Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as high...Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.展开更多
An open-framework ammonium ferricborophosphate compound was synthesized by mild hydrothermal condition at 110C. The crystal structure has been determined by single-crystal X-ray diffraction analysis: hexagonal, P6522,...An open-framework ammonium ferricborophosphate compound was synthesized by mild hydrothermal condition at 110C. The crystal structure has been determined by single-crystal X-ray diffraction analysis: hexagonal, P6522, a = 9.452(2) , c = 15.698(5) , a = 90, g = 120, Z = 6, Mr = 310.58, V = 1214.0(5) 3, Dc = 2.549 g/cm3, m = 2.311mm-1, F(000) = 930. The chiral tetrahedral-tetrahedral helical ribbons are linked by the mixed valance FeII/FeIIIO6 coordinated octahedra. The ammonium ions are located inside the free loop of helical ribbons close to the inner wall of the helical channels1{[BP2O8]3-}, effecting on balancing charge and stabilizing helical ribbons.展开更多
A novel 3-D inorganic bimetallic compound Ag2Mo2O7 has been hydrothermally synthesized and structurally characterized by X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 6.1274（3...A novel 3-D inorganic bimetallic compound Ag2Mo2O7 has been hydrothermally synthesized and structurally characterized by X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 6.1274（3）, b = 13.1836（6）, c = 7.8780（3）A, β= 110.673（3）°, V = 595.42（5）A3, Z= 4, Mr= 519.62, Dc = 5.797g/cm^3, F（000） = 936,μ（MoKα） = 10.579 mm^-1, F（000） = 936, the final R = 0.0204 and wR = 0.0477 for 1268 observed reflections with I〉 2σ（I）. In the title compound, the [Mo4O16]n^8n-chains are linked through O-Ag-O bridging bonds to form a 3D network. It represents an unprecedented linking mode between the isopolyoxomolybdate chain and the transition metal oxide cluster. IR, TGA and fluorescence properties of the title compound are also studied.展开更多
A novel open-framework vanadium(W) phosphate(H_3NCH_2CH_2NH_3)_3[(VO)_4(PP_4)_2(HPO_4)_4] (short for V_2P_3-en) has been prepared. It issynthesized hydrothermally in the presence of ethylenediamine (en) at 170 deg C f...A novel open-framework vanadium(W) phosphate(H_3NCH_2CH_2NH_3)_3[(VO)_4(PP_4)_2(HPO_4)_4] (short for V_2P_3-en) has been prepared. It issynthesized hydrothermally in the presence of ethylenediamine (en) at 170 deg C for 5 days byself-assembly from structurally simple precursors V_2O_5, H_3PO_4 and H_2O. The compound ischaracterized by means of Fourier transform-infrared spectroscopy (FT-IR),Thermogravimetry-differential thermal analysis (TG-DTA), X-ray powder diffraction analysis (XRD) andScanning electron microscopy (SEM). Furthermore, the composition-structure-thermal stabilityrelation of V_2P_3-en is explored in terms of crystal chemistry, and the potential approach to theenhancement of its thermal stability is proposed.展开更多
Using n-propylamine as a template,deioned water and secondary-butanol(butan-2-ol)as solvents,a three-dimensional(3D)open-framework aluminophosphate[C_(3)NH_(10)]·[HA_(13)P_(3)O_(13)](1)and a two-dimensional layer...Using n-propylamine as a template,deioned water and secondary-butanol(butan-2-ol)as solvents,a three-dimensional(3D)open-framework aluminophosphate[C_(3)NH_(10)]·[HA_(13)P_(3)O_(13)](1)and a two-dimensional layered aluminophosphate[C_(3)NH_(10)]_(3)·[A_(13)P_(4)O_(16)](2)were crystallized from the initial mixtures with compositions of Al_(2)O_(3):2.4 P_(2)O_(5):5.0 n-propylamine:100 H_(2)O/butan-2-ol,respectively.They are characterized by X-ray powder diffraction(XRD),thermogravimetric(TG),and elemental(CHN)analyses and structurally determined by single-crystal X-ray diffraction analysis.Compound 1 crystallizes in the monoclinic space group P2_(1)/c with a=0.85831(13)nm,b=1.7677(3)nm,c=1.04353(12)nm,=123.887(9)°,and V=1.3143(3)nm3.Compound 2 crystallizes in the monoclinic space group P2_(1)/c with a=1.1313(2)nm,b=1.4874(3)nm,c=1.8020(6)nm,=125.07(2)°,and V=2.4817(11)nm^(3).The results show that the properties of solvent have a significant influence on the structure-directing effect of n-propylamine in the crystallization of the open-framework aluminophosphates.展开更多
