The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clu...The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.展开更多
基于重庆市气象局业务运行的风暴尺度快速同化和预报系统(Storm-Scale Rapid Assimilation and Forecast System,SSRAFS)、气象信息综合分析处理系统(Meteorological Information Comprehensive Analysis And Process System,MICAPS)地...基于重庆市气象局业务运行的风暴尺度快速同化和预报系统(Storm-Scale Rapid Assimilation and Forecast System,SSRAFS)、气象信息综合分析处理系统(Meteorological Information Comprehensive Analysis And Process System,MICAPS)地面观测和高空观测资料,进行模式输出统计(Model Output Statistics,MOS)方法和纳入超前实况因子的MOS(MOS with Prior Observation Predictors,OMOS)方法对重庆地区地面气温96 h内逐小时预报试验,并以SSRAFS地面气温预报结果作为参考进行对比分析。结果表明:MOS方法在1~96 h预报时效内的预报技巧高于SSRAFS,气温预报均方根误差(Root Mean Square Error,RMSE)平均减小1.22℃,CC和HR2分别平均增大0.006和20.4%;在1~7 h预报时效,RMSE平均减小1.70℃,CC和HR2分别平均增大0.07和34.5%;且MOS方法在重庆东北部及中南部地区改进效果较为明显。OMOS方法在气温短期预报中表现优于MOS方法,尤其在1~7 h预报时效,比MOS方法RMSE平均减小0.43℃,CC和HR2分别平均增大0.008和8.3%;其在1~4 h预报时效时表现更加优异,与MOS方法相比,RMSE平均减小0.66℃,CC和HR2分别平均增大0.13和12.3%。因此,在MOS的基础上,OMOS能够进一步提升地面气温的预报技巧,且在重庆东北部及中南部地区的预报效果有明显改进。展开更多
TiO_(2)is the dominant and most widely researched photocatalyst for environmental remediation,however,the drawbacks,such as only responding to UV light(<5%of sunlight),low charge separation efficiency,and difficult...TiO_(2)is the dominant and most widely researched photocatalyst for environmental remediation,however,the drawbacks,such as only responding to UV light(<5%of sunlight),low charge separation efficiency,and difficulties in recycling,have severely hindered its practical application.Herein,we synthesized magnetically separable Fe_(3)O_(4)@MoS_(2)@mesoporous TiO_(2)(FMmT)photocatalysts via a simple,green,and template-free solvothermal method combined with ultrasonic hydrolysis.It is found that FMmT possesses a high specific surface area(55.09 m2·g−1),enhanced visible-light responsiveness(~521 nm),and remarkable photogenerated charge separation efficiency.In addition,the photocatalytic degradation efficiencies of FMmT for methylene blue(MB),rhodamine B(RhB),and tetracycline(TC)are 99.4%,98.5%,and 89.3%within 300 min,respectively.The corresponding degradation rates are 4.5,4.3,and 3.1 times higher than those of pure TiO_(2)separately.Owing to the high saturation magnetization(43.1 A·m^(2)·kg^(−1)),FMmT can achieve effective recycling with an applied magnetic field.The improved photocatalytic activity is closely related to the effective transport of photogenerated electrons by the active interlayer MoS_(2) and the electron–hole separation caused by the MoS_(2)@TiO_(2)heterojunction.Meanwhile,the excellent light-harvesting ability and abundant reactive sites of the mesoporous TiO_(2)shell further boost the photocatalytic efficiency of FMmT.This work provides a new approach and some experimental basis for the design and performance improvement of magnetic photocatalysts by innovatively incorporating MoS2 as the active interlayer and integrating it with a mesoporous shell.展开更多
基金supported by the National Natural Science Foundation of China(22205209,52202373 and U21A200972)China Postdoctoral Science Foundation(2022M722867)Key Research Project of Higher Education Institutions in Henan Province(23A530001)。
文摘The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.
