Abstract
Nano-scaled polyoxometalates (POMs) clusters with sizes ranging from 1 to 10 nm attract tremendous attention and have been extensively studied due to POMs’ fascinating structural characteristics and prospects for wide-ranging applications. As a unique class of nanoparticles with well-defined structural topologies and monodispersed masses, the structures and properties of POMs in both bulk state and solutions have been explored with several well-developed protocols. Small-angle X-ray scattering (SAXS) technique, as a powerful tool for studying polymers and nanoparticles, has been recently extended to the investigating of solution behaviors of POMs. In this mini-review, the general principle and typical experimental procedures of SAXS are illustrated first. The applications of SAXS in characterizing POMs’ morphology, counterion distribution around POMs, and short-range interactions among POMs in solutions are highlighted.
ᅟ
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Antonio MR, Chiang MH, Seifert S, Tiede DM, Thiyagarajan P (2009a) In situ measurement of the Preyssler polyoxometalate morphology upon electrochemical reduction: a redox system with Born electrostatic ion solvation behavior. J Electroanal Chem 626:103–110. https://doi.org/10.1016/j.jelechem.2008.11.009
Antonio MR, Nyman M, Anderson TM (2009b) Direct observation of contact ion-pair formation in aqueous solution. Angew Chem Int Ed 48:6136–6140. https://doi.org/10.1002/anie.200805323
Bera MK, Antonio MR (2016) Crystallization of Keggin heteropolyanions via a two-step process in aqueous solutions. J Am Chem Soc 138:7282–7288. https://doi.org/10.1021/jacs.5b13375
Bera MK, Ellis RJ, Burton-Pye BP, Antonio MR (2014) Structural aspects of heteropolyacid microemulsions. Phys Chem Chem Phys 16:22566–22574. https://doi.org/10.1039/c4cp03014a
Bera MK, Qiao B, Seifert S, Burton-Pye BP, Olvera de la Cruz M, Antonio MR (2015) Aggregation of heteropolyanions in aqueous solutions exhibiting short-range attractions and long-range repulsions. J Phys Chem C 120:1317–1327. https://doi.org/10.1021/acs.jpcc.5b10609
Clemente-Juan JM, Coronado E, Gaita-Arino A (2012) Magnetic polyoxometalates: from molecular magnetism to molecular spintronics and quantum computing. Chem Soc Rev 41:7464–7478. https://doi.org/10.1039/c2cs35205b
Cronin L, Müller A (2012) From serendipity to design of polyoxometalates at the nanoscale, aesthetic beauty and applications. Chem Soc Rev 41:7333–7334. https://doi.org/10.1039/c2cs90087d
Dembowski M et al (2017a) Hierarchy of pyrophosphate-functionalized uranyl peroxide nanocluster synthesis. Inorg Chem 56:5478–5487. https://doi.org/10.1021/acs.inorgchem.7b00649
Dembowski M, Colla CA, Yu P, Qiu J, Szymanowski JES, Casey WH, Burns PC (2017b) The Propensity of uranium-peroxide systems to preserve nanosized assemblies. Inorg Chem 56:9602–9608. https://doi.org/10.1021/acs.inorgchem.7b01095
Falaise C, Nyman M (2016) The key role of U-28 in the aqueous self-assembly of Uranyl peroxide Nanocages. Chem Eur J 22:14678–14687. https://doi.org/10.1002/chem.201602130
Falaise C, Neal HA, Nyman M (2017) U(IV) aqueous speciation from the monomer to uo2 nanoparticles: two levels of control from zwitterionic glycine ligands. Inorg Chem 56:6591–6598. https://doi.org/10.1021/acs.inorgchem.7b00616
Fielden J, Cronin L (eds) (2005) Coordination clusters. Encyclopedia of Supramolecular Chemistry. Taylor & Francis, Didcot
Fullmer LB, Molina PI, Antonio MR, Nyman M (2014) Contrasting ion-association behaviour of Ta and Nb polyoxometalates. Dalton Trans 43:15295–15299. https://doi.org/10.1039/c4dt02394c
Fullmer LB, Malmberg CE, Fast DB, Wills LA, Cheong PH-Y, Dolgos MR, Nyman M (2017) Aqueous tantalum polyoxometalate reactivity with peroxide. Dalton Trans 46:8486–8493. https://doi.org/10.1039/c7dt01478c
Gao JB et al. (2008) A direct imaging of amphiphilic catalysts assembled at the interface of emulsion droplets using fluorescence microscopy Chem Commun 332–334. https://doi.org/10.1039/b713831h
