DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Spatiotemporal Studies of Soluble Inorganic Nanostructures with X‐rays and Neutrons

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [1];  [3];  [1];  [1];  [2];  [4]; ORCiD logo [1]
  1. State Key Laboratory of Luminescent Materials and Devices South China Advanced Institute for Soft Matter Science and Technology South China University of Technology Guangzhou 510640 China
  2. The Rossendorf Beamline at ESRF The European Synchrotron CS40220, 38043 Grenoble Cedex 9 France, Institute of Resource Ecology Helmholtz Zentrum Dresden-Rossendorf (HZDR) P.O. Box 510119 01314 Dresden Germany
  3. Institute of Advanced Science Facilities Shenzhen 518107 China
  4. Department of Chemistry Oregon State University Corvallis OR, 97330 USA

Abstract This Review addresses the use of X‐ray and neutron scattering as well as X‐ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub‐Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal‐organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small‐ and wide‐angle X‐ray or neutron scattering), 2) PDF (pair‐distribution function analysis of X‐ray total scattering), and 3) XANES and EXAFS (X‐ray absorption near‐edge structure and extended X‐ray absorption fine structure, respectively). While the scattering techniques provide structural information, X‐ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.

Sponsoring Organization:
USDOE
OSTI ID:
2263506
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Vol. 63 Journal Issue: 1; ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (148)

Base hydrolysis of aqueous chromium( III ) solutions: on the existence of [Cr(OH) 4 ] , and speculation regarding a new chromium polyoxocation journal January 1993
The structure of plutonium( iv ) oxide as hydrolysed clusters in aqueous suspensions journal January 2013
Ferrihydrite Formation: The Role of Fe 13 Keggin Clusters journal August 2016
Closing Uranyl Polyoxometalate Capsules with Bismuth and Lead Polyoxocations journal September 2016
Multiscale and Multistep Ordering of Flow-Induced Nucleation of Polymers journal January 2018
A Comparison of Neptunyl(V) and Neptunyl(VI) Solution Coordination: The Stability of Cation−Cation Interactions journal June 2008
pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions: pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions journal December 2018
Confinement Effect on the Surface of a Metal–Organic Polyhedron: Tunable Thermoresponsiveness and Water Permeability journal August 2020
First observation of [Pu6(OH)4O4]12+ cluster during the hydrolytic formation of PuO2 nanoparticles using H/D kinetic isotope effect journal January 2022
Solvated and Deformed Hairy Metal–Organic Polyhedron journal June 2020
Electronic structure studies reveal 4f/5d mixing and its effect on bonding characteristics in Ce-imido and -oxo complexes journal January 2022
Lewis Acid Guests in a {P8W48} Archetypal Polyoxotungstate Host: Enhanced Proton Conductivity via Metal‐Oxo Cluster within Cluster Assemblies journal July 2018
Self-assembly of a short amphiphile in water controlled by superchaotropic polyoxometalates: H4SiW12O40 vs. H3PW12O40 journal April 2021
Structural Changes during the Growth of Atomically Precise Metal Oxido Nanoclusters from Combined Pair Distribution Function and Small‐Angle X‐ray Scattering Analysis journal July 2021
Complex modeling: a strategy and software program for combining multiple information sources to solve ill posed structure and nanostructure inverse problems journal September 2015
Peroxide-Promoted Disassembly Reassembly of Zr-Polyoxocations journal September 2019
Beyond Charge Balance: Counter‐Cations in Polyoxometalate Chemistry journal January 2020
A Toroidal Zr 70 Oxysulfate Cluster and Its Diverse Packing Structures journal November 2020
Metal Chalcogenide Supertetrahedral Clusters: Synthetic Control over Assembly, Dispersibility, and Their Functional Applications journal September 2020
Functional Molecular Granular Materials: Advances and Perspectives journal April 2023
Precise Modulation of Surface Layer Dynamics for Tunable Flowability and Gas Absorption Properties of Molecular Porous Liquids journal January 2023
Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments journal June 2017
Colloidal nanoparticle clusters: functional materials by design journal January 2012
Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores journal February 2022
Direct Observation of Contact Ion-Pair Formation in Aqueous Solution journal August 2009
