The mismatch between the photovoltaic(PV)cells absorption and the solar irradiance on earth is one of the major limitations towards more efficient PV energy conversion.This aspect was addressed by downshifting the sol...The mismatch between the photovoltaic(PV)cells absorption and the solar irradiance on earth is one of the major limitations towards more efficient PV energy conversion.This aspect was addressed by downshifting the solar irradiance on Earth through luminescent down-shifting layers based on lanthanidedoped surface-functionalized ionosilicas(ISs)embedded in poly(methyl methacrylate)(PMMA)coated on the surface of commercial Si-based PV cells.The IS-PMMA hybrid materials exhibit efficient solar radiation harvesting(spectral overlap of^9.5×10^19 photons/(s·m2))and conversion(quantum yield^52%).The direct solar radiation and the down-shifted radiation are partially guided and lost through total internal reflection to the layer edges being unavailable for PV conversion of the coated PV cell.By tuning the down-shifting layer thickness,it also acts as luminescent solar concentrator enabling the collection of the guided radiation by flexible PV cells applied on the borders of the down-shifting layer leading to an enhancement of the PV energy conversion from^5%(in the case of the single-use of the luminescent down-shifting layer)to^13%comparing with the bare PV cell.The overall electrical output of the device resulted in an absolute external quantum efficiency increase of^32%for the optimized Eu^3+-based films in the UV spectral region(compared with the bare PV device,which is among the best values reported so far).展开更多
We report new heterogeneous organocatalyst based on silica hybrid supported N-heterocyclic carbene(NHC-)species.The organocatalyst is formed from an imidazolium iodide based ionosilica material,followed by iodide/acet...We report new heterogeneous organocatalyst based on silica hybrid supported N-heterocyclic carbene(NHC-)species.The organocatalyst is formed from an imidazolium iodide based ionosilica material,followed by iodide/acetate anion exchange.The imidazolium acetate generates the organocatalytic carbene via partial deprotonation of the imidazolium ring in situ.As monitored via EDX,solid state NMR and ion chromatography measurements,the iodide/acetate exchange involving the imidazolium ionosilica material took place only in small extent.Despite the fact that the exchanged material contains only a very small amount of acetate,we observed good catalytic activity and recyclability in cyanosilylation reactions of ketones with trimethylsilyl cyanide.The versatility of the catalyst was highlighted via reaction with several substrates,yielding the corresponding cyanohydrins in good yields.In recycling experiments,the material showed decreasing catalytic activity starting from the third reaction cycle,but high catalytic activity can be regenerated via another acetate treatment.Our work is important as it highlights the possibility to combine carbene chemistry and silica,which are antagonistic at a first glance.We show that imidazolium acetate based ionosilicas are therefore heterogeneous'proto-carbenes',and that there is no need to form strongly basic silica supported NHCs to obtain heterogeneous NHC-organocatalysts.This work therefore opens the route towards heterogeneous and re-usable NHC-organocatalysts from supported ionic liquid imidazolium acetates.展开更多
基金Project supported by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership in the frame of Operational Competitiveness and Internationalization Programme(projects UIDB/50011/2020&UIDP/50011/2020,UID/EEA/50008/2020,UID/QUI/50006/2019,CENTRO-01-0145-FEDER-030186,CENTRO-01-0145-FEDER-000005,Pest-OE/QUI/UI0616/2014,POCI-01-0145-FEDER-016884,PTDC/CTM-NAN/0956/2014,UID/QUI/00686/2016,UID/QUI/00686/2018,UID/QUI/00686/2019 and NORTE-01-0145-FEDER-030858)。
文摘The mismatch between the photovoltaic(PV)cells absorption and the solar irradiance on earth is one of the major limitations towards more efficient PV energy conversion.This aspect was addressed by downshifting the solar irradiance on Earth through luminescent down-shifting layers based on lanthanidedoped surface-functionalized ionosilicas(ISs)embedded in poly(methyl methacrylate)(PMMA)coated on the surface of commercial Si-based PV cells.The IS-PMMA hybrid materials exhibit efficient solar radiation harvesting(spectral overlap of^9.5×10^19 photons/(s·m2))and conversion(quantum yield^52%).The direct solar radiation and the down-shifted radiation are partially guided and lost through total internal reflection to the layer edges being unavailable for PV conversion of the coated PV cell.By tuning the down-shifting layer thickness,it also acts as luminescent solar concentrator enabling the collection of the guided radiation by flexible PV cells applied on the borders of the down-shifting layer leading to an enhancement of the PV energy conversion from^5%(in the case of the single-use of the luminescent down-shifting layer)to^13%comparing with the bare PV cell.The overall electrical output of the device resulted in an absolute external quantum efficiency increase of^32%for the optimized Eu^3+-based films in the UV spectral region(compared with the bare PV device,which is among the best values reported so far).
基金The authors thank the GDR LIPS#3585 for financial support.
文摘We report new heterogeneous organocatalyst based on silica hybrid supported N-heterocyclic carbene(NHC-)species.The organocatalyst is formed from an imidazolium iodide based ionosilica material,followed by iodide/acetate anion exchange.The imidazolium acetate generates the organocatalytic carbene via partial deprotonation of the imidazolium ring in situ.As monitored via EDX,solid state NMR and ion chromatography measurements,the iodide/acetate exchange involving the imidazolium ionosilica material took place only in small extent.Despite the fact that the exchanged material contains only a very small amount of acetate,we observed good catalytic activity and recyclability in cyanosilylation reactions of ketones with trimethylsilyl cyanide.The versatility of the catalyst was highlighted via reaction with several substrates,yielding the corresponding cyanohydrins in good yields.In recycling experiments,the material showed decreasing catalytic activity starting from the third reaction cycle,but high catalytic activity can be regenerated via another acetate treatment.Our work is important as it highlights the possibility to combine carbene chemistry and silica,which are antagonistic at a first glance.We show that imidazolium acetate based ionosilicas are therefore heterogeneous'proto-carbenes',and that there is no need to form strongly basic silica supported NHCs to obtain heterogeneous NHC-organocatalysts.This work therefore opens the route towards heterogeneous and re-usable NHC-organocatalysts from supported ionic liquid imidazolium acetates.
