Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion ...Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion and doping kinetics of precursors with high melting points,along with imprecise regulation,have raised the debate on whether Cs doping could make sense.For this matter,we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation.The optimized Csdoped g-C_(3)N_(4)(CCN)shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction(HER)compared to pure g-C_(3)N_(4) and impressive degradation capability,especially with 77%refractory tetracycline and almost 100%rhodamine B degradedwithin an hour.The penetration ofCs+is demonstrated to be a mode of interlayer doping,and Cs–N bonds(especially with sp^(2) pyridine N in C═N–C),along with robust chemical interaction and electron exchange,are fabricated.This atomic configuration triggers the broadened spectral response,the improved charge migration,and the activated photocatalytic capacity.Furthermore,we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration,promoting the visible HER yield to 9.02 mmol g^(−1) h^(−1),which is the highest ever reported among all CCN systems.This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.展开更多
Tin halide perovskites recently have attracted extensive research attention due to their similar electronic and band structures but non-toxicity compared with their lead analogues. In this work, we prepare high-qualit...Tin halide perovskites recently have attracted extensive research attention due to their similar electronic and band structures but non-toxicity compared with their lead analogues. In this work, we prepare high-quality CsSnX_(3)(X=Br,I) microplates with lateral sizes of around 1–4 μm by chemical vapor deposition and investigate their low-temperature photoluminescence(PL) properties. A remarkable splitting of PL peaks of the CsSnBr_(3)microplate is observed at low temperatures. Besides the possible structural phase transition at below 70 K, the multi-peak fittings using Gauss functions and the power-dependent saturation phenomenon suggest that the PL could also be influenced by the conversion from the emission of bound excitons into free excitons. With the increase of temperature, the peak position shows a blueshift tendency for CsSnI_(3), which is governed by thermal expansion. However, the peak position of the CsSnBr3microplate exhibits a transition from redshift to blueshift at ~160 K. The full width at half maximum of CsSnX_(3)broadens with increasing temperature, and the fitting results imply that longitudinal optical phonons dominate the electron–phonon coupling and the coupling strength is much more robust in CsSnBr3than in CsSnI_(3). The PL intensity of CsSnX_(3)microplates is suppressed due to the enhanced non-radiative relaxation and exciton dissociation competing with radiative recombination. According to the Arrhenius law, the exciton binding energy of CsSnBr_(3)is ~38.4 meV, slightly smaller than that of CsSnI_(3).展开更多
基金supported primarily by the National Natural Science Foundation of China(Contract No.21975245,51972300,62274155,and U20A20206)the National Key Research and Development Program of China(Grant No.2018YFE0204000)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB43000000)the National Natural Science Foundation of China under Grant No.62175231.Prof.Kong Liu appreciates the support from the Youth Innovation Promotion Association,the Chinese Academy of Sciences(No.2020114)the Beijing Nova Program(No.2020117).
文摘Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion and doping kinetics of precursors with high melting points,along with imprecise regulation,have raised the debate on whether Cs doping could make sense.For this matter,we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation.The optimized Csdoped g-C_(3)N_(4)(CCN)shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction(HER)compared to pure g-C_(3)N_(4) and impressive degradation capability,especially with 77%refractory tetracycline and almost 100%rhodamine B degradedwithin an hour.The penetration ofCs+is demonstrated to be a mode of interlayer doping,and Cs–N bonds(especially with sp^(2) pyridine N in C═N–C),along with robust chemical interaction and electron exchange,are fabricated.This atomic configuration triggers the broadened spectral response,the improved charge migration,and the activated photocatalytic capacity.Furthermore,we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration,promoting the visible HER yield to 9.02 mmol g^(−1) h^(−1),which is the highest ever reported among all CCN systems.This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 11974279, 12074311, 12004310, and 12261141662)。
文摘Tin halide perovskites recently have attracted extensive research attention due to their similar electronic and band structures but non-toxicity compared with their lead analogues. In this work, we prepare high-quality CsSnX_(3)(X=Br,I) microplates with lateral sizes of around 1–4 μm by chemical vapor deposition and investigate their low-temperature photoluminescence(PL) properties. A remarkable splitting of PL peaks of the CsSnBr_(3)microplate is observed at low temperatures. Besides the possible structural phase transition at below 70 K, the multi-peak fittings using Gauss functions and the power-dependent saturation phenomenon suggest that the PL could also be influenced by the conversion from the emission of bound excitons into free excitons. With the increase of temperature, the peak position shows a blueshift tendency for CsSnI_(3), which is governed by thermal expansion. However, the peak position of the CsSnBr3microplate exhibits a transition from redshift to blueshift at ~160 K. The full width at half maximum of CsSnX_(3)broadens with increasing temperature, and the fitting results imply that longitudinal optical phonons dominate the electron–phonon coupling and the coupling strength is much more robust in CsSnBr3than in CsSnI_(3). The PL intensity of CsSnX_(3)microplates is suppressed due to the enhanced non-radiative relaxation and exciton dissociation competing with radiative recombination. According to the Arrhenius law, the exciton binding energy of CsSnBr_(3)is ~38.4 meV, slightly smaller than that of CsSnI_(3).
