It is a challenging task to efficiently convert deleterious hydrogen sulfide(H_(2)S)into less harmful products such as SO_(4)^(2-)species.In an effort to address such issue,a step-scheme(S-scheme)heterojunction photoc...It is a challenging task to efficiently convert deleterious hydrogen sulfide(H_(2)S)into less harmful products such as SO_(4)^(2-)species.In an effort to address such issue,a step-scheme(S-scheme)heterojunction photocatalyst has been built by concatenating TiO_(2)(P25)and ultrathin Bi_(4)O_(5)Br_(2)into TiO_(2)/Bi_(4)O_(5)Br_(2)(namely,x-TB-y:x and y denote the molar ratio of TiO_(2):Bi_(4)O_(5)Br_(2)and pH value for solution-based synthesis,respectively)via in-situ hydrothermal method.The S-scheme charge transfer pathway in TB is confirmed by electron spin resonance and band structure analysis while experimental data and density functional theory calculations suggest the formation of an internal electric field to facilitate the separation and transfer of photoinduced charge carriers.Accordingly,the optimized heterojunction photocatalyst,i.e.,5-TB-9,showcases significantly high(>99%)removal efficiency against 10 ppm H_(2)S in a 17 L chamber within 12 minutes(removal kinetic rate r:0.7 mmol·h^(-1)·g^(-1),specific clean air delivery rate SCADR:5554 L·h^(-1)·g^(-1),quantum yield QY:3.24 E-3 molecules·photon^(-1),and space-time yield STY:3.24 E-3 molecules·photon^(-1)·mg^(-1)).Combined analysis of in-situ diffuse reflectance infrared Fourier transform adsorption spectra and gas chromatography-mass spectrometry allows to evaluate the mechanisms leading to the complete degradation of H_(2)S(i.e.,into SO_(4)^(2-)without forming any intermediate species).This work demonstrates the promising remediation potential of an S-scheme TiO_(2)/Bi_(4)O_(5)Br_(2)photocatalyst against hazardous H_(2)S gas for sustainable environmental remediation.展开更多
The bounds on the discrepancy of approximate solutions constructed by Gedunov's scheme to IVP of isentropic equations of gas dynamics are obtained, Three well-knowu results obtained by Lax for shock waves with sma...The bounds on the discrepancy of approximate solutions constructed by Gedunov's scheme to IVP of isentropic equations of gas dynamics are obtained, Three well-knowu results obtained by Lax for shock waves with small jumps for general quasilinear hyperbolic systems of conservation laws are extended to shock waves for isentropic equations of gas dynamics in a bounded invariant region with ρ=0 as one of boundries of the region. Two counterexamples are given to show that two iuequalities given by Godunov do not hold for all rational numbers γ∈(1, 3]. It seems that the approach by Godunov to obtain the forementioned bounds may not be possible.展开更多
Extended light absorption and dynamic charge separation are vital factors that determine the effectivenessof photocatalysts.In this study,a nonmetallic plasmonic S‐scheme photocatalyst was fabricatedby loading 1D pla...Extended light absorption and dynamic charge separation are vital factors that determine the effectivenessof photocatalysts.In this study,a nonmetallic plasmonic S‐scheme photocatalyst was fabricatedby loading 1D plasmonic W_(18)O_(49)nanowires onto 2D g‐C_(3)N_(4)nanosheets.W_(18)O_(49)nanowiresplay the dual role of a light absorption antenna—that extends light adsorption—and a hot electrondonor—that assists the water reduction reaction in a wider light spectrum range.Moreover,S‐scheme charge transfer resulting from the matching bandgaps of W_(18)O_(49)and g‐C_(3)N_(4)can lead tostrong redox capability and high migration speed of the photoinduced charges.Consequently,in thisstudy,W_(18)O_(49)/g‐C_(3)N_(4)hybrids exhibited higher photocatalytic H2 generation than that of pristineg‐C_(3)N_(4)under light irradiation of 420–550 nm.Furthermore,the H2 production rate of thebest‐performing W_(18)O_(49)/g‐C_(3)N_(4)hybrid was 41.5μmol·g^(−1)·h^(−1)upon exposure to monochromaticlight at 550 nm,whereas pure g‐C_(3)N_(4)showed negligible activity.This study promotes novel andenvironmentally friendly hot‐electron‐assisted S‐scheme photocatalysts for the broad‐spectrumutilization of solar light.展开更多
Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high...Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.展开更多
The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In...The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In this study,2D/2D BiOBr/g‐C_(3)N_(4)heterojunctions were successfully obtained by a convenient in situ self‐assembly route.Under simulated sunlight irradiation,99%of RhB(10 mg·L–1,100 mL)was efficiently degraded by 1.5‐BiOBr/g‐C_(3)N_(4)within 30 min,which is better than the performance of both BiOBr and g‐C_(3)N_(4),and it has superior stability.In addition,the composite also exhibits enhanced photocatalytic activity for H2 production.The enhanced activity can be attributed to the intimate interface contact,the larger surface area,and the highly efficient separation of photoinduced electron–hole pairs.Based on the experimental results,a novel S‐scheme model was proposed to illuminate the transfer process of charge carriers.This study presents a simple way to develop novel step‐scheme photocatalysts for environmental and related applications.展开更多
The construction of S‐scheme heterojunction photocatalysts has been regarded as an effective avenue to facilitate the conversion of solar energy to fuel.However,there are still considerable challenges with regard to ...The construction of S‐scheme heterojunction photocatalysts has been regarded as an effective avenue to facilitate the conversion of solar energy to fuel.However,there are still considerable challenges with regard to efficient charge transfer,the abundance of catalytic sites,and extended light absorption.Herein,an S‐scheme heterojunction of 2D/2D zinc porphyrin‐based metal‐organic frameworks/BiVO_(4)nanosheets(Zn‐MOF/BVON)was fabricated for efficient photocatalytic CO_(2)conversion.The optimal one shows a 22‐fold photoactivity enhancement when compared to the previously reported BiVO4 nanoflake(ca.15 nm),and even exhibits~2‐time improvement than the traditional g‐C3N4/BiVO4 heterojunction.The excellent photoactivities are ascribed to the strengthened S‐scheme charge transfer and separation,promoted CO_(2)activation by the well‐dispersed metal nodes Zn_(2)(COO)_(4)in the Zn‐MOF,and extended visible light response range based on the results of the electrochemical reduction,electron paramagnetic resonance,and in‐situ diffuse reflectance infrared Fourier transform spectroscopy.The dimension‐matched Zn‐MOF/BVON S‐scheme heterojunction endowed with highly efficient charge separation and abundant catalytic active sites contributed to the superior CO2 conversion.This study offers a facile strategy for constructing S‐scheme heterojunctions involving porphyrin‐based MOFs for solar fuel production.展开更多
This paper presents a statistical scheme for the seasonal forecasting of North China's surface air temperature (NCSAT) during winter. Firstly, a prediction model for an decrease or increase of winter NCSAT is esta...This paper presents a statistical scheme for the seasonal forecasting of North China's surface air temperature (NCSAT) during winter. Firstly, a prediction model for an decrease or increase of winter NCSAT is established, whose predictors are available for no later than the previous September, as this is the most favorable month for seasonal forecasting up to two months ahead.The predicted NCSAT is then derived as the sum of the predicted increment of NCSAT and the previous NCSAT. The scheme successfully predicts the interannual and the decadal variability of NCSAT. Additionally, the advantages of the prediction scheme are discussed.展开更多
