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  • Investigation on the Influence of Fold Conformation on PLLA Lamellar Splaying by Film Crystallization in Supercritical CO2
    CrystEngComm (IF 3.382) Pub Date : 2020-01-15
    Lei Zhang; Guoqun Zhao; Guilong Wang

    Lamellar splaying is an important non-crystallographic branching phenomenon in the polymer spherulite growth. The common cognition on the origin of lamellar splaying is attributed to the repulsive action caused by cilia, but the recent researches using solid nuclear magnetic resonance indicate that there are no cilia in the amorphous phase between adjacent lamellae. In order to further understand the origination of lamellar splaying, we reported a method to prepare Poly(L-lactic acid) (PLLA) multilayer lamellae by film isothermal crystallization from melt state in supercritical CO2. We obtained the screw terrace crystals with three different surface amorphous conformations assembled from three PLLA samples with different molecular weights. According to the characterizations results of atomic force microscopy, transmission electron microscopy, nuclear magnetic resonance and X-ray diffraction, three kind of intercrystalline phases were determined as no-fold, tight fold, and loose fold, respectively. It was further found that the no-fold and tight fold rarely contribute to lamellar splaying of PLLA, but the loose fold on lamellar surface obviously contributes to lamellar splaying of PLLA. Furthermore, the molecular weight dependence and film thickness dependence of PLLA crystal form indicated that loose fold may be caused by the limit of in-plane entanglements in the lamellar thickening growth.

    更新日期:2020-01-15
  • An organic–inorganic hybrid ferroelectric with strong luminescence and high Curie temperature
    CrystEngComm (IF 3.382) Pub Date : 2020-01-15
    Hanmei Fu; Chunli Jiang; Jie Lao; Chunhua Luo; Hechun Lin; Hui Peng; Chun-Gang Duan

    Coexistence of ferroelectricity and luminescence in a material makes it a very interesting multifunctional material for fabricating new optoelectronic devices. As a single-component system with flexibility and structure tunability, the organic-inorganic hybrid luminescent ferroelectrics are more attractive than the previous reported rare-earth-doped ones. We herein report a new organic-inorganic hybrid ferroelectric, (C10H16N)2MnBr4, which exhibits ferroelectricity with Curie temperature of 421 K and green-light emission with a high photoluminescence quantum yield (PL QY) of 88.52%. Furthermore, it shows excellent film-forming ability. The thin film with high quality can be easily prepared by spin-coating method. These advantages endows it great potential application in optoelectronic devices.

    更新日期:2020-01-15
  • Switching-on Superparamagnetism in diluted magnetic Fe (Ⅲ) doped CdSe Quantum Dots
    CrystEngComm (IF 3.382) Pub Date : 2020-01-15
    Amar Nath Yadav; Jasleen K. Bindra; Narendra Jakhar; Kedar Singh

    Chemically prepared 0.5% iron (Fe) doped CdSe (Fe: CdSe) quantum dots (QDs) are isolated as ~3 nm in the diameter with a wurtzite crystal structure. The oxidation state of Fe was confirmed by electron paramagnetic resonance (EPR) spectroscopy, from which it is evident that iron is in Fe+3 oxidation state. Magnetic properties of Fe: CdSe QDs explored by superconducting quantum interference device (SQUID), reveal multiple magnetic transitions. DC magnetic susceptibility plot shows low-temperature antiferromagnetism (AFM) transition observed below 25 K and followed by another event occurring between 25 and ~80 K. Further, the material shows superparamagnetic behaviour with a weak ferromagnetic exchange interaction as observed by field-dependent magnetization. At lowest dopant concentration, we do not expect dopants to cluster or to form inclusions. Therefore, the observed magnetic behaviour is believed to be arising from the random substitution of the dopant ions and their magnetic exchange interaction with CdSe host lattice.

    更新日期:2020-01-15
  • Characteristics and performance of rutile/anatase/brookite TiO2 or TiO2-Ti2O3(H2O)2(C2O4)·H2O multiphase mixed crystal for catalytic degradation of emerging contaminants
    CrystEngComm (IF 3.382) Pub Date : 2020-01-15
    Kangkai Hu; Lei E; Dan Zhao; Yajing Li; Wei Zhao; Hui Rong

    Rutile TiO2 or binary/ternary/quaternary TiO2-Ti2O3(H2O)2(C2O4)·H2O mixed crystal, possessing self-assembly morphology and serving as a catalyst for photocatalysis degradation of organic pollutants or photoanode for photoelectrochemical (PEC) water splitting, are prepared by in-site growth through changing the concentration of potassium titanyl oxalate. The rutile/anatase TiO2 with mesoporous structure has a specific surface area of 27.896 m2 g-1 and an average pore size of 3.411 nm. The sample has a relatively more regular self-assembly morphology after heat-treated at different temperatures, however its photocatalytic activity is reduced. Excellent catalytic oxidation of methyl orange (MO) and hydroxylbenzoic acid (HBA) is observed on the as-synthesized samples, wherein rutile/anatase TiO2 and rutile/anatase/brookite TiO2-Ti2O3(H2O)2(C2O4)·H2O show excellent photocatalytic activity under UV-light. With the novel TiO2-Ti2O3(H2O)2(C2O4)·H2O mixed crystal catalyst, this study illustrates the photocatalysis mechanism of multiphase mixed crystal for removal of emerging contaminants in water. Based on the Mott-Schottky, XPS and energy band structure, we consider that an indirect Z-scheme transmission mode is generated between rutile/anatase TiO2 or TiO2-Ti2O3(H2O)2(C2O4)·H2O mixed crystal, wherein the photo-induced electrons in rutile TiO2 combined with the holes in anatase TiO2 or Ti2O3(H2O)2(C2O4)·H2O, leading to enhanced charge carrier extraction and utilization upon photoexcitation.

