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
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
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
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.
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.
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.
