Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical fun...Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical functionality and low polarity,making it one of the most challenging environmental hazards globally.Herein,we developed a phosphorylated CeO_(2)catalyst by an organophosphate precursor and featured efficient photocatalysis of low-density polyethylene(LDPE)without the acid or alkaline pre-treatment.Compared to pristine CeO_(2),the surface phosphorylation allows to introduce Brønsted acid sites,which facilitate to form carbonium ions on LDPE via protonation.In addition,the suitable band structure of the phosphorylated CeO_(2)catalyst enables efficient photoabsorption and generates reactive oxygen species,leading to the C–C bond cleavage of LDPE.As a result,the phosphorylated CeO_(2)catalyst exhibited an outstanding carbon conversion rate of>94%after 48 h of photocatalysis under 50 mW/cm^(2)of simulated sunlight,with a high CO_(2)product selectivity of>99%.Furthermore,the PE microparticles with sizes larger than 10μm released from LDPE plastic wrap were directly and completely degraded by photocatalysis within 12 h,suggesting an attractive and environmentally benign strategy of utilizing solar energy-based photocatalysis for reducing potential hazards of LDPE plastic trashes.展开更多
Lead halide hybrid perovskites(LHP)have emerged as one of the most promising photovoltaic materials for their remarkable solar energy conversion ability.The transportation of the photoinduced carriers in LHP could scr...Lead halide hybrid perovskites(LHP)have emerged as one of the most promising photovoltaic materials for their remarkable solar energy conversion ability.The transportation of the photoinduced carriers in LHP could screen the defect recombination with the help of the large polaron formation.However,the physical insight of the relationship between the superior optical-electronic performance of perovskite and its polaron dynamics related to the electron-lattice strong coupling induced by the substitution engineering is still lack of investigation.Here,the bandgap modulated thin films ofα-FAPbI_(3)with different element substitution is investigated by the time resolved Terahertz spectroscopy.We find the polaron recombination dynamics could be prolonged in LHP with a relatively smaller bandgap,even though the formation of polaron will not be affected apparently.Intuitively,the large polaron mobility in(FAPb I_(3))0.95(MAPbI_(3))0.05thin film is~30%larger than that in(FAPb I_(3))0.85(MAPbBr_(3))0.15.The larger mobility in(FAPb I_(3))0.95(MAPb I_(3))0.05could be assigned to the slowing down of the carrier scattering time.Therefore,the physical origin of the higher carrier mobility in the(FAPb I_(3))0.95(MAPbI_(3))0.05should be related with the lattice distortion and enhanced electron–phonon coupling induced by the substitution.In addition,(FAPbI_(3))0.95(MAPbI_(3))0.05will lose fewer active carriers during the polaron cooling process than that in(FAPb I_(3))0.85(MAPbBr_(3)),indicating lower thermal dissipation in(FAPbI_(3))0.95(MAPbI_(3))0.05.Our results suggest that besides the smaller bandgap,the higher polaron mobility improved by the substitution engineering inα-FAPbI_(3)can also be an important factor for the high PCE of the black phaseα-FAPbI_(3)based solar cell devices.展开更多
基金the following funding agencies for supporting this work: the National Natural Science Foundation of China (22025502, U23A20552, 22379026, 22222901, 22175022)the Natural Science Foundation of Shanghai (23ZR1407000)the Science and Technology Commission of Shanghai Municipality (21DZ1206800)
文摘Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical functionality and low polarity,making it one of the most challenging environmental hazards globally.Herein,we developed a phosphorylated CeO_(2)catalyst by an organophosphate precursor and featured efficient photocatalysis of low-density polyethylene(LDPE)without the acid or alkaline pre-treatment.Compared to pristine CeO_(2),the surface phosphorylation allows to introduce Brønsted acid sites,which facilitate to form carbonium ions on LDPE via protonation.In addition,the suitable band structure of the phosphorylated CeO_(2)catalyst enables efficient photoabsorption and generates reactive oxygen species,leading to the C–C bond cleavage of LDPE.As a result,the phosphorylated CeO_(2)catalyst exhibited an outstanding carbon conversion rate of>94%after 48 h of photocatalysis under 50 mW/cm^(2)of simulated sunlight,with a high CO_(2)product selectivity of>99%.Furthermore,the PE microparticles with sizes larger than 10μm released from LDPE plastic wrap were directly and completely degraded by photocatalysis within 12 h,suggesting an attractive and environmentally benign strategy of utilizing solar energy-based photocatalysis for reducing potential hazards of LDPE plastic trashes.
基金supported by the National Natural Science Foundation of China(Nos.92050203,61905264,61925507,61875211,61674023,62005296,and 62105347)the National Key R&D Program of China 2017YFE0123700+1 种基金Shanghai Pilot Program for Basic Research(22JC1403200)the CAS Interdisciplinary Innovation Team。
文摘Lead halide hybrid perovskites(LHP)have emerged as one of the most promising photovoltaic materials for their remarkable solar energy conversion ability.The transportation of the photoinduced carriers in LHP could screen the defect recombination with the help of the large polaron formation.However,the physical insight of the relationship between the superior optical-electronic performance of perovskite and its polaron dynamics related to the electron-lattice strong coupling induced by the substitution engineering is still lack of investigation.Here,the bandgap modulated thin films ofα-FAPbI_(3)with different element substitution is investigated by the time resolved Terahertz spectroscopy.We find the polaron recombination dynamics could be prolonged in LHP with a relatively smaller bandgap,even though the formation of polaron will not be affected apparently.Intuitively,the large polaron mobility in(FAPb I_(3))0.95(MAPbI_(3))0.05thin film is~30%larger than that in(FAPb I_(3))0.85(MAPbBr_(3))0.15.The larger mobility in(FAPb I_(3))0.95(MAPb I_(3))0.05could be assigned to the slowing down of the carrier scattering time.Therefore,the physical origin of the higher carrier mobility in the(FAPb I_(3))0.95(MAPbI_(3))0.05should be related with the lattice distortion and enhanced electron–phonon coupling induced by the substitution.In addition,(FAPbI_(3))0.95(MAPbI_(3))0.05will lose fewer active carriers during the polaron cooling process than that in(FAPb I_(3))0.85(MAPbBr_(3)),indicating lower thermal dissipation in(FAPbI_(3))0.95(MAPbI_(3))0.05.Our results suggest that besides the smaller bandgap,the higher polaron mobility improved by the substitution engineering inα-FAPbI_(3)can also be an important factor for the high PCE of the black phaseα-FAPbI_(3)based solar cell devices.