    更新日期:2020-01-15
  • 更新日期:2020-01-15
  • From partial to complete neutralization of 2,5-dihydroxyterephthalic acid in the Li–Na system: crystal chemistry and electrochemical behavior of Na2Li2C8H2O6vs. Li†
    CrystEngComm (IF 3.382) Pub Date : 2020-01-08
    Éric Quarez; Alia Jouhara; Stéphane Grolleau; Franck Dolhem; Nicolas Dupré; Philippe Poizot
    更新日期:2020-01-15
  • Metal–organic architectures driven by a multifunctional 6-aminouracil spacer: structures, noncovalent interactions, and conductivity†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-16
    Atanu Purkayastha; Sourab Dhar; Suvra Prakash Mondal; Antonio Franconetti; Antonio Frontera; Rakesh Ganguly; Alexander M. Kirillov; Tarun Kumar Misra
    更新日期:2020-01-15
  • 更新日期:2020-01-15
  • Structural investigations on two typical lithium germanate melts by in situ Raman spectroscopy and density functional theory calculations†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-12
    Songming Wan; Shujie Zhang; Xiaoye Gong; Yu Zeng; Shengjie Jiang; Jinglin You
    更新日期:2020-01-15
  • Substituent effect on the packing architecture of adamantane and memantine derivatives of sulfonamide molecular crystals†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-03
    Alexander P. Voronin; Tatyana V. Volkova; Andrey B. Ilyukhin; Alexey N. Proshin; German L. Perlovich
    更新日期:2020-01-15
  • 更新日期:2020-01-15
  • A microporous zinc–organic framework with Lewis basic pyridyl sites for highly selective C2H2/CH4 and C2H2/CO2 gas separation†
    CrystEngComm (IF 3.382) Pub Date : 2019-11-25
    Peng Yan; Jucai Yang; Xiangying Hao; Zhisheng Chen; Guanhua Shen; Yanhua Zhao; Deyun Ma; Jiaxin Zhu
    更新日期:2020-01-15
  • 更新日期:2020-01-15
  • Heteromolecular compounds in binary systems of amino acids with opposite and same chiralities†
    CrystEngComm (IF 3.382) Pub Date : 2020-01-14
    Anton I. Isakov; Heike Lorenz; Andrey A. Zolotarev, Jr; Elena N. Kotelnikova
    更新日期:2020-01-14
  • Dual-responsive luminescent sensor based on water-stable Cd(II)-MOF for highly selective and sensitive detection of acetylacetone and Cr2O72- in aqueous solution
    CrystEngComm (IF 3.382) Pub Date : 2020-01-14
    Ying-Jie Yang; Yuehua Li; Dong Liu; Guang Hua Cui

    Two new water-stable cadmium(II)-metal organic frameworks (MOFs), namely, [Cd2(L1)(1,4-NDC)2]n (1) and [Cd(L2)(1,4-NDC)]n (2) (L1 = 1,4-bis(benzimidazol-1-yl)-2-butylene, L2 = 1,4-bis(2-methylbenzimidazol-1-yl)-2-butylene and 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid) were synthesized and characterized. 1 exhibits a unusual 3D framework with the Schläfli symbol of {42.5.62.7}{42.52.72}{42.53.62.73}2 and 2 is a classical sqc6 network. 1 and 2 display excellent pH stability and water stability, and the integrity of the frameworks was well maintained after different pH (pH = 3~13) and long term water treatment. 1 is the seldom dual-function luminescent sensor for sensing acetylacetone and Cr2O72- in aqueous solution with high sensitivity, selectivity and excellent recyclable behaviors. This material is an excellent dual-responsive recyclable luminescence sensor.

    更新日期:2020-01-14
  • 更新日期:2020-01-14
  • Vacancy-engineered catalysts for water electrolysis
    CrystEngComm (IF 3.382) Pub Date : 2020-01-07
    Songa Choi; Yeji Park; Heesu Yang; Haneul Jin; Gracita M. Tomboc; Kwangyeol Lee
    更新日期:2020-01-14
  • 更新日期:2020-01-14
  • Capturing an amorphous BaSO4 intermediate precursor to barite
    CrystEngComm (IF 3.382) Pub Date : 2020-01-13
    Cristina Ruiz-Agudo; David McDonogh; Jonathan Thomas Avaro; David Joshua Schupp; Denis Gebauer

    The work presented here investigates the early stages of barium sulfate crystallization from aqueous solutions. By monitoring free-barium activity during the crystallization, we identified a metastable BaSO4 phase that precedes barite formation. Ex-situ investigations provide direct, unambiguous experimental evidences of an amorphous BaSO4 phase in an additive-free scenario.

    更新日期:2020-01-13
  • Nickel/Iron-Based Bimetallic MOFs derived nickel ferrite materials for triethylamine sensing performance
    CrystEngComm (IF 3.382) Pub Date : 2020-01-13
    Chengbo Zhai; Hongpeng Zhang; Liyong Du; Dongxue Wang; Dianjun Xing; Mingzhe Zhang

    Nowadays, the metal-organic framework (MOF) based oxides have been gradually regarded as promising gas-sensing materials. In this study, the small-sized NiFe2O4 polyhedrons are synthesized at first through pyrolysis of bimetallic Fe/Ni-based bimetallic MOF precursors that synthesied by ligand acid complexation. Subsequently, a large-sized NFO polyhedrons with more stable morphology and structure were synthesized by changing the solvent composition. The concrete microstructure of the as-synthesized samples was characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The large-sized NFO polyhedrons based sensors present all-right triethylamine (TEA) gas sensing performances, such as fast response speed (6 s to 50 ppm TEA), enhanced response values (18.9 to 50 ppm TEA), good selectivity and repeatability at relatively low working temperature (190°C). Note that only few literatures have reported on the use of MOF-derived NFO materials in the TEA detection. Hence, our work expands the application fields of MOF-derived NFO materials. In addition, the sensing performances and sensing mechanism have been discussed in detail.

