Bridging Component Strategy in Phosphomolybdate-Based Sensors for Electrochemical Determination of Trace Cr(VI).

Rapid and sensitive electrochemical determination of trace carcinogenic Cr(VI) pollutants remains an urgent and important task, which requires the development of active sensing materials. Herein, four cases of reduced phosphomolybdates with formulas of the (H2bib)3[Zn(H2PO4)]2{Mn[P4Mo6O31H7]2}·6H2O (1), (H2bib)2[Na(H2O)]2[Mn(H2O)]2{Mn[P4Mo6O31H6]2}·5H2O (2), (H2bib)3[Mo2(µ2-O)2(H2O)4]2{Ni[P4Mo6O31H2]2}·4H2O (3), and (H2bib)2{Ni[P4Mo6O31H9]2}·9H2O (4) (bib = 4,4'-bis(1-imidazolyl)-biphenyl) were hydrothermally synthesized under the guidance of a bridging component strategy, which function as effective electrochemical sensors to detect trace Cr(VI). The difference of hybrids 1-4 is in the inorganic moiety, in which the reduced phosphomolybdates {M[P4MoV6O31]2} (M{P4Mo6}2) exhibited different arrangements bridged by different cationic components ({Zn(H2PO4)} subunit for 1, [Mn2(H2O)2]4+ dimer for 2, and [MoV2(µ2-O)2(H2O)4]6+ for 3). As a result, hybrids 1 and 3 display noticeable Cr(VI) detection activity with low detection limits of 14.3 nM (1.48 ppb) for 1 and 6.61 nM (0.69 ppb) for 3 and high sensitivities of 97.3 and 95.3 µA·mM-1, respectively, which are much beyond the World Health Organization's detection threshold (0.05 ppm) and superior to those of the contrast samples (inorganic Mn{P4Mo6}2 salt and hybrid 4), even the most reported noble-metal catalysts. This work supplies a prospective pathway to build effective electrochemical sensors based on phosphomolybdates for environmental pollutant treatment.

Preparation of paramagnetic ferroferric oxide-calcined layered double hydroxide core-shell adsorbent for selective removal of anionic pollutants.

Adsorption is one of the most common methods of pollution treatment. The selectivity for pollutants and recyclability of adsorbents are crucial to reduce the treatment cost. Layered double hydroxide (LDH) materials are one type of adsorbent with poor recyclability. Prussian blue (PB) is a sturdy and inexpensive metal-organic framework material that can be used as the precursor for synthesizing paramagnetic ferroferric oxide (Fe3O4). It is intriguing to build some reusable adsorbents with magnetic separation by integrating LDH and PB. In this work, paramagnetic Fe3O4-calcined LDH (Fe3O4@cLDH) core-shell adsorbent was designed and prepared by the calcination of PB-ZnAl layered double hydroxide (PB@LDH) core-shell precursor, which exhibits high anionic dyes selectivity in wastewater solutions. The paramagnetism and adsorption capability of Fe3O4@cLDH come from the Fe3O4 core and calcined ZnAl-LDH shell, respectively. Fe3O4@cLDH shows an adsorption capacity of 230 mg g-1 for acid orange and a high selectivity for anionic dyes in cation-anion mixed dye solutions. The regeneration process indicates that the high selectivity for anions is related to the specific hydration recovery process of ZnAl-LDH. The synergistic effect of the paramagnetic Fe3O4 core and calcined ZnAl-LDH shell makes Fe3O4@cLDH an excellent magnetic separation adsorbent with high selectivity to anions.

Bio-Inspired FeMo2S4 Microspheres as Bifunctional Electrocatalysts for Boosting Hydrogen Oxidation/Evolution Reactions in Alkaline Solution.

