Review
Materials Science, Multidisciplinary
Joao Batista Souza Junior, Gabriel Ravanhani Schleder, Jefferson Bettini, Icamira Costa Nogueira, Adalberto Fazzio, Edson Roberto Leite
Summary: Atomic-scale structure determination is crucial for nanomaterial understanding and new technology development. Electron diffraction offers advantages for atomic structure characterization, with potential to become a routine tool in nanomaterial science.
Review
Chemistry, Multidisciplinary
Maxwell W. Terban, Simon J. L. Billinge
Summary: This article reviews the application of atomic pair distribution function (PDF) analysis in the study of molecular materials. The PDF method is a powerful tool for investigating short- and intermediate-range order in nanoscale materials. It can provide structural details that are obscured in reciprocal space by defects, disorder, or structural ambiguities. While its use in inorganic and nanomaterials research has been highlighted, significant progress has also been made in applying PDF analysis to molecular materials such as carbon, pharmaceuticals, polymers, liquids, coordination compounds, and composites. The article provides an overview of applications in a wide variety of molecular compounds and systems, and offers pedagogical descriptions and tips for implementation.
Article
Materials Science, Ceramics
Toshihiro Isobe, Yuri Adachi, Sachiko Matsushita, Akira Nakajima
Summary: This paper investigates the effect of Ti substitution on the thermal expansion behavior of Zr2-xTixS0.9P2O12-δ, finding that Ti has two effects: reduction of the lattice constant and inhibition of the phase transition. Ti showed a solid solubility limit of approximately x=0.7 in Zr2-xTixS0.9P2O12-δ, leading to two types of compounds with different thermal expansion behaviors.
CERAMICS INTERNATIONAL
(2021)
Article
Chemistry, Multidisciplinary
Rasmus S. Christensen, Magnus Klove, Martin Roelsgaard, Sanna Sommer, Bo B. Iversen
Summary: Hafnia (HfO2), a wide band gap semiconducting oxide, is studied for the formation of nanocrystals from hafnium tetrachloride in methanol under solvothermal conditions using in situ PXRD and PDF analysis. The precursor solution consists of a Hf oxide trimer with similar local structure to m-HfO2. Heating leads to the nucleation of m-HfO2 nanocrystals, with complex chemical processes occurring during growth.
Article
Engineering, Electrical & Electronic
Zein K. Heiba, Lutfi Arda, Nurcan Dogan, Ozgul Karatas, Mohamed Bakr Mohamed
Summary: The sol-gel technique was used to synthesize Er2-xCoxO3 mixed oxides with varying Co concentrations. Rietveld analyses showed single phase nanoparticles up to x = 0.1, with Co3O4 phase appearing for x >= 0.2. The magnetic analysis revealed super-paramagnetism as the reason for S-shaped hysteresis loops and non-zero magnetic moments, with both Mr and Ms increasing with higher Co+2 concentrations.
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
(2022)
Article
Chemistry, Multidisciplinary
Zhu-Lin Xie, Xiaolin Liu, Andrew J. S. Valentine, Vincent M. Lynch, David M. Tiede, Xiaosong Li, Karen L. Mulfort
Summary: High-energy X-ray scattering and pair distribution function analysis is a powerful method for detecting the structure of molecular complexes in solution, revealing pairwise distances in local coordination spheres of metal centers and metal...metal distances. Comparing metal...metal distances detected in solution with crystal structure and molecular models can confirm unique distortions to metal bridging ligands in the solid state. This work demonstrates the potential for observing sub-angstrom conformational differences by comparing solution and solid-state structures directly.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Guanjie Zhang, Hui Liu, Jun Chen, He Lin, Nan Zhang
Summary: This work presents a general spherical harmonics method for extracting anisotropic pair distribution functions (PDFs). It addresses the need for investigating local structures under external stimuli in studies of functional crystallized materials. The traditional method of extracting X-ray PDF data based on isotropic X-ray structure functions is no longer valid for materials with orientation-dependent responses. To overcome this limitation, an advanced spherical harmonics method is developed to transform 2D X-ray total-scattering data into anisotropic PDF data based on 3D diffraction geometry and Fourier transform. The effectiveness of this method is demonstrated through the analysis of electric-field-induced local structural changes in PbZr0.54Ti0.46O3 ceramics.