Structural Correspondence between Uranyl Chloride Complexes in Solution and Their Stability Constants journal May 2011
Nanoscale Atoms in Solid-State Chemistry journal June 2013
HERFD-XANES and RIXS Study on the Electronic Structure of Trivalent Lanthanides across a Series of Isostructural Compounds journal January 2022
Deliberate Construction of Polyoxoniobates Exploiting the Carbonate Ligand journal April 2021
Erbium(III) Coordination at the Surface of an Aqueous Electrolyte journal May 2015
High-Resolution X-ray Emission and X-ray Absorption Spectroscopy journal June 2001
Alkali-Driven Disassembly and Reassembly of Molecular Niobium Oxide in Water journal July 2018
{Np 38 } clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides journal January 2018
From Molecular Oxo-Hydroxo Ce Clusters to Crystalline CeO2 journal February 2023
The Microscopic Structure–Property Relationship of Metal–Organic Polyhedron Nanocomposites journal November 2019
Plutonium Co-precipitation with Calcite journal November 2021
Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters journal August 2016
Structure of the Homoleptic Thorium(IV) Aqua Ion [Th(H2O)10]Br4 journal October 2007
Counterion Interaction and Association in Metal-Oxide Cluster Macroanionic Solutions and the Consequent Self-Assembly journal February 2011
Nano-Confinement inside Molecular Metal Oxide Clusters: Dynamics and Modified Encapsulation Behavior journal July 2016
Nb2O5, LiNbO3, and (Na, K)NbO3 Thin Films from High-Concentration Aqueous Nb-Polyoxometalates journal February 2022
Solution-processed, high-performance light-emitting diodes based on quantum dots journal October 2014
A comprehensive comparison of transition-metal and actinyl polyoxometalates journal January 2012
Unique Dynamics of Hierarchical Constrained Macromolecular Ligands on Coordination Nanocage Surface Promotes Facile and Precise Assembly of Polymers journal June 2021
Hybrid Liquid-Crystalline Electrolytes with High-Temperature-Stable Channels for Anhydrous Proton Conduction journal December 2021
Solution behaviors and self-assembly of polyoxometalates as models of macroions and amphiphilic polyoxometalate–organic hybrids as novel surfactants journal January 2012
A novel stable zinc–oxo cluster for advanced lithography patterning journal January 2023
Synthetic Ion Channel Based on Metal–Organic Polyhedra journal July 2008
Robust structure and morphology parameters for CdS nanoparticles by combining small-angle X-ray scattering and atomic pair distribution function data in a complex modeling framework journal March 2014
Spatial-Temporal Characteristics of Confined Polymer Motion Determine Proton Conduction of Polyoxometalate–Poly(ethylene glycol) Hybrid Nanocomposites journal August 2018
Crystal Structure, Dissolution, and Deposition of a 5 nm Functionalized Metal−Organic Great Rhombicuboctahedron journal July 2006
Highly branched and loop-rich gels via formation of metal–organic cages linked by polymers journal November 2015
Stability, Composition, and Core–Shell Particle Structure of Uranium(IV)-Silicate Colloids journal July 2018
Complex phase transitions and phase engineering in the aqueous solution of an isopolyoxometalate cluster journal May 2023
Unique Ligand Exchange Dynamics of Metal–Organic Polyhedra for Vitrimer-like Gas Separation Membranes journal November 2022
The Structure of the Plutonium Oxide Nanocluster [Pu38O56Cl54(H2O)8]14− journal January 2008
Self-Recognition of Structurally Identical, Rod-Shaped Macroions with Different Central Metal Atoms during Their Assembly Process journal March 2013
Superchaotropic Nano‐ion Binding as a Gelation Motif in Cellulose Ether Solutions journal December 2022
The fate of "active" chromium hydroxide, Cr(OH)3.3H2O, in aqueous suspension. Study of the chemical changes involved in its aging journal January 1986
Probing the local structure of nanoscale actinide oxides: a comparison between PuO 2 and ThO 2 nanoparticles rules out PuO 2+x hypothesis journal January 2020
Application of Differential Anomalous X-Ray Scattering to Structural Studies of Amorphous Materials journal June 1981
n -Hexanol Enhances the Cetyltrimethylammonium Bromide Stabilization of Small Gold Nanoparticles and Promotes the Growth of Gold Nanorods journal April 2019
X-ray Absorption Spectroscopy book January 2003
A Complete Macroion−“Blackberry” Assembly−Macroion Transition with Continuously Adjustable Assembly Sizes in {Mo 132 } Water/Acetone Systems journal May 2007
Bismuth-Polyoxocation Coordination Networks: Controlling Nuclearity and Dimension-Dependent Photocatalysis journal March 2023