Developing robust and effectual nonprecious electrocatalysts for the bifunctional hydrogen oxidation and evolution reactions (HOR and HER) in alkaline electrolyte is of critical significance for the realization of future hydrogen economy but challenging. Herein, this work demonstrates a new routine for the preparation of bio-inspired FeMo2S4 microspheres via the one-step sulfuration of Keplerate-type polyoxometalate {Mo72Fe30}. The bio-inspired FeMo2S4 microspheres feature potential-abundant structural defects and atomically precise iron doping and act as an effective bifunctional electrocatalyst for hydrogen oxidation/reduction reactions. The FeMo2S4 catalyst presents an impressive alkaline HOR activity compared to FeS2 and MoS2 with the high mass activity of 1.85 mA·mg-1 and high specific activity as well as excellent tolerance to carbon monoxide poisoning. Meanwhile, FeMo2S4 electrocatalyst also displayed prominent alkaline HER activity with a low overpotential of 78 mV at a current density of 10 mA·cm-2 and robust long-term durableness. Density functional theory (DFT) calculations indicate that the bio-inspired FeMo2S4 with a unique electron structure possesses the optimal hydrogen adsorption energy and enhanced adsorption of hydroxyl intermediates, which accelerates the potential-determining Volmer step, thus promoting the HOR and HER performance. This work provides a new pathway for designing efficient noble-metal-free electrocatalysts for the hydrogen economy.

Three-Dimensional Silver-Containing Polyoxotungstate Frameworks for Photocatalytic Aerobic Oxidation of Benzyl Alcohol.

Photocatalytic organic transformation derived by functionalized polyoxometalate (POM)-based metal-organic frameworks provides a feasible route for fine chemical synthesis. Herein, three kinds of photoactive three-dimensional silver-containing polyoxotungstate frameworks are synthesized with the formulas [Ag3L2(OH)][Na(H2O)0.5][PW12O40]·H2O (1), [Ag4L3][SiW12O40] (2), and [Ag(H2O)][Ag4L3][BW12O40]·9H2O (3) (L = 1,4-di(4H-1,2,4-triazol-4-yl)benzene). In compounds 1-3, the cationic Ag-triazole clusters with diverse nuclei serve as nodes to assemble with rigid bridging ligands (L) and polyoxoanions to extend into stable three-dimensional frameworks, in which Keggin-type anions act as guests or pendants. When using them as heterogeneous photocatalysts, compounds 1-3 show high catalytic activity and selectivity for the photocatalytic aerobic oxidation of benzyl alcohol to benzoic acid under 10 W 365 nm light irradiation. Among them, compound 1 exhibits the highest performance with ca. 99% benzyl alcohol conversion and 99% selectivity of benzoic acid in 9 h. Compounds 2 and 3 show ca. 79 and 88% conversions of benzyl alcohol, respectively, which are higher than those of the individual Keggin-type precursors. Moreover, mechanism investigation suggests that the synergistic cooperation occurring between cationic Ag-triazole clusters and Keggin-type polyoxoanions modulates the energy band structures of compounds 1-3, resulting in the efficient separation of photogenerated carriers and accelerating the aerobic oxidation of benzyl alcohol. This work provides some important guidance for the design and development of efficient POM-based photocatalysts for practical organic transformation.

Bifunctional Sensors Based on Phosphomolybdates for Detection of Inorganic Hexavalent Chromium and Organic Tetracycline.

Exploring effective sensors for detecting possible hazards in a water system are greatly significant. This work proposed a strategy for stable and effective bifunctional sensors via incorporating hourglass-type phosphomolybdates into metal-organic fragments to construct a high-dimensional framework. Two hourglass-type phosphomolybdate-based electrochemical sensors toward heavy metal ion Cr(VI) and tetracycline (TC) detection were designed with the formula [CoII2(H2O)4NaI2][CoII(Hbpe)][NaI(bpe)1.5]{CoII[PV4MoV6O31H6]2}·9H2O (1) and [CoII(H2O)4NaI3][CoII(Hbpe)][CoII(bpe)]{CoII[PV4MoV6O31H6]2}·9H2O (2) [bpe = 1,2-di(4-pyridyl)ethylene]. Structural analysis showed that hybrids 1 and 2 possess three-dimensional POM-supported network features with favorable stability and exhibit reversible redox properties. Experiments found that this kind of hybrids as efficient sensors have excellent electrochemical performance toward Cr(VI) detection with high sensitivities of 0.111 µA·µM-1 for 1 and 0.141 µA·µM-1 for 2, fast response time of 1 s, and low detection limits of 30 nM for 1 and 27 nM for 2, which far meet the standard of WHO for drinking water. Moreover, hybrids 1-2 also exhibit fast responses to TC detection with sensitivities of 0.0073 and 0.022 µA·mM-1 and detection limits of 0.426 and 0.084 mM. This work offers a novel strategy for the purposeful design of efficient POM-based electrochemical sensors for accurate determination of contaminants in a practical water system.

