Three-dimensional electron diffraction as a complementary technique to powder X-ray diffraction for phase identification and structure solution of powders

Phase identification and structure determination are important and widely used techniques in chemistry, physics and materials science. Recently, two methods for automated three-dimensional electron diffraction (ED) data collection, namely automated diffraction tomography (ADT) and rotation electron diffraction (RED), have been developed. Compared with X-ray diffraction (XRD) and two-dimensional zonal ED, three-dimensional ED methods have many advantages in identifying phases and determining unknown structures. Almost complete three-dimensional ED data can be collected using the ADT and RED methods. Since each ED pattern is usually measured off the zone axes by three-dimensional ED methods, dynamic effects are much reduced compared with zonal ED patterns. Data collection is easy and fast, and can start at any arbitrary orientation of the crystal, which facilitates automation. Three-dimensional ED is a powerful technique for structure identification and structure solution from individual nano- or micron-sized particles, while powder X-ray diffraction (PXRD) provides information from all phases present in a sample. ED suffers from dynamic scattering, while PXRD data are kinematic. Three-dimensional ED methods and PXRD are complementary and their combinations are promising for studying multiphase samples and complicated crystal structures. Here, two three-dimensional ED methods, ADT and RED, are described. Examples are given of combinations of three-dimensional ED methods and PXRD for phase identification and structure determination over a large number of different materials, from Ni–Se–O–Cl crystals, zeolites, germanates, metal–organic frameworks and organic compounds to intermetallics with modulated structures. It is shown that three-dimensional ED is now as feasible as X-ray diffraction for phase identification and structure solution, but still needs further development in order to be as accurate as X-ray diffraction. It is expected that three-dimensional ED methods will become crucially important in the near future.

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A complex pseudo-decagonal quasicrystal approximant, Al37(Co,Ni)15.5, solved by rotation electron diffraction

Journal of Applied Crystallography ◽

10.1107/s1600576713029294 ◽

2014 ◽

Vol 47 (1) ◽

pp. 215-221 ◽

Cited By ~ 14

Author(s):

Devinder Singh ◽

Yifeng Yun ◽

Wei Wan ◽

Benjamin Grushko ◽

Xiaodong Zou ◽

...

Keyword(s):

Electron Diffraction ◽

Single Crystal ◽

Diffraction Data ◽

Three Dimensional ◽

Basic Structure ◽

Electron Diffraction Data ◽

Dimensional Electron ◽

X Ray Diffraction ◽

X Ray ◽

Diffraction Patterns

Electron diffraction is a complementary technique to single-crystal X-ray diffraction and powder X-ray diffraction for structure solution of unknown crystals. Crystals too small to be studied by single-crystal X-ray diffraction or too complex to be solved by powder X-ray diffraction can be studied by electron diffraction. The main drawbacks of electron diffraction have been the difficulties in collecting complete three-dimensional electron diffraction data by conventional electron diffraction methods and the very time-consuming data collection. In addition, the intensities of electron diffraction suffer from dynamical scattering. Recently, a new electron diffraction method, rotation electron diffraction (RED), was developed, which can overcome the drawbacks and reduce dynamical effects. A complete three-dimensional electron diffraction data set can be collected from a sub-micrometre-sized single crystal in less than 2 h. Here the RED method is applied forab initiostructure determination of an unknown complex intermetallic phase, the pseudo-decagonal (PD) quasicrystal approximant Al37.0(Co,Ni)15.5, denoted as PD2. RED shows that the crystal is F-centered, witha= 46.4,b= 64.6,c= 8.2 Å. However, as with other approximants in the PD series, the reflections with oddlindices are much weaker than those withleven, so it was decided to first solve the PD2 structure in the smaller, primitive unit cell. The basic structure of PD2 with unit-cell parametersa= 23.2,b= 32.3,c= 4.1 Å and space groupPnmmhas been solved in the present study. The structure withc= 8.2 Å will be taken up in the near future. The basic structure contains 55 unique atoms (17 Co/Ni and 38 Al) and is one of the most complex structures solved by electron diffraction. PD2 is built of characteristic 2 nm wheel clusters with fivefold rotational symmetry, which agrees with results from high-resolution electron microscopy images. Simulated electron diffraction patterns for the structure model are in good agreement with the experimental electron diffraction patterns obtained by RED.

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Three-dimensional electron diffraction for porous crystalline materials: structural determination and beyond

Chemical Science ◽

10.1039/d0sc05731b ◽

2021 ◽

Author(s):

Zhehao Huang ◽

Tom Willhammar ◽

Xiaodong Zou

Keyword(s):

Electron Diffraction ◽

Three Dimensional ◽

Structural Determination ◽

New Materials ◽

Dimensional Electron ◽

X Ray Diffraction ◽

Crystalline Materials ◽

X Ray ◽

Structural Details

Three-dimensional electron diffraction is a powerful tool for accurate structure determination of zeolite, MOF, and COF crystals that are too small for X-ray diffraction. By revealing the structural details, the properties of the materials can be understood, and new materials and applications can be designed.