This research paper represents a numerical approximation to three interesting equations of Fisher, which are linear, non-linear and coupled linear one dimensional reaction diffusion equations from population genetics....This research paper represents a numerical approximation to three interesting equations of Fisher, which are linear, non-linear and coupled linear one dimensional reaction diffusion equations from population genetics. We studied accuracy in term of L∞ error norm by random selected grids along time levels for comparison with exact results. The test example demonstrates the accuracy, efficiency and versatility of the proposed schemes. It is shown that the numerical schemes give better solutions. Moreover, the schemes can be easily applied to a wide class of higher dimension non-linear reaction diffusion equations.展开更多
文摘It is a challenging task to efficiently convert deleterious hydrogen sulfide(H_(2)S)into less harmful products such as SO_(4)^(2-)species.In an effort to address such issue,a step-scheme(S-scheme)heterojunction photocatalyst has been built by concatenating TiO_(2)(P25)and ultrathin Bi_(4)O_(5)Br_(2)into TiO_(2)/Bi_(4)O_(5)Br_(2)(namely,x-TB-y:x and y denote the molar ratio of TiO_(2):Bi_(4)O_(5)Br_(2)and pH value for solution-based synthesis,respectively)via in-situ hydrothermal method.The S-scheme charge transfer pathway in TB is confirmed by electron spin resonance and band structure analysis while experimental data and density functional theory calculations suggest the formation of an internal electric field to facilitate the separation and transfer of photoinduced charge carriers.Accordingly,the optimized heterojunction photocatalyst,i.e.,5-TB-9,showcases significantly high(>99%)removal efficiency against 10 ppm H_(2)S in a 17 L chamber within 12 minutes(removal kinetic rate r:0.7 mmol·h^(-1)·g^(-1),specific clean air delivery rate SCADR:5554 L·h^(-1)·g^(-1),quantum yield QY:3.24 E-3 molecules·photon^(-1),and space-time yield STY:3.24 E-3 molecules·photon^(-1)·mg^(-1)).Combined analysis of in-situ diffuse reflectance infrared Fourier transform adsorption spectra and gas chromatography-mass spectrometry allows to evaluate the mechanisms leading to the complete degradation of H_(2)S(i.e.,into SO_(4)^(2-)without forming any intermediate species).This work demonstrates the promising remediation potential of an S-scheme TiO_(2)/Bi_(4)O_(5)Br_(2)photocatalyst against hazardous H_(2)S gas for sustainable environmental remediation.
基金Project supported by National Natural Science Foundation of China.
文摘The bounds on the discrepancy of approximate solutions constructed by Gedunov's scheme to IVP of isentropic equations of gas dynamics are obtained, Three well-knowu results obtained by Lax for shock waves with small jumps for general quasilinear hyperbolic systems of conservation laws are extended to shock waves for isentropic equations of gas dynamics in a bounded invariant region with ρ=0 as one of boundries of the region. Two counterexamples are given to show that two iuequalities given by Godunov do not hold for all rational numbers γ∈(1, 3]. It seems that the approach by Godunov to obtain the forementioned bounds may not be possible.
文摘Extended light absorption and dynamic charge separation are vital factors that determine the effectivenessof photocatalysts.In this study,a nonmetallic plasmonic S‐scheme photocatalyst was fabricatedby loading 1D plasmonic W_(18)O_(49)nanowires onto 2D g‐C_(3)N_(4)nanosheets.W_(18)O_(49)nanowiresplay the dual role of a light absorption antenna—that extends light adsorption—and a hot electrondonor—that assists the water reduction reaction in a wider light spectrum range.Moreover,S‐scheme charge transfer resulting from the matching bandgaps of W_(18)O_(49)and g‐C_(3)N_(4)can lead tostrong redox capability and high migration speed of the photoinduced charges.Consequently,in thisstudy,W_(18)O_(49)/g‐C_(3)N_(4)hybrids exhibited higher photocatalytic H2 generation than that of pristineg‐C_(3)N_(4)under light irradiation of 420–550 nm.Furthermore,the H2 production rate of thebest‐performing W_(18)O_(49)/g‐C_(3)N_(4)hybrid was 41.5μmol·g^(−1)·h^(−1)upon exposure to monochromaticlight at 550 nm,whereas pure g‐C_(3)N_(4)showed negligible activity.This study promotes novel andenvironmentally friendly hot‐electron‐assisted S‐scheme photocatalysts for the broad‐spectrumutilization of solar light.
