Co-assembled T4-Cu4In16S35 and Cubic Cu12S8 Clusters: A Crystal Precursor for Near-Infrared Absorption Material

Zhao, Xiaowei; Qian, Li-Wen; Su, Hu-Chao; Mo, Chong-Jiao; Que, Chen-Jie; Zhu, Qian‐Jiang; Dai, Jie

doi:10.1021/acs.cgd.5b00960

Cited by 20 publications

(14 citation statements)

References 30 publications

(51 reference statements)

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“…Generally speaking, to perfectly satisfy Pauling’s electrostatic valence rule, the four metal sites combined with central Q 2– (Q = S, Se) are typically metal ions with a +2 valence. It has been widely accepted that the typical metal proportion in this type of T4 cluster is 4/16. − Although infrequent, the metal ratio of 3/17 in our compounds does not breach Pauling’s electrostatic valence rule.…”

Section: Resultsmentioning

confidence: 64%

Soluble Supertetrahedral Chalcogenido T4 Clusters: High Stability and Enhanced Hydrogen Evolution Activities

Hao

Zhang

et al. 2019

Inorg. Chem.

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The discrete supertetrahedral chalcogenido Tn clusters can be regarded as a type of quantum dot (QD) with precise structure and uniform size. They were commonly studied in the solid state because of their poor solubility or highly negative charge that leads to instability in common solvents. These drawbacks limit their potential applications as efficient photocatalysts. Herein we first obtained a sulfide compound via an ionic-liquid-assisted precursor method, namely, (BMMim)9(Cd3In17S31Cl4) (T4-1, BMMim = 1-butyl-2,3-dimethylimidazolium). T4-1 is characteristic of the discrete anionic T4 cluster and is insoluble in common solvents. Introducing Se into the structure resulted in compounds (BMMim)9(Cd3In17S13Se18Cl4) (T4-2) and (BMMim)9(Cd3In17Se31Cl4)(4,4′-bpy) (T4-3) with narrower band gaps. Moreover, T4-2 and T4-3 were soluble in dimethyl sulfoxide (DMSO) probably because of weaker interactions between cations and anions than in T4-1. The solution stability of these clusters has been confirmed by mass spectrometry. Further characterization reveals that the highly dispersed T4 clusters exposed more active sites in solution, so their rates of relevant H2 production were improved to be ∼5 times that in the solid state. To our knowledge, this is the first time that highly dispersed Tn clusters have been applied in photocatalytic H2 generation.

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Section: Resultsmentioning

confidence: 64%

Soluble Supertetrahedral Chalcogenido T4 Clusters: High Stability and Enhanced Hydrogen Evolution Activities

Hao

Zhang

et al. 2019

Inorg. Chem.

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“…Hitherto, although some A–Cu–M–S (A = organic amine, M = In/Ga) sulfides have been synthesized by solvothermal methods, their crystal structures are quite different from compounds 1 and 2 . In these reported A–Cu–M–S compounds, − MS 4 tetrahedra polymerize to decrease the high negative charge of single MS 4 , and generate T n clusters, while lower charge metal Cu + ions partially substitute for M 3+ and produce supertetrahedral clusters (T 4 or T 5 ), which results in a lower Cu/M ratio framework. Nevertheless, compounds 1 and 2 feature novel 3D frameworks, in which M 3+ ions are incorporated into the Cu–S frameworks (Figures S2a and S3) and possess the highest ratio (3/1) of Cu/M that has never be found in related compounds synthesized by solvothermal methods before.…”

Section: Resultsmentioning

confidence: 99%

Solvothermal Syntheses and Characterizations of Four Quaternary Copper Sulfides BaCu₃MS₄ (M = In, Ga) and BaCu₂MS₄ (M = Sn, Ge)

et al. 2019

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Hydro(solvo)thermal syntheses of quaternary copper sulfides containing alkaline earth metal ions remain a great challenge because of the low solubility of Cu–S compounds. Herein, a new facile solvothermal method was developed, and four quaternary copper sulfides, i.e., BaCu3InS4 (1), BaCu3GaS4 (2), BaCu2SnS4 (3), and BaCu2GeS4 (4), were prepared using excess sulfur as a mineralizer. Compound 1 possesses a novel three-dimensional (3D) anionic [Cu3InS4]2– framework constructed by an 8-membered ring of [Cu4S4] and [Cu2In2S4] alternatively. Compound 2 features a unique 3D anionic [Cu3GaS4]2– framework composed of [Cu3GaS10] n 14n– anionic chains and 8-membered rings, in which [Cu4S4] and [Cu2Ga2S4] reside alternatively. Compounds 3 and 4 feature 3D anionic [Cu2MS4]2– (M = Sn, Ge) frameworks composed of CuS4 and MS4 tetrahedra with Ba2+ located in the channels. It is worth noting that different 3D Cu–S frameworks exist in the title crystal structures, in which main group ions are incorporated. This paper provides a new synthetic strategy for new quaternary sulfides.