    更新日期:2020-01-13
  • Polarization screening-induced epitaxial growth and interfacial magnetism of BiFeO3/PbTiO3 nanoplates†
    CrystEngComm (IF 3.382) Pub Date : 2020-01-09
    Gangjie Fu; Wei Li; Haiwen Cao; Xing Chen; Shanpeng Wang; Liang Luo; Mengjiao Wu; He Tian; Zhaohui Ren; Gaorong Han
    更新日期:2020-01-13
  • Unexpected crystalline memory effect in poly(l-lactide)-based block copolymers†
    CrystEngComm (IF 3.382) Pub Date : 2020-01-02
    Zaizai Tong; Yawei Su; Rui-Yang Wang; Jun-Ting Xu
    更新日期:2020-01-13
  • A series of anionic MOFs with cluster-based, pillared-layer and rod-spacer motifs: near-sunlight white-light emission and selective dye capture†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-17
    Ce Wang; Zheng Yin; Zhao Cheng; Wei-Min Ma; Xi-Yao Li; Xiao-Ting Hu; Rong Shi; Ao-Wei Chen; Yang-Min Ma
    更新日期:2020-01-13
  • Complex Cobalt Silicates and Germanates Crystallizing in a Porous Three-Dimensional Framework Structure
    CrystEngComm (IF 3.382) Pub Date : 2020-01-10
    Mohammad Usman; Mark D. Smith; Vancho Kocevski; Theodore Besmann; Hans-Conrad Zur Loye

    Four new cesium containing complex cobalt oxides, Cs(Co0.5Si0.5)SiO4 (1), Cs1.29(5)Co0.69(5)Ge1.81(5)O5 (2) and its ordered analogue Cs2CoGe4O10 (3), were synthesized using a mixed CsCl-CsF flux at 850 °C and 900 °C, respectively. The structure of (1) closely resembles that of known zeolite and feldspar structure types and crystallizes in the noncentrosymmetric monoclinic space group Im with lattice parameters of a = 8.9926(4) Å, b = 5.4599(2) Å, c = 9.3958(6) Å and β = 91.5928(18)°. Structures (2) and (3) crystallize in the same new structure type, a highly porous three-dimensional framework, in the tetragonal space group I-4 with lattice parameters of a = 7.4239(14) Å and c = 13.169(3) Å and a = 7.3540(6) Å and c = 13.1122(11) Å, respectively. The formation of (2) vs (3) can be targeted by using slight variations in the quantities of starting materials. Single crystal to single crystal ion exchange experiment on (1) carried out in a molten RbNO3 bath results in 14% Cs exchange with Rb, affording the composition, Cs0.86Rb0.14(Co0.5Si0.5)SiO4 (4). First-principles calculations in the form of density functional theory (DFT) were performed for (1) and (3) to elucidate their electronic and magnetic properties, and stability at 0 K.

    更新日期:2020-01-10
  • Supramolecular Organisation of Sulphate Salt Hydrates exemplified with Brucine Sulphate
    CrystEngComm (IF 3.382) Pub Date : 2020-01-10
    Doris Elfriede Braun

    The solid form landscape of brucine sulphate (BS) was elucidated, resulting in three hydrate forms (HyA-C) and amorphous BS. Interconversion of the hydrates of BS with small changes in the relative humidity complicated identifying and characterising the solid forms. The hydrate obtained from crystallisation experiments (from water), HyA, is the only solid form described in literature. The other two hydrates were produced by dehydration starting from the known hydrate. HyA contains 6.5 to 7.4 molecules of water per BS and is only stable in the realtive humidity (RH) range ≥ 26% at RT. HyB is only observable in a very narrow RH window at room temperature (22% – 25%) and shows a hexahydrate stoichiometry. At RH values ≤ 20% the third hydrate, HyC, forms. Similar to HyA the latter hydrate shows a variable water content of five and less water molecules per BS. Removal of the essential water molecules stabilising the hydrate structures causes a collapse to the amorphous state, a process which was not finished within 3.5 years of storing HyC at driest conditions (approx. 0%) at room temperature. Only the combination of intermolecular interaction and electronic structure calculations with thermal analytical techniques, X-ray diffraction, IR spectroscopy and gravimetric moisture (de)sorption studies and careful control of the external conditions allowed the finding and rationalisation of the three hydrates of BS. The investigations on BS were complemented with an exploitation of the Cambridge Structural Database (CSD) to unravel the incidence of hydrates of sulphate salts. The analysis indicates that 56.5% of the sulphate salts (C,H,N,O,S atoms only) are hydrate structures, with higher hydrates being more commonly present amongst sulphate salts than amongst all organic hydrates.

    更新日期:2020-01-10
  • Mesoscale regulation of β-NaYF4: Yb/Er with desired size and morphology via introducing Li+/K+ into the hydrothermal environment
    CrystEngComm (IF 3.382) Pub Date : 2020-01-10
    Sheng Yang; Meng Duan; Yongying Li; Xueying Ding; Yulan Shen; Hui Cheng; Gao Guo; Daxiang Cui

    Controllable sysnthsis NaYF4:Yb3+/Er3+ via mesoscale regulation through introducing Li+/K+ into the hydrothermal system has been developed. The crystal evolution process of β-NaYF4:Yb3+/Er3+ is investigated based on the reaction parameters. The mesoscale growing process include four stages: (1) nucleation; (2) aggregation; (3) orientation growth; (4) ripening. Through introducing Li+/K+ into the hydrothermal environment, super-small β- NaYF4:Yb3+/Er3+ upconversion nanoparticles can be obtained.

    更新日期:2020-01-10
  • Tilts and shifts in molecular perovskites†
    CrystEngComm (IF 3.382) Pub Date : 2020-01-03
    Hanna L. B. Boström
    更新日期:2020-01-10
  • The synthesis of bayberry-like mesoporous TiO2 microspheres by a kinetics-controlled method and their hydrophilic films
    CrystEngComm (IF 3.382) Pub Date : 2019-12-24
    Li Li; Liang Wang; Xinhong Chen; Changyuan Tao; Jun Du; Zuohua Liua
    更新日期:2020-01-10
  • Solution-mediated and single-crystal to single-crystal transformations of cucurbit[6]uril host–guest complexes with dopamine†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-20
    Oksana Danylyuk; Marta Worzakowska; Joanna Osypiuk-Tomasik; Volodymyr Sashuk; Karolina Kedra-Krolik
    更新日期:2020-01-10
  • Growth behavior of columnar grains in TiAl alloy during directional induction heat treatment
    CrystEngComm (IF 3.382) Pub Date : 2020-01-09
    Yangli Liu; Xiang Xue; Hongze Fang; Yingmei Tan; Ruirun Chen; Yanqing Su; Jingjie Guo

    Columnar grains are often obtained by directional solidification. In this study, columnar grains were achieved by directional induction heat treatment (DHT). TiAl ingot with equiaxed grains was induction heated at 1750 K for 20 minutes and pulled down with velocity of 4.17 μm/s. Liquid Ga-In alloy was used for cooling the ingot at the bottom. Results show that grains grow from equiaxed to columnar after competitive growth. The length of directional growth zone is about 25 mm and the maximum length of columnar grain is 15.5 mm. Lamellae direction with small angle (less than 60°) is about 90% in all columnar grains, which is higher than that of the ingot prepared by traditional directioal solidification. The driving force for columnar grain growth is bending interfacial tension that caused by heat transfer from the induction heating zone to the bottom. Atoms in front of the interface will diffuse downward under the action of interfacial tension during DHT, grains will grow up along axial direction. The interface migration rate (that is growth rate) of columnar grains is calculated based on the model of interface continuous moving. Calculated results indicate that the interface migration rate is ranged from 0.350 - 0.505 μm/s at 1750 K. Columnar grains will be obtained through atoms diffusion during DHT.