Employing 4,4＇-trimethylenedipyridine as a template, a new two-dimensional zinc phosphite （4,4＇-（CsH4N）2（CH2）3）＂ [Zna（HPO3）4] has been prepared at room temperature and characterized by single-crystal X-ray ...Employing 4,4＇-trimethylenedipyridine as a template, a new two-dimensional zinc phosphite （4,4＇-（CsH4N）2（CH2）3）＂ [Zna（HPO3）4] has been prepared at room temperature and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The compound crystallizes in the monoclinic space group P21/c, with cell parameters, a = 9.3309（19）/k, b = 14.798（3）A, c = 33.637（7）/k, β= 91.11（3）°, V = 4643.8（16） nm3 and Z = 4. The connectivity of the ZnO4 tetrahedra and HPO3 pseudo pyramids results in infinite corner-sharing 4-membered ring chains as second building units which are further linked by Zn-O-P bonds to form a 2-D layer that with interesting 8-membered ring channels along the [100] direction. The diprotonated 4,4＇-trimethylenedipyridine molecules sit in the middle of the layers along the [100] direction and interact with the framework via hydrogen bonds.展开更多
The database of open-framework aluminophosphate(AlPO) syntheses has been established,which includes about 1600 synthetic records.Data analysis has been done on the basis of the framework composition,structure dimensio...The database of open-framework aluminophosphate(AlPO) syntheses has been established,which includes about 1600 synthetic records.Data analysis has been done on the basis of the framework composition,structure dimension,pore ring,and organic template.This database will serve as useful guidance for the rational synthesis of microporous functional materials.展开更多
The open-framework iron phosphate IIIII21.543FeFe(PO) was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized...The open-framework iron phosphate IIIII21.543FeFe(PO) was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized in the triclinic, space group P1with a=0.64724(4) nm, b=0.79651(6) nm, c=0.94229(5) nm, =104.447(2)? =108.919(4)? =101.741(4)? V=0.42302(5) nm3, Z=1 and R1 (wR2)=0.0307 (0.0793). Crystal data were collected on a Rigaku R-AXIS RAPID IP diffractometer with Mo K?(=0.071073 nm) at 293(2) K in the range of 2.43埃迹?7.46? The structure of 1 consists of 19 non-hydrogen atoms including three and a half crystallographically in-dependent Fe and three P atoms. Fe(1) connects its symmetrical Fe(1A) through bridging oxygen forming a dimer and the dimers are connected by Fe(4) forming an infinite staircase-like chain. Fe(2) and Fe(3) connect the infinite chains into a layer with bridging oxygen. Layers are interconnected via Fe(4) forming the six-membered and eight-membered channel systems.展开更多
To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis,two new lanthanum phosphite-oxalates with 3D...To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis,two new lanthanum phosphite-oxalates with 3D frameworks,designated as[La(HPO_(3))(C_(2)O_(4))0.5(H_(2)O)_(2)](La‑1)and(C_(6)H_(16)N_(2))(H_(3)O)[La_(2)(H_(2)PO_(3))_(3)(C_(2)O_(4))_(3)(H_(2)O)](La‑2)(C_(6)H_(14)N_(2)=cis-2,6-dimethylpiperazine),were prepared by hydrothermal and solvothermal conduction,respectively.La‑1 was constructed with lanthanum phosphite 2D layers and C_(2)O_(4)^(2-)groups,whereas La‑2 was constructed with lanthanum oxalate 2D layers and H_(2)PO^(3-)groups.Alternating current(AC)impedance spectra indicate that the pro-ton conductivities of both compounds could reach 10^(-4)S·cm^(-1)and remain highly durable at 75℃and 98%of rela-tive humidity(RH).Due to the abundance of H-bonds in La‑2,theσof La‑2 was higher than that of La‑1.La‑1 exhibited excellent water and pH stability.CCDC:2439965,La‑1;443776,La‑2.展开更多
随着数字经济的快速发展,对三维重建技术的需求显著增加。然而,现有商用三维重建系统多依赖于封闭的单机或集群架构,导致灵活性和效率受限,而开源框架在绝对坐标和尺度恢复方面存在不足。对此,提出了一种基于GCP(Ground Control Point)...随着数字经济的快速发展,对三维重建技术的需求显著增加。然而,现有商用三维重建系统多依赖于封闭的单机或集群架构,导致灵活性和效率受限,而开源框架在绝对坐标和尺度恢复方面存在不足。对此,提出了一种基于GCP(Ground Control Point)辅助的Colmap框架中的SFM(Structure from Motion)算法。该算法通过构建残差方程、应用相似变换和全局光束法平差,将Colmap中SFM的自由网结果精确转换为绝对坐标。实验结果表明,该方法在计算精度上与商用系统Agisoft和大疆智图相当,且在尺度恢复上保持了较高的计算效率。所提方法不仅提升了开源三维重建系统的绝对尺度恢复能力,还为未来云端应用和大规模数据处理提供了理论和实践基础。未来将致力于实现全流程自动化三维重建的云架构,并探讨与物联网设备在三维监管中的应用前景。展开更多
基金financial supports provided by the Natural Science Foundation of Fujian Province(No.2024J01195)the National Nature Science Foundation of China(No.21905279)+1 种基金Sanming University(Nos.22YG11 and PYT2201)the Education Scientific Research Project of Youth Teachers in the Education Department of Fujian Province(No.JAT220351).
