m A g^(-1)).We characterized as-made T/F samples via the Xray photoelectron spectroscopy(XPS),Fourier transformed infrared(FT-IR)and Raman spectroscopy,and found that the terminated functional groups(-O and-OH)in T/F are Li^(+) storage sites.Fe^(3+)-stabilization makes-O/-OH groups in MXene interlayers become active towards Li^(+),leading to much more active sites and thus an enhanced capacity and well cyclic stability.In contrast,only-O/-OH groups on the top and bottom surfaces of pure Ti_(3)C_(2)T_(x) MXene can be used to adsorb Li^(+),resulting in a low capacity.Transmission electron microscopy(TEM)and XPS data confirm that T/F-4:1 holds the highly stable solid electrolyte interphase(SEI)layer during the cycling at-10℃.Density functional theory(DFT)calculations further uncover that T/F has fast diffusion of Li^(+) and consequent better electrochemical performances than pure Ti_(3)C_(2)T_(x) MXene.It is believed that the new strategy used here will help to fabricate advanced MXene-based electrode materials in the energy storage application.展开更多
Up to now,three kinds of ion-storage mechanisms are summarized towards anode materials in lithium/sodium-ion batteries,but they have low capacity and poor cyclic performance.Therefore,it is necessary to develop a new ...Up to now,three kinds of ion-storage mechanisms are summarized towards anode materials in lithium/sodium-ion batteries,but they have low capacity and poor cyclic performance.Therefore,it is necessary to develop a new approach to optimize ion storage.Herein,we report an adsorption/desorption storage route through engineering electronic structure of cation-deficient Ti_(1-x)O_(2)nanosheets.Ti_(1-x)O_(2)nanosheets indeed exhibit higher capacity(332.1 mA h g^(-1)vs.137.7 mA h g^(-1)for LIBs,195.7 mA h g^(-1)vs.111 mA h g^(-1)for SIBs),and more stable cyclic performance(296 mA h g^(-1)vs.99 mA h g^(-1)for LIBs,178.1 mA h g^(-1)vs.80.2 mA h g^(-1)for SIBs after 100 cycles)at 0.1 A g^(-1)than TiO_(2)nanosheets.Kinetics analysis and density functional theory(DFT)calculations reveal that electronic structures of vacancy within Ti_(1-x)O_(2) nanosheets encourage a novel adsorption-desorption storage route.These results highlight the benefits of the engineered electronic structures within electrode material and implement novel ion-storage mechanism towards broad energy storage applications.展开更多
Precise catalysis is critical for the high-quality catalysis industry.However,it remains challenging to fundamentally understand precise catalysis at the atomic orbital level.Herein,we propose a new strategy to unrave...Precise catalysis is critical for the high-quality catalysis industry.However,it remains challenging to fundamentally understand precise catalysis at the atomic orbital level.Herein,we propose a new strategy to unravel the role of specific d orbitals in catalysis.The oxygen reduction reaction(ORR)catalyzed by atomically dispersed Pt/Co-doped Ti_(1−x)O_(2) nanosheets(Pt_(1)/Co_(1)-Ti_(1−x)O_(2))is used as a model catalysis.The z-axis d orbitals of Pt/Co-Ti realms dominate the O2 adsorption,thus triggering ORR.In light of orbital-resolved analysis,Pt_(1)/Co_(1)-Ti_(1−x)O_(2) is experimentally fabricated,and the excellent ORR catalytic performance is further demonstrated.Further analysis reveals that the superior ORR performance of Pt_(1)-Ti_(1−x)O_(2) to Co_(1)-Ti_(1−x)O_(2) is ascribed to stronger activation of Ti by Pt than Co via the d-d hybridization.Overall,this work provides a useful tool to understand the underlying catalytic mechanisms at the atomic orbital level and opens new opportunities for precise catalyst design.展开更多