    更新日期:2020-01-09
  • In situ fabrication of core–shell-structured Beta@Silicalite-1 catalysts by a novel steam-assisted crystallization strategy†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-27
    Lanjian Xu; Yangyang Yuan; Jie Zhang; Yanfei Zhang; Xiaomin Zhang; Lei Chen; Lei Xu
    更新日期:2020-01-09
  • Cracking mechanism and spectral properties of Er,Yb:CaGdAlO4 crystals grown by the LHPG method
    CrystEngComm (IF 3.382) Pub Date : 2019-12-13
    Na Zhang; Haoyuan Wang; Yuqing Yin; Tao Wang; Zhitai Jia; Jian Zhang; Qiangqiang Hu; Na Lin; Xiuwei Fu; Xutang Tao
    更新日期:2020-01-09
  • Investigating the effects of activating agent morphology on the porosity and related capacitance of nanoporous carbons.
    CrystEngComm (IF 3.382) Pub Date : 2020-01-08
    Servann Herou; Maria Crespo-Ribadeneyra; Magdalena Titirici

    The increasing interest in nanostructured porous carbon materials in the field of energy storage and electrocatalysis has led to drastic improvement in their properties. These materials are still expensive to manufacture, often due to the harsh chemical treatments required to enhance porosity. In this article, we demonstrate that the process of activating carbons does not uniquely depend on the amount of activating agent (NaOH) but also on the contact area between the salt and the carbonaceous framework to be activated. We compare the microstructure, double layer capacitance and microporosity of carbon materials of the same chemical composition but obtained through two different protocols: electrospinning, which allows the formation of small NaOH domains (~ 60 nm) homogeneously distributed across lignin fibres, and standard activation, which leads to the growth of larger NaOH domains within the lignin framework. As intimate contact between both phases ensures maximum activation, our electrospun material shows a remarkable capacitance (~ 180 F.g-1) in comparison to the material prepared through standard “mix and dry” activation procedure (~ 10 F.g-1). This is attributed to the generation of micropores (~ 670 m2.g-1), tailored from the small activating salt template domains in intimate contact with the lignin framework. In summary, through this work we establish a relationship between the activating agent´s morphology and its effect in porosity and energy storage performance. We present a facile method to interpenetrate the chemical activating agent within the carbon precursor structure before pyrolysis, through the efficient usage of the activating agent.

    更新日期:2020-01-08
  • Mechanochemical Synthesis of Drug-Drug and Drug-Nutraceutical Multicomponent Solids of Olanzapine
    CrystEngComm (IF 3.382) Pub Date : 2020-01-08
    Kashyap Kumar Sarmah; Nilamoni Nath; Dharmaraj R. Rao; Ranjit Thakuria

    Drug-drug and drug-nutraceutical multicomponent solids of antipsychotic drug olanzapine (OLN) are prepared using mechanochemistry. Drug molecules viz. nateglinide (NAT) and pyrazinoic acid (PZO) as well as nutraceuticals- 2,4,6-trihydroxybenzoic acid (246THBA), gallic acid (GA) and sinapic acid (SPA) are used as coformer for this study. Under neat grinding (NG), incomplete conversion (partially amorphous) was observed, whereas liquid assisted grinding (LAG) resulted comorphous OLN-NAT and crystalline salts/ salt hydrates with rest of the coformers characterized using combination of techniques including single crystal X-ray diffraction. OLN-NAT coamorphous salt has potential scope for the development as combination drug in order to suppress increase blood sugar level, a common side-effect observed during monotherapy of psychiatric patients using OLN. Equilibrium solubility study shows substantial enhancement in solubility of olanzapinium pyrazinoate compared to pure base.

    更新日期:2020-01-08
  • Growth of few-layer graphene on Cu foil by regulating the pressure of reaction gases
    CrystEngComm (IF 3.382) Pub Date : 2020-01-08
    Weiwei Hou; Jianyu Wang; Zhendong Wang; Kai Cao; Liyun Qin; Li Wang

    A method to grow few-layer graphene in form of “Inverted Pagoda” is proposed by controlling the pressure and the flow rate in circulating chemical vapor deposition system. Such the single-crystal few-layer graphene consist of one- to eight-layer graphene areas exhibiting layer growth characteristics. Moreover, each layer within this kind of few-layer graphene are in Bernal stacking. In this work, with the increasing growth pressure, the self-limiting effect of graphene was successfully broken, and the growth of graphene in the vertical direction was achieved. By controlling the ratio of H2 / CH4, the morphology and number of layers of the multilayer layer under the single-layer graphene were modulated.

    更新日期:2020-01-08
  • Manipulating clusters by regulating N,O chelating ligands: structures and multistep assembly mechanisms†
    CrystEngComm (IF 3.382) Pub Date : 2020-01-02
    Hai-Ling Wang; Zi-Yuan Liu; Zhong-Hong Zhu; Jin-Mei Peng; Xiong-Feng Ma; Juan Bai; Hua-Hong Zou; Kai-Qiang Mo; Fu-Pei Liang
    更新日期:2020-01-08
  • 更新日期:2020-01-08
  • 更新日期:2020-01-08
  • ZnSe/CdSe core–shell nanoribbon arrays for photocatalytic applications†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-23
    Chengcheng Sun; Tingting Li; Weijia Wen; Xiangdong Luo; Lijuan Zhao
    更新日期:2020-01-08
  • Inhibition of volatilization and polycrystalline cracking, and the optical properties of β-Ga2O3 grown by the EFG method
    CrystEngComm (IF 3.382) Pub Date : 2019-12-20
    Huili Tang; Nuotian He; Hao Zhang; Bo Liu; Zhichao Zhu; Mengxuan Xu; Liang Chen; Jinliang Liu; Xiaoping Ouyang; Jun Xu
    更新日期:2020-01-08
  • 更新日期:2020-01-08
  • Five naphthalene-amide-bridged Ni(II) complexes: electrochemistry, bifunctional fluorescence responses, removal of contaminants and optimization by CVD
    CrystEngComm (IF 3.382) Pub Date : 2020-01-07
    Jing Zhao; Jian Luan; Huixuan Yu; Guocheng Liu; Hongyan Lin; Xiuli Wang; Baokuan Chen