Polyoxometalate-Incorporated Metal-Organic Network as a Heterogeneous Catalyst for Selective Oxidation of Aryl Alkenes.

Selective oxidation of aryl alkenes is important for chemical synthesis reactions, in which the key lies in the rational design of efficient catalysts. Herein, four polyoxometalate (POM)-incorporated metal-organic networks, with the formulas of [Co(ttb)(H2O)3]2[SiMo12O40]·2H2O (1), [Co(ttb)(H2O)2]2[SiW12O40]·8H2O (2), [Zn(Httb)(H2ttb)][BW12O40]·9H2O (3) and {[Zn(H2O)3(ttb)]4[Zn3(H2O)6]}[H3SiW10.5Zn1.5O40]2·24H2O (4) (ttb = 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene), were hydrothermally synthesized and structurally characterized. Structural analysis showed that compound 1 consists of a POM-encapsulated three-dimensional (3-D) supramolecular framework; compound 2 is composed of a POM-supported 3-D coordination network; and compounds 3-4 show POM-incorporated 3-D supramolecular networks. Using selective catalytic oxidation of styrene as the model reaction, compounds 1-4 as heterogeneous catalysts display excellent performance with the double advantages of high styrene conversion and benzaldehyde selectivity owing to the synergistic effect among POM anions and transition metal (TM) centers. Among them, compound 1 exhibits the highest performance with ca. 96% styrene conversion and ca. 99% benzaldehyde selectivity in 3 h. In addition, compound 1 also displays excellent substrate compatibility, good reusability, and structural stability. Thus, a plausible reaction pathway for the selective oxidation of styrene is proposed. This study on the structure-function relationship paves a way for the rational design of POM-based heterogeneous catalysts for important catalysis applications.

Organic Moiety-Regulated Photocatalytic Performance of Phosphomolybdate Hybrids for Hexavalent Chromium Reduction.

Visible-light-driven photocatalytic Cr(VI) reduction is a promising pathway to moderate environmental pollution, in which the development of photocatalysts is pivotal. Herein, three hourglass-type phosphomolybdate-based hybrids with the formula of: (H2 bpe)3 [Zn(H2 PO4 )][Zn(bpe)(H2 O)2 ]H{Zn[P4 Mo6 O31 H6 ]2 } ⋅ 6H2 O (1) Na6 [H2 bz]2 [ZnNa4 (H2 O)5 ]{Zn [P4 Mo6 O31 H3 ]2 } ⋅ 2H2 O (2) and (H2 mbpy) {[Zn(mbpy)(H2 O)]2 [Zn(H2 O)]2 }{Zn[P4 Mo6 O31 H6 ]2 } ⋅ 10H2 O (3) (bpe=trans-1,2-bi(4-pyridyl)-ethylene; bz=4,4'-diaminobiphenyl; mbpy=4,4'-dimethyl-2,2'bipyridine) were synthesized under the guidance of the functional organic moiety modification strategy. Structural analysis showed that hybrids 1-3 have similar 2D layer-like spatial arrangements constructed by {Zn[P4 Mo6 ]2 } clusters and organic components with different conjugated degree. With excellent redox properties and wide visible-light absorption capacities, hybrids 1-3 display favourable photocatalytic activity for Cr(VI) reduction with 79%, 70% and 64% reduction rates, which are superior to that of only inorganic {Zn[P4 Mo6 ]2 } itself (21%). The investigation of organic components on photocatalytic performance of hybrids 1-3 suggested that the organic counter cations (bpe, bz and mbpy) can effectively affect the visible-light absorption, as well as the recombination of photogenerated carriers stemmed from {Zn[P4 Mo6 ]2 } clusters, further promoting their photocatalytic performances towards Cr(VI) reduction. This work provides an experimental basis for the design of functionalized photocatalysts via the modification of organic species.