Glatter O, Kratky O (1982) Small angle X-ray scattering. Academic press, Cambridge
Goberna-Ferrón S, Soriano-López J, Galán-Mascarós JR, Nyman M (2015) Solution speciation and stability of cobalt-polyoxometalate water oxidation catalysts by X-ray scattering. Eur J Inorg Chem 2015:2833–2840. https://doi.org/10.1002/ejic.201500404
Goberna-Ferron S, Park DH, Amador JM, Keszler DA, Nyman M (2016) Amphoteric aqueous hafnium cluster chemistry. Angew Chem Int Ed 55:6221–6224. https://doi.org/10.1002/anie.201601134
Haso F et al (2015) Exploring the effect of surface functionality on the self-assembly of polyoxopalladate macroions. Chem Eur J 21:9048–9052. https://doi.org/10.1002/chem.201500810
Hou Y, Zakharov LN, Nyman M (2013) Observing assembly of complex inorganic materials from polyoxometalate building blocks. J Am Chem Soc 135:16651–16657. https://doi.org/10.1021/ja4085484
Izzet G et al (2016) Hierarchical self-assembly of polyoxometalate-based hybrids driven by metal coordination and electrostatic interactions: from discrete supramolecular species to dense monodisperse nanoparticles. J Am Chem Soc 138:5093–5099. https://doi.org/10.1021/jacs.6b00972
Jackson MN, Kamunde-Devonish MK, Hammann BA, Wills LA, Fullmer LB, Hayes SE, Cheong PHY, Casey WH, Nyman M, Johnson DW (2015) An overview of selected current approaches to the characterization of aqueous inorganic clusters. Dalton Trans 44:16982–17006. https://doi.org/10.1039/c5dt01268f
Jadzinsky PD, Calero G, Ackerson CJ, Bushnell DA, Kornberg RD (2007) Structure of a thiol monolayer-protected gold nanoparticle at 1.1 Å. Resolution Science 318:430–433. https://doi.org/10.1126/science.1148624
Kistler ML, Bhatt A, Liu G, Casa D, Liu T (2007) A complete macroion−“blackberry” assembly−macroion transition with continuously adjustable assembly sizes in {Mo132} water/acetone systems. J Am Chem Soc 129:6453–6460. https://doi.org/10.1021/ja0685809
Kratky O (1963) X-ray small angle scattering with substances of biological interest in diluted solutions. Prog Biophys Mol Biol 13:105–173
Kratky O, Porod G (1949) Diffuse small-angle scattering of X-rays in colloid systems. J Colloid Sci 4:35–70. https://doi.org/10.1016/0095-8522(49)90032-X
Li M, Wang W, Yin P (2018) A general approach to access morphologies of polyoxometalate in solutions using saxs: an ab initio modeling protocol. Chem Eur J. https://doi.org/10.1002/chem.201800344
Ling J, Qiu J, Burns PC (2012) Uranyl peroxide oxalate cage and core-shell clusters containing 50 and 120 uranyl ions. Inorg Chem 51:2403–2408. https://doi.org/10.1021/ic202380g
Liu T (2010) Hydrophilic macroionic solutions: what happens when soluble ions reach the size of nanometer scale? Langmuir 26:9202–9213. https://doi.org/10.1021/la902917q
Liu Z, Liu T, Tsige M (2016) Elucidating the origin of the attractive force among hydrophilic macroions. Sci Rep 6:26595. https://doi.org/10.1038/srep26595
Lv H et al (2012) Polyoxometalate water oxidation catalysts and the production of green fuel. Chem Soc Rev 41:7572–7589. https://doi.org/10.1039/C2CS35292C
Müller A, Gouzerh P (2012) From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry. Chem Soc Rev 41:7431–7463. https://doi.org/10.1039/c2cs35169b
Müller A, Kögerler P (1999) From simple building blocks to structures with increasing size and complexity. Coord Chem Rev 182:3–17. https://doi.org/10.1016/S0010-8545(98)00226-4
Müller A, Peters F, Pope MT, Gatteschi D (1998) Polyoxometalates: very large clusters nanoscale magnets. Chem Rev 98:239–272. https://doi.org/10.1021/cr9603946
Müller A, Kögerler P, Dress AWM (2001) Giant metal-oxide-based spheres and their topology: from pentagonal building blocks to keplerates and unusual spin systems. Coord Chem Rev 222:193–218. https://doi.org/10.1016/S0010-8545(01)00391-5
