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
The photocatalytic reduction of CO2 with H2O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes.Thus far,only a very limited number of photocatalysts has been reported ...The photocatalytic reduction of CO2 with H2O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes.Thus far,only a very limited number of photocatalysts has been reported to be capable of catalyzing the photocatalytic reduction of CO2 under visible light.The utilization of the localized surface plasmon resonance(LSPR)phenomenon is an attractive strategy for developing visible-light photocatalysts.Herein,we have succeeded in synthesizing plasmonic MoO3?x-TiO2 nanocomposites with tunable LSPR by a simple solvothermal method.The well-structured nanocomposite containing two-dimensional(2D)molybdenum oxide(MoO3?x)nanosheets and one-dimensional(1D)titanium oxide nanotubes(TiO2-NT)showed LSPR absorption band in the visible-light region,and the incorporation of TiO2-NT significantly enhanced the LSPR absorption band.The MoO3?x-TiO2-NT nanocomposite is promising for application in the photocatalytic reduction of CO2 with H2O under visible light irradiation.展开更多
Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparallele...Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparalleled selectivity.Herein,through a laser microfabrication method in situ,the free-standing,super hydrophilic and vacancy-rich TiO_(2-x)/Ti is successfully synthesized.Using blue TiO_(x)/Ti(B-TiO_(x)/Ti)as preconcentrated substrate,a nanomolar-level limit of detection of 12 nmol/L at 1385 cm–1,is confirmed using crystal violet(CV)bacteriostat as a model under 532 nm excitation.Furthermore,the results demonstrate that the SERS enhancement mechanism is via the moderate adulteration of oxygen vacancy,which leads to a narrow value of band gap and increases the ICTP of substrate to molecules.Using a hand-held extractor assembled with B-TiO_(x)/Ti microfiber,the operando analysis of mixtures distributed information excited in different parts of Asian carp is facilely achieved.This work guides the controlled synthesis of vacancy-rich TiO_(2-x)/Ti nanostructure and its application in ultrasensitive extraction-SERS detection.It also provides the direction for the rapid and operando transmission of biological information with temporal and spatial concentration distribution in human tissues by highly sensitized materials.展开更多
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.
文摘The photocatalytic reduction of CO2 with H2O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes.Thus far,only a very limited number of photocatalysts has been reported to be capable of catalyzing the photocatalytic reduction of CO2 under visible light.The utilization of the localized surface plasmon resonance(LSPR)phenomenon is an attractive strategy for developing visible-light photocatalysts.Herein,we have succeeded in synthesizing plasmonic MoO3?x-TiO2 nanocomposites with tunable LSPR by a simple solvothermal method.The well-structured nanocomposite containing two-dimensional(2D)molybdenum oxide(MoO3?x)nanosheets and one-dimensional(1D)titanium oxide nanotubes(TiO2-NT)showed LSPR absorption band in the visible-light region,and the incorporation of TiO2-NT significantly enhanced the LSPR absorption band.The MoO3?x-TiO2-NT nanocomposite is promising for application in the photocatalytic reduction of CO2 with H2O under visible light irradiation.
基金supported by National Key Research and Development Program of China(No.2023YFB3210400)Major Scientific and Technological Innovation Project of Shandong Province(No.2021CXGC010603)+1 种基金Natural Science Foundation of Shandong Province(Nos.ZR2020QE057,ZR2020QE071,ZR2020LLZ006)Innovative Team Project of Jinan(No.2021GXRC019)。
文摘Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparalleled selectivity.Herein,through a laser microfabrication method in situ,the free-standing,super hydrophilic and vacancy-rich TiO_(2-x)/Ti is successfully synthesized.Using blue TiO_(x)/Ti(B-TiO_(x)/Ti)as preconcentrated substrate,a nanomolar-level limit of detection of 12 nmol/L at 1385 cm–1,is confirmed using crystal violet(CV)bacteriostat as a model under 532 nm excitation.Furthermore,the results demonstrate that the SERS enhancement mechanism is via the moderate adulteration of oxygen vacancy,which leads to a narrow value of band gap and increases the ICTP of substrate to molecules.Using a hand-held extractor assembled with B-TiO_(x)/Ti microfiber,the operando analysis of mixtures distributed information excited in different parts of Asian carp is facilely achieved.This work guides the controlled synthesis of vacancy-rich TiO_(2-x)/Ti nanostructure and its application in ultrasensitive extraction-SERS detection.It also provides the direction for the rapid and operando transmission of biological information with temporal and spatial concentration distribution in human tissues by highly sensitized materials.
