Atomically precise metal-chalcogenide semiconductor molecular nanoclusters with high dispersibility: Designed synthesis and intracluster photocarrier dynamics

Zhang, Jiaxu; Qin, Chaochao; Zhong, Yeshuang; Xiang, Wang; Wang, Wei; Hu, Dandan; Liu, Xiaoshuang; Xue, Chaozhuang; Zhou, Rui; Shen, Li; Song, Yinglin; Xu, Dingguo; Lin, Zhien; Guo, Jun; Su, Hai‐Feng; Li, Dongsheng; Wu, Tao

doi:10.1007/s12274-020-2936-0

Cited by 26 publications

(40 citation statements)

References 51 publications

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“…It is known that b = 0.5 implies the electrochemical reaction principally counts on ionic diffusion, while b = 1 implies a capacitance-controlled process is involved [39]. For Z-Co2NiSe4/BWC, the b values of two sets of peaks are 0.68 and 0.63, illustrating the emergence of diffusion-controlled batterytype behavior in the electrochemical reaction process (Fig.…”

Section: Resultsmentioning

confidence: 96%

Zephyranthes-like Co2NiSe4 arrays grown on 3D porous carbon frame-work as electrodes for advanced supercapacitors and sodium-ion batteries

Xue

Guo

et al. 2021

Nano Res.

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Developing suitable electrode materials for electrochemical energy storage devices by biomorph assisted design has become a fascinating topic due to the fantastic properties derived from bio-architectures. Herein, zephyranthes-like Co 2 NiSe 4 arrays grown on butterfly wings derived three-dimensional (3D) carbon framework (Z-Co 2 NiSe 4 /BWC) is fabricated via hydrothermal assembly and further conversion method. Benefiting from its unique structure and multi-components, the obtained Z-Co 2 NiSe 4 /BWC electrode for supercapacitor delivers an excellent specific capacitance of 2,280 F•g −1 at 1 A•g −1 . Impressively, the constructed asymmetric supercapacitor using Co 2 NiSe 4 /BWC as positive electrode and activated butterfly wings carbon as negative electrode acquires a high energy density of 42.9 Wh•kg −1 at a power density of 800 W•kg −1 with robust stability of 94.6% capacitance retention at 10 A•g −1 after 5,000 cycles. Moreover, the Z-Co 2 NiSe 4 /BWC as anode for sodium-ion batteries exhibits a high specific capacity of 568 mAh•g −1 at 0.1 A•g −1 and high cycling stability (maintaining 80.1% of the second cycle after 100 cycles). The outstanding electrochemical performances are ascribed to that the synergistic effect of bimetallic selenides and N-doped carbon improves electrochemical activities and conductivity. One-dimensional (1D) nanoneedles grown on 3D porous framework increase the exposure of redox-active sites, endow adequate transmission channels of electrons/ions, and guarantee stability of the electrode during charge/discharge processes. This study will shed light on the avenue towards extending such nanohybrids to excellent energy storage applications.

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Section: Resultsmentioning

confidence: 96%

Zephyranthes-like Co2NiSe4 arrays grown on 3D porous carbon frame-work as electrodes for advanced supercapacitors and sodium-ion batteries

Xue

Guo

et al. 2021

Nano Res.

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“…Metal chalcogenide supertetrahedral T n clusters with atomically defined structures span the size gap between isolated molecular species and semiconductor nanoparticles. − They can exist in the form of discrete clusters whose dispersibility in solvents bears great importance for their solution processable applications in electrocatalysis, , photocatalysis, − photoluminescence, − and so on. In addition, these clusters can also spontaneously coassemble into extended frameworks with specific applications in solid electrolyte, solar energy conversion, ion exchange, − and so on.…”

Section: Introductionmentioning

confidence: 99%

Mixed Solvothermal Synthesis of Tn Cluster-Based Indium and Gallium Sulfides Using Versatile Ammonia or Amine Structure-Directing Agents

et al. 2021

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Metal chalcogenide supertetrahedral Tn clusters are of current interest for their unique compositions and structures, which rely highly on the structure-directing agents. Herein, we report four novel Tn cluster-based indium and gallium sulfides, namely, [NH(CH 3 ) 3 ] 4 In 4 S 10 H 4 (1), (NH 3 ) 4 Ga 4 S 6 (2), [NH 3 CH 2 CH 3 ] 5 (NH 2 CH 2 CH 3 ) 2 Ga 11 S 19 (3), and [NH 3 CH 2 -CH 2 OH] 6 Ga 10 S 18 •2NH 2 CH 2 CH 2 OH ( 4). All four compounds were solvothermally synthesized in mixed amine−ethanol solutions or deep eutectic solvent (DES), where ammonia/amine molecules play significant structure-directing roles in the speciation and crystal growth. (1) Being protonated, the trimethylamine and ethanolamine molecules surround the T2-[In 4 S 10 H 4 ] 4− clusters (for 1) and [Ga 10 S 18 ] n 6n− open framework (for 4), respectively, compensating for the negative charge of the inorganic moieties. (2) With the lone pair of electrons, the ammonia molecules in 2 coordinate directly to corner Ga 3+ ions of the {Ga 4 S 6 } cage to give a neutral T2-(NH 3 ) 4 Ga 4 S 6 cluster. (3) For compound 3, part of the ethylamine molecules act as terminating ligands for the T1 and T3 units in the [Ga 11 S 19 (NH 2 CH 2 CH 3 ) 2 ] n 5n− layer, while the rest act as interlamellar countercations upon protonation. Theoretical studies reveal the contributions of N, C, and H to the density of states (DOS) for 2 and 3 because of their hybrid structures that combine the ammonia/amine ligands with sulfide moieties together.