    To research the effect of carboxylates on the assembly of Ni(II) coordination polymers, a naphthalene-amide ligand L (N,N′-bis(pyridin-3-ylmethyl) naphthalene-2,6-dicarboxamide) and five dicarboxylates [1,4-H2BDC = 1,4-benzenedicarboxylic acid, 1,4-H2PDC =1,4-phenyldiacetic acid, 5-H2HIP = 5-hydroxyisophthalic acid, 3,4-H2TDC = 3,4-thiophenedicarboxylic acid, 2,5-H2TDC = 2,5-thiophenedicarboxylic acid] were selected to combine with Ni(II) under hydrothermal condition. Five coordination polymers [Ni(L)(1,4-BDC)(H2O)2] (1), [Ni(L)(1,4-PDC)(H2O)2] (2), [Ni(L)(5-HIP)(H2O)2] (3), [Ni(L)(3,4-TDC)(H2O)2]•3H2O (4) and [Ni(L)(2,5-TDC)(H2O)]2•3H2O (5) were synthesized and structurally characterized by IR, PXRD and X-ray single-crystal diffraction. The title complexes show various structures: 2D 4-connected sql nets (1 and 2), 3D cds framework of 3, 1D zigzag chain of 4 and 3D irl framework of 5. The electrochemical behaviors of 1–5, the solid-state luminescent and fluorescent responses of 5 for Fe3+ and bovine serum albumin (BSA) were studied. Encouraged by functional thiophene components, 4 and 5 were used as catalyst precursors to synthesize carbon nanotubes (CNT-4 and CNT-5) by the chemical vapor deposition (CVD) method and characterized by XPS, SEM, TEM and Raman spectra. The removals of contaminants (Rhodamine B and Congo red) by 4 and 5 and their derived CNT-4 and CNT-5 in aqueous phase were also comparatively investigated.

    更新日期:2020-01-08
  • Bandgap engineering of TiO2 nanotube photonic crystals for enhancement of photocatalytic capability
    CrystEngComm (IF 3.382) Pub Date : 2020-01-07
    Jian-feng Li; Jian Wang; Xiao-Tian Wang; Xiao-Gang Wang; Yan Li; Cheng-Wei Wang

    The slow photon effect can significantly increase the effective optical path length of light and thereby enhance the interaction of light with matter, which would be realized by light propagating at the edges of the photonic band gap (PBG) in photonic crystals (PCs). In this paper, a novel anodic oxidation method with the effective voltage-pulse compensation was developed to prepare the one-dimensional titania nanotube photonic crystals (1D TiO2 NT PCs) with high quality of PBG, which could be continuously adjusted and precisely tailored just by modulating the anodization parameters. With the increase of low voltage (LV) duration, the precise blue shift of the PBG of 1D TiO2 NT PCs was recorded. Through the precise tailoring of PBG in bandgap engineering, the edges of PBG could be designed and purposely tuned to overlap with the electronic band gap range of TiO2 material, and the as-prepared 1D TiO2 NT PCs were used as photocatalyst to degrade the methyl orange (MO) molecules due to the enhanced slow photon effect and scattering effect in their highly ordered channel structures. Meanwhile, the strategies to enhance the slow photon effect at the edge of PBG were discussed and evaluated in detail according to our experimental and simulated results. This study would provide a new guidance for taking advantage of the slow photon effect to enhance photocatalytic activities, photoluminescence, and other optoelectronic devices performances.

    更新日期:2020-01-07
  • Irregular PtNi nanocrystal and PtNiRu nanodendrite: Comparison of structure and methanol electrooxidation ability
    CrystEngComm (IF 3.382) Pub Date : 2020-01-07
    Zirong Li; Guan Zhongyue; Yuting Chang; Die Hu; Bao-Kang Jin; Lei Bai

    In this work, platinum-nickel-ruthenium (PtNiRu) nanocrystals with different amount of Ru were synthesized by one-pot solvothermal method. In the absence and presence of ruthenium trichloride, the evolution of the structure and composition of the obtained Pt alloys was clearly observed. In comparison with the PtNi irregular nanocrystals, the PtNiRu nanospheres and nanodendrites were obtained under the same reaction condition. The structure, composition as well as the formation path of PtNiRu nanodendrites were investigated in detail. Finally, the catalytic results from the methanol oxidation suggested that the mass activity as well as the area specific activity of the PtNiRu nanodendrites shown 3.5 and 3.1 time fold higher than those of commercial Pt/C as well as a better durability, which was due to the porous structure and synergistic effect of Ni/Ru. It is expected that the present study could provide a new example for designing the low amount Ru modified Pt based alloys for the application in energy conversion.

    更新日期:2020-01-07
  • Hydroperoxo double hydrogen bonding: Stabilization of hydroperoxo complexes exemplified by triphenylsilicon and triphenylgermanium hydroperoxides
    CrystEngComm (IF 3.382) Pub Date : 2020-01-07
    Alexander G. Medvedev; Dmitry A. Grishanov; Churakov Andrei; Alexey A. Mikhaylov; Ovadia Lev; Petr V Prikhodchenko

    Triphenyl silicon hydroperoxide and its isostructural germanium complex were characterized by single crystal X-ray analysis revealing H-bonding of two triphenylhydroperoxocomplexes, with each hydroperoxo ligand acting as a hydrogen donor and a hydrogen acceptor. Only two other structures with localized protons of hydroperoxo complexes main group elements (boron and tin) are known (compared to 130 p-block element peroxo compounds) and both exhibit the same hydroperoxo double hydrogen bonding motif. The reaction of the hydroperoxo complexes with triphenylgermanium chloride to give the dinuclear peroxobridged germanium complex demonstrates the higher reactivity of the hydroperoxo moieties compared to the peroxo moiety. DFT calculations provide an estimate of the hydroperoxo double hydrogen bond energies: 62.8 and 63.6 kJ mol-1 for triphenyl silicon, 63.6 and 65 kJ mol-1 for the germanium complex.

