Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electro...Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electronic configuration in valley bottom exhibits inert activity,which seriously fetters the development of catalytic materials with great potentials.Herein,In d^(10)electronic configuration of In_(2)O_(3)was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band(Inɛ5p)and descended O 2p-band(Oɛ2p)centers as efficient active sites for chemisorption to*OH and*H during forward HOS,respectively,along with a declined In 4d-band center(Inɛ4d)to inhibit its backward reaction.A stable STH efficiency of 2.23%under AM 1.5 G irradiation at 65°C has been obtained over the activated d^(10)electronic configuration with a lowered activation energy for H_(2)evolution,verified by femtosecond transient absorption spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics.These findings devote to activating d^(10)electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS,which expands the exploration of high-efficiency catalytic materials.展开更多
β-FeOOH nanorods of 40 nm wide and 450 nm long were fabricated through precisely regulating the hydrolysis kinetics of Fe3＋ in polyethylene glycol and the concentration of C1- as the structure-directing agent. Detai...β-FeOOH nanorods of 40 nm wide and 450 nm long were fabricated through precisely regulating the hydrolysis kinetics of Fe3＋ in polyethylene glycol and the concentration of C1- as the structure-directing agent. Detailed structural and chemical analyses of the intermediates during the synthesis identified that the strong interaction between PEG and Fe3＋ modulated the hydrolysis kinetics of Fe3＋and prevented the aggregation of β-FeOOH nanorods; while C1- provided sufficient nucleation sites, stabilized the hollow channel of β-FeOOH, and more importantly induced the growth of the nanorods along [001] direction.展开更多
文摘Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electronic configuration in valley bottom exhibits inert activity,which seriously fetters the development of catalytic materials with great potentials.Herein,In d^(10)electronic configuration of In_(2)O_(3)was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band(Inɛ5p)and descended O 2p-band(Oɛ2p)centers as efficient active sites for chemisorption to*OH and*H during forward HOS,respectively,along with a declined In 4d-band center(Inɛ4d)to inhibit its backward reaction.A stable STH efficiency of 2.23%under AM 1.5 G irradiation at 65°C has been obtained over the activated d^(10)electronic configuration with a lowered activation energy for H_(2)evolution,verified by femtosecond transient absorption spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics.These findings devote to activating d^(10)electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS,which expands the exploration of high-efficiency catalytic materials.
基金supported by the National Natural Science Foundation of China (21025312, 21303193, 21321002)the National Key Basic Research Program of China (2013CB933100)
文摘β-FeOOH nanorods of 40 nm wide and 450 nm long were fabricated through precisely regulating the hydrolysis kinetics of Fe3＋ in polyethylene glycol and the concentration of C1- as the structure-directing agent. Detailed structural and chemical analyses of the intermediates during the synthesis identified that the strong interaction between PEG and Fe3＋ modulated the hydrolysis kinetics of Fe3＋and prevented the aggregation of β-FeOOH nanorods; while C1- provided sufficient nucleation sites, stabilized the hollow channel of β-FeOOH, and more importantly induced the growth of the nanorods along [001] direction.
