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Yong-Jiang Wang, Shi-Yu Wu, Yan-Qiong Sun, Xin-Xiong Li, Shou-Tian Zheng
A series of new Ln14-substituted polyoxometalates, H27Na16[(Ln14(H2O)W4(OH)O14)(WO4)4(GeW10O38)6]·nH2O (n ≈ 86) (1-Ln, Ln = Eu, Gd, Tb, Dy, Ho, Er), which contain 14 Ln3+ and 6 {α(1,5)-[GeW10O38]12-} units, has been synthesized in one-pot reactions. As the first 14-Ln-containing polyoxometalates, the octahedron-shaped three-shell structure of the [(Ln14(H2O)W4(OH)O14)(WO4)4(GeW10O38)6]43- polyanion is made up of a W4 tetrahedron, a Ln14W4 tetrahedron and a Ge6W60 octahedron. Compound 1-Dy exhibits frequency dependent magnetic properties...
February 18, 2019: Chemical Communications: Chem Comm
Xiaoxiong Cai, Qionghao Xu, Gaomei Tu, Yanghe Fu, Fumin Zhang, Weidong Zhu
The synthesis of heterogeneous cooperative catalysts in which two or more catalytically active components are spatially separated within a single material has generated considerable research efforts. The multiple functionalities of catalysts can significantly improve the efficiency of existing organic chemical transformations. Herein, we introduce ruthenium (Ru) nanoparticles (NPs) on the surfaces of a metal-organic framework pre-encapsulated with polyoxometalate silicotungstic acid (SiW) UiO-66 (University of Oslo [UiO]) and prepared a 2...
2019: Frontiers in Chemistry
Jin Yuan, Ling Wang, Yitong Wang, Shuli Dong, Jingcheng Hao
By appropriate substitution, polyoxometalates (POMs) can be modified to be organic-inorganic supramolecules (OISMs) that are nonaqueous or water soluble and form aggregates in solution. Here we report a new OISM, (TBA)3POM-PPCT, that can self-assemble to form bilayer vesicles controlled by Eu3+ in nonaqueous solution. Dynamic laser light scattering (DLS), transmission and scanning electron microscopies (SEM and TEM) and atomic force microscopy (AFM) clearly demonstrated the controllable formation of stable bilayer vesicles with an average hydrodynamic radius of about 510 nanometers...
February 16, 2019: Langmuir: the ACS Journal of Surfaces and Colloids
Ming-Hua Jing, Xi-Ming Song, Da-Wei Fang, Ling Zhang, Qian Zhang
In this article, a novel electroactivity-adjustable poly (ionic liquids)/reduced graphene oxide (PIL-GP) was developed and utilized for the fabrication of multifunctional, high stable electrochemical sensors. The structure, morphology and surface charge properties of PIL-GP have been systematically studied. And the selective detection performance of dopamine (DA) on PIL-GP modified glassy carbon electrode (GCE) were further explored by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). More importantly, by virtue of the anion exchange property of PIL, electroactive Fe(CN)6 3- /PIL-GP/GCE and Polyoxometalates (PWA)/PIL-GP/GCE were easily fabricated and their electrochemical detection performance of ascorbic acid (AA) and bromate were investigated respectively...
May 15, 2019: Talanta
Fernando Maya, Brett Paull
This review summarizes recent development made in the incorporation of functional materials into organic polymer monoliths, together with new monolithic forms and formats, which enhance their application as supports and stationary phase materials for sample preparation and chromatographic separations. While polymer monoliths are well known supports for the separation of large molecules, recent development have been made to improve their features for the separation of small molecules. The selectivity and performance of organic polymer monoliths has been improved by the incorporation of different materials, such as metal-organic frameworks, covalent organic frameworks, or other types of nanostructured materials (carbon nanohorns, nanodiamonds, polyoxometalates, layered double hydroxides, or attapulgite)...
