To acquire efficient photocatalysts,it is necessary to make effective use of visible light/Near Infrared(NIR)light,which takes up a large percentage of sunlight.Integrating upconversion materials with visible light ac...To acquire efficient photocatalysts,it is necessary to make effective use of visible light/Near Infrared(NIR)light,which takes up a large percentage of sunlight.Integrating upconversion materials with visible light active photocatalysts has attracted much attention in this regard.The interface contact between upcon-version material and photocatalyst has potential influence on the properties and thus the performance of the system.In this work,NaYF_(4):Yb,Er/CdS composites of the upconversion material NaYF_(4):Yb,Er nanorods and CdS nanoparticles were synthesized by ion adsorption/precipitation process and were then annealed in an argon atmosphere at different temperatures to modulate the microstructures.The annealing pro-cess endows the crystal transformation of cubic CdS with low crystallinity to hexagonal CdS with high crystallinity and,importantly,good interface contact between NaYF_(4):Yb,Er and CdS.Consequently,the hy-drogen evolution activity greatly increases from 171 to 2539μmol h^(−1) g^(−1) under the light irradiation ofλ>400 nm,and from 0 to 19μmol h^(−1) g^(−1) under the light irradiation ofλ>600 nm.This work might provide a useful reference for the rational design of promising photocatalyst involving upconversion ma-terials.展开更多
High sensitizer and activator concentrations have been increasingly examined to improve the performance of multi-color emissive upconversion(UC)nanocrystals(UCNC)like NaYF_(4):Yb,Er and first strategies were reported ...High sensitizer and activator concentrations have been increasingly examined to improve the performance of multi-color emissive upconversion(UC)nanocrystals(UCNC)like NaYF_(4):Yb,Er and first strategies were reported to reduce concentration quenching in highly doped UCNC.UC luminescence(UCL)is,however,controlled not only by dopant concentration,yet by an interplay of different parameters including size,crystal and shell quality,and excitation power density(P).Thus,identifying optimum dopant concentrations requires systematic studies of UCNC designed to minimize additional quenching pathways and quantitative spectroscopy.Here,we quantify the dopant concentration dependence of the UCL quantum yield(ΦUC)of solid NaYF_(4):Yb,Er/NaYF_(4):Lu upconversion core/shell nanocrystals of varying Yb3+and Er3+concentrations(Yb3+series:20%‒98%Yb3+;2%Er3+;Er3+series:60%Yb3+;2%‒40%Er3+).To circumvent other luminescence quenching processes,an elaborate synthesis yielding OH-free UCNC with recordΦUC of~9%and~25 nm core particles with a thick surface shell were used.High Yb3+concentrations barely reduceΦUC from~9%(20%Yb3+)to~7%(98%Yb3+)for an Er3+concentration of 2%,thereby allowing to strongly increase the particle absorption cross section and UCNC brightness.Although an increased Er3+concentration reducesΦUC from~7%(2%Er3+)to 1%(40%)for 60%Yb3+.Nevertheless,at very high P(>1 MW/cm^(2))used for microscopic studies,highly Er3+-doped UCNC display a high brightness because of reduced saturation.These findings underline the importance of synthesis control and will pave the road to many fundamental studies of UC materials.展开更多
In the most popular NaYF_(4):Yb/Er upconversion nanoparticles(UCNPs),the red emission is attributed to four potential excitation routes encompassing two-and threephoton excitation processes.Consequently,this red emiss...In the most popular NaYF_(4):Yb/Er upconversion nanoparticles(UCNPs),the red emission is attributed to four potential excitation routes encompassing two-and threephoton excitation processes.Consequently,this red emission typically exhibits a super-quadratic dependency on near-infrared(NIR)excitation intensity,with the nonlinear order n being dependent on the individual contributions(Cis)of these four excitation routes.Notably,the Cis values are not constant but significantly impacted by the surface quenching of the UCNPs,leading to a decrease in the n value.However,a quantitative assessment of these variable Cis has not been undertaken,hindering a comprehensive understanding of the quenching effect on the UC mechanisms.In this work,we prepare four NaYF_(4):Yb/Er nanocrystal samples with varying degrees of surface quenching,achieving through the modulation of particle size and core-shell structure.We quantitatively evaluate the Cis values and identify the primary excitation route responsible for the red emission.Our results reveal that the contribution of three-photon excitation increases from 7%in the 30 nm bare core to 74%in 90 nm core with shell at an excitation intensity of 200 mW cm^(−2).This observation highlights the impact of surface quenching suppression.Furthermore,we discover that the quenching effect operates by reducing the lifetimes of the Yb^(3+)2F_(5/2)and Er^(3+)4S3/2 levels,while enhancing the NIR emission intensity ratio of the Er^(3+)4I_(13/2)→4I_(15/2)transition to the Yb^(3+)2F_(5/2)→2F_(7/2)transition.Our findings provide physical insights into the excitation mechanisms underlying the red UC emission in NaYF_(4):Yb/Er UCNPs.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 51825204 and 52072379)。
文摘To acquire efficient photocatalysts,it is necessary to make effective use of visible light/Near Infrared(NIR)light,which takes up a large percentage of sunlight.Integrating upconversion materials with visible light active photocatalysts has attracted much attention in this regard.The interface contact between upcon-version material and photocatalyst has potential influence on the properties and thus the performance of the system.In this work,NaYF_(4):Yb,Er/CdS composites of the upconversion material NaYF_(4):Yb,Er nanorods and CdS nanoparticles were synthesized by ion adsorption/precipitation process and were then annealed in an argon atmosphere at different temperatures to modulate the microstructures.The annealing pro-cess endows the crystal transformation of cubic CdS with low crystallinity to hexagonal CdS with high crystallinity and,importantly,good interface contact between NaYF_(4):Yb,Er and CdS.Consequently,the hy-drogen evolution activity greatly increases from 171 to 2539μmol h^(−1) g^(−1) under the light irradiation ofλ>400 nm,and from 0 to 19μmol h^(−1) g^(−1) under the light irradiation ofλ>600 nm.This work might provide a useful reference for the rational design of promising photocatalyst involving upconversion ma-terials.
