Synthesis and characterization of single crystals of the layered copper hydroxide acetate Cu2(OH)3(CH3COO)·H2O

Švarcová, Silvie; Klementová, Mariana; Bezdička, Petr; Łasocha, Wiesław; Dušek, Michal; Hradil, David

doi:10.1002/crat.201100262

Cited by 42 publications

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“…Information regarding the conformation and binding properties of intercalated anions allows for the assessment of structure−property relationships. The binding modes of anion−host interactions vary from diffuse electrostatic interactions in LDHs to coordination monodentate interactions in layered copper hydroxides 16 with the variety of anion conformations caused by temperature or air humidity. 17 Because of their layered structure, LDHs and LZHs are usually poorly crystalline materials due to stacking faults, turbostraticity, and interstratification, rendering the description of the structure and related properties of these materials difficult.…”

Section: ■ Introductionmentioning

confidence: 99%

Insight into the Structure of Layered Zinc Hydroxide Salts Intercalated with Dodecyl Sulfate Anions

et al. 2014

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This Article presents the systematic experimental and theoretical investigation of the structural arrangements of dodecyl sulfate (DS) anions in the interlayer space of layered zinc hydroxide salts (LZH-DS) and of the structure of zinc hydroxide layers, with a detailed description of the zinc ions' coordination environment. As-prepared, well-crystalline LZH-DS has a basal spacing of 31.5 Å. After treatment with methanol at room temperature, zinc hydroxide layers shrank to form two new layered phases with basal spacings of 26.4 and 24.7 Å. The shrinking was accompanied by a decrease in the content of DS anions in the interlayer space, indicating a change in the alignment of the intercalated anions and a decrease in the charge density of the zinc hydroxide layers. The latter effect was assessed by the atomic pair distribution function (PDF) analysis of powder X-ray diffraction patterns, revealing the successive removal of Zn ion tetrahedra from the hydroxide layers, with the octahedrally coordinated Zn ions left unaffected. The interlayer space of all three phases was modeled by molecular dynamics, and the models were validated by the comparison of modeled and experimental powder XRD patterns and one-dimensional electron density maps. The arrangement of DS anions in the interlayer space of LZH-DS also depended on temperature. Remarkably, the basal spacing was considerably increased at 55°C, which was explained by the formation of a second-staging heterostructure with the regular alternation of layers with two basal spacings, 31.5 and 34.2 Å. This is the first reported interstratification phenomenon in layered hydroxides intercalated with aliphatic molecules. Our results provide insight into the great variability of layered hydroxide structures controlled by external stimuli. ■ INTRODUCTIONLayered hydroxides are two-dimensional layered materials composed of positively charged brucite-like layers with anions intercalated in the interlayer space. The structures most often studied are layered double hydroxides (LDH) of the generalwhere M 2+ = Mg 2+ , Zn 2+ , Co 2+ , Ni 2+ , etc.; M 3+ = Al 3+ , Fe 3+ , Co 3+ , etc.; and A n− is the intercalated anion, which can vary from a simple inorganic to a targeted organic anion introducing a synergistic functionality to this organic/inorganic hybrid. The distance between inorganic hydroxide layers depends on the size and arrangement of the intercalated anions. 1,2 In recent years, extensive research has been devoted to studying layered simple hydroxides that contain a single type of metal cation with a positive charge created by hydroxyl vacancies. 3 − 5 The representative hydroxides are M 2 (OH) 3 (A n− ) 1/n ·mH 2 O (M = Co 2+ , Cu 2+ , Ni 2+ ) or layered zinc hydroxide salts Zn 5 (OH) 8 (A n− ) 2/n ·2H 2 O (LZHs). In the hydroxide layers of LZHs, one-quarter of octahedrally coordinated zinc ions are replaced by two tetrahedrally coordinated zinc ions located below and above the plane, with water molecules coordinated at the apexes of the tetrahedra. 6 LZHs are widely used as i...

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Section: ■ Introductionmentioning

confidence: 99%

Insight into the Structure of Layered Zinc Hydroxide Salts Intercalated with Dodecyl Sulfate Anions

et al. 2014

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“…7,8,15 In addition, carboxylate related oxygen atoms are located in the extended coordination sphere (Fig. 5a, grey, dashed bonds) with Cu-O distances ranging from 2.29 Å to 2.41 Å resulting in squared pyramidal extended coordination spheres of Cu(1) and Cu (2) and in a Jahn-Teller-like distorted octahedra extended coordination sphere of Cu(3).…”

Section: Crystal Structure Descriptionmentioning

confidence: 99%

“…Considering the unit cell volume, the site multiplicities in space group P2 1 /c (14) and the packing densities of the related copper(II)-acetate-hydroxide hydrates, 7,8,15 35 the positions of the acetate and hydroxide ions and water molecules were determined. Rigid bodies for the acetate ions were defined in z-matrix notation and translated and rotated freely through the unit cell.…”

Section: Crystal Structure Solutionmentioning

confidence: 99%

“…The crystal structure of the 1-3-2 phase was solved both from powder 7 and single crystal 8 X-ray diffraction. Crystalline powders of the 1-3-2 phase were obtained by adding NaOH 7 or NH 3(aq) 4,5 to concentrated Cu(CH 3 COO) 2 solution 8 at 60°C. Single crystals were grown by refluxing a 0.1 M Cu(CH 3 COO) 2 solution at 60°C for 60 h without stirring 8 or by crystallisation from gel.…”