JOURNAL OF APPLIED CRYSTALLOGRAPHY
(2023)
Article
Chemistry, Multidisciplinary
Ida Gjerlevsen Nielsen, Sanna Sommer, Ann-Christin Dippel, Jorgen Skibsted, Bo Brummerstedt Iversen
Summary: The study directly determined the atomic structures of Ga3+ ion complexes in aqueous solutions across a wide range of pH, counter anions and concentrations using X-ray pair distribution function analysis and Ga-71 NMR. Different coordination structures of gallium ions were observed at different pH levels, with octahedral coordination dominating at low pH and polyoxogallate structures forming at slightly higher pH. The study provides valuable insights into the aqueous chemistry of Ga3+ ions with atomic resolution, relevant for semiconductor fabrication and medical applications.
Article
Physics, Multidisciplinary
Mahdi Ghasemifard, Misagh Ghamari, Meysam Iziy
Summary: In this study, the three-dimensional atomic structure of 0.65[Ba(Mg-1/3, Ti-2/3)]-0.35[BaTiO3] (BMT-BT) was investigated using x-ray diffraction (XRD) with molybdenum radiation (MoKα(1)), Rietveld refinement, and the atomic pair distribution function (PDF) technique. The results showed that BMT has a cubic perovskite bulk crystal structure. The analysis of the PDF data provided information about interatomic bond distances and nearest neighbor distances in the structure.
Article
Physics, Applied
Anna Zink Eikeland, Jennifer Holscher, Mogens Christensen
Summary: Platelet shaped strontium hexaferrite crystallites were synthesized hydrothermally to study the effect of different reaction parameters on their phase composition, structure, and magnetic properties. The use of NaOH as a base resulted in samples mainly composed of SrFe12O19 with small crystallite sizes, while the use of KOH led to phase composition variations depending on Fe/Sr molar ratios and KOH concentrations, with larger crystallites observed. The study highlights the importance of meticulous control of reaction parameters and structural analysis for the preparation and understanding of hard-magnetic SrFe12O19.
JOURNAL OF PHYSICS D-APPLIED PHYSICS
(2021)
Article
Chemistry, Physical
S. S. Setayandeh, E. G. Obbard, J. Stansby, D. Frost, Jack O. Astbury, C. L. Wilson, P. A. Burr
Summary: There is no consensus on the structure and composition of the epsilon phase in the W-B system. Ab initio calculations and experimental comparisons suggest that the epsilon phase is most likely a hypo-stoichiometric W2B5-x compound.
JOURNAL OF ALLOYS AND COMPOUNDS
(2022)
Article
Chemistry, Physical
Nathan J. Szymanski, Zhengyan Lun, Jue Liu, Ethan C. Self, Christopher J. Bartel, Jagjit Nanda, Bin Ouyang, Gerbrand Ceder
Summary: Pair distribution function (PDF) analysis is a powerful technique for characterizing short-range order (SRO) in disordered materials. This study outlines an approach to model SRO using first-principles calculations based on the cluster-expansion formalism and validates it on neutron scattering data from two disordered rocksalt oxyfluorides. The results demonstrate the importance of considering local variations in site occupancies and bond lengths in accurately interpreting experimental PDF data.
CHEMISTRY OF MATERIALS
(2023)
Article
Materials Science, Ceramics
Amine Bendahhou, Karim Chourti, Soufian El Barkany, Mohamed Abou-Salama
Summary: Ba-4(Nd1-xSmx)(28/3)(Ti0,95Zr0,05)(18)O-54 ceramics with varying Nd/Sm ratio were studied for their structure and dielectric behavior. The crystal structure was found to belong to the tungsten bronze type, with dense microstructure and significant temperature-dependent dielectric properties.
CERAMICS INTERNATIONAL
(2022)
Article
Materials Science, Ceramics
Ryosuke Uehara, Sachiko Matsushita, Akira Nakajima, Toshihiro Isobe
Summary: Zr(2-x)Sn(x)S(y)P(2)O(12-delta) was prepared using a hydrothermal synthesis method, with solid solubility limit of Sn found to be approximately x = 0.6. The substitution of Sn influenced the formation of defects at S sites, resulting in samples with smaller coefficients of thermal expansion compared to Zr2SP2O12.
JOURNAL OF ASIAN CERAMIC SOCIETIES
(2021)
Article
Materials Science, Multidisciplinary
Emily T. Nienhuis, Manzila Tuheen, Jincheng Du, John S. McCloy
Summary: This study characterized the structures of a series of Na2O-FeO-Fe2O3-SiO2 melts using synchrotron X-ray total scattering with aerodynamic levitation and laser heating. The actual redox of the melts was found to be intermediate, with some Fe2+ present. Cooling of the melts resulted in the formation of magnetite on the sample surface, without any silica-containing crystalline phases observed.