    更新日期:2020-01-07
  • [DMEDA]PbCl4: One-dimensional Organic Lead Halide Perovskite with Efficient Yellow Emission
    CrystEngComm (IF 3.382) Pub Date : 2020-01-07
    Chen Sun; Yun-Di Yue; Weifeng zhang; Xingyu sun; Yan Du; Hongmei Pan; Yueyu Ma; Yuan-Chun He; Mengting Li; Zhihong Jing

    In recent years, low-dimensional organic-inorganic hybrid lead halide perovskites have been explored as photoluminescent (PL) materials with high photoluminescence quantum efficiencies and tunable band structures arising from the structural regulating functions of organic cations. Herein, by using a simple solution reaction, we prepared one new type of one-dimensional (1D) hybrid lead halide, namely as, [DMEDA]PbCl4 (DMEDA = N, N'-dimethylethylenediamine). The compound contains 1D edge sharing octahedral lead chloride [PbCl4]2- anionic chains, which are surrounded and separated by the organic cations of [DMEDA]2+. This 1D structure enables the formation of self-trapped excited states that give bright yellow emissions with photoluminescence quantum efficiency (PLQE) of approximately 4.81 %. The white light emitting device can also be easily fabricated by coating the sample of [DMEDA]PbCl4 on a blue light chip. The PL stability and nature are also investigated by using various experiments. This work provides a new type of structural models to probe into the PL property and understand the structure-property relationship of low-dimensional lead halide perovskites.

    更新日期:2020-01-07
  • Coordination polymer templated engineering of YVO4:Eu submicron crystals and photoluminescence
    CrystEngComm (IF 3.382) Pub Date : 2020-01-07
    Sai Huang; Zhenshu Fan; Qi Zhu; Xiaodong Li; Xudong Sun; Ji-Guang Li

    Submicron-sized cuboidal and octahedral (Y0.95Eu0.05)VO4 crystals were selectively synthesized via hydrothermally reacting sodium vanadate with a (Y0.95Eu0.05)-tartrate coordination polymer (CP) precipitated at room temperature, where the CP compound was analyzed to be an amorphous mass having particle sizes of ~300 nm and an approximate composition of (Y0.95Eu0.05)2(C4H4O6)3•7.4H2O. A series of well controlled experiments clearly revealed that a stoichiometric amount of VO43- [VO43-/(Y0.95Eu0.05)3+ molar ratio R=1.0] favors cuboidal crystals (~300-500 nm), which are formed via tartrate-directed [001] stacking of ~15 nm thick nanosquares exposed with high energy {001} facets, whereas superfluous VO43- (R = 1.5 and 2.0) promotes the crystallization of octahedral crystals (~600-800 nm) enclosed by low energy {101} facets. The acting mechanisms of reaction temperature (80-200 °C) and time (1-24 h) in structure and morphology evolution were discussed in detail. The octahedrons were also analyzed to have a ~60% stronger 619 nm red emission and a larger (5D0 → 7F2)/( 5D0 → 7F1) intensity ratio, though both the types of crystals have similar fluorescence lifetimes of ~0.9 ms for their 619 nm main emissions.

    更新日期:2020-01-07
  • Role of substituents on resonance assisted hydrogen bonding vs. intermolecular hydrogen bonding†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-20
    Atash V. Gurbanov; Maxim L. Kuznetsov; Svetlana D. Demukhamedova; Irada N. Alieva; Niftali M. Godjaev; Fedor I. Zubkov; Kamran T. Mahmudov; Armando J. L. Pombeiro
    更新日期:2020-01-07
  • 更新日期:2020-01-07
  • Ferroelectricity and antiferromagnetism in organic–inorganic hybrid (1,4-bis(imidazol-1-ylmethyl)benzene)CuCl4·H2O†
    CrystEngComm (IF 3.382) Pub Date : 2019-11-18
    Chunli Jiang; Qianqian Luo; Hanmei Fu; Hechun Lin; Chunhua Luo; Jianlu Wang; Xiangjian Meng; Hui Peng; Chun-Gang Duan; Junhao Chu
    更新日期:2020-01-07
  • Metal/N-donor-induced versatile structures and properties of seven 0D→3D complexes based on dpq/dppz and O-bridged tricarboxylate: fluorescent and electrochemical behaviors
    CrystEngComm (IF 3.382) Pub Date : 2020-01-06
    Guocheng Liu; Shuang Liang; Qiaomin Li; Jiao Guo; Na Xu; Xiuli Wang; Yan Li; Baokuan Chen

    To investigate the effect of the metal ions on the assembly of complexes derived from a semirigid tripodal carboxylic acid 5-(4'-carboxylphenoxy) isophthalic acid (H3L) and two rigid chelating terminal N-donor ligands dipyrazino[2, 3-d: 2′ 3′-f]quinoxaline (dpq), dipyrido[3, 2-a: 2', 3'-c]phenazine (dppz), seven 0D→3D complexes of [Cu(HL)(dpq)(H2O)2] (1), [Co(HL)(dpq)(H2O)]·H2O (2), [Ni3(L)2(dpq)3(H2O)4]·4H2O (3), [Zn(HL)(dpq)(H2O)]·H2O (4), [Cu2(L)(dppz)]·H2O (5), [Co(HL)(dppz)]·H2O (6) and [Ni3(L)2(dppz)3(H2O)3] (7) have been hydrothermally synthesized and structural characterized by IR, TG and X-ray single-crystal diffraction. Complex 1 is a 0D complex processing an unusual μ1-HL2– anion. Complex 2 features 1D single chain based on Co(II) ions with 6 coordinated mode. Complex 3 is the first (2,3,4)-connected 3D dpq-based framework derived from single/bimetallic mixed nodes with {83}2{84·122}{8} topology. Complex 4 is a 1D structure based on Zn(II) ions with 5 coordinated mode. Complex 5 can be described as a 2D (6,3)-c structure based on carboxyl-bridged Cu4 cores. Complex 6 is a 1D double chain derived from bimetallic nodes. Complex 7 exhibits a 2D double layer with the (2,2,3,3,4)-c nodes. The structural details of 1–7 were discussed. The solid-state luminescent properties of 1–7 and electrochemical properties of 1–3 have been investigated. The luminescent investigations show that 4 is an effective fluorescent probe for environmentally relevant Fe3+ ions. The electrochemical properties of carbon paste electrode modified by the complexes 1–3 (1-CPE, 2-CPE and 3-CPE) were studied. 1-CPE has good electrocatalytic activity toward the reduction of nitrite, bromate and hydrogen peroxide in solution.