文摘Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.
文摘The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In this study,2D/2D BiOBr/g‐C_(3)N_(4)heterojunctions were successfully obtained by a convenient in situ self‐assembly route.Under simulated sunlight irradiation,99%of RhB(10 mg·L–1,100 mL)was efficiently degraded by 1.5‐BiOBr/g‐C_(3)N_(4)within 30 min,which is better than the performance of both BiOBr and g‐C_(3)N_(4),and it has superior stability.In addition,the composite also exhibits enhanced photocatalytic activity for H2 production.The enhanced activity can be attributed to the intimate interface contact,the larger surface area,and the highly efficient separation of photoinduced electron–hole pairs.Based on the experimental results,a novel S‐scheme model was proposed to illuminate the transfer process of charge carriers.This study presents a simple way to develop novel step‐scheme photocatalysts for environmental and related applications.
文摘The construction of S‐scheme heterojunction photocatalysts has been regarded as an effective avenue to facilitate the conversion of solar energy to fuel.However,there are still considerable challenges with regard to efficient charge transfer,the abundance of catalytic sites,and extended light absorption.Herein,an S‐scheme heterojunction of 2D/2D zinc porphyrin‐based metal‐organic frameworks/BiVO_(4)nanosheets(Zn‐MOF/BVON)was fabricated for efficient photocatalytic CO_(2)conversion.The optimal one shows a 22‐fold photoactivity enhancement when compared to the previously reported BiVO4 nanoflake(ca.15 nm),and even exhibits~2‐time improvement than the traditional g‐C3N4/BiVO4 heterojunction.The excellent photoactivities are ascribed to the strengthened S‐scheme charge transfer and separation,promoted CO_(2)activation by the well‐dispersed metal nodes Zn_(2)(COO)_(4)in the Zn‐MOF,and extended visible light response range based on the results of the electrochemical reduction,electron paramagnetic resonance,and in‐situ diffuse reflectance infrared Fourier transform spectroscopy.The dimension‐matched Zn‐MOF/BVON S‐scheme heterojunction endowed with highly efficient charge separation and abundant catalytic active sites contributed to the superior CO2 conversion.This study offers a facile strategy for constructing S‐scheme heterojunctions involving porphyrin‐based MOFs for solar fuel production.
基金jointly supported by the Knowledge Innovation Program of the Chinese Academy of Sciences(Grant No.KZCX2-YW-QN202)the National Basic Research Program of China(Grant Nos.2010CB9503042 and 2009CB421406)strategic technological program of the Chinese Academy of Sciences(Grant No.XDA05090426)
文摘This paper presents a statistical scheme for the seasonal forecasting of North China's surface air temperature (NCSAT) during winter. Firstly, a prediction model for an decrease or increase of winter NCSAT is established, whose predictors are available for no later than the previous September, as this is the most favorable month for seasonal forecasting up to two months ahead.The predicted NCSAT is then derived as the sum of the predicted increment of NCSAT and the previous NCSAT. The scheme successfully predicts the interannual and the decadal variability of NCSAT. Additionally, the advantages of the prediction scheme are discussed.
文摘This research paper represents a numerical approximation to three interesting equations of Fisher, which are linear, non-linear and coupled linear one dimensional reaction diffusion equations from population genetics. We studied accuracy in term of L∞ error norm by random selected grids along time levels for comparison with exact results. The test example demonstrates the accuracy, efficiency and versatility of the proposed schemes. It is shown that the numerical schemes give better solutions. Moreover, the schemes can be easily applied to a wide class of higher dimension non-linear reaction diffusion equations.
