Coupling photocatalysis with thermocatalysis is considered the best way for CO_(2)reduction to produce useful hydrocarbons.Particularly,photocatalytic CO_(2)reduction activity could be improved via the photothermal ef...Coupling photocatalysis with thermocatalysis is considered the best way for CO_(2)reduction to produce useful hydrocarbons.Particularly,photocatalytic CO_(2)reduction activity could be improved via the photothermal effect induced by local heat and subsequently,enhance visible light harvesting from noble metal nanoparticles.However,the sluggish hot electron transfer between noble metal and semiconducting materials remains an Achilles heel to achieve an applicable CO_(2)reduction.Herein,a highly efficient“Pt···Ti”hot electron transportation bridge between Pt nanoparticles and hierarchically porous TiO_(2)(HP-TiO_(2))was paved.Such photothermocatalyst lowered the barrier of charge migration and exhibited significantly boosted CO_(2)reduction with an outstanding hydrocarbon productivity of 29.68μmol·h^(−1)·g^(−1),which was around 21 times higher than that of bulk-TiO_(2);besides,an extraordinary selectivity to CH4 of over 99%under simulated sunlight irradiation was achieved.In-situ characterizations and first-principle calculations confirmed that the manufactured“Pt···Ti”hot electron transportation bridge exerted a significant role in promoting CO_(2)molecule activation and conversion.The innovative concept of paving an efficient hot electron shift bridge,acting as a crucial springboard promises a practical application of advanced photothermocatalyst for efficient industrial CO_(2)reduction and highvalued chemical production.展开更多
Comprehensive Summary Regioselective electrochemical hydroalkylations of[60]fullerene-fused furochromenone with alky halides under different acidic conditions unexpectedly afford three types of tetra-functionalized[60...Comprehensive Summary Regioselective electrochemical hydroalkylations of[60]fullerene-fused furochromenone with alky halides under different acidic conditions unexpectedly afford three types of tetra-functionalized[60]fullerene derivatives in high yields.When acetic acid is used as the proton source,two 1,2,3,4-adducts with retained or rearranged five-membered heterocycle are obtained as major and minor products,respectively.While trifluoroacetic acid is employed as the proton source,1,2,3,16-adducts and 1,2,3,4-adducts,both with the five-membered heterocycle rearranged from[6,6]-junction to[5,6]-junction,are generated.Intriguingly,the obtained 1,2,3,16-adducts can be transformed into 1,2,3,4-adducts accompanied by rearrangement of the fused five-membered heterocycle from[5,6]-junction to[6,6]-junction.These products have been characterized by spectroscopic data and single-crystal X-ray analysis.Moreover,the two 1,2,3,4-adducts with the heterocycle fused to[5,6]-junction or[6,6]-junction show diagnostic UV-vis spectra,which may be useful for the identification of these two types of 1,2,3,4-adducts in the future.A plausible reaction mechanism has been proposed to elucidate the formation of hydroalkylation products in the presence of different acids.展开更多
基金supported by the National Key R&D Program of China(grant no.2022YFB3504000)the National Natural Science Foundation of China(grant nos.U20A20122,22402044,22293022,and U22B6011)+3 种基金the Zhejiang Provincial Natural Science Foundation of China(grant no.LQ24E020011)the Program of Introducing Talents of Discipline to Universities-Plan 111(grant no.B20002)from the Ministry of Science and Technology and the Ministry of Education of Chinasupported by the European Commission Interreg V France-Wallonie-Vlaanderen project“DepollutAir,”the Program Win2Wal(TCHARBONACTIF:2110120)the Wallonia Region of Belgium and the National Key R&D Program Intergovernmental Technological Innovation Special Cooperation Project Wallonia-Belgium-China,Ministry of Science and Technology(MOST)(grant no.SUB/2021/IND493971/524448).
文摘Coupling photocatalysis with thermocatalysis is considered the best way for CO_(2)reduction to produce useful hydrocarbons.Particularly,photocatalytic CO_(2)reduction activity could be improved via the photothermal effect induced by local heat and subsequently,enhance visible light harvesting from noble metal nanoparticles.However,the sluggish hot electron transfer between noble metal and semiconducting materials remains an Achilles heel to achieve an applicable CO_(2)reduction.Herein,a highly efficient“Pt···Ti”hot electron transportation bridge between Pt nanoparticles and hierarchically porous TiO_(2)(HP-TiO_(2))was paved.Such photothermocatalyst lowered the barrier of charge migration and exhibited significantly boosted CO_(2)reduction with an outstanding hydrocarbon productivity of 29.68μmol·h^(−1)·g^(−1),which was around 21 times higher than that of bulk-TiO_(2);besides,an extraordinary selectivity to CH4 of over 99%under simulated sunlight irradiation was achieved.In-situ characterizations and first-principle calculations confirmed that the manufactured“Pt···Ti”hot electron transportation bridge exerted a significant role in promoting CO_(2)molecule activation and conversion.The innovative concept of paving an efficient hot electron shift bridge,acting as a crucial springboard promises a practical application of advanced photothermocatalyst for efficient industrial CO_(2)reduction and highvalued chemical production.
基金financial support from the National Natural Science Foundation of China(22071231).
文摘Comprehensive Summary Regioselective electrochemical hydroalkylations of[60]fullerene-fused furochromenone with alky halides under different acidic conditions unexpectedly afford three types of tetra-functionalized[60]fullerene derivatives in high yields.When acetic acid is used as the proton source,two 1,2,3,4-adducts with retained or rearranged five-membered heterocycle are obtained as major and minor products,respectively.While trifluoroacetic acid is employed as the proton source,1,2,3,16-adducts and 1,2,3,4-adducts,both with the five-membered heterocycle rearranged from[6,6]-junction to[5,6]-junction,are generated.Intriguingly,the obtained 1,2,3,16-adducts can be transformed into 1,2,3,4-adducts accompanied by rearrangement of the fused five-membered heterocycle from[5,6]-junction to[6,6]-junction.These products have been characterized by spectroscopic data and single-crystal X-ray analysis.Moreover,the two 1,2,3,4-adducts with the heterocycle fused to[5,6]-junction or[6,6]-junction show diagnostic UV-vis spectra,which may be useful for the identification of these two types of 1,2,3,4-adducts in the future.A plausible reaction mechanism has been proposed to elucidate the formation of hydroalkylation products in the presence of different acids.