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“…proposed an extension of microporous materials from oxides to chalcogenides . Since then, microporous chalcogenides have attracted a great deal of research attention, because of their prominent semiconductivity and potential applications in areas ranging from fast-ion conductivity to selective ion exchange, photovoltaic conversion, and visible-light photocatalysis. − …”

Section: Introductionmentioning

confidence: 99%

Unusual Flexibility of Microporous Sulfides during Ion Exchange

Zhang

Cao

et al. 2018

Inorg. Chem.

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Open-framework chalcogenides with ion-exchange capacity are promising materials for removing hazardous heavymetal ions and for capturing radioactive Cs + . However, research on the exchange mechanism is limited, especially for the framework chalcogenides that have multiple bridging anions. Generally, openframework chalcogenides that have multiple bridging anions at the window or wall of the channels are rigid during the ion-exchange process. We show here that microporous sulfides with μ 3 -S 2− (where μ 3 = triple bridging mode) at the windows exhibit framework flexibility upon ion exchange. Three new microporous sulfides Na 4 Cu 8 Ge 3 S 12 •2H 2 O (1), Na 3 (Hen)Cu 8 Sn 3 S 12 (where en = ethylenediamine) (2) and (dap) 2 (Hdap) 4 Cu 8 Ge 3 S 18 (where dap = 1,2-diaminopropane) (3) were synthesized under solvothermal conditions. Compounds 1 and 2 contain a copper-rich framework composed of icosahedral [Cu 8 S 12 ] 16− units linked via monomeric GeS 4 4− or SnS 4 4− tetrahedral units, whereas compound 3 features an expanded framework composed of icosahedral [Cu 8 S 12 ] 16units interconnected with dimeric Ge 2 S 6 4− units. These compounds exhibit unusual ion-exchange properties. Specifically, the frameworks of 1 and 2 (with μ 3 -S at the small windows) show "breathing action" upon ion exchange of K + or Rb + , which have relative large sizes, and compound 3 exhibits framework flexibility upon Cs + ion exchange with both space group and channels changed.

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Co-assembled T4-Cu₄In₁₆S₃₅ and Cubic Cu₁₂S₈ Clusters: A Crystal Precursor for Near-Infrared Absorption Material

Cited by 20 publications

References 30 publications

Soluble Supertetrahedral Chalcogenido T4 Clusters: High Stability and Enhanced Hydrogen Evolution Activities

Soluble Supertetrahedral Chalcogenido T4 Clusters: High Stability and Enhanced Hydrogen Evolution Activities

Solvothermal Syntheses and Characterizations of Four Quaternary Copper Sulfides BaCu₃MS₄ (M = In, Ga) and BaCu₂MS₄ (M = Sn, Ge)

Unusual Flexibility of Microporous Sulfides during Ion Exchange

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Co-assembled T4-Cu4In16S35 and Cubic Cu12S8 Clusters: A Crystal Precursor for Near-Infrared Absorption Material

Cited by 20 publications

References 30 publications

Soluble Supertetrahedral Chalcogenido T4 Clusters: High Stability and Enhanced Hydrogen Evolution Activities

Soluble Supertetrahedral Chalcogenido T4 Clusters: High Stability and Enhanced Hydrogen Evolution Activities

Solvothermal Syntheses and Characterizations of Four Quaternary Copper Sulfides BaCu3MS4 (M = In, Ga) and BaCu2MS4 (M = Sn, Ge)

Unusual Flexibility of Microporous Sulfides during Ion Exchange

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Co-assembled T4-Cu₄In₁₆S₃₅ and Cubic Cu₁₂S₈ Clusters: A Crystal Precursor for Near-Infrared Absorption Material

Solvothermal Syntheses and Characterizations of Four Quaternary Copper Sulfides BaCu₃MS₄ (M = In, Ga) and BaCu₂MS₄ (M = Sn, Ge)