JOURNAL OF MATERIALS SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Magnus Klove, Sanna Sommer, Bo B. Iversen, Bjork Hammer, Wilke Dononelli
Summary: A machine learning model incorporating density functional theory calculations and comparison of PDFs can be used to determine the crystal structure of unknown compounds, allowing for the identification of metastable configurations and stacking disorders.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Jonas Ruby Sandemann, Thomas Bjorn Egede Gronbech, Kristoffer Andreas Holm Stockler, Feng Ye, Bryan C. Chakoumakos, Bo Brummerstedt Iversen
Summary: ZnFe2O4 exhibits spin-glass transition and has dominant ferromagnetic and antiferromagnetic correlations. The 3D-m Delta PDF method is used to visualize the local magnetic ordering preferences.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Nils Lau Nyborg Broge, Andreas Dueholm Bertelsen, Frederik Sondergaard-Pedersen, Bo Brummerstedt Iversen
Summary: High-entropy alloys (HEAs) are a promising class of materials with extraordinary properties and customization potential through stoichiometry changes. This study presents a solvothermal method for synthesizing eight-component Pt-Ir-Pd-Rh-Ru-Cu-Ni-Co nano-HEA nanoparticles, which can be produced in large quantities. The method relies on simple autoclaves and in situ X-ray scattering experiments suggest auto-catalyzed growth of the particles, extending understanding of HEA nanomaterials.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Peter Skjott Thorup, Rasmus Stubkjaer Christensen, Martin Roelsgaard, Bo Brummerstedt Iversen
Summary: The segmented beta-Zn4Sb3 pellets with ion-blocking steel interfaces exhibit improved stability under thermoelectric operating conditions, as shown by quantitative phase analysis and microstructure analysis.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Rohan Pokratath, Laurent Lermusiaux, Stefano Checchia, Jikson Pulparayil Mathew, Susan Rudd Cooper, Jette Katja Mathiesen, Guillaume Landaburu, Soham Banerjee, Songsheng Tao, Nico Reichholf, Simon J. L. Billinge, Benjamin Abecassis, Kirsten M. O. Jensen, Jonathan De Roo
Summary: In this study, the nucleation and growth of zirconia nanocrystals from zirconium chloride and zirconium isopropoxide were investigated using various analysis methods. It was found that amorphous particles nucleate into nanocrystals through a second order process, and they are also the source of nanocrystal growth. By using different zirconium precursors, the precursor decomposition rate and nanocrystal size can be controlled. These findings are expected to aid in the further development of colloidal syntheses.
Article
Chemistry, Physical
Jonathan Quinson, Olivia Aalling-Frederiksen, Waynah L. Dacayan, Joachim D. Bjerregaard, Kim D. Jensen, Mads R. V. Jorgensen, Innokenty Kantor, Daniel R. Sorensen, Luise Theil Kuhn, Matthew S. Johnson, Maria Escudero-Escribano, Soren B. Simonsen, Kirsten M. O. Jensen
Summary: This article introduces a surfactant-free synthesis method for gold nanoparticles, which can achieve stable and size-controlled colloidal gold nanoparticles for months by reducing HAuCl4 with low-viscosity mono-alcohols and water at room temperature in alkaline solutions, without the need for other additives. Pd and bimetallic AuxPdy NPs, nanocomposites, and multimetallic samples can also be obtained and act as active (electro)catalysts. This simple synthesis method has multiple advantages over the state-of-the-art syntheses in fundamental and applied research.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Paulraj Arunkumar, Sampath Gayathri, Dipankar Saha, Jong Hun Han
Summary: In this study, a 2D/2D heterostructure made of hierarchical pseudocapacitive cobalt phosphide/oxide and P-doped reduced graphene oxide (PrGO) nanosheets (CoP/CoO@PrGO) was fabricated using porous zeolitic-imidazolate framework precursor. This structure exhibits a high specific capacitance of 405 F g-1 at 5 A g-1 and excellent cycling stability. Therefore, this heterostructure holds great potential for the development of high-performance supercapacitors.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Nikolaj Roth, Bo Brummerstedt Iversen
Summary: The superionic conductor Cu2-xSe has been studied and the large vibrations with extreme anharmonicity of Cu ions within a tetrahedron-shaped volume in the structure have been observed. The analysis of electron density suggests infrequent jumps between sites, supporting recent quasi-elastic neutron scattering data and challenging the phonon-liquid picture. The low thermal conductivity is likely not caused by the diffusion of Cu ions.