The palladium(Pd)-catalyzed Suzuki reaction is widely applied in the pharmaceutical industry,where constructing highly active and low-cost Pd sites are impendent.Here,we report the fabrication of a heterogeneous Pd/Ti...The palladium(Pd)-catalyzed Suzuki reaction is widely applied in the pharmaceutical industry,where constructing highly active and low-cost Pd sites are impendent.Here,we report the fabrication of a heterogeneous Pd/Tio2 catalyst via engineering of an electronic structure of a single Pd_(1)atom on monolayered Ti_(0.87)O_(2)nanosheet(Pd_(1)-Ti_(0.87)O_(2)).This catalyst motivated the kinetically sluggish C-Br cleavage,thus boosting the Suzuki reaction at room temperature.Pd_(1)-Ti_(0.87)O_(2)exhibited an outstanding activity with turnover frequency(TOF)of 11,110 h-1,exceeding that of PdCl_(2)and Pd(OAc)_(2)catalysts by a factor of>200.Various in situ techniques were employed to investigate the C-Br activation process,which showed that Pd_(1)kinetic-feasibly dissociated the chemisorbed bromobenzene,especially the C-Br bond cleavage.Theoretical calculations further revealed that the improved activity is ascribed to the optimized charge state of Pd_(1)within the Pd_(1)O4 realm via charge transfer.展开更多
基金supported financially by the Fundamental Research Funds for the Central Universities(Nos.2019RC021,2018JBZ107,2019RC035)the National Natural Science Foundation of China(Nos.51971056,91961125,51802013,21905019)+3 种基金the Key Program for International S&T Cooperation Projects of China from the Ministry of Science and Technology of China(No.2018YFE0124600)the Chemistry and Chemical Engineering Guangdong Laboratory(Nos.1932004 and 1911021)the financial support from Natural Science Foundation of Liaoning Province(No.20180510003)support from the“Excellent One Hundred”Project of Beijing Jiaotong University。
文摘It is highly important to develop ultrastable electrode materials for Li-ion batteries(LIBs),especially in the low temperature.Herein,we report Fe^(3+)-stabilized Ti_(3)C_(2)T_(x) MXene(donated as T/F-4:1)as the anode material,which exhibits an ultrastable low-temperature Li-ion storage property(135.2 m A h g^(-1)after300 cycles under the current density of 200 m A g^(-1)at-10℃),compared with the negligible capacity for the pure Ti_(3)C_(2)T_(x) MXene(26 m A h g^(-1)at 200 m A g^(-1)).We characterized as-made T/F samples via the Xray photoelectron spectroscopy(XPS),Fourier transformed infrared(FT-IR)and Raman spectroscopy,and found that the terminated functional groups(-O and-OH)in T/F are Li^(+) storage sites.Fe^(3+)-stabilization makes-O/-OH groups in MXene interlayers become active towards Li^(+),leading to much more active sites and thus an enhanced capacity and well cyclic stability.In contrast,only-O/-OH groups on the top and bottom surfaces of pure Ti_(3)C_(2)T_(x) MXene can be used to adsorb Li^(+),resulting in a low capacity.Transmission electron microscopy(TEM)and XPS data confirm that T/F-4:1 holds the highly stable solid electrolyte interphase(SEI)layer during the cycling at-10℃.Density functional theory(DFT)calculations further uncover that T/F has fast diffusion of Li^(+) and consequent better electrochemical performances than pure Ti_(3)C_(2)T_(x) MXene.It is believed that the new strategy used here will help to fabricate advanced MXene-based electrode materials in the energy storage application.