To form or not to form: PuO2 nanoparticles at acidic pH journal January 2022
Hydrolytic trimer of chromium(III). Synthesis through chromite cleavage and use in the preparation of the "active" trimer hydroxide journal July 1988
Thorium nanochemistry: the solution structure of the Th(iv)–hydroxo pentamer journal January 2012
XAFS and LIBD Investigation of the Formation and Structure of Colloidal Pu(IV) Hydrolysis Products journal July 2004
Crystallization of Keggin Heteropolyanions via a Two-Step Process in Aqueous Solutions journal June 2016
The Surface Chemistry of Metal Oxide Clusters: From Metal–Organic Frameworks to Minerals journal August 2020
Evolution of Polyoxoniobate Cluster Anions journal October 2006
The Structure of Ferrihydrite, a Nanocrystalline Material journal June 2007
Chemical Modification Mechanisms in Hybrid Hafnium Oxo-methacrylate Nanocluster Photoresists for Extreme Ultraviolet Patterning journal August 2018
Simultaneous SAXS/SANS Method at D22 of ILL: Instrument Upgrade journal June 2021
Ce IV 70 Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity** journal February 2021
The Application of HEXS and HERFD XANES for Accurate Structural Characterisation of Actinide Nanomaterials: The Case of ThO 2 journal November 2020
Solvent-Driven Association and Dissociation of the Hydrogen-Bonded Protonated Decavanadates journal May 2011
Quantifying the Solution Structure of Metal Nanoclusters Using Small‐Angle Neutron Scattering journal September 2022
Nanometer-Size Polyoxometalate Anions Adsorb Strongly on Neutral Soft Surfaces journal August 2015
“Host in Host” Supramolecular Core–Shell Type Systems Based on Giant Ring‐Shaped Polyoxometalates journal March 2021
Thorium(IV) Molecular Clusters with a Hexanuclear Th Core journal October 2011
A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO 2 Nanoparticles journal December 2019
Insight into the structure–property relationship of UO 2 nanoparticles journal January 2021
Metal–Organic Polyhedral Core as a Versatile Scaffold for Divergent and Convergent Star Polymer Synthesis journal May 2016
X-ray diffraction "fingerprinting" of DNA structure in solution for quantitative evaluation of molecular dynamics simulation journal February 2006
X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates journal February 2016
Soluble Molybdenum Blues“des Pudels Kern” journal January 2000
Reaction Pathway to the Only Open-Shell Transition-Metal Keggin Ion without Organic Ligation: Reaction Pathway to the Only Open-Shell Transition-Metal Keggin Ion without Organic Ligation journal October 2018
Synthetic Factors Determining the Curvature and Nuclearity of the Giant Mn70 and Mn84 Clusters with a Torus Structure of ∼4 nm Diameter journal April 2023
Small-angle X-ray scattering studies of emergent polyoxometalates in solution journal October 2020
Chemical Stabilization and Electrochemical Destabilization of the Iron Keggin Ion in Water journal October 2016
Modern X-ray spectroscopy: XAS and XES in the laboratory journal November 2020
Small-Angle X-ray Scattering of Polymers journal June 2001
Model2SAS: software for small-angle scattering data calculation from custom shapes journal May 2022
Aqueous formation and manipulation of the iron-oxo Keggin ion journal February 2015
A novel experimental approach for nanostructure analysis: simultaneous small-angle X-ray and neutron scattering journal May 2020
The Key Role of U 28 in the Aqueous Self-Assembly of Uranyl Peroxide Nanocages journal August 2016
Accurate Determination of the Quantity and Spatial Distribution of Counterions around a Spherical Macroion journal January 2021
Dispersions of Two-Dimensional Titanium Carbide MXene in Organic Solvents journal February 2017
Isolation of the Large {Actinide} 38 Poly-oxo Cluster with Uranium journal October 2013
Controllable gelation of coordination nanocages from the physical interactions among surface grafted cholesteryl groups journal January 2022
Oxo-Cluster-Based Zr/Hf IV Separation: Shedding Light on a 70-Year-Old Process journal February 2022
Revealing the Effects of the Non-solvent on the Ligand Shell of Nanoparticles and Their Crystallization journal September 2019
Unexpected Elasticity in Assemblies of Glassy Supra‐Nanoparticle Clusters journal January 2021
Self-Assembly and Ionic-Lattice-like Secondary Structure of a Flexible Linear Polymer of Highly Charged Inorganic Building Blocks journal April 2020
Polyhedral oligomeric silsesquioxane meets “click” chemistry: Rational design and facile preparation of functional hybrid materials journal September 2017