    更新日期:2020-01-06
  • From organic ligand to metal-organic coordination polymer, and to metal-organic coordination polymer-cocrystal composite: a continuous promotion of proton conductivity of crystalline materials
    CrystEngComm (IF 3.382) Pub Date : 2020-01-06
    Xiaoqiang Liang; Tingting Cao; Li Wang; Chang-Zheng Zheng; Yamei Zhao; Feng Zhang; Chen Wen; Lei Feng; Chengan Wan

    Improving proton conductivity is of great importance for the further application of metal-organic frameworks (MOFs) or metal-organic coordination polymers (MOCPs) in proton exchange membrane fuel cells. In this paper, we proposed a new approach to raise proton conductivities in MOCPs commencing from organic ligand, e.g. coordination inducement and forming MOCPs-cocrystal composite strategy which is based on the potential function of organic ligand. Employing the approach, we have successfully synthesized and characterized three crystalline compounds, PPA (1), [Cu(PPA)I] (2) and [Co(PPA)2(BDC)(H2O)2·(PPA)2(H2BDC)2(H2O)] (3) (PPA= 4-(3-pyridinyl)-2-amino pyrimidine, H2BDC = 1, 4-benzenedicarboxylic acid). These compounds show high water stabilities and different proton conducting behaviours, especially for compound 3 with a proton conductivity of 2.29 × 10-4 S cm-1 at 325 K and ~97% RH, which is higher than or comparable to those of some reported compounds. More importantly, a persistent increase in proton conductivity is observed from 1 to 3, which is about one order of magnitude. Furthermore, single crystal analyses show that coordination and hydrogen-bonding interactions play a crucial role in improving proton-conductive properties for these compounds. The study reveals that it is practical to boost proton conductivity of crystal materials by means of their intrinsic merits and the strategy of molecular design.

    更新日期:2020-01-06
  • Morphology-preserved Transformation of CdS Hollow Structures Toward Photocatalytic H2 Evolution
    CrystEngComm (IF 3.382) Pub Date : 2020-01-06
    Ye Liu; Cheng Huang; Tengfei Zhou; Juncheng Hu

    Hollow-structured nanomaterials with complex interiors have drawn a great deal of attention due to their unique properties in various fields. Herein, we present the controllable synthesis of CdS hollow microspheres for photocatalytic H2 production. The quasi-emulsion microdroplets formed by glycerol-isopropanol mixed solution work as soft templates of the solid Cd-glycerol precursors, which offers a scaffold for the subsequent topological transformation of the hollow-structured CdS. In virtue of this, single-shelled and double-shelled CdS hollow microspheres could be attained by simply control the reaction time. Experimental results reveal that the double-shelled hollow structure endowed the CdS photocatalyst with better H2 production capability comparing to the single-shelled analogue. This work could offer a new approach toward the synthesis of complex hollow-structured nanomaterials with enhanced photoactivities.

    更新日期:2020-01-06
  • Core-mediated synthesis, growth mechanism and near-infrared luminescence enhancement of α-NaGdF4@β-NaLuF4:Nd3+ core-shell nanocrystals
    CrystEngComm (IF 3.382) Pub Date : 2020-01-04
    Qinqin Shao; Chao Yang; Xiaoxu Chen; Hong Zhang; Guoying Feng; Shouhuan Zhou

    Lanthanide doped hexagonal phase (β) rare earth fluorides (NaREF4) nanocrystals have considerable promise in laser and especially bio-application. However, the large size and extreme synthetic conditions have become the unavoidable obstacles in their path to various applications. Herein, a core-mediated hetero-shell growth method was adopted to synthesize α-NaGdF4@β-NaLuF4: Nd3+ nanocrystals, in which cubic phase (α) NaGdF4 was used as the core to induce the subsequent growth of β-NaLuF4: Nd3+ shell via the two-step solvothermal reaction. The resulting α-NaGdF4@β-NaLuF4: Nd3+ core-shell nanocrystals were characterized by structural analysis, photoluminescence spectroscopy and decay lifetime. Besides, the persuasive lattice-disordered heterointerface-induced mechanism was proposed to understand the core-mediated hetero-shell growth. Meanwhile, the influence of heterointerface on the dynamic growth of the shell nanocrystals was also investigated in detail. Most importantly, the near-infrared luminescence intensity at 1.06 μm was enhanced by over two times via coating the lattice-matched homogeneous NaLuF4 shell on the surface of α-NaGdF4@β-NaLuF4: Nd3+ nanocrystals. The high-performance α-NaGdF4@β-NaLuF4: Nd3+ nanocrystals thus obtained are expected to be used for laser output and depth detection of biological tissues

    更新日期:2020-01-04
  • Mg0.8Zn0.2O Microspheres: Preparation, Characterization and Application for Degrading Organic Dyes
    CrystEngComm (IF 3.382) Pub Date : 2020-01-03
    Yajun Zheng; Liyun Cao; Gaoxuan Xing; Jianfeng Huang; Zhiping Zhang