基金supported financially by the National Natural Science Foundation of China(Grant Nos.91961125 and 21905019)“Key Program for International S&T Cooperation Projects of China”from the Ministry of Science and Technology of China(Grant No.2018YFE0124600)+2 种基金“the Fundamental Research Funds for the Central Universities”(Grant No.2018JBZ107)the Chemistry and Chemical Engineering Guangdong Laboratory(Grant No.1932004)support from the“Excellent One Hundred”project of Beijing Jiaotong University。
文摘Up to now,three kinds of ion-storage mechanisms are summarized towards anode materials in lithium/sodium-ion batteries,but they have low capacity and poor cyclic performance.Therefore,it is necessary to develop a new approach to optimize ion storage.Herein,we report an adsorption/desorption storage route through engineering electronic structure of cation-deficient Ti_(1-x)O_(2)nanosheets.Ti_(1-x)O_(2)nanosheets indeed exhibit higher capacity(332.1 mA h g^(-1)vs.137.7 mA h g^(-1)for LIBs,195.7 mA h g^(-1)vs.111 mA h g^(-1)for SIBs),and more stable cyclic performance(296 mA h g^(-1)vs.99 mA h g^(-1)for LIBs,178.1 mA h g^(-1)vs.80.2 mA h g^(-1)for SIBs after 100 cycles)at 0.1 A g^(-1)than TiO_(2)nanosheets.Kinetics analysis and density functional theory(DFT)calculations reveal that electronic structures of vacancy within Ti_(1-x)O_(2) nanosheets encourage a novel adsorption-desorption storage route.These results highlight the benefits of the engineered electronic structures within electrode material and implement novel ion-storage mechanism towards broad energy storage applications.
基金supported by the Fundamental Research Funds for the Central Universities(grant nos.2018JBZ107 and 2019RC035)supported financially by the National Natural Science Foundation of China(grant nos.91961125 and 21905019)+1 种基金the Key Program for International S&T Cooperation Projects of China from the Ministry of Science and Technology of China(grant no.2018YFE0124600)the Chemistry and Chemical Engineering Guangdong Laboratory(nos.1932001,1932004,1911020,and 1911023).
文摘Precise catalysis is critical for the high-quality catalysis industry.However,it remains challenging to fundamentally understand precise catalysis at the atomic orbital level.Herein,we propose a new strategy to unravel the role of specific d orbitals in catalysis.The oxygen reduction reaction(ORR)catalyzed by atomically dispersed Pt/Co-doped Ti_(1−x)O_(2) nanosheets(Pt_(1)/Co_(1)-Ti_(1−x)O_(2))is used as a model catalysis.The z-axis d orbitals of Pt/Co-Ti realms dominate the O2 adsorption,thus triggering ORR.In light of orbital-resolved analysis,Pt_(1)/Co_(1)-Ti_(1−x)O_(2) is experimentally fabricated,and the excellent ORR catalytic performance is further demonstrated.Further analysis reveals that the superior ORR performance of Pt_(1)-Ti_(1−x)O_(2) to Co_(1)-Ti_(1−x)O_(2) is ascribed to stronger activation of Ti by Pt than Co via the d-d hybridization.Overall,this work provides a useful tool to understand the underlying catalytic mechanisms at the atomic orbital level and opens new opportunities for precise catalyst design.
基金This study was supported financially by the National Natural Science Foundation of China(grant nos.91961125,21905019,and 21903001)the Fundamental Research Funds for the Central Universities(grant nos.2018JBZ107 and 2019RC035)+2 种基金the Ministry of Science and Technology of China(grant no.2018YFE0124600)the Chemistry and Chemical Engineering Guangdong Laboratory(grant no.1932004)the Natural Science Foundation of Anhui Province(grant no.1908085QB58)。
文摘The palladium(Pd)-catalyzed Suzuki reaction is widely applied in the pharmaceutical industry,where constructing highly active and low-cost Pd sites are impendent.Here,we report the fabrication of a heterogeneous Pd/Tio2 catalyst via engineering of an electronic structure of a single Pd_(1)atom on monolayered Ti_(0.87)O_(2)nanosheet(Pd_(1)-Ti_(0.87)O_(2)).This catalyst motivated the kinetically sluggish C-Br cleavage,thus boosting the Suzuki reaction at room temperature.Pd_(1)-Ti_(0.87)O_(2)exhibited an outstanding activity with turnover frequency(TOF)of 11,110 h-1,exceeding that of PdCl_(2)and Pd(OAc)_(2)catalysts by a factor of>200.Various in situ techniques were employed to investigate the C-Br activation process,which showed that Pd_(1)kinetic-feasibly dissociated the chemisorbed bromobenzene,especially the C-Br bond cleavage.Theoretical calculations further revealed that the improved activity is ascribed to the optimized charge state of Pd_(1)within the Pd_(1)O4 realm via charge transfer.