文摘基于重庆市气象局业务运行的风暴尺度快速同化和预报系统(Storm-Scale Rapid Assimilation and Forecast System,SSRAFS)、气象信息综合分析处理系统(Meteorological Information Comprehensive Analysis And Process System,MICAPS)地面观测和高空观测资料,进行模式输出统计(Model Output Statistics,MOS)方法和纳入超前实况因子的MOS(MOS with Prior Observation Predictors,OMOS)方法对重庆地区地面气温96 h内逐小时预报试验,并以SSRAFS地面气温预报结果作为参考进行对比分析。结果表明:MOS方法在1~96 h预报时效内的预报技巧高于SSRAFS,气温预报均方根误差(Root Mean Square Error,RMSE)平均减小1.22℃,CC和HR2分别平均增大0.006和20.4%;在1~7 h预报时效,RMSE平均减小1.70℃,CC和HR2分别平均增大0.07和34.5%;且MOS方法在重庆东北部及中南部地区改进效果较为明显。OMOS方法在气温短期预报中表现优于MOS方法,尤其在1~7 h预报时效,比MOS方法RMSE平均减小0.43℃,CC和HR2分别平均增大0.008和8.3%;其在1~4 h预报时效时表现更加优异,与MOS方法相比,RMSE平均减小0.66℃,CC和HR2分别平均增大0.13和12.3%。因此,在MOS的基础上,OMOS能够进一步提升地面气温的预报技巧,且在重庆东北部及中南部地区的预报效果有明显改进。
基金financially supported by the National Key R & D Projects (Nos. 2021YFC1910504, 2019YFC1907101, 2019YFC1907103, and 2017YFB0702304)the Key R & D Project in Ningxia Hui Autonomous Region, China (No. 2020BCE01001)+6 种基金the Key and Normal Projects National Natural Science Foundation of China (Nos. U2002212 and 51672024)the Xijiang Innovation and Entrepreneurship Team (No. 2017A0109004)the Fundamental Research Funds for the Central Universities (Nos. FRF-BD-20-24A, FRF-TP-20-031A1, FRF-IC-19-017Z, FRF-GF-19-032B, and 06500141)the Integration of Green Key Process Systems MIIT, Natural Science Foundation of Beijing Municipality (No. 2214073)the Guangdong Basic and Applied Research Foundation, China (No. 2020A1515110408)the Foshan Science and Technology Innovation Special Foundation, China (No. BK21BE002)the Postdoctor Research Foundation of Shunde Graduate School of University of Science and Technology Beijing (No. 2020BH004)
文摘TiO_(2)is the dominant and most widely researched photocatalyst for environmental remediation,however,the drawbacks,such as only responding to UV light(<5%of sunlight),low charge separation efficiency,and difficulties in recycling,have severely hindered its practical application.Herein,we synthesized magnetically separable Fe_(3)O_(4)@MoS_(2)@mesoporous TiO_(2)(FMmT)photocatalysts via a simple,green,and template-free solvothermal method combined with ultrasonic hydrolysis.It is found that FMmT possesses a high specific surface area(55.09 m2·g−1),enhanced visible-light responsiveness(~521 nm),and remarkable photogenerated charge separation efficiency.In addition,the photocatalytic degradation efficiencies of FMmT for methylene blue(MB),rhodamine B(RhB),and tetracycline(TC)are 99.4%,98.5%,and 89.3%within 300 min,respectively.The corresponding degradation rates are 4.5,4.3,and 3.1 times higher than those of pure TiO_(2)separately.Owing to the high saturation magnetization(43.1 A·m^(2)·kg^(−1)),FMmT can achieve effective recycling with an applied magnetic field.The improved photocatalytic activity is closely related to the effective transport of photogenerated electrons by the active interlayer MoS_(2) and the electron–hole separation caused by the MoS_(2)@TiO_(2)heterojunction.Meanwhile,the excellent light-harvesting ability and abundant reactive sites of the mesoporous TiO_(2)shell further boost the photocatalytic efficiency of FMmT.This work provides a new approach and some experimental basis for the design and performance improvement of magnetic photocatalysts by innovatively incorporating MoS2 as the active interlayer and integrating it with a mesoporous shell.