文摘Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.
基金We thank the national Natural Science Foundation(No.20173017)of ChinaState Key Basic Program(No.G2000048)for financial support.
文摘An open-framework ammonium ferricborophosphate compound was synthesized by mild hydrothermal condition at 110C. The crystal structure has been determined by single-crystal X-ray diffraction analysis: hexagonal, P6522, a = 9.452(2) , c = 15.698(5) , a = 90, g = 120, Z = 6, Mr = 310.58, V = 1214.0(5) 3, Dc = 2.549 g/cm3, m = 2.311mm-1, F(000) = 930. The chiral tetrahedral-tetrahedral helical ribbons are linked by the mixed valance FeII/FeIIIO6 coordinated octahedra. The ammonium ions are located inside the free loop of helical ribbons close to the inner wall of the helical channels1{[BP2O8]3-}, effecting on balancing charge and stabilizing helical ribbons.
基金The project was supported by the National Natural Science Foundation of China (20171012) and the Natural Science Foundation of Fujian Province, China (E0110010).
文摘A novel 3-D inorganic bimetallic compound Ag2Mo2O7 has been hydrothermally synthesized and structurally characterized by X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 6.1274（3）, b = 13.1836（6）, c = 7.8780（3）A, β= 110.673（3）°, V = 595.42（5）A3, Z= 4, Mr= 519.62, Dc = 5.797g/cm^3, F（000） = 936,μ（MoKα） = 10.579 mm^-1, F（000） = 936, the final R = 0.0204 and wR = 0.0477 for 1268 observed reflections with I〉 2σ（I）. In the title compound, the [Mo4O16]n^8n-chains are linked through O-Ag-O bridging bonds to form a 3D network. It represents an unprecedented linking mode between the isopolyoxomolybdate chain and the transition metal oxide cluster. IR, TGA and fluorescence properties of the title compound are also studied.
基金This research was kindly supported by the Research Fund for the Doctoral Program of Higher Education (RFDP) and the OpeningFou
文摘A novel open-framework vanadium(W) phosphate(H_3NCH_2CH_2NH_3)_3[(VO)_4(PP_4)_2(HPO_4)_4] (short for V_2P_3-en) has been prepared. It issynthesized hydrothermally in the presence of ethylenediamine (en) at 170 deg C for 5 days byself-assembly from structurally simple precursors V_2O_5, H_3PO_4 and H_2O. The compound ischaracterized by means of Fourier transform-infrared spectroscopy (FT-IR),Thermogravimetry-differential thermal analysis (TG-DTA), X-ray powder diffraction analysis (XRD) andScanning electron microscopy (SEM). Furthermore, the composition-structure-thermal stabilityrelation of V_2P_3-en is explored in terms of crystal chemistry, and the potential approach to theenhancement of its thermal stability is proposed.
基金supported by the National Natural Science Foundation of China(21171063)the Excellent Young Scientists Fund(21222103)+1 种基金the National Basic Research Program of China(2011CB808-703)the Specialized Research Fund for the Doctoral Program of Higher Education
文摘Using n-propylamine as a template,deioned water and secondary-butanol(butan-2-ol)as solvents,a three-dimensional(3D)open-framework aluminophosphate[C_(3)NH_(10)]·[HA_(13)P_(3)O_(13)](1)and a two-dimensional layered aluminophosphate[C_(3)NH_(10)]_(3)·[A_(13)P_(4)O_(16)](2)were crystallized from the initial mixtures with compositions of Al_(2)O_(3):2.4 P_(2)O_(5):5.0 n-propylamine:100 H_(2)O/butan-2-ol,respectively.They are characterized by X-ray powder diffraction(XRD),thermogravimetric(TG),and elemental(CHN)analyses and structurally determined by single-crystal X-ray diffraction analysis.Compound 1 crystallizes in the monoclinic space group P2_(1)/c with a=0.85831(13)nm,b=1.7677(3)nm,c=1.04353(12)nm,=123.887(9)°,and V=1.3143(3)nm3.Compound 2 crystallizes in the monoclinic space group P2_(1)/c with a=1.1313(2)nm,b=1.4874(3)nm,c=1.8020(6)nm,=125.07(2)°,and V=2.4817(11)nm^(3).The results show that the properties of solvent have a significant influence on the structure-directing effect of n-propylamine in the crystallization of the open-framework aluminophosphates.
