Electrical Network of Single‐Crystalline Metal Oxide Nanoclusters Wired by π‐Molecules

Abstract

In a mixed-valence polyoxometalate, electrons are usually delocalized within the cluster anion because of low level of inter-cluster interaction. Herein, we report the structure and electrical properties of a single crystal in which mixed-valence polyoxometalates were electrically wired by cationic π-molecules of tetrathiafulvalene substituted with pyridinium. Electron-transport characteristics are suggested to represent electron hopping through strong interactions between cluster and cationic π-molecules.

Transformation of Polyoxometalate into 3D Porous Li‐Containing Oxide: A Case Study of γ‐LiV2O5 for High‐Performance Cathodes of Li‐Ion Batteries

“…Unfortunately, POM‐based electrode materials suffer badly from inherent drawbacks, including poor intrinsic electronic conductivity, dissolution in the electrolyte, and low voltage plateaus. To overcome the negligible electronic conductivity of POMs (e.g., 10 −11 S cm −1 for [( n ‐C 4 H 9 ) 4 N] 3 [PMo 12 O 40 ] and 8.99 × 10 −13 S cm −1 for [( n ‐C 4 H 9 ) 4 N] 5 H[Mo 18 O 54 (SO 3 ) 2 ]), the strategy of compositing POMs with high conductive substrates, such as carbon nanotubes, graphene, and conductive polymers, was developed . However, ≈70 wt% of conductive additives (including conductive substrates and carbon black) was generally needed to prepare the POM‐based cathodes, which greatly reduced the energy density of electrode materials and sacrificed the high‐capacity advantage of POM compounds.…”

Free‐Standing 3D Electrodes for Electrochemical Detection of Hydrogen Peroxide

“…[22][23] As summarized in previous reviews, the electrocatalysts cover metal and alloys (Au, Ag, Pt, Pd, AuAg, [a] Dr. PtPd, RuRh, et al), metal oxides (MnO 2 , TiO 2 , Co 3 O 4 , Fe 3 O 4 , CuO, et al), metal complexes (ferric hexacyanoferrate, metallophthalocyanines, metalloporphyrins, et al), organic and polymeric materials (redox dyes, conductive polymers, et al), carbon nanomaterials (carbon nanotubes, graphene, doped carbon materials, et al), as well as their hybrids with two or more composites. [24][25][26] Recent researches further develop cheap, abundant, easy-accessible materials including transition metal sulfides (TMSs), [27][28][29][30] metal-organic frameworks (MOFs), [31][32][33][34] layered double hydroxides (LDHs), [35][36] metal hydroxides, [37][38] polyoxometalates (POMs), [39][40][41] MXene, [42][43][44] zeolites [45][46][47] black phosphorus, [48][49] and porous silicon [50][51][52][53] based catalysts, et al Some non-enzyme biomaterials, like hemin, G-quadruplex, are also involved in inorganic-organic nanohybrid catalysts.…”

Non‐Aqueous Microwave‐Assisted Syntheses of Deca‐ and Hexa‐Molybdovanadates

“…Combustion and ICP-OES analysis are in excellent agreement with the formulation of (TBA) 2 -[V 3 Mo 3 O 16 (O 3 C 5 H 9 )] while ESI-MS gave the parent ion at m/z 814.53 with the distinctive isotopic envelope owing to its heterometallic nature ( Figures S3 and S4). Compound 2 crystallized in the polar non-centrosymmetric space group P n with ar efined Flack parameter of 0.01 (3). Similarly,t othat observed in the crystallography of 1,crystallographic analysis of 2 revealed the probability of several structural isomers with variability in electron density observed at each of the six metal sites of the two crystallographically independent polyanions located in the asymmetric unit.…”

“…[2] Given this compositional and structural versatility,POMs have been utilized for catalytic, biological, and molecular electronic applications. [3][4][5][6][7][8][9][10][11] Historically the compositional diversification of POMs has been achieved via:reaction of stoichiometric mixtures of the desired constituents in pH controlled media;the addition of electrophiles to preformed plenary or lacunary POMs;o r the covalent functionalization of the POM surface by organic moieties. [12][13][14][15][16][17][18][19][20][21][22][23][24] Often the precise atomic ratios of early transition metals in the products can be controlled, however, occasionally the solution chemistry is sufficiently complex that separation and structural characterization of all products is not possible.…”

“…[27,28] Herein, we build upon our recent efforts towards the microwave-assisted synthesis of POMs [29,30] and report the characterization of two elusive molybdovanadates as their tetrabutylammonium salts (TBA). Thedecametalate (TBA) 3…”