February 15, 2019: Journal of Separation Science
Yamin Li, Hailou Li, Jun Jiang, Lijuan Chen, Junwei Zhao
Three kinds of distinguishing ala-decorated RE-incorporated (ala = l-alanine, RE = rare-earth) polytungstoarsenate hybrids containing {As2 W19 O68 } building blocks [H2 N(CH3 )2 ]13 Na3 H2 [Eu4 W5 (H2 O)10 (ala)3 O14 (As2 W19 O68 )2 ]·35H2 O (1), [H2 N(CH3 )2 ]12 Na2 H2 [RE4 W6 (H2 O)8 (ala)4 O15 (OH)2 (As2 W19 O68 )2 ]·36H2 O [RE = Gd3+ (2), Tb3+ (3)], and [H2 N(CH3 )2 ]12 Na4 [RE4 W6 (H2 O)10 (ala)2 O15 (OH)2 (As2 W19 O68 )2 ]·40H2 O [RE = Dy3+ (4), Ho3+ (5), Er3+ (6), Yb3+ (7), Lu3+ (8)] were made in a facile one-step assembly strategy...
February 14, 2019: Inorganic Chemistry
Sanghyun Bae, Hyunwoo Kim, Dasom Jeon, Jungki Ryu
We studied the kinetics of photoelectrochemical (PEC) water oxidation using a model photoanode BiVO4 modified with various water oxidation catalysts (WOCs) by electrochemical impedance spectroscopy (EIS). In particular, we prepared BiVO4 photoanodes with catalytic multilayers (CMs), where cationic polyelectrolytes and anionic polyoxometalate (POM) WOCs were assembled in a desired amount at a nanoscale precision, and compared their performance with those with well-known WOCs such as cobalt phosphate (CoPi) and NiOOH...
February 13, 2019: ACS Applied Materials & Interfaces
Colm Healy, Friedrich W Steuber, Paul Wix, Lauren K Macreadie, Amal Cherian Kathalikkattil, Wolfgang Schmitt
Polyoxometalates (POMs) are commonly prepared using a "bottom-up" synthetic procedure. The alternative "top-down" approach of disassembling a pre-formed POM unit to generate new synthetic intermediates is promising, but relatively comparatively underused. In this paper, a rationale for the top-down method is provided, demonstrating that this approach can generate compounds that are fundamentally inaccessible from simple bottom-up assembly. We demonstrate this principle through the synthesis of a series of 10, new, mixed-metal, hybrid compounds with the general formula [TBA]2[MoVI10CoII6O30(RpPO3)6(RcCOO)2(L)x(H2O)6] (TBA = tetrabutylammonium, Rp = phosphonate moiety, Rc = carboxylate moiety, L = pyridyl ligand, and x = 2-4), including a one-dimensional polyoxometalate-based coordination polymer...
February 12, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
Shuai-Lei Xie, Jiang Liu, Long-Zhang Dong, Shun-Li Li, Ya-Qian Lan, Zhong-Min Su
The photocatalytic reduction of CO2 to value-added methane (CH4 ) has been a promising strategy for sustainable energy development, but it is challenging to trigger this reaction because of its necessary eight-electron transfer process. In this work, an efficient photocatalytic CO2 -to-CH4 reduction reaction was achieved for the first time in aqueous solution by using two crystalline heterogeneous catalysts, H{[Na2 K4 Mn4 (PO4 ) (H2 O)4 ]⊂{[Mo6 O12 (OH)3 (HPO4 )3 (PO4 )]4 [Mn6 (H2 O)4 ]}·16H2 O ( NENU-605 ) and H{[Na6 CoMn3 (PO4 )(H2 O)4 ]⊂{[Mo6 O12 (OH)3 (HPO4 )3 (PO4 )]4 [Co1...
January 7, 2019: Chemical Science
Dan Zhang, Yiming Li, Yinuo Gao, Mbage Bawa, Mingxin Huo, Xiaohong Wang, Suiyi Zhu
A novel route was created to facilitate the degradation of diethyl phthalate (DEP) upon micellar polyoxometalate (POM) catalysts and H2 O2 . The best catalytic activity was obtained using [C16 H33 N(CH3 )3 ]H4 PMo10 V2 O40 (N-hexadecyl-N,N,N-trimethylammonium tetrahydrogen decamolybdo-divanadophosphate, abbreviated as (CTA)H4 PMoV) with 90.2% degradation efficiency within 30 min, while the chemical oxygen demand (COD) and total organic carbon (TOC) removal efficiency were about 77.7% and 74.3% within 40 min...
