A Two-Dimensional Inorganic–Organic Hybrid Solid of Manganese(II) Hydrogenophosphate Showing High Proton Conductivity at Room Temperature

Zhao, Hai-rong; Xue, Chengshan; Li, Cuiping; Zhang, Kaiming; Luo, Hui; Liu, Shao-Xian; Ren, Xiao‐Ming

doi:10.1021/acs.inorgchem.6b01438

Cited by 43 publications

(22 citation statements)

References 47 publications

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“…The thermal gravimetric analysis (Fig. S8, ESI†) shows similar weight losses to reported results 36. The molar ratio of Mn : P in Mn-LNPs is 2 : 3.01 based on the EDX analysis.…”

Section: Resultssupporting

confidence: 83%

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Manganese(ii) phosphate nanosheet assembly with native out-of-plane Mn centres for electrocatalytic water oxidation

et al. 2019

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“…The thermal gravimetric analysis (Fig. S8, ESI†) shows similar weight losses to reported results 36. The molar ratio of Mn : P in Mn-LNPs is 2 : 3.01 based on the EDX analysis.…”

Section: Resultssupporting

confidence: 83%

“…2D). The crystalline phase of Mn-LNPs can be indexed to reported crystal structures of (C 2 H 10 N 2 )[Mn 2 (HPO 4 ) 3 ]·H 2 O, which is a layered material with intercalated amine molecules between the phosphate layers 36. The strong diffraction peak at 8.0° indicates the long-range well-organized stacking of manganese phosphate layers.…”

Section: Resultsmentioning

confidence: 99%

Manganese(ii) phosphate nanosheet assembly with native out-of-plane Mn centres for electrocatalytic water oxidation

et al. 2019

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“…At 230 °C, the (200) diffraction peak splits, and a weak new peak with higher 2θ value appears. Due to the loss of some lattice water, the interlayer space was reduced for partial layers of the sample 46 . At 235 °C, the original (200) diffraction peak is very weak, indicating that the lattice water molecules disappear completely.…”

Section: Resultsmentioning

confidence: 99%

Biomimicking Hydrogen-Bonding Network by Ammoniated and Hydrated Manganese (II) Phosphate for Electrocatalytic Water Oxidation

Gao¹,

Yang²,

Zhang³

et al. 2020

Acta Physico Chimica Sinica

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Asymmetric manganese cluster, the active center of photosystem II (PSII) in nature, is hydrogen-bonded to surrounding amino acid residues and water molecules. This phenomenon is of great inspiration significance for developing and studying artificial Mn-based oxygen evolution reaction (OER) catalysts. Herein, we prepared manganese phosphate nanosheets through intercalation of ethylenediamine ions and water molecules ((EDAI)(H2O)MnPi) using a simple coprecipitation method. (EDAI)(H2O)MnPi is also hydrogen-bonded to interlayer ethylenediamine ions and water molecules, forming a hydrogen-bonding network. The morphology of the (EDAI)(H2O)MnPi sample was characterized by scanning electron microscopy (SEM) and transmission electron microscopy. The thickness of (EDAI)(H2O)MnPi was characterized by atomic force microscopy. The composition and structure of (EDAI)(H2O)MnPi were characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy. For control studies, manganese phosphate (EDAI)MnPi and (H2O)MnPi samples were also synthesized. The structure and morphology of (EDAI)MnPi and (H2O)MnPi samples were characterized by XRD and SEM. The difference between (EDAI)(H2O)MnPi, (EDAI)MnPi, and (H2O)MnPi were further characterized by thermal gravimetric analysis and derivative thermogravimetric analysis. Electrocatalytic properties of the (EDAI)(H2O)MnPi, (EDAI)MnPi, and (H2O)MnPi for OER were studied in 0.05 mol•L −1 pH = 7 phosphate buffered saline solution, through linear sweep voltammetry, electrochemical impedance spectroscopy, and controlled potential electrolysis (CPE) test. The electrochemical surface area (ECSA) analyses of (EDAI)(H2O)MnPi, (EDAI)MnPi, and (H2O)MnPi samples were recorded by charging currents in the non-Faradaic potential region at different scan rates. Considering the different ECSAs of different materials, the water oxidation activities of three materials were normalized by ECSA. Compared with counterparts of (EDAI)MnPi (610 mV) and (H2O)MnPi (580 mV), manganese phosphate nanosheets (EDAI)(H2O)MnPi exhibited a lower overpotential of 520 mV when driving a current density of 1 mA•cm −2 in neutral conditions. The CPE experiment revealed that (EDAI)(H2O)MnPi remained active for at least 10 h. Manganese phosphate nanosheets containing a rich, extensive, and continuous hydrogen bond network exhibited improved OER performance in neutral conditions. The hydrogen-bonding network in manganese phosphate nanosheets has similar functions to the hydrogen-bonding network in PSII, which could accelerate the transfer rate of protons and facilitate electrocatalytic water oxidation. This study may provide guidance for the design of water oxidation catalysts with rich hydrogen bond network.