Nakamura I, Miras HN, Fujiwara A, Fujibayashi M, Song Y-F, Cronin L, Tsunashima R (2015) Investigating the formation of “molybdenum blues” with gel electrophoresis and mass spectrometry. J Am Chem Soc 137:6524–6530. https://doi.org/10.1021/ja512758j
Nyman M (2017) Small-angle X-ray scattering to determine solution speciation of metal-oxo clusters. Coord Chem Rev 352:461–472. https://doi.org/10.1016/j.ccr.2016.11.014
Palilis LC et al (2013) Solution processable tungsten polyoxometalate as highly effective cathode interlayer for improved efficiency and stability polymer solar cells. Sol Energy Mater Sol Cells 114:205–213. https://doi.org/10.1016/j.solmat.2013.02.034
Pigga JM, Kistler ML, Shew C-Y, Antonio MR, Liu T (2009) Counterion distribution around hydrophilic molecular macroanions: the source of the attractive force in self-assembly. Angew Chem Int Ed 48:6538–6542. https://doi.org/10.1002/anie.200902050
Pigga JM, Teprovich JA, Flowers RA, Antonio MR, Liu TB (2010) Selective monovalent cation association and exchange around keplerate polyoxometalate macroanions in dilute aqueous solutions. Langmuir 26:9449–9456. https://doi.org/10.1021/la100467p
Pope M, Müller A (eds) (1994) Polyoxometalates: from platonic solids to anti-retroviral activity Topics in Molecular Organization and Engineering, vol 10. Springer, Netherlands
Qiu J, Nguyen K, Jouffret L, Szymanowski JES, Burns PC (2013) Time-resolved assembly of chiral uranyl peroxo cage clusters containing belts of polyhedra. Inorg Chem 52:337–345. https://doi.org/10.1021/ic3020817
Qiu J, Ling J, Jouffret L, Thomas R, Szymanowski JES, Burns PC (2014) Water-soluble multi-cage super tetrahedral uranyl peroxide phosphate clusters. Chem Sci 5:303–310. https://doi.org/10.1039/c3sc52357h
Qiu J, Dembowski M, Szymanowski JES, Toh WC, Burns PC (2016) Time-resolved X-ray scattering and Raman spectroscopic studies of formation of a uranium-vanadium-phosphorus-peroxide cage cluster. Inorg Chem 55:7061–7067. https://doi.org/10.1021/acs.inorgchem.6b00918
Qiu J, Spano TL, Dembowski M, Kokot AM, Szymanowski JES, Burns PC (2017) Sulfate-centered sodium-lcosahedron-templated uranyl peroxide phosphate cages with uranyl bridged by mu-eta(1):eta(2) peroxide. Inorg Chem 56:1874–1880. https://doi.org/10.1021/acs.inorgchem.6b02429
Renier O, Falaise C, Neal H, Kozma K, Nyman M (2016) Closing uranyl polyoxometalate capsules with bismuth and lead polyoxocations. Angew Chem Int Ed 55:13480–13484. https://doi.org/10.1002/anie.201607151
Rickert PG, Antonio MR, Firestone MA, Kubatko KA, Szreder T, Wishart JF, Dietz ML (2007) Tetraalkylphosphonium polyoxometalate ionic liquids: novel, organic-inorganic hybrid materials. J Phys Chem B 111:4685–4692. https://doi.org/10.1021/jp0671751
Robbins PJ, Surman AJ, Thiel J, Long D-L, Cronin L (2013) Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies. Chem Commun 49:1909–1911. https://doi.org/10.1039/C3CC38615E
Song Y-F, Tsunashima R (2012) Recent advances on polyoxometalate-based molecular and composite materials. Chem Soc Rev 41:7384–7402. https://doi.org/10.1039/C2CS35143A
Svergun DI (1992) Determination of the regularization parameter in indirect-transform methods using perceptual criteria. J Appl Crystallogr 25:495–503. https://doi.org/10.1107/s0021889892001663
Svergun D, Barberato C, Koch MHJ (1995) CRYSOL—a Program to Evaluate X-ray Solution Scattering of Biological Macromolecules from Atomic Coordinates. J Appl Crystallogr 28:768–773. https://doi.org/10.1107/S0021889895007047
Sztucki M, Di Cola E, Narayanan T (2012) Anomalous small-angle X-ray scattering from charged soft matter. Eur Phys J-Spec Top 208:319–331. https://doi.org/10.1140/epjst/e2012-01627-x
Takeda N, Umemoto K, Yamaguchi K, Fujita M (1999) A nanometre-sized hexahedral coordination capsule assembled from 24 components. Nature 398:794–796. https://doi.org/10.1038/19734
Toma FM et al (2010) Efficient water oxidation at carbon nanotube-polyoxometalate electrocatalytic interfaces. Nat Chem 2:826–831. https://doi.org/10.1038/nchem.761