A Bicadmium-Substituted Polyoxometalate Network Based on a Vanadosilicate Cluster for the Selective Oxidation of Styrene to Benzaldehyde.

A new bicadmium-substituted vanadosilicate, [Cd(en)2]2[(en)2Cd2Si8V12O40(OH)8(H2O)0.5]·5H2O (1; en = ethylenediamine), had been hydrothermally synthesized and characterized. Structural analysis revealed that the kind of new [(en)2Cd2Si8V12O40(OH)8(H2O)0.5]4- polyoxoanionic cluster was derived from the classical {V18O42} cluster by replacing six {VO5} square pyramids with four {Si2O7} and two [Cd(en)]2+ groups. Notably, such mixed substitution of both main-group and transition metals in polyoxovanadates is much less developed. Furthermore, compound 1 displays efficient catalytic activity toward the selective oxidation of styrene to benzaldehyde with a conversion of 97% and a selectivity of 87% in 8 h.

Stable monovalent aluminum(i) in a reduced phosphomolybdate cluster as an active acid catalyst.

Low-valent aluminum Al(i) chemistry has attracted extensive research interest due to its unique chemical and catalytic properties but is limited by its low stability. Herein, a hourglass phosphomolybdate cluster with a metal-center sandwiched by two benzene-like planar subunits and large steric-hindrance is used as a scaffold to stabilize low-valent Al(i) species. Two hybrid structures, (H3O)2(H2bpe)11[AlIII(H2O)2]3{[AlI(P4MoV 6O31H6)2]3·7H2O (abbr. Al6{P4Mo6}6) and (H3O)3(H2bpe)3[AlI(P4MoV 6O31H7)2]·3.5H2O (abbr. Al{P4Mo6}2) (bpe = trans-1,2-di-(4-pyridyl)-ethylene) were successfully synthesized with Al(i)-sandwiched polyoxoanionic clusters as the first inorganic-ferrocene analogues of a monovalent group 13 element with dual Lewis and Brønsted acid sites. As dual-acid catalysts, these hourglass structures efficiently catalyze a solvent-free four-component domino reaction to synthesize 1,5-benzodiazepines. This work provides a new strategy to stabilize low-valent Al(i) species using a polyoxometalate scaffold.

Sandwich-Type Polyoxotungstate Consisting of Two Different Trilacunary Keggin-Type Units.

A unique mixed W/Sb/Mn/Ag sandwich-type metal-O cluster was isolated, in which the six-membered {Ag4O3[Mn(OH2)]2}2+ cationic belt is sandwiched between two different anionic slices: the trilacunary B-ß-[SbW9O33]9- and the central-atom-lost A-α-{[Mn(OH2)]2W7O32}18-.

Copper-organic cationic ring with an inserted arsenic-vanadium polyanionic cluster for efficient catalytic Cr(VI) reduction using formic acid.

Polyanionic cluster [ß-As8V14O42(H2O)](4-) is well embedded in a large porous eight-membered cationic ring of the copper ligand, giving a stable host-guest supramolecular system. The assembly exhibits an efficient heterogeneous catalytic performance for the reduction of Cr(VI) using formic acid at ambient temperature.

An unusual metallic oxygen cluster consisting of a {AlMo12O40(MoO2)}.

A novel aluminum-containing, bimolybdenum-capped Keggin-type polyoxomolybate cluster of the {AlMo12O40(MoO2)2} anion has been synthesized and characterized. This is the first experimentally determined Keggin-type {AlMo12O40} polyoxoanion. The polyoxometalate crystal exhibits high selectivity toward the heterogeneous catalytic oxidation of cyclohexanol to cyclohexanone.

Transformation from [W6O19](2-) to [W6O22](8-) stabilized by Cu(II) complexation.

A rare [W6O22](8-) fragment has been first captured in aqueous solution of [W6O19](2-) by using a transition-metal complex and isolated as a new compound [Cu4(W6O22)(L1)2(H2O)2]·2H2O (1; L1 = 2-amino-4,6-bis(2-pyridyl)pyrimidine), indicating that [W6O19](2-) could also transform to [W6O22](8-) in aqueous solution besides the earlier proven ψ-metatungstates, [W10O32](4-), ß-[(H2)W12O40](6-) and [W7O24](6-).

Lanthanide-organic cation frameworks with zeolite gismondine topology and large cavities from intersected channels templated by polyoxometalate counterions.

A family of organic-inorganic hybrid frameworks, {[Ln(H(2)O)(4)(pdc)](4)} [XMo(12)O(40)].2H(2)O (Ln = La, Ce, and Nd; X = Si and Ge; H(2)pdc = pyridine-2,6-dicarboxylate), have been prepared under hydrothermal conditions and characterized by single crystal X-ray diffraction analyses, elemental analyses, IR, and thermal gravimetric analyses. Single crystal X-ray diffraction reveals that all six compounds are isostructural, and each consists of a zeolite-like four-connected three-dimensional cationic framework {[Ln(H(2)O)(4)(pdc)](4)}(4+) and ball-shaped Keggin type [XMo(12)O(40)](4-) as templates. Interesting channels exist in the cationic framework with the gismondine topology, and these channels intersect each other to form large cavities, which array in a zigzag fashion and are occupied by nanosized [XMo(12)O(40)](4-) counterions. Moreover, these compounds display strong photoluminescent properties in the solid state at room temperature.

Assembly of the highest connectivity Wells-Dawson polyoxometalate coordination polymer: the use of organic ligand flexibility.

Through tuning the length of flexible bis(triazole) ligands and different metal ion coordination geometries, four Wells-Dawson polyoxoanion-based hybrid compounds, [Cu 6(btp) 3(P 2W 18O 62)].3H 2O ( 1) (btp = 1,3-bis(1,2,4-triazol-1-y1)propane), [Cu 6(btb) 3((P 2W 18O 62)].2H 2O ( 2), [Cu 3(btb) 6(P 2W 18O 62)].6H 2O (btb = 1,4-bis(1,2,4-triazol-1-y1)butane) ( 3), and [Cu 3(btx) 5.5((P 2W 18O 62)].4H 2O (btx = 1,6-bis(1,2,4-triazol-1-y1)hexane) ( 4), were synthesized and structurally characterized. In compound 1, the metal-organic motif exhibits a ladder-like chain, which is further fused by the ennead-dentate [P 2W 18O 62] (6-) anions to construct a 3D structure. In compound 2, the metal-organic motif exhibits an interesting Cu-btb grid layer, and the ennead-dentate polyoxoanions are sandwiched by two Cu-btb layers to construct a 3D structure. Compound 3 exhibits a (4 (2).6 (2).8 (2)) 3D Cu-btb framework with square and hexagonal channels arranged alternately. The hexa-dentate polyoxoanions incorporate only into the hexagonal channels. In compound 4, there exist two sets of (6 (1).10 (2)) 2(6 (1).8 (2).10 (3)) 3D Cu-btx frameworks to generate a 2-fold interpenetrated structure into which the penta-dentate polyoxoanions are inserted to construct a 3D structure. The structural analyses reveal that the length of flexible bis(triazole) ligands and metal ion coordination geometries have a synergic influence on the structures of this series. To our knowledge, they have the highest connectivity for the Wells-Dawson polyoxometalate coordination polymers to date.

A novel copper(II) coordination polymer with 2,2'-bipyridyl-3,3'-dicarboxylic acid.

A novel copper(II) coordination polymer, poly[[[aquacopper(II)]-mu3-2,2'-bipyridyl-3,3'-dicarboxylato-kappa4N,N':O:O'] dihydrate], {[Cu(C12H6N2O4)(H2O)].2H2O}n, was obtained by the reaction of CuCl2.2H2O and 2,2'-bipyridyl-3,3'-dicarboxylic acid (H2L) in water. In the molecule, each Cu(II) atom is five-coordinated and lies at the centre of a square-pyramidal basal plane, bridged by three L ligands to form a two-dimensional (4,4)-network. Each L moiety acts as a bridging tetradentate ligand, coordinating to three Cu(II) atoms through its two aromatic N atoms and two O atoms of the two carboxyl groups. The two-dimensional square-grid sheets superimpose in an off-set fashion through the inorganic water layer.