Gold(Au)as co-catalyst is remarkable for activating methane(CH4),especially atomically dispersed Au with maximized exposing active sites and specific electronic structure.Furthermore,singlet oxygen(^(1)O_(2))typically...Gold(Au)as co-catalyst is remarkable for activating methane(CH4),especially atomically dispersed Au with maximized exposing active sites and specific electronic structure.Furthermore,singlet oxygen(^(1)O_(2))typically manifests a mild redox capacity with a high selectivity to attack organic substrates.Peroxomonosulfate(PMS)favors to produce oxidative species 102 during the photocatalytic reactions.Thus,combining atomic Au as co-catalyst and ^(1)O_(2) as oxidant is an effective strategy to selectively convert CH4.Herein,we synthesized atomically dispersed Au on WO_(3)(Au/WO_(3)),where Au was in the forms of single atoms and clusters.At room temperature,such Au/WO_(3) exhibited enhanced photocata lytic conversion of CH4 to CH3 CH3 with a selectivity,up to 94%,under visible light.The radicals-pathway mechanism of CH4 coupling has also been investigated through detection and trapping experiment of active species.Theoretical calculations further interpret the electronic structure of Au/WO_(3) and tip-enhanced local electric field at the Au sites for promoting CH4 conversion.展开更多
Developing low-energy input route for conversion of methane(CH_(4))to value-added methanol(CH_(3)OH)at room temperature is important in environment and industry.Bonding in electron donor-acceptor hybrid can potentiall...Developing low-energy input route for conversion of methane(CH_(4))to value-added methanol(CH_(3)OH)at room temperature is important in environment and industry.Bonding in electron donor-acceptor hybrid can potentially promote charge transfer and photocatalytic efficiency of CH_(4) conversion.Herein,bonding in electron donor rhodamine B(RhB)-acceptor(TiO_(2))hybrid(RhB/TiO_(2))significantly promotes the selectivity of photocatalytic oxidation of CH4 to CH3OH and utilization of visible light(low-energy photons)at ambient condition.Even under green light irradiation(λ=550 nm),the noble-metal-free RhB/TiO_(2) hybrid synthesized presents enhanced oxidation of CH4 to CH_(3)OH with a generation rate of 143µmol·g^(−1)·h^(−1) and selectivity of 94%.This work demonstrates the possibility and feasibility of noble-metal-free catalysts for activating CH4 under visible light at room temperature.展开更多
基金sponsored by Shanghai Pujiang Program(No.19PJ1405200)the Startup Fund for Youngman Research at SJTU(SFYR at SJTU,No.WF220516003)。
文摘Gold(Au)as co-catalyst is remarkable for activating methane(CH4),especially atomically dispersed Au with maximized exposing active sites and specific electronic structure.Furthermore,singlet oxygen(^(1)O_(2))typically manifests a mild redox capacity with a high selectivity to attack organic substrates.Peroxomonosulfate(PMS)favors to produce oxidative species 102 during the photocatalytic reactions.Thus,combining atomic Au as co-catalyst and ^(1)O_(2) as oxidant is an effective strategy to selectively convert CH4.Herein,we synthesized atomically dispersed Au on WO_(3)(Au/WO_(3)),where Au was in the forms of single atoms and clusters.At room temperature,such Au/WO_(3) exhibited enhanced photocata lytic conversion of CH4 to CH3 CH3 with a selectivity,up to 94%,under visible light.The radicals-pathway mechanism of CH4 coupling has also been investigated through detection and trapping experiment of active species.Theoretical calculations further interpret the electronic structure of Au/WO_(3) and tip-enhanced local electric field at the Au sites for promoting CH4 conversion.
基金This work was sponsored by Shanghai Pujiang Program(No.19PJ1405200)the Startup Fund for Youngman Research at SJTU(SFYR at SJTU,No.WF220516003)。
文摘Developing low-energy input route for conversion of methane(CH_(4))to value-added methanol(CH_(3)OH)at room temperature is important in environment and industry.Bonding in electron donor-acceptor hybrid can potentially promote charge transfer and photocatalytic efficiency of CH_(4) conversion.Herein,bonding in electron donor rhodamine B(RhB)-acceptor(TiO_(2))hybrid(RhB/TiO_(2))significantly promotes the selectivity of photocatalytic oxidation of CH4 to CH3OH and utilization of visible light(low-energy photons)at ambient condition.Even under green light irradiation(λ=550 nm),the noble-metal-free RhB/TiO_(2) hybrid synthesized presents enhanced oxidation of CH4 to CH_(3)OH with a generation rate of 143µmol·g^(−1)·h^(−1) and selectivity of 94%.This work demonstrates the possibility and feasibility of noble-metal-free catalysts for activating CH4 under visible light at room temperature.