基金supported by the National Natural Science Foundation of China (20701023 & 20971076)the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry (2010-17)the Natural Science Foundation of Shandong Province,China (BS2010NJ004 & 2009ZRB019KH)
文摘Employing 4,4＇-trimethylenedipyridine as a template, a new two-dimensional zinc phosphite （4,4＇-（CsH4N）2（CH2）3）＂ [Zna（HPO3）4] has been prepared at room temperature and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The compound crystallizes in the monoclinic space group P21/c, with cell parameters, a = 9.3309（19）/k, b = 14.798（3）A, c = 33.637（7）/k, β= 91.11（3）°, V = 4643.8（16） nm3 and Z = 4. The connectivity of the ZnO4 tetrahedra and HPO3 pseudo pyramids results in infinite corner-sharing 4-membered ring chains as second building units which are further linked by Zn-O-P bonds to form a 2-D layer that with interesting 8-membered ring channels along the [100] direction. The diprotonated 4,4＇-trimethylenedipyridine molecules sit in the middle of the layers along the [100] direction and interact with the framework via hydrogen bonds.
基金Supported by the National Natural Science Foundation of China (Grant No. 20871051)the State Basic Research Project of China (2006CB806103)the Major International Joint Research Project of China (20720102039)
文摘The database of open-framework aluminophosphate(AlPO) syntheses has been established,which includes about 1600 synthetic records.Data analysis has been done on the basis of the framework composition,structure dimension,pore ring,and organic template.This database will serve as useful guidance for the rational synthesis of microporous functional materials.
基金the National Natural Science Foundation of China (No. 20171010).
文摘The open-framework iron phosphate IIIII21.543FeFe(PO) was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized in the triclinic, space group P1with a=0.64724(4) nm, b=0.79651(6) nm, c=0.94229(5) nm, =104.447(2)? =108.919(4)? =101.741(4)? V=0.42302(5) nm3, Z=1 and R1 (wR2)=0.0307 (0.0793). Crystal data were collected on a Rigaku R-AXIS RAPID IP diffractometer with Mo K?(=0.071073 nm) at 293(2) K in the range of 2.43埃迹?7.46? The structure of 1 consists of 19 non-hydrogen atoms including three and a half crystallographically in-dependent Fe and three P atoms. Fe(1) connects its symmetrical Fe(1A) through bridging oxygen forming a dimer and the dimers are connected by Fe(4) forming an infinite staircase-like chain. Fe(2) and Fe(3) connect the infinite chains into a layer with bridging oxygen. Layers are interconnected via Fe(4) forming the six-membered and eight-membered channel systems.
文摘To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis,two new lanthanum phosphite-oxalates with 3D frameworks,designated as[La(HPO_(3))(C_(2)O_(4))0.5(H_(2)O)_(2)](La‑1)and(C_(6)H_(16)N_(2))(H_(3)O)[La_(2)(H_(2)PO_(3))_(3)(C_(2)O_(4))_(3)(H_(2)O)](La‑2)(C_(6)H_(14)N_(2)=cis-2,6-dimethylpiperazine),were prepared by hydrothermal and solvothermal conduction,respectively.La‑1 was constructed with lanthanum phosphite 2D layers and C_(2)O_(4)^(2-)groups,whereas La‑2 was constructed with lanthanum oxalate 2D layers and H_(2)PO^(3-)groups.Alternating current(AC)impedance spectra indicate that the pro-ton conductivities of both compounds could reach 10^(-4)S·cm^(-1)and remain highly durable at 75℃and 98%of rela-tive humidity(RH).Due to the abundance of H-bonds in La‑2,theσof La‑2 was higher than that of La‑1.La‑1 exhibited excellent water and pH stability.CCDC:2439965,La‑1;443776,La‑2.
文摘随着数字经济的快速发展,对三维重建技术的需求显著增加。然而,现有商用三维重建系统多依赖于封闭的单机或集群架构,导致灵活性和效率受限,而开源框架在绝对坐标和尺度恢复方面存在不足。对此,提出了一种基于GCP(Ground Control Point)辅助的Colmap框架中的SFM(Structure from Motion)算法。该算法通过构建残差方程、应用相似变换和全局光束法平差,将Colmap中SFM的自由网结果精确转换为绝对坐标。实验结果表明,该方法在计算精度上与商用系统Agisoft和大疆智图相当,且在尺度恢复上保持了较高的计算效率。所提方法不仅提升了开源三维重建系统的绝对尺度恢复能力,还为未来云端应用和大规模数据处理提供了理论和实践基础。未来将致力于实现全流程自动化三维重建的云架构,并探讨与物联网设备在三维监管中的应用前景。