The applications of small-angle X-ray scattering in studying nano-scaled polyoxometalate clusters in solutions journal April 2018
Polymer Topology Reinforced Synergistic Interactions among Nanoscale Molecular Clusters for Impact Resistance with Facile Processability and Recoverability journal August 2021
Investigating the Formation of Giant {Pd 72 } Prop and {Pd 84 } Gly Macrocycles Using NMR, HPLC, and Mass Spectrometry journal July 2018
Alkynyl Approach toward the Protection of Metal Nanoclusters journal September 2018
Cage-like silsesquioxanes-based hybrid materials journal January 2020
Porous Salts Containing Cationic Al24‐Hydroxide‐Acetate Clusters from Scalable, Green and Aqueous Synthesis Routes journal June 2023
Small-angle X-ray scattering to determine solution speciation of metal-oxo clusters journal December 2017
Selective Monovalent Cation Association and Exchange around Keplerate Polyoxometalate Macroanions in Dilute Aqueous Solutions journal June 2010
The rise of metal–organic polyhedra journal January 2021
Heterometallic Ce IV / V V Oxo Clusters with Adjustable Catalytic Reactivities journal December 2021
Actinide Colloids and Particles of Environmental Concern journal October 2012
Surface Functionality-Regulated and Entropy-Driven Thermodynamics of the Formation of Coordination Nanocages journal November 2021
How Nano‐Ions Act Like Ionic Surfactants journal March 2020
Transformation of Ferrihydrite to Goethite and the Fate of Plutonium journal October 2020
Gold Nanoparticles in Chemical and Biological Sensing journal February 2012
Aggregate Formation of Surface-Modified Nanoparticles in Solvents and Polymer Nanocomposites journal February 2018
Polyoxometalate Clusters: Sub-nanometer Building Blocks for Construction of Advanced Materials journal April 2020
Mesoporous Silica Nanoparticles for Drug Delivery journal August 2019
The missing pieces of the PuO 2 nanoparticle puzzle journal January 2020
Local and Nanoscale Structure and Speciation in the PuO 2+ x - y (OH) 2 y · z H 2 O System journal October 2004
Effective coordination numbers from EXAFS: general approaches for lanthanide and actinide dioxides journal January 2022
Are Keggin’s POMs Charged Nanocolloids or Multicharged Anions? journal January 2018
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953
journal October 2008
First Hexanuclear U IV and Th IV Formate Complexes - Structure and Stability Range in Aqueous Solution : First Hexanuclear U journal October 2009
Strategic Capture of the {Nb 7 } Polyoxometalate journal July 2019
Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations journal April 2020
Polyoxometalate/Polyethylene Glycol Interactions in Water: From Nanoassemblies in Water to Crystal Formation by Electrostatic Screening journal April 2017
Direct study of the f-electron configuration in lanthanide systems journal January 2011
Polyoxometalate, Cationic Cluster, and γ-Cyclodextrin: From Primary Interactions to Supramolecular Hybrid Materials journal September 2017
Relevance of formation conditions to the size, morphology and local structure of intrinsic plutonium colloids journal January 2020
High-energy resolution X-ray spectroscopy at actinide M4,5 and ligand K edges: what we know, what we want to know, and what we can know journal January 2022
Spontaneous Stepwise Self-Assembly of a Polyoxometalate-Organic Hybrid into Catalytically Active One-Dimensional Anisotropic Structures journal July 2014
A Photo-driven Polyoxometalate Complex Shuttle and Its Homogeneous Catalysis and Heterogeneous Separation journal September 2013
Synthesis and multi-scale properties of PuO2 nanoparticles: recent advances and open questions journal January 2022
Crystallizing Elusive Chromium Polycations journal December 2016
Aggregation of Heteropolyanions in Aqueous Solutions Exhibiting Short-Range Attractions and Long-Range Repulsions journal December 2015
Impact of Preparation and Handling on the Hydrogen Storage Properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5) journal November 2007
Photoswitching topology in polymer networks with metal–organic cages as crosslinks journal July 2018
Host‐Guest Complexation Between Cyclodextrins and Hybrid Hexavanadates: What are the Driving Forces? journal October 2021
Dimension-Controlled Dewetting in Hydrophobic Porous Nanocapsules journal April 2020
Towards Main-Chain-Polyoxometalate-Containing Hybrid Polymers: A Highly Efficient Approach to Bifunctionalized Organoimido Derivatives of Hexamolybdates journal November 2002

Related Subjects