February 1, 2019: Journal of Hazardous Materials
Hai-Dan Wang, Xing-Fang Wang, Fang Su, Jian-Sheng Li, Lan-Cui Zhang, Xiao-Jing Sang, Zai-Ming Zhu
Carboxyethyltin and first-row transition metals (TMs) were firstly introduced into trivacant Keggin-type tungstoantimonate in an aqueous solution, leading to the formation of four crystalline organic-inorganic hybrid sandwich-type polyoxometalates (POMs), formulated as Na10-x-yKyHx[((TM)(H2O)3)2(Sn(CH2)2COO)2(SbW9O33)2]·nH2O (SbW9-TM-SnR, TM = Mn, Co, Ni, Zn; x = 1, 1, 0, 0; y = 0, 5, 5, 2; n = 18, 24, 24, 22, respectively). SbW9-TM-SnR exhibit high catalytic ability for the oxidation of cyclohexanol. Meanwhile, SbW9-TM-SnR were composited with polypyrrole (PPy) through an electropolymerization process, forming PPy-SbW9-TM-SnR, on which platinum (Pt) was further electro-deposited to prepare PPy-SbW9-TM-SnR/Pt for electrocatalytic methanol (CH3OH) oxidation in acid solution...
February 11, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
Shujun Li, Yue Zhao, Huihui Qi, Yanfang Zhou, Shuxia Liu, Xiaoming Ma, Jie Zhang, Xuenian Chen
Three new boronic acid derivatized lanthanide-polyoxometalates (BA-Ln-POMs) were synthesized, in which boronic acids served as bi- or tri-dentate ligands and exhibited interesting coordination ability towards POMs and LnIII. The pH was found to be crucial in controlling the coordination modes of boronic acid and the formation of B-O-Ln and B-O-Nb bridges. Compared with the boronic acid-free Ln-POM, a longer lifetime was observed for compound 2Eu due to the coordination of boronic acids to the EuIII center.
February 11, 2019: Chemical Communications: Chem Comm
Luning Chen, Xibo Zhang, Jinhong Zhou, Zhaoxiong Xie, Qin Kuang, Lansun Zheng
Tandem catalysis (i.e., a process in which a desirable product is synthesized by a one-step process consisting of sequential reactions) has attracted intensive attention owing to its sustainable green and atom-economical characteristics. In this process, the utilization of a high-efficiency multifunctional catalyst is key. However, different functional sites integrated within the catalyst are required to be rationally designed and precisely engineered to guarantee the synergy between the catalytic reactions...
February 5, 2019: Nanoscale
Mengyan Zeng, Junyan Tan, Kun Chen, Dejin Zang, Yang Yang, Jie Zhang, Yongge Wei
The two-dimensional nanostructures comprised of polyoxometalate-based building blocks are of great value in nanoarchitectures which are with unique properties and widespread potential applications, but it is still challenging in mature preparation. Herein a new strategy to build Cr (III) centered Anderson type polyoxometalate 2D nanostructures based on the modulation of host-guest interaction between cationic pillar[5]arenes and SDS in aqueous media was exploited in this work. Through regulating stoichiometry of SDS, the morphology of assemblies vary from nanobones to 2D nanosheets...
February 4, 2019: ACS Applied Materials & Interfaces
Xi-Ming Luo, Ning-Fang Li, Zhao-Bo Hu, Jia-Peng Cao, Chen-Hui Cui, Qing-Fang Lin, Yan Xu
The unpredictability of the polyoxometalate (POM) coordination model and the diversity of organic ligands provide more possibilities for the exploration and fabrication of various novel POM-based materials. In this work, a series of POM-based lanthanide (Ln)-Schiff base nanoclusters, [Ln(H2 O)2 (DAPSC)]2 [Ln(H2 O)3 (DAPSC)]2 [(SiW12 O40 )]3 ·15H2 O (Ln = Sm, 1; Eu, 2; Tb, 3), have been successfully isolated by the reaction of classical Keggin POMs, a Ln3+ ion, and a Schiff-base ligand [2,6-diacetylpyridine bis(semicarbazone), abbreviated as DAPSC]...
