An MOF-like Interpenetrated 2D Plus 2D to 3D Inorganic Grid Assembled by Linear Inorganic Pillars, Structures, and Properties in Supercapacitance

Abstract

Remarkable progresses regarding pure inorganic frameworks and metal-organic frameworks (MOF) have been made. However, pure inorganic frameworks with MOF-like grid structures are rarely reported due to the weakness of inorganic moiety as a long linear linker. We report herein a fascinating inorganic framework assembled by a [GeS] cluster node and a linear [-Cu-MS-Cu-] (M = Mo (1) and W (2)) inorganic pillar. Their network shows MOF-like orthogonal structure with two interpenetrated two-dimensional (2D) plus 2D to 3D framework and a 1D nano tunnel. Electrodes with crystalline sample of 1 and 2, inorganic sulfide framework, were prepared, and their quasi-capacitance behaviors were investigated. Electrochemical performances were evaluated by cyclic voltammetry and galvanostatic charge-discharge techniques in CsOH, KOH, NaOH, and LiOH electrolytes. The results revealed that the crystal materials exhibit moderate specific capacitance values that are comparable to those of porous sulfide materials.

Cotemplating Assembly and Structural Variation of Three-Dimensional Open-Framework Sulfides

“…Continual efforts have been devoted to exploring open-framework sulfides because of their fascinating structures , and potential applications in nonlinear-optical properties, , visible-light photocatalysis, , and fast-ion conductivity. , Sulfides have higher covalent frameworks than zeolites owing to the large size of S 2– compared to O 2– . The covalency of sulfides is reflected in the fact that large clusters (such as supertetrahedral clusters − and the icosahedral [Cu 8 S 12 ] 16– cluster , ) can be used as secondary building units, , which have never been found in zeolites. Sulfide is different from zeolite in that the negative charge is mainly localized on AlO 4 .…”

Stepwise Conversion from GeO2 to [MGe4S10]n3n– (M = Cu, Ag) Polymer via Isolatable [Ge2S6]4– and [Ge4S10]4– Anions by Virtue of Templating Technique

“…Condensation of [Ge 4 S 10 ] 4– via Cu + or Ag + cations has proven to be an effective strategy for the construction of heterometallic sulfides, whose structures vary greatly depending upon the coordination geometry of Cu + or Ag + and the number of connecting S atoms on the [Ge 4 S 10 ] 4– cluster (listed in Table S3). − For instance, the polymerization of [Ge 4 S 10 ] 4– through two-coordinate Cu + contributes to a [CuGe 2 S 5 ] n n – framework expanding in 3D directions, whereas a 3,3-connection of [Ge 4 S 10 ] 4– and Ag + results in an infinite [AgGe 4 S 10 ] n 3 n – double chain . Under certain conditions, the Cu + or Ag + cations can even dimerize into metal–metal bonded Cu 2 2+ or Ag 2 2+ linkers, adopting a twisted four-connected fashion, to string up the [Ge 4 S 10 ] 4– clusters into a zinc blend type of framework [M 2 Ge 4 S 10 ] n 2 n – (M = Cu, Ag) .…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[260,263,272,275,281,[549][550][551][552] By utilizing two different transition metal complexes during the synthesis, a more complex Cu2MS6 (M = Mo, W) linker between Ge/S adamantane-type compounds was obtained to form the MOF like {[Me4N]4[(Ge4S10)Cu4M2S8]}n (995-996, Figure 21). [553] The concept could also be used to introduce another group 14 element, here tin, to Ge/S adamantanes by adding SnCl2 to K+ or Cs+ salts of [Ge4S10] 4− in ionic liquids, with the exact outcome dependent on the ionic liquid used (997-999). [554,555] In one case, {[BMIm]2[Ge4Se9]}n (997), this approach did not lead to the incorporation of Sn into the structure.…”

“…21). 553 The concept could also be used to introduce another group 14 element, here tin, to Ge/S adamantanes by adding SnCl 2 to K+ or Cs+ salts of [Ge 4 S 10 ] 4− in ionic liquids, with the exact outcome dependent on the ionic liquid used (997-999). 554,555 In one case, {[BMIm] 2 [Ge 4 Se 9 ]} n (997), this approach did not lead to the incorporation of Sn into the structure.…”