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“…On the one hand, the molecular structure, synthetic approach and functional properties of organic molecule are easily tailored.O nt he other hand, the inorganic network of materials has generally chemical, thermal, mechanical stabilities and aw ide range of electric characteristics as well. These advantages make them suitable for av ariety of low-cost optoelectronic devices and materials,s uch as lightemitting diodes, [29][30][31] switching materials, [32][33][34][35][36] proton-conducting materials [37,38] and solar cells. [39][40][41] Meanwhile, much progress has been achieved for organic-inorganic hybridc ompounds in ferroelectricity.I nt he wide field of hybrid ferroelectrics, the hybrid halometallates of M II (M = Pb, Mn, Cd) represent at echnologically important class, since they preserve the structural characteristics of perovskites.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, the inorganic network of materials has generally chemical, thermal, mechanical stabilities and a wide range of electric characteristics as well. These advantages make them suitable for a variety of low‐cost optoelectronic devices and materials, such as light‐emitting diodes, switching materials, proton‐conducting materials and solar cells . Meanwhile, much progress has been achieved for organic‐inorganic hybrid compounds in ferroelectricity.…”

Section: Introductionmentioning

confidence: 99%

Dielectric Relaxation and Beyond Limiting Behavior of Alternating‐Current Conductivity in a Supermolecular Ferroelectric

Tong

Tian

Duan

et al. 2019

Chemistry An Asian Journal

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A cyclen‐based hybrid supermolecule crystal, [(FeCl2)(cyclen)]Cl (1), where cyclen=1,4,7,10‐tetraazacyclododecane, was prepared using a liquid–liquid diffusion approach. The variable crystal structures exhibit that compound 1 belongs to an orthorhombic crystal system, Pna21 space group (point group C2V) in the temperature range of 150–400 K. This hybrid supermolecule shows a dielectric relaxation behavior around room temperature, and the ferroelectric nature of 1 has been directly verified by hysteresis measurements. In addition, the AC (alternating current) conductivity study reveals that the 1 displays a beyond limiting behavior. These interesting findings are for the first time reported in the field of supermolecular ferroelectrics. This study may open a new way to construct supermolecular ferroelectrics and give insights into their conductor behavior.

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A Two-Dimensional Inorganic–Organic Hybrid Solid of Manganese(II) Hydrogenophosphate Showing High Proton Conductivity at Room Temperature

Cited by 43 publications

References 47 publications

Manganese(ii) phosphate nanosheet assembly with native out-of-plane Mn centres for electrocatalytic water oxidation

Manganese(ii) phosphate nanosheet assembly with native out-of-plane Mn centres for electrocatalytic water oxidation

Biomimicking Hydrogen-Bonding Network by Ammoniated and Hydrated Manganese (II) Phosphate for Electrocatalytic Water Oxidation

Dielectric Relaxation and Beyond Limiting Behavior of Alternating‐Current Conductivity in a Supermolecular Ferroelectric

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