February 4, 2019: Inorganic Chemistry
Yan-Min Su, Zhi Wang, Gui-Lin Zhuang, Quan-Qin Zhao, Xing-Po Wang, Chen-Ho Tung, Di Sun
Controlled trapping atom-precise ultrasmall silver nanoparticles into silver nanoclusters is challenging; thus only limited progress has been made in this area. We are therefore inspired to isolate two novel silver nanoclusters, Ag10 @Ag70 ( SD/Ag80a and SD/Ag80b ; SD = SunDi), where a novel fcc-structured Ag10 kernel built from two single-edge opened Ag6 octahedra by sharing one edge is trapped. The bioctahedral Ag10 kernel is locked by a pair of Mo7 O26 10- anions to form an inner Ag10 @(Mo7 O26 )2 core which is further encapsulated by an outer Ag70 shell to form three-shell Ag10 @(Mo7 O26 )2 @Ag70 nanoclusters...
January 14, 2019: Chemical Science
Wanli Zhou, Yanping Zheng, Gang Yuan, Jun Peng
By adjusting polyoxometalates in the same POM/Cu/terpyridine reaction systems, three new organic-inorganic hybrid solid materials based on Cu-terpyridine complexes, [Cu3(tpy)3(H2O)2(HPMoVI8VIV4O40(VIVO)2)]·2H2O (1), Cu5(tpy)5(H2O)2(α-PW12O40)2 (2), and [Cu3(tpy)3(H2O)4(α-P2W18O62)]·4H2O (3) (tpy = 2,2':6',2''-terpyridine), were prepared by using one-pot methods. X-ray structural analyses show that compounds 1-3 with a 1D chain structure constructed from Cu/tpy complexes were modified using bi-capped Keggin, Keggin and Wells-Dawson POMs...
January 31, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
Fucong Lyu, Shanshan Zeng, Zhifang Sun, Ning Qin, Lujie Cao, Zhenyu Wang, Zhe Jia, Shaofei Wu, Fei-Xiang Ma, Minchan Li, Wenxi Wang, Yang Yang Li, Jian Lu, Zhouguang Lu
Layered stacking and highly porous N, P co-doped Mo2 C/C nanosheets are prepared from a stable Mo-enhanced hydrogel. The hydrogel is formed through the ultrafast cross-linking of phosphomolybdic acid and chitosan. During the reduction of the composite hydrogel framework under inert gas protection, highly porous N and P co-doped carbon nanosheets are produced with the in situ formation of ultrafine Mo2 C nanoparticles highly distributed throughout the nanosheets which are entangled via a hierarchical lamellar infrastructure...
January 30, 2019: Small
Yu Gao, Wei Guan, Likai Yan, Yanhong Xu
A series of Zn-porphyrin dyes with different donor and π-linker groups based on the dye SM315 were systematically investigated to screen highly efficient candidates based on density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. Compared with SM315, dye 1 not only has stronger and broader absorption spectra and larger intramolecular charge transition (ICT) parameters, but also has a larger maximum short circuit density (JmaxSC) and an open-circuit photovoltage (VOC) due to the insertion of polyoxometalate (POM)...
January 30, 2019: Physical Chemistry Chemical Physics: PCCP
Benjamin E Valley, Benxin Jing, Manuela Ferreira, Yingxi Zhu
Effluent wastewater containing dyes from textile, paint, and various other industrial wastes have long posed environmental damage. Functional nanomaterials offer new opportunities to treat these effluent wastes in an unprecedentedly rapid and efficient fashion due to their large surface area-to-volume ratio. In this work, we explore a new approach of wastewater treatment using macroionic coacervate complexes formed with zwitterionic polyampholytes and anionic inorganic polyoxometalate (POM) nanoclusters to extract methylene blue (MB) dye as well as other cationic industrial dyes from model wastewater...
January 28, 2019: ACS Applied Materials & Interfaces
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