Section: Introductionmentioning

confidence: 99%

“…Crystalline powders of the 1-3-2 phase were obtained by adding NaOH 7 or NH 3(aq) 4,5 to concentrated Cu(CH 3 COO) 2 solution 8 at 60°C. Single crystals were grown by refluxing a 0.1 M Cu(CH 3 COO) 2 solution at 60°C for 60 h without stirring 8 or by crystallisation from gel. 25 The 1-3-2 phase can be converted into the 1-2-0 phase by ageing in concentrated Cu(CH 3 COO) 2 solution at 60°C.…”

Section: Introductionmentioning

confidence: 99%

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On verdigris, part II: synthesis of the 2-1-5 phase, Cu₃(CH₃COO)₄(OH)₂·5H₂O, by long-term crystallisation from aqueous solution at room temperature

et al. 2018

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PAPERemployed to confirm selected aspects of the determined crystal structure. The magnetic properties of the 2-1-5 phase decompose into two independent subsystems: a strongly antiferromagnetically spin exchange coupled magnetic Cu-Cu dimer and a significantly weaker coupled Cu monomer. The light blue colour of the sample originates from a reflectance maximum at 488 nm and significantly differs from the known verdigris phases. An investigation of several historic verdigris pigment samples revealed that this phase occurs both as a minor and a major component. Hence, our reference data for the title compound will help to improve the understanding of the multiphase mixtures occurring in historic verdigris samples.

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Ultrathin Layered Hydroxide Cobalt Acetate Nanoplates Face‐to‐Face Anchored to Graphene Nanosheets for High‐Efficiency Lithium Storage

Hei

et al. 2017

Adv Funct Materials

111

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The dramatically increasing demand of high‐energy lithium‐ion batteries (LIBs) urgently requires advanced substitution for graphite‐based anodes. Herein, inspired from the extra capacity of lithium storage in solid‐electrolyte interface (SEI) films, layered hydroxide cobalt acetates (LHCA, Co(Ac)0.48(OH)1.52·0.55H2O) are introduced as novel and high‐efficiency anode materials. Furthermore, ultrathin LHCA nanoplates are face‐to‐face anchored on the surface of graphene nanosheets (GNS) through a facile solvothermal method to improve the electronic transport and avoid agglomeration during repeated cycles. Profiting from the parallel structure, LHCA//GNS nanosheets exhibit extraordinary long‐term and high‐rate performance. At the current densities of 1000 and 4000 mA g−1, the reversible capacities maintain ≈1050 mAh g−1 after 200 cycles and ≈780 mAh g−1 after 300 cycles, respectively, much higher than the theoretical value of LHCA according to the conversion mechanism. Fourier transform infrared spectroscopy confirms the conversion from acetate to acetaldehyde after lithiation. A reasonable mechanism is proposed to elucidate the lithium storage behaviors referring to the electrocatalytic conversion of OH groups with Co nanocatalysts. This work can help further understand the contribution of SEI components (especially LiOH and LiAc) to lithium storage. It is envisaged that layered transition metal hydroxides can be used as advanced materials for energy storage devices.

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Synthesis and characterization of single crystals of the layered copper hydroxide acetate Cu₂(OH)₃(CH₃COO)·H₂O

Cited by 42 publications

References 23 publications

Insight into the Structure of Layered Zinc Hydroxide Salts Intercalated with Dodecyl Sulfate Anions

Insight into the Structure of Layered Zinc Hydroxide Salts Intercalated with Dodecyl Sulfate Anions

On verdigris, part II: synthesis of the 2-1-5 phase, Cu₃(CH₃COO)₄(OH)₂·5H₂O, by long-term crystallisation from aqueous solution at room temperature

Ultrathin Layered Hydroxide Cobalt Acetate Nanoplates Face‐to‐Face Anchored to Graphene Nanosheets for High‐Efficiency Lithium Storage

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Synthesis and characterization of single crystals of the layered copper hydroxide acetate Cu2(OH)3(CH3COO)·H2O

Cited by 42 publications

References 23 publications

Insight into the Structure of Layered Zinc Hydroxide Salts Intercalated with Dodecyl Sulfate Anions

Insight into the Structure of Layered Zinc Hydroxide Salts Intercalated with Dodecyl Sulfate Anions

On verdigris, part II: synthesis of the 2-1-5 phase, Cu3(CH3COO)4(OH)2·5H2O, by long-term crystallisation from aqueous solution at room temperature

Ultrathin Layered Hydroxide Cobalt Acetate Nanoplates Face‐to‐Face Anchored to Graphene Nanosheets for High‐Efficiency Lithium Storage

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Synthesis and characterization of single crystals of the layered copper hydroxide acetate Cu₂(OH)₃(CH₃COO)·H₂O

On verdigris, part II: synthesis of the 2-1-5 phase, Cu₃(CH₃COO)₄(OH)₂·5H₂O, by long-term crystallisation from aqueous solution at room temperature