    Photocatalytic degradation of organic pollutants in wastewater is one the most promising strategies for environmental remediation, and photocatalysts as the prerequisite have received considerable attention. Herein we reported a highly efficient, nontoxic, and inexpensive Mg0.8Zn0.2O microspheres with a diameter of around 36 μm through the reaction between CO32-, Mg2+ and Zn2+ for degrading organic dyes. The molar ratio between Mg2+ and Zn2+ was found playing a crucial role in determining the morphology and photocatalytic performance of resulting product. According to time-dependent experiments, the plausible formation mechanism for spherical-like Mg0.8Zn0.2O composite was proposed, in which irregular agglomerates composed of fine powders were first formed followed by their transformation into rod-like structures. Due to the thermal instability, the rod-like particles underwent further self-assembly and became more stable spherical-like product with ZnCO3 embedded in the space between sheet-like Mg5(CO3)4(OH)2·4H2O. After investigating the photocatalytic performance, the results demonstrated that the developed Mg0.8Zn0.2O composite was not only superior to other state-of-the-art catalysts such as P25 TiO2 and g-C3N4 in degrading organic dyes upon irradiation in either UV light or visible light, but also was an amphoteric photocatalyst more favorable to degrade organic dyes in both strongly acidic (pH 2-4) and strongly alkaline (pH 12) solutions. Moreover, it catalytic efficiency remained as high as 98.3% after six recycles. These features made the developed Mg0.8Zn0.2O composite promising in practical utilization for treatment of organic dyes. Further experiments from photoluminescence spectra, adsorption and photoelectrochemical measurement accounted for the underlying photocatalytic mechanism of Mg0.8Zn0.2O composite for organic dyes.

    更新日期:2020-01-04
  • Research progress on preparation methods of VO2 nanoparticles and its application in smart windows
    CrystEngComm (IF 3.382) Pub Date : 2020-01-03
    Wen Zeng; Nan Chen; Weiguang Xie

    Accompanied with drastic changes in photoelectric properties, vanadium dioxide (VO2) exhibits a metal-insulator phase transition (MIT) at first order with the temperature of about 68°C. These excellent thermochromic properties made VO2 an enormously potential material in the application of smart windows. VO2 nanoparticles have been extensively studying due to their unique size effect and grain boundary conditions, which can effectively reduce the temperature of metal-insulator phase transition (MIT) and hysteresis widths and improve thermochromic properties. In this paper, the preparation of VO2 nanoparticles with solution method, sputtering method, PLD deposition method and gas phase method are reviewed and also the advantages and disadvantages of various preparation methods are compared and analyzed, which considered that the solution method is the most industrial preparation method. Moreover, the recent progresses in the application of VO2 nanoparticle films on smart coatings have been reviewed, and the possible research directions of VO2 nanoparticles in the future are briefly discussed.

    更新日期:2020-01-04
  • Effects of pillar size modulation on the magneto-structural coupling in self-assembled BiFeO3–CoFe2O4 heteroepitaxy†
    CrystEngComm (IF 3.382) Pub Date : 2020-01-03
    Tahta Amrillah; Yu-Xun Chen; My Ngoc Duong; Wildan Abdussalam; Firman Mangasa Simanjuntak; Chia-Hao Chen; Ying-Hao Chu; Jenh-Yih Juang
    更新日期:2020-01-04
  • 2D organ-like molybdenum carbide (MXene) coupled with MoS2 nanoflowers enhances catalytic activity in the hydrogen evolution reaction
    CrystEngComm (IF 3.382) Pub Date : 2020-01-03
    Jie Ren; Hui Zong; Yuyun Sun; Shijing Gong; Yu Feng; Zhenguo Wang; Le Hu; Ke Yu; Ziqiang Zhu

    Two-dimensional (2D) carbides, nitrides and carbonitrides called MXene are noval materials with a lot of useful applications. However, the range of transition metals capable of forming stable MXenes is limited mostly to early transition metals of 3rd-5th groups. To deal with the inaccessibility of MXene phases derived from mid transition metals, we have developed a synthetic strategy that preparing Mo2Ga2C crystal and 2D organ-like Mo2C MXene matrix coupled with MoS2 nanoflowers. Compared with Mo2CTx (where Tx are O, OH, and F surface terminations) MXene catalyst, MoS2@Mo2CTx nanohybrids showed significantly enhanced hydrogen evolution reaction (HER) activity in alkaline media, with a low overpotential of 176 mV at the current density of 10 mA cm-2 and a very small transfer resistance of 26 Ω. Density functional theory (DFT) calculations attribute the enhanced reaction kinetics of MoS2@Mo2CTx to the favorable binding of hydrogen on the oxygen terminated Mo2C surface, which is strongly influenced by MoS2. The synthetic approach illustrates that tailoring the properties of MXenes for a specific application can be achieved via preparing organ-like molybdenum carbide coupled with MoS2 nanoflowers.

    更新日期:2020-01-04
  • Double-shell SnO2@Fe2O3 hollow spheres as high-performance anode material for lithium-ion batteries
    CrystEngComm (IF 3.382) Pub Date : 2020-01-03
    Zhipeng Cui; Meng Sun; Huanqing Liu; Sijie Li; Qingye Zhang; Yang Chengpeng; Guiju Liu; Junyu Zhong; Yiqian Wang

    Construction of novel electrode materials is an effective way to enhance the electrochemical performance of lithium ion batteries (LIBs). In this work, double-shell SnO2@Fe2O3 hollow spheres are fabricated through simple template method. It reveals that the α-Fe2O3 nanorods are heterogeneously assembled on the surfaces of hollow SnO2 spheres. The double-shell SnO2@Fe2O3 hollow spheres, as an anode material for LIBs, demonstrate excellent lithium storage capacity and cycling stability. Their discharge specific capacity decreases to 464 mAh·g-1 at 46th cycles at a current density of 100 mA·g-1, and then increases significantly to 1043 mAh·g-1 up to 190th cycles. Compared with SiO2@SnO2 (221 mAh·g-1 after 190 cycles) and SnO2 (336 mAh·g-1 after 190 cycles) electrodes, the better electrochemical performance of SnO2@Fe2O3 electrode is ascribed to hierarchical hollow urchin-like structure, SnO2@Fe2O3 heterojunctions and oxygen vacancies in α-Fe2O3 nanorods. The sea urchin-like heterostructures dramatically inhibit the agglomeration and prevent the volume expansion during cycling process. This work provides a novel way to construct a promising material with enhanced performance as an anode for LIBs.

    更新日期:2020-01-04
  • In-plane enhanced epitaxy for step-flow AlN yielding a high-performance vacuum-ultraviolet photovoltaic detector†
    CrystEngComm (IF 3.382) Pub Date : 2019-12-18
    Titao Li; Fei Wang; Richeng Lin; Wentao Xie; Yuqiang Li; Wei Zheng; Feng Huang
    更新日期:2020-01-04
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