INORGANIC CHEMISTRY
·
2020
·
IF 4.825
Xuehua Dong,Ying Long,Xiaoyu Zhao,Ling Huang,Hongmei Zeng,Zhien Lin,Xin Wang,Guohong Zou
Two new antimony fluoride sulfates named A6Sb4F12(SO4)3 (A = Rb, Cs) with unique crown-like clusters have been successfully synthesized by introducing Sb3+ with a stereochemically active lone pair in the sulfate system through a facile hydrothermal method. The structure regulation induced by the cation sizes results in the symmetry difference in these two title compounds, i.e., Rb6Sb4F12(SO4)3 crystallizing in the polar noncentrosymmetric (NCS) space group of P3 and Cs6Sb4F12(SO4)3 in the centrosymmetric (CS) space group of P1̅. Detailed characterizations, including XRD, thermal behaviors, optical properties, and the theoretical calculations, for these two compounds have been performed. The discovery of the unique crown-like clusters observed in A6Sb4F12(SO4)3 (A = Rb, Cs) enriches the diversity of structures for antimony sulfates systems. Simultaneously, a summary and comparison for all reported antimony halide sulfates has been made to illustrate the synergistic effect of the stoichiometric ratio and cation sizes on the macroscopic centricity and the framework structure, which will guide the systematical discovery of antimony(III)-based functional materials in future.
研究领域:
无机化学
·
材料科学
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INORGANIC CHEMISTRY
·
2019
·
IF 4.85
Ya-Ping Gong,Yun-Xiang Ma,Shao-Ming Ying,Jiang-Gao Mao,Fang Kong
Two new indium sulfate tellurites, namely, In2(SO4)(TeO3)(OH)2(H2O) and In3(SO4)(TeO3)2F3(H2O), were synthesized by hydrothermal method in a one-pot reaction. Their pure phase yields have been successfully optimized to 76% and 21%, respectively. In2(SO4)(TeO3)(OH)2(H2O) crystallized in centrosymmetric (CS) space group P21/n, while In3(SO4)(TeO3)2F3(H2O) formed a non-centrosymmetric (NCS) and chiral space group P212121. The CS compound features a 2D layered structure composed of 2D indium oxide layers decorated by sulfate tetrahedra and tellurite groups. The NCS compound displays a 3D network consisting of indium tellurite layers bridged by sulfate tetrahedra. Powder second harmonic generation measurements disclosed that In3(SO4)(TeO3)2F3(H2O) exhibits a weak frequency-doubling efficiency about 11% of the commercial KDP. Its powder laser damage threshold quantity was estimated to be 79.6 MW/cm2, which is about 36 times that of AGS. The two samples present wide optical band gaps of 4.86 and 4.10 eV, respectively, which were determined by Te, In, and O atoms based on density functional theory calculations.
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高影响因子
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
·
2021
·Vol. 647
·期 12
·1269-1276
·
IF 1.492
Jiayuan Zhang,Xiao Zhao,Yuandong Wu,Dajiang Mei,Shaoguo Wen,Thomas Doert
Two new antimony (III) tellurite sulfates [Sb 2 (TeO 4 )](SO 4 ) ( 1 ) and [Sb 2 (TeO 3 ) 2 ](SO 4 ) ( 2 ) were successfully synthesized through a conventional hydrothermal method and their crystal structures were determined by X-ray single crystal analysis. [Sb 2 (TeO 4 )](SO 4 ) crystallizes in the triclinic space group P ī (No. 2) with lattice parameters a=5.572(2), b=7.247(2), c=9.540(3) Å, V=358.5(2) Å 3 , and Z=2, while [Sb 2 (TeO 3 ) 2 ](SO 4 ) crystallizes in the orthorhombic space group Pbca (No. 61) with lattice parameters a=7.368(2), b=14.571(3), c=16.521(3) Å, V=1773.7(6) Å 3 , and Z=8. The structure of [Sb 2 (TeO 4 )](SO 4 ) features a three-dimensional framework, composed of [SbO 4 ] trigonal bipyramids and [TeO 4 ] polyhedra to form a cationic 2 ∞[Sb 2 (TeO 4 )] 2+ corrugated cationic layers along [100], linked by SO 4 2− anions. [Sb 2 (TeO 3 ) 2 ](SO 4 ) forms a three-dimensional framework consisting of two dimensional wrinkled layers of 2 ∞[Sb 2 (TeO 3 ) 2 ] 2+ that are linked by SO 4 2− anions. The band gaps of 4.16 eV and 3.72 eV for [Sb 2 (TeO 4 )](SO 4 ) and [Sb 2 (TeO 3 ) 2 ](SO 4 ) respectively are estimated from the solid state UV-vis-NIR diffuse reflectance spectra. Thermal analysis indicated that both compounds are thermally stable up to about 500 °C. The electrochemical specific capacity of [Sb 2 (TeO 4 )](SO 4 ) was determined to 245 mA h g −1 on the first cycle in a Li-ion half-cell, the capacity remains at about 106 mA h g −1 after 500 cycles.