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“…Some large isolated clusters, such as iso-T5 in ISC-9 with the organic ligand terminated at the corner, 37 coreless iso-T5 in ISC-10, 24 and iso-P2-CuM(III)SnS (M = In or Ga), have also been reported by our research group. 38 The dispersibility of the discrete Tn or Pn clusters is severely limited by the electrostatic interaction between the close packing of the organic cations and polyanionic MCSCs in a crystal lattice. To resolve this, Dai's group proposed a strategy to overcome the strong ionic force in crystals using a medium with high ionic strength (LiBr−DMF) and subsequently achieved the dispersibility of discrete T5-CuInS.…”

Section: Discretization and Dispersibility Of Mcscsmentioning

confidence: 99%

“…41 Contrary to the substitution of anions, high content of Sn 4+ was intentionally introduced into P2 clusters to decrease the global charge of the individual cluster, which also afforded excellent aqueous dispersibility and stability to the P2 clusters (Figure 4a). 38 Notably, the packing of the isolated T4 clusters in a crystal lattice was recently determined to play an important role in tuning their dispersibility (Figure 4b). 42 For more detailed information about the synthesis, yield, stability, and solubility of discrete MCSCs, please see Table S1.…”

Section: Discretization and Dispersibility Of Mcscsmentioning

confidence: 99%

Metal Chalcogenide Supertetrahedral Clusters: Synthetic Control over Assembly, Dispersibility, and Their Functional Applications

et al. 2020

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Conspectus Metal chalcogenide supertetrahedral clusters (MCSCs) bear the closest structural resemblance to II–VI or I–III–VI semiconductor nanocrystals and can be considered as well-defined ultrasmall “quantum dots” (QDs). Compared to traditional colloidal QDs that are typically associated with size dispersity, irregular surface atomic structures, poorly defined core–ligand interfaces, and random defect/dopant sites, the nano- or subnano-sized MCSCs feature precise structural properties such as atomically uniform size, precise structure, and ordered dopant distribution, all of which offer ample opportunities for a broad and in-depth understanding of the correlation between the precise local structure and site- or size-dependent properties, which are critical to the exploitation of their functional applications. Our previous Account in 2005 provided a narrative on the efforts to expand the structural diversity of open-framework materials using different-sized and compositionally tunable clusters as building blocks with a primary objective of integrating the semiconducting properties with porosity in zeolite-type solids. Over the past 15 years, significant progress has been made, particularly in the synthetic control of discrete clusters, allowing the establishment of the composition–structure–property correlation of the MCSCs to guide the optimization of their properties for various applications. In the present Account, the recent progress in MCSC-based chemistry is reviewed from three aspects: (1) controllable synthesis of new members and types of MCSC models and the development of organic-ligand-directed hybrid assembly modes for MCSC-based open frameworks; (2) new synthetic strategies for the discretization of MCSCs in crystal lattice and their dispersibility in solvents, affording practical applications of pure inorganic MCSCs as nanomaterials; and (3) functionality of MCSC-based materials including photochemical and electrochemical properties triggered by precise dopant/defect sites, open-framework-related functional expansion via host–guest chemistry, and dispersed cluster-based composite materials with synergy from functional multimetallic components. All these advances show that MCSCs with well-defined structures and atomically precise dopant/defect sites are powerful model systems for establishing the precise structure–composition–property correlation and understanding the photophysical dynamic behaviors, both of which are difficult or impossible to achieve in the traditional QD system. Perspectives on their potential applications are presented in terms of the amorphous assemblies of monodispersed MCSCs, MCSC-based two-dimensional layered materials, and optical/electronic devices.

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Atomically precise metal-chalcogenide semiconductor molecular nanoclusters with high dispersibility: Designed synthesis and intracluster photocarrier dynamics

Cited by 26 publications

References 51 publications

Zephyranthes-like Co2NiSe4 arrays grown on 3D porous carbon frame-work as electrodes for advanced supercapacitors and sodium-ion batteries

Zephyranthes-like Co2NiSe4 arrays grown on 3D porous carbon frame-work as electrodes for advanced supercapacitors and sodium-ion batteries

Mixed Solvothermal Synthesis of Tn Cluster-Based Indium and Gallium Sulfides Using Versatile Ammonia or Amine Structure-Directing Agents

Metal Chalcogenide Supertetrahedral Clusters: Synthetic Control over Assembly, Dispersibility, and Their Functional Applications

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