基金the German Science Foundation DFG(grants RE 1203/18-1 and HA 1649/7-1)the EU(COST 1403)for financial support.
文摘High sensitizer and activator concentrations have been increasingly examined to improve the performance of multi-color emissive upconversion(UC)nanocrystals(UCNC)like NaYF_(4):Yb,Er and first strategies were reported to reduce concentration quenching in highly doped UCNC.UC luminescence(UCL)is,however,controlled not only by dopant concentration,yet by an interplay of different parameters including size,crystal and shell quality,and excitation power density(P).Thus,identifying optimum dopant concentrations requires systematic studies of UCNC designed to minimize additional quenching pathways and quantitative spectroscopy.Here,we quantify the dopant concentration dependence of the UCL quantum yield(ΦUC)of solid NaYF_(4):Yb,Er/NaYF_(4):Lu upconversion core/shell nanocrystals of varying Yb3+and Er3+concentrations(Yb3+series:20%‒98%Yb3+;2%Er3+;Er3+series:60%Yb3+;2%‒40%Er3+).To circumvent other luminescence quenching processes,an elaborate synthesis yielding OH-free UCNC with recordΦUC of~9%and~25 nm core particles with a thick surface shell were used.High Yb3+concentrations barely reduceΦUC from~9%(20%Yb3+)to~7%(98%Yb3+)for an Er3+concentration of 2%,thereby allowing to strongly increase the particle absorption cross section and UCNC brightness.Although an increased Er3+concentration reducesΦUC from~7%(2%Er3+)to 1%(40%)for 60%Yb3+.Nevertheless,at very high P(>1 MW/cm^(2))used for microscopic studies,highly Er3+-doped UCNC display a high brightness because of reduced saturation.These findings underline the importance of synthesis control and will pave the road to many fundamental studies of UC materials.
基金supported by the National Natural Science Foundation of China(11874055,U22A20139,11904361,and 52102192)the Natural Science Foundation of Jilin Province(SKL202302024,20210201024GX,20220101208JC,and 20230101123JC)+1 种基金the Independent Innovation Project on State Key Laboratory of Luminescence and Applications(SKLA-Z-2023-11)the Opening Project Key Laboratory of Transparent Opto-functional Inorganic Material,Chinese Academy of Sciences。
文摘In the most popular NaYF_(4):Yb/Er upconversion nanoparticles(UCNPs),the red emission is attributed to four potential excitation routes encompassing two-and threephoton excitation processes.Consequently,this red emission typically exhibits a super-quadratic dependency on near-infrared(NIR)excitation intensity,with the nonlinear order n being dependent on the individual contributions(Cis)of these four excitation routes.Notably,the Cis values are not constant but significantly impacted by the surface quenching of the UCNPs,leading to a decrease in the n value.However,a quantitative assessment of these variable Cis has not been undertaken,hindering a comprehensive understanding of the quenching effect on the UC mechanisms.In this work,we prepare four NaYF_(4):Yb/Er nanocrystal samples with varying degrees of surface quenching,achieving through the modulation of particle size and core-shell structure.We quantitatively evaluate the Cis values and identify the primary excitation route responsible for the red emission.Our results reveal that the contribution of three-photon excitation increases from 7%in the 30 nm bare core to 74%in 90 nm core with shell at an excitation intensity of 200 mW cm^(−2).This observation highlights the impact of surface quenching suppression.Furthermore,we discover that the quenching effect operates by reducing the lifetimes of the Yb^(3+)2F_(5/2)and Er^(3+)4S3/2 levels,while enhancing the NIR emission intensity ratio of the Er^(3+)4I_(13/2)→4I_(15/2)transition to the Yb^(3+)2F_(5/2)→2F_(7/2)transition.Our findings provide physical insights into the excitation mechanisms underlying the red UC emission in NaYF_(4):Yb/Er UCNPs.