Tomalia DA (2005) Birth of a new macromolecular architecture: dendrimers as quantized building blocks for nanoscale synthetic polymer chemistry. Prog Polym Sci 30:294–324. https://doi.org/10.1016/j.progpolymsci.2005.01.007
Tomalia DA, Frechet JM (eds) (2002) Introduction to the dendritic state. Dendrimers and Other Dendritic Polymers. John Wiley & Sons, Ltd, Hoboken
Tomalia DA et al (1985) A new class of polymers: starburst-dendritic macromolecules. Polym J 17:117. https://doi.org/10.1295/polymj.17.117
Wang Y, Weinstock IA (2012) Polyoxometalate-decorated nanoparticles. Chem Soc Rev 41:7479–7496. https://doi.org/10.1039/C2CS35126A
Wang S-S, Yang G-Y (2015) Recent advances in polyoxometalate-catalyzed reactions. Chem Rev 115:4893–4962. https://doi.org/10.1021/cr500390v
Wang YL, Li W, Wu LX (2009) Organic-inorganic hybrid Supramolecular gels of surfactant-encapsulated polyoxometalates. Langmuir 25:13194–13200. https://doi.org/10.1021/la901869t
Wylie EM, Peruski KM, Weidman JL, Phillip WA, Burns PC (2014) Ultrafiltration of uranyl peroxide nanoclusters for the separation of uranium from aqueous solution. ACS Appl Mater Interfaces 6:473–479. https://doi.org/10.1021/am404520b
Yin P, Li D, Liu T (2011) Counterion interaction and association in metal-oxide cluster macroanionic solutions and the consequent self-assembly. Isr J Chem 51:191–204. https://doi.org/10.1002/ijch.201000079
Yin P, Li D, Liu T (2012) Solution behaviors and self-assembly of polyoxometalates as models of macroions and amphiphilic polyoxometalate-organic hybrids as novel surfactants. Chem Soc Rev 41:7368–7383. https://doi.org/10.1039/c2cs35176e
Yin P, Li T, Forgan RS, Lydon C, Zuo X, Zheng ZN, Lee B, Long D, Cronin L, Liu T (2013) Exploring the programmable assembly of a polyoxometalate-organic hybrid via metal ion coordination. J Am Chem Soc 135:13425–13432. https://doi.org/10.1021/ja404777g
Yin P et al (2014) Spontaneous stepwise self-assembly of a polyoxometalate—organic hybrid into catalytically active one-dimensional anisotropic structures. Chem Eur J 20:9589–9595. https://doi.org/10.1002/chem.201402974
Yin P, Wu B, Li T, Bonnesen PV, Hong K, Seifert S, Porcar L, Do C, Keum JK (2016a) Reduction-triggered self-assembly of nanoscale molybdenum oxide molecular clusters. J Am Chem Soc 138:10623–10629. https://doi.org/10.1021/jacs.6b05882
Yin P, Wu B, Mamontov E, Daemen LL, Cheng Y, Li T, Seifert S, Hong K, Bonnesen PV, Keum JK, Ramirez-Cuesta AJ (2016b) X-ray and neutron scattering study of the formation of core-shell-type polyoxometalates. J Am Chem Soc 138:2638–2643. https://doi.org/10.1021/jacs.5b11465
Zemb T, Lindner P (2002) Neutrons, X-rays and light: scattering methods applied to soft condensed matter. Elsevier, New York
Acknowledgements
We are grateful to the support of the Program for Guangdong Introducing Innovative and Entrepreneurial Teams (No.2016ZT06C322), the Thousand Talents Plan for Young Professionals from Chinese Government, and the start-up support from South China University of Technology.
Funding
This study was funded by the Program for Guangdong Introducing Innovative and Entrepreneurial Teams (No.2016ZT06C322), the Thousand Talents Plan for Young Professionals from Chinese Government, and the startup support from South China University of Technology.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
This article is part of the topical collection: Unifying Concepts for Nanoscience and Nanosystems: 20th Anniversary Issue
Donald Tomalia, Paolo Milani, and Kenneth Dawson, co-editors
Rights and permissions
About this article
Cite this article
Li, M., Zhang, M., Wang, W. et al. The applications of small-angle X-ray scattering in studying nano-scaled polyoxometalate clusters in solutions. J Nanopart Res 20, 124 (2018). https://doi.org/10.1007/s11051-018-4216-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-018-4216-4