Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of...Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 10<sup>7</sup> atomic units (10<sup><span style="color:#4F4F4F;font-family:-apple-system, " font-size:14px;white-space:normal;background-color:#ffffff;"="">-</span>33</sup> esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH<sub>3</sub>)<sub>2</sub> or -NHCH<sub>3</sub>) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.展开更多
Bedrock weathering performs a significant influence on the evolution of Earth’s critical zone.Carbonate rock(dolostone),metamorphic rock(gneiss),and sedimentary rock(sandstone)geological formations in Yanshan Mountai...Bedrock weathering performs a significant influence on the evolution of Earth’s critical zone.Carbonate rock(dolostone),metamorphic rock(gneiss),and sedimentary rock(sandstone)geological formations in Yanshan Mountain,Hebei Province,are taken as objects to probe the controlling of geological formations on weathering characteristics,migration,and enrichment of elements as well as structure of Earth’s critical zone under the identical climate conditions through geological field survey,analysis on minerals component,element distribution in the weathering profile.The dolostone geological formation(DGF)is lithologically dominated by dolostone,characterized by the strongest and predominant chemical weathering.During bedrock weathering and pedogenesis,DGF is marked by significant depletion of CaO,Mg O,S,Mn,Mo and enrichment of N,K,Fe_(2)O_(3),and Zn with concentrations of P,Cu,and B keeping stable.Shortage of soil-forming materials and significant loss are driven by soil erosion,which results in thin regolith and soil.The soil thickness is less than 10 cm,and the regolith thickness is less than 30 cm.The vegetation community is predominantly rock arbor or brush,which is calcivorous and tolerant of barrenness.Plagiogneiss is a dominant rock type of gneiss geological formation(GGF),characterized by the weakest weathering and fast chemical and physical weathering rate.GGF is masked by significant depletion of P,K,CaO,MgO,Fe_(2)O_(3),Mn,Cu and enrichment of N,S,Mo,and B,with contents of Zn keeping stable.Both soil and regolith developed in GGF are relatively thick for one of the reasons that biotite expands during weathering.The soil thickness is more than 50 cm,and the regolith thickness ranges from 100 to 200 cm.The vegetation community is predominantly high-quality economic forests and various arbors because of the enrichment of nutrients in GGF.Sandstone is primarily a rock type of sandstone geological formation(SGF),characterized by moderate weathering degree and slow chemical weathering rate.SGF is marked by significant depletion of P,K,CaO,MgO,Fe_(2)O_(3),and enrichment of N,S,Mn,Cu,Zn,and Mo,with fluctuant changes of Zn and B.The thickness of soil developed in SGF varies between that of DGF and GGF.The soil thickness ranges from 30 to 50 cm,and the regolith thickness ranges from 50 to 100 cm.Chinese pines are widely spread on the shady slopes of SGF.Research provides theoretical support for screening dominant ecological resource areas,ecological industry development and ecological protection and restoration for Yanshan Mountain,Hebei Province.展开更多
Artificial photosynthesis of valuable chemicals from CO_(2)is a potential way to achieve sustainable carbon cycle.The CO_(2)conversion activity is still inhibited by the sluggish charge kinetics and poor CO_(2)activat...Artificial photosynthesis of valuable chemicals from CO_(2)is a potential way to achieve sustainable carbon cycle.The CO_(2)conversion activity is still inhibited by the sluggish charge kinetics and poor CO_(2)activation.Herein,Ag nanoparticles coupled Bi OBr have been constructed by in-situ photoreduction strategy.The crafting of interface between Ag nanoparticles and Bi OBr nanosheets,achieving an ultra-fast charge transfer.The Bi OBr semiconductor excited electrons and plasmonic Ag nanoparticles generated high-energy hot electrons synchronous accelerates the C=O double bond activation.Thus,the optimized Ag/BiOBr-2 heterostructure shows excellent CO_(2)photoreduction activity with CO production of 133.75 and 6.83μmol/g under 5 h of 300 W Xe lamp and visible light(λ>400 nm)irradiation,which is 1.51 and 2.81 folds versus the pristine Bi OBr,respectively.The mechanism of CO_(2)photoreduction was in-depth understood through in-situ FT-IR spectrum and density functional theory calculations.This study provides some new perspectives into efficient photocatalytic CO_(2)reduction.展开更多
Integrating semiconductor photocatalysts with outstanding visible light absorption and fast surface/interface charge transfer kinetics is still an enormous challenge for efficient CO_(2)photoreduction.In this work,the...Integrating semiconductor photocatalysts with outstanding visible light absorption and fast surface/interface charge transfer kinetics is still an enormous challenge for efficient CO_(2)photoreduction.In this work,the Au nanoparticles have been coupled with ultrathin BiOBr nanosheets,the formed heterostructure(Au/BiOBr)pos-sesses a localized surface plasmon resonance(LSPR)and enhances the visible light absorption ability,as well as forms a fast charge transport channel on the interface between Au and BiOBr.Thus,the heterostructure photo-catalyst exhibits higher photocatalytic CO_(2)to CO performance(135.3/16.43μmol g^(-1))than that of BiOBr(89.0/6.46μmol g^(-1))under 300 W Xe lamp and visible light(λ>400 nm)irradiation for 5 h,respectively.Finally,the in situ FT-IR spectroscopy revealed CO_(2)photoreduction process and found that the*COOH is the key intermediate for CO_(2)to CO.This work provides an effective method to construct multielectron transfer scheme for efficient photocatalytic CO_(2)reduction.展开更多
文摘Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 10<sup>7</sup> atomic units (10<sup><span style="color:#4F4F4F;font-family:-apple-system, " font-size:14px;white-space:normal;background-color:#ffffff;"="">-</span>33</sup> esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH<sub>3</sub>)<sub>2</sub> or -NHCH<sub>3</sub>) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.
基金Research Program of Tianjin North China Geological Exploration BureauHK2021-B15,Daqing Fu+4 种基金Geological Survey Program of China Geological SurveyMinistry of Natural ResourcesDD20190822,Xiaofeng WeiS&T Program of Hebei(CN),19224205DHao Wei。
文摘Bedrock weathering performs a significant influence on the evolution of Earth’s critical zone.Carbonate rock(dolostone),metamorphic rock(gneiss),and sedimentary rock(sandstone)geological formations in Yanshan Mountain,Hebei Province,are taken as objects to probe the controlling of geological formations on weathering characteristics,migration,and enrichment of elements as well as structure of Earth’s critical zone under the identical climate conditions through geological field survey,analysis on minerals component,element distribution in the weathering profile.The dolostone geological formation(DGF)is lithologically dominated by dolostone,characterized by the strongest and predominant chemical weathering.During bedrock weathering and pedogenesis,DGF is marked by significant depletion of CaO,Mg O,S,Mn,Mo and enrichment of N,K,Fe_(2)O_(3),and Zn with concentrations of P,Cu,and B keeping stable.Shortage of soil-forming materials and significant loss are driven by soil erosion,which results in thin regolith and soil.The soil thickness is less than 10 cm,and the regolith thickness is less than 30 cm.The vegetation community is predominantly rock arbor or brush,which is calcivorous and tolerant of barrenness.Plagiogneiss is a dominant rock type of gneiss geological formation(GGF),characterized by the weakest weathering and fast chemical and physical weathering rate.GGF is masked by significant depletion of P,K,CaO,MgO,Fe_(2)O_(3),Mn,Cu and enrichment of N,S,Mo,and B,with contents of Zn keeping stable.Both soil and regolith developed in GGF are relatively thick for one of the reasons that biotite expands during weathering.The soil thickness is more than 50 cm,and the regolith thickness ranges from 100 to 200 cm.The vegetation community is predominantly high-quality economic forests and various arbors because of the enrichment of nutrients in GGF.Sandstone is primarily a rock type of sandstone geological formation(SGF),characterized by moderate weathering degree and slow chemical weathering rate.SGF is marked by significant depletion of P,K,CaO,MgO,Fe_(2)O_(3),and enrichment of N,S,Mn,Cu,Zn,and Mo,with fluctuant changes of Zn and B.The thickness of soil developed in SGF varies between that of DGF and GGF.The soil thickness ranges from 30 to 50 cm,and the regolith thickness ranges from 50 to 100 cm.Chinese pines are widely spread on the shady slopes of SGF.Research provides theoretical support for screening dominant ecological resource areas,ecological industry development and ecological protection and restoration for Yanshan Mountain,Hebei Province.
基金financially supported by the National Natural Science Foundation of China(Nos.22108106,21878134,21576123)China Postdoctoral Science Foundation(No.2020M680065)+1 种基金Hong Kong Scholar Program(No.XJ2021021)Key Laboratory of Electrochemical Energy Storage and Energy Conversion of Hainan Province(No.KFKT2021005)。
文摘Artificial photosynthesis of valuable chemicals from CO_(2)is a potential way to achieve sustainable carbon cycle.The CO_(2)conversion activity is still inhibited by the sluggish charge kinetics and poor CO_(2)activation.Herein,Ag nanoparticles coupled Bi OBr have been constructed by in-situ photoreduction strategy.The crafting of interface between Ag nanoparticles and Bi OBr nanosheets,achieving an ultra-fast charge transfer.The Bi OBr semiconductor excited electrons and plasmonic Ag nanoparticles generated high-energy hot electrons synchronous accelerates the C=O double bond activation.Thus,the optimized Ag/BiOBr-2 heterostructure shows excellent CO_(2)photoreduction activity with CO production of 133.75 and 6.83μmol/g under 5 h of 300 W Xe lamp and visible light(λ>400 nm)irradiation,which is 1.51 and 2.81 folds versus the pristine Bi OBr,respectively.The mechanism of CO_(2)photoreduction was in-depth understood through in-situ FT-IR spectrum and density functional theory calculations.This study provides some new perspectives into efficient photocatalytic CO_(2)reduction.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21878134,21576123)China Postdoctoral Science Foundation(No.2020M680065).
文摘Integrating semiconductor photocatalysts with outstanding visible light absorption and fast surface/interface charge transfer kinetics is still an enormous challenge for efficient CO_(2)photoreduction.In this work,the Au nanoparticles have been coupled with ultrathin BiOBr nanosheets,the formed heterostructure(Au/BiOBr)pos-sesses a localized surface plasmon resonance(LSPR)and enhances the visible light absorption ability,as well as forms a fast charge transport channel on the interface between Au and BiOBr.Thus,the heterostructure photo-catalyst exhibits higher photocatalytic CO_(2)to CO performance(135.3/16.43μmol g^(-1))than that of BiOBr(89.0/6.46μmol g^(-1))under 300 W Xe lamp and visible light(λ>400 nm)irradiation for 5 h,respectively.Finally,the in situ FT-IR spectroscopy revealed CO_(2)photoreduction process and found that the*COOH is the key intermediate for CO_(2)to CO.This work provides an effective method to construct multielectron transfer scheme for efficient photocatalytic CO_(2)reduction.