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Can 3D Electron Diffraction Provide Accurate Atomic Structures of Metal-Organic Frameworks?

10.26434/chemrxiv.11688270 ◽

2020 ◽

Author(s):

Zhehao Huang ◽

meng ge ◽

Francesco Carraro ◽

Christian Doonan ◽

paolo falcaro ◽

...

Keyword(s):

Electron Diffraction ◽

Data Collection ◽

Single Crystal ◽

Structure Determination ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Continuous Rotation ◽

Metal Organic ◽

3D Electron

Many framework materials such as metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) are synthesized as polycrystalline powders, which are too small for structure determination by single crystal X-ray diffraction (SCXRD). Here, we show that a three-dimensional (3D) electron diffraction method, namely continuous rotation electron diffraction (cRED), can be used for <i>ab initio</i> structure determination of such materials. As an example, we present a complete structural analysis of a biocomposite, denoted BSA@ZIF-C, where Bovin Serum Albumin (BSA) was encapsulated in a zeolitic imidazolate framework (ZIF). Low electron dose was combined with ultrafast cRED data collection to minimize electron beam damage of the sample. We demonstrate that the atomic structure obtained by cRED is as reliable and accurate as that obtained by single crystal X-ray diffraction. The high accuracy and fast data collection open new opportunities for investigation of cooperative phenomena in framework structures at atomic level.

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Phase Identification and Structure Solution by Three-Dimensional Electron Diffraction Tomography: Gd–Phosphate Nanorods

Inorganic Chemistry ◽

10.1021/ic500056r ◽

2014 ◽

Vol 53 (10) ◽

pp. 5067-5072 ◽

Cited By ~ 13

Author(s):

Arnaud Mayence ◽

Julien R. G. Navarro ◽

Yanhang Ma ◽

Osamu Terasaki ◽

Lennart Bergström ◽

...

Keyword(s):

Electron Diffraction ◽

Three Dimensional ◽

Phase Identification ◽

Diffraction Tomography ◽

Dimensional Electron ◽

Structure Solution

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Phase Identification by Rotation Electron Diffraction from Multiphasic Samples

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314089190 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C1080-C1080

Author(s):

Yifeng Yun ◽

Wei Wan ◽

Faiz Rabbani ◽

Jie Su ◽

Sven Hovmöller ◽

...

Keyword(s):

Electron Diffraction ◽

Three Dimensional ◽

Phase Identification ◽

X Ray Diffraction ◽

X Ray ◽

Space Groups ◽

Transmission Electron ◽

Diffraction Patterns ◽

Five Phases ◽

Oxide Sample

Electron Crystallography is an important technique for studying micro- and nano-sized crystals[1]. Crystals considered as powder by X-ray diffraction behave as single crystals by electron diffraction. Recently we developed a new method, Rotation Electron Diffraction (RED) for three-dimensional diffraction data collection by combining electron beam tilt with goniometer tilt on a transmission electron microscope (TEM)[2]. Here we apply the RED method on an unknown oxide sample in a Ni-Se-Cl-O system, which may show special physical properties, for example magnetic properties. The crystals in the sample were less than a few micrometers in sizes. Powder X-ray diffraction patterns of the sample could not be indexed by existing known phases. The sample was thus studied by TEM. Five 3D RED datasets were collected from five crystals with different morphologies using the software package RED. The data processing was also performed using the software RED-processing. The unit cell and space groups of all the five phases were obtained using RED and the structures of four of five phases were solved. Nearly all peaks in the powder X-ray diffraction pattern could be indexed using these five phases. To conclude, five phases from a powder sample have been identified using RED. RED is a powerful method for phase identification of multiphasic samples with nano-sized crystals.

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Can 3D Electron Diffraction Provide Accurate Atomic Structures of Metal-Organic Frameworks?

10.26434/chemrxiv.11688270.v1 ◽

2020 ◽

Author(s):

Zhehao Huang ◽

meng ge ◽

Francesco Carraro ◽

Christian Doonan ◽

paolo falcaro ◽

...

Keyword(s):

Electron Diffraction ◽

Data Collection ◽

Single Crystal ◽

Structure Determination ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Continuous Rotation ◽

Metal Organic ◽

3D Electron

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Phase identification and structure determination from multiphase crystalline powder samples by rotation electron diffraction

Journal of Applied Crystallography ◽

10.1107/s1600576714023875 ◽

2014 ◽

Vol 47 (6) ◽

pp. 2048-2054 ◽

Cited By ~ 14

Author(s):

Yifeng Yun ◽