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ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
·
2019
·Vol. 645
·期 10
·745-751
·
IF 1.337
Xiaofang Li,Yuandong Wu,Dajiang Mei,Thomas Doert
Three new alkali metal transition metal sulfate-oxalates, RbFe(SO 4 )(C 2 O 4 ) 0.5 · H 2 O and Cs M (SO 4 )(C 2 O 4 ) 0.5 · H 2 O ( M = Mn, Fe) were prepared through hydrothermal reactions and characterized by single-crystal X-ray diffraction, solid state UV/Vis/NIR diffuse reflectance spectroscopy, infrared spectra, thermogravimetric analysis, and powder X-ray diffraction. The title compounds all crystallize in the monoclinic space group P 2 1 / c (no. 14) with lattice parameters: a = 7.9193(5), b = 9.4907(6), c = 8.8090(6) Å, β = 95.180(2)°, Z = 4 for RbFe(SO 4 )(C 2 O 4 ) 0.5 · H 2 O; a = 8.0654(11), b = 9.6103(13), c = 9.2189(13) Å, β = 94.564(4)°, Z = 4 for CsMn(SO 4 )(C 2 O 4 ) 0.5 · H 2 O; and a = 7.9377(3), b = 9.5757(4), c = 9.1474(4) Å, β = 96.1040(10)°, Z = 4 for CsFe(SO 4 )(C 2 O 4 ) 0.5 · H 2 O. All compounds exhibit three-dimensional frameworks composed of [ M O 6 ] octahedra, [SO 4 ] 2– tetrahedra, and [C 2 O 4 ] 2– anions. The alkali cations are located in one-dimensional tunnels.
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JOURNAL OF SOLID STATE CHEMISTRY
·
2024
·
IF 3.2
Wencheng Lu,Yaoguo Shen,Qiong Wu
The SO 4 tetrahedral group exhibits a low degree of polarization anisotropy, leading to a minimal level of birefringence of sulfates. Our report introduces a novel sulfate compound, RbY(SO 4 ) 2 ·4H 2 O, which exhibits exceptional birefringence in deep ultraviolet sulfates. This crystal possesses dimensions of 6 mm × 4 mm × 1 mm and was synthesized using a straightforward technique involving the evaporation of an aqueous solution. The structure of this substance is characterized by a unique arrangement of SO 4 tetrahedra YO 9 polyhedra, and H 2 O molecules. Each SO 4 moiety contribution two oxygen atoms to share edges with a neighboring YO 9 polyhedron, resulting in significant deformation of these groups. The unique arrangement of edge-sharing arrangement in RbY(SO 4 ) 2 ·4H 2 O results in a birefringence of about 0.045@546 nm. This sets a new record for sulfates in the deep ultraviolet range that have similar non-π-conjugated anionic groups. We elucidate UV–Vis–NIR diffuse-reflection, IR spectra, transmission spectra, and conduct theoretical calculations. These fascinating discoveries will improve our understanding of sulfates and provide valuable insights for studying deep-UV sulfates with strong birefringence.
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JOURNAL OF SOLID STATE CHEMISTRY
·
2018
·
IF 2.179
Ting-Ting Ruan,Wen-Wen Wang,Chun-Li Hu,Xiang Xu,Jiang-Gao Mao
Two new lead(II) borate-sulfate mixed-anion compounds, namely, Pb 4 (BO 3 ) 2 (SO 4 ) and Pb 2 [(BO 2 )(OH)](SO 4 ), have been prepared by using high-temperature melt method or hydrothermal reaction . These compounds exhibit two different types of 3D structures composed of the same anionic units of BO 3 triangles and SO 4 tetrahedra which are interconnected by lead(II) cations. In Pb 4 (BO 3 ) 2 (SO 4 ), the lead(II) ions are bridged by borate anions into 3D [Pb 4 (BO 3 ) 2 ] 2+ architectures with 1D tunnels of 8-member rings along the a -axis, which are filled by the sulfate anions. In Pb 2 [(BO 2 )(OH)](SO 4 ), the lead(II) ions are interconnected by borate and sulfate anions into 2D Pb-B-O and Pb-S-O layers parallel to the ab plane, respectively, and these layers are further condensed into the 3D lead(II) borate-sulfate framework. TGA and DSC studies indicate that Pb 4 (BO 3 ) 2 (SO 4 ) is congruently melting with a melting point of 689 °C whereas Pb 2 [(BO 2 )(OH)](SO 4 ) decomposes at approximately 335 °C. UV/Vis/NIR optical diffuse reflectance spectrum measurements reveal the optical band gaps of 4.03 and 4.08 eV for Pb 4 (BO 3 ) 2 (SO 4 ) and Pb 2 [(BO 2 )(OH)](SO 4 ), respectively. Furthermore, the electronic structures of Pb 4 (BO 3 ) 2 (SO 4 ) have also been calculated.