Article
Chemistry, Multidisciplinary
Martin Roelsgaard, Magnus Klove, Rasmus Christensen, Andreas D. Bertelsen, Nils L. N. Broge, Innokenty Kantor, Daniel Risskov Sorensen, Ann-Christin Dippel, Soham Banerjee, Martin V. Zimmermann, Philipp Glaevecke, Olof Gutowski, Mads Ry Vogel Jorgensen, Bo Brummerstedt Iversen
Summary: Understanding nucleation and growth mechanisms in hydro- and solvothermal conditions is crucial for tailoring functional nanomaterials. High-energy synchrotron radiation enables real-time characterization of nanocrystals using powder X-ray diffraction and X-ray total scattering. Recent developments in in situ setups at PETRA III and MAX IV beamlines allow for studying nucleation and growth phenomena in solvothermal synthesis, providing data for Rietveld refinement and pair distribution function refinement within 4 ms.
JOURNAL OF APPLIED CRYSTALLOGRAPHY
(2023)
Article
Chemistry, Physical
Andrea Kirsch, Espen Drath Bojesen, Niels Lefeld, Rasmus Larsen, Jette Katja Mathiesen, Susanne Linn Skjaervo, Rebecca Katharina Pittkowski, Denis Sheptyakov, Kirsten M. O. Jensen
Summary: High-entropy materials (HEMs) are a class of solid solutions containing at least five different elements, which has promising potential for the development of functional materials. Researchers synthesized new HEMs in a mullite-type structure and showed that they are mixed solid solutions. Using X-ray techniques, they found that the HEMs form through a metastable amorphous phase without the formation of any crystalline intermediates.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Jonas Ruby Sandemann, Kristoffer Andreas Holm Stockler, Xiaoping Wang, Bryan C. Chakoumakos, Bo Brummerstedt Iversen
Summary: Accurate structural models are crucial for understanding the structure-property relationships in functional materials. This study focuses on the complex crystal structures of spinels and establishes a benchmark crystal structure for defect-free spinel ferrite ZnFe2O4. Various diffraction techniques are used to provide reference data for testing and refining structural models. The results demonstrate the significance of atomic displacement parameters in accurately describing the cation inversion in spinel-type materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Susanne Linn Skjaervo, Andy S. Anker, Magnus C. Wied, Emil T. S. Kjaer, Mikkel Juelsholt, Troels Lindahl Christiansen, Kirsten M. O. Jensen
Summary: We use in situ X-ray total scattering experiments to study the hydrothermal synthesis of wolframite-type MWO4 (M: Mn, Fe, Co, Ni), and map the material formation pathway in detail. We find that a crystalline precursor forms for MnWO4 synthesis, while amorphous pastes form for FeWO4, CoWO4, and NiWO4 syntheses. The amorphous precursor structure can be described through polyoxometalate chemistry, and the disorder in the precursor phase appears to be a barrier for crystallization.
Article
Chemistry, Physical
Jette K. Mathiesen, Sofie Colding-Fagerholt, Kim D. Jensen, Jack K. Pedersen, Tom Vosch, Jan Rossmeisl, Stig Helveg, Kirsten M. o. Jensen
Summary: Bimetallic nanocrystals exhibit different behaviors compared to monometallic nanocrystals under gas environments. Under oxygen exposure, bimetallic nanocrystals lose metallic Cu and form metal oxide phases, but can reappear and reincorporate into the crystalline phase under a reducing atmosphere. Cu mobility promotes segregation and formation of CuO along with the formation of a monometallic phase, altering the active surface sites of the nanocatalyst.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Ines C. B. Martins, Anders S. Larsen, Anders O. Madsen, Olivia Aalling Frederiksen, Alexandra Correia, Kirsten M. O. Jensen, Henrik S. Jeppesen, Thomas Rades
Summary: Polyamorphism is a controversial solid-state phenomenon that is still not fully understood. In this study, three distinct polyamorphic forms of hydrochlorothiazide were discovered and their interconversions were investigated. Molecular dynamics simulations revealed differences in dihedral angle distributions between two of the polyamorphs, which may explain their different physicochemical properties.
Article
Chemistry, Multidisciplinary
Emil T. S. Kjaer, Andy S. Anker, Marcus N. Weng, Simon J. L. Billinge, Raghavendra Selvan, Kirsten M. O. Jensen
Summary: In this study, a deep learning algorithm called DeepStruc is introduced for solving the structure of monometallic nanoparticles directly from Pair Distribution Function (PDF) obtained from total scattering data. DeepStruc is able to successfully determine the structures of various monometallic nanoparticles, including those that are not present in the training distribution. Moreover, DeepStruc can also solve the structures of stacking faulted nanoparticles in a system of hcp, fcc, and stacking faulted nanoparticles.