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高影响因子
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
·
2020
·Vol. 646
·期 20
·1688-1695
·
IF 1.24
Shuangsheng Cheng,YuanDong Wu,Dajiang Mei,Shaoguo Wen,Thomas Doert
Four alkali metal bismuth sulfates, NaBi(SO 4 ) 2 · H 2 O ( 1 ) and ABi(SO 4 ) 2 [A = K ( 2 ), Rb ( 3 ), Cs ( 4 )], were successfully synthesized by hydrothermal methods. The crystal structure of 1 features a three-dimensional tunnel framework constructed by BiO 9 tri-capped trigonal prisms and SO 4 tetrahedra interconnected via common corners and edges. Compound 2 exhibits a two-dimensional 2 ∞ [Bi(SO 4 ) 2 ] – double-layered structure, assembled by one-dimensional 1 ∞ [BiS(1)O 4 ] + chains which are linked via S(2)O 4 2– tetrahedra. The isostructural compounds 3 and 4 possess a two-dimensional layered structure, and the layers being composed by BiO 8 square antiprism and SO 4 tetrahedra. The alkali metal cations are located between the layers or in the tunnels of the structures, respectively. The differences in the crystal structures of the title compounds can mainly be attributed to the different sizes of the alkali metal cations and their different coordination environments. Thermogravimetric analysis evidence that compound 1 losses one equivalent of water at 120 °C whereas the anhydrous compounds 2 – 4 are stable up to about 450, 575, and 578 °C, respectively. The solid-state UV/Vis/NIR diffuse reflectance spectra indicate bandgaps of approximately 4.48, 4.43, 3.98, and 3.96 eV for compounds 1 – 4 , respectively.
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Catalysts
·
2020
·Vol. 10
·期 4
·384
·
IF 3.52
Pei Yu,Can Chen,Guangci Li,Zhong Wang,Xuebing Li
The esterification of malic acid using traditional homogenous catalysts suffers from the difficulty in reuse of the catalyst and undesirable side reactions. In this work, Zr(SO4)2/SiO2and Zr(SO4)2/activated carbon (AC) as solid acid catalysts were prepared for malic acid esterification with methanol. The conversion of malic acid over these two catalysts is comparable to that over H2SO4and unsupported Zr(SO4)2∙4H2O catalysts; however; a 99% selectivity of dimethyl malate can be realized on these two supported catalysts, which is much higher than that of conventional H2SO4(75%) and unsupported Zr(SO4)2∙4H2O (80%) catalysts, highlighting the critical role of AC and SiO2supports in tuning the selectivity. We suggest that the surface hydroxyls of AC or lattice O2−ions from SiO2donate electrons to Zr4+in Zr(SO4)2/AC and Zr(SO4)2/SiO2catalysts, which results in the increase in electron density on Zr4+. The enhanced electron density on Zr4+reduces the degree of H delocalization from crystal water and then decreases the Brønsted acid strength. Consequently, the reduced Brønsted acid strength of Zr(SO4)2/AC and Zr(SO4)2/SiO2catalysts suppresses the intermolecular dehydration side reaction. In addition, these two supported catalysts can be easily separated from the reaction system by simple filtration with almost no loss of activity.Keywords:malic acid;catalytic esterification;solid acid catalyst;Zr(SO4)2;intermolecular dehydration
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SOLID STATE SCIENCES
·
2015
·
IF 1.839
Xiao Zhao,Dajiang Mei,Jingli Xu,Yuandong Wu
The reactions of A 2 SO 4 ( A = K, Cs) and Sb 2 O 3 with H 2 SO 4 (98%) yielded single crystals of A Sb(SO 4 ) 2 ( A = K, Cs). The crystal structures were investigated by single crystal X-ray diffraction. KSb(SO 4 ) 2 crystallizes in the monoclinic space group P 2 1 / c (No. 14) with lattice parameters a = 10.6745(18), b = 7.1579(12), c = 8.7597(15) Å, β = 91.466(3) ° , V = 669.1(2) Å 3 , Z = 4. CsSb(SO 4 ) 2 crystallizes in the orthorhombic space group P 2 1 2 1 2 1 (No.19) with lattice parameters of a = 5.2429(8), b = 9.5942(16), c = 14.850(2) Å, V = 746.98(20) Å 3 , Z = 4. Both compounds show the Sb 3+ cations in same seesaw-type coordination of oxygen atoms from different SO 4 2 − anions, but exhibit complex two-dimensionally and one-dimensionally linked anionic structures. The alkali cations are located between the layers or chains. The compounds were characterized with FT-IR spectra and solid state UV–vis–NIR diffuse reflectance spectroscopy . The band gaps were estimated at 4.64 eV for KSb(SO 4 ) 2 and 4.68 eV for CsSb(SO 4 ) 2 .
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CHEMICAL ENGINEERING JOURNAL
·
2019
·
IF 8.355
Tiezheng Niu,Junzhuo Cai,Penghui Shi,Guohua Zhao
Sulfate-based electrochemical advanced oxidation is of rising importance for pollutant removal , however, adscititious sulfate has adverse effects on water salinity . A novel electrochemical system which could exploit the existed SO 4 2− for in situ generation of SO 4 − was successfully constructed with boron doped diamond (BDD) anode and hierarchical 1D Co 3 O 4 nanowire array cathode. The in situ electrochemical electron paramagnetic spectroscopy and titration were used to study the positive correlation between the increase of sulfate radicals (SRs) and the efficient activation of peroxydisulfate (PDS) by hierarchical 1D Co 3 O 4 nanowire array cathode. Electrochemical impedance and X-ray photoelectron spectroscopy revealed that the efficient activation of PDS by the Co 3 O 4 cathode was derived from the excellent electron transport capability of the 1D nanostructure , and the electric field accelerates the reduction of Co(III). The novel hierarchical 1D Co 3 O 4 nanowire array cathode can completely degrade dibutyl phthalate in 45% less time with 38% less energy compared to a traditional graphite cathode without the requirement of extra chemicals. The possible mechanism of anodic PDS accumulation and cathodic SRs generation was firstly revealed, and this advanced electrochemical oxidation system provides a good reference for the in situ sustainable remediation in sulfate-containing water.
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高影响因子
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
·
2014
·
IF 1.251
Fengting Chen,Jiachang Zhao,Jingli Xu,Yuandong Wu
The hetero-bimetallic polyanionic compound BiCu 2 (TeO 3 )(SO 4 )(OH) 3 was synthesized using hydrothermal techniques. Single-crystal X-ray diffraction analysis revealed that title compound crystallizes in the monoclinic space group P 2 1 / n (No. 14) with lattice parameters a = 9.5513(15), b = 6.3022(10), c = 13.955(2) Å, β = 102.845(3)°, and Z = 4. The structure of title compound is a three-dimensional tunnel framework consisting of edge-sharing two-dimensional [Cu 3 O 10 ] 14– layers linked by BiO 8 bicapped trigonal prisms, TeO 3 2– trigonal pyramids and SO 4 2– tetrahedra. Along [010], each Cu(1)O 6 octahedron shares two edges with adjacent Cu(1)O 6 units to form infinite one-dimensional zigzag chains, which are connected by double inverted Cu(2)O 6 octahedral units via edge sharing (O9 ··· O8). The suitability of crystal for optical applications was investigated by UV/Vis/NIR spectroscopy. Raman and FTIR spectra were used to confirm the presence of various functional groups such as TeO 3 2– , SO 4 2– , OH – in the crystals.
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CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2020
·
IF 2.627
Jiyuan Li,Mifen Cui,Zhuxiu Zhang,Xian Chen,Qing Liu,Zhaoyang Fei,Jihai Tang,Xu Qiao
Isooctane attracts great interest in recent years because of its promising potential as friendly-environmental gasoline, which is obtained by dimerization of isobutene with a hydrogenation step. Herein, a solid acid catalyst sulfated zirconia modified by ZnO was prepared. The oligomerization of isobutene had been investigated over ZrO 2 -SO 4 and ZnO( X )/ZrO 2 -SO 4 catalyst in order to find efficient catalysts for the production of isobutene oligomers . The presence of ZnO obviously enhanced the dimerization of isobutene and ZnO( X )/ZrO 2 -SO 4 exhibited the highest di-isobutene yield of 60%. Kinetic studies showed the higher trimerization-to-dimerization activation energy ratios of ZnO( X )/ZrO 2 -SO 4 than those of ZrO 2 -SO 4 from 353 to 393 K. In addition, reaction rate of dimerization was higher than trimerization over ZnO( X )/ZrO 2 -SO 4 . The high L/B ratio manifested the capability to enhance the selectivity of C 8 in isobutene dimerization. Furthermore, ZnO( X )/ZrO 2 -SO 4 exhibited stable conversion for the dimerization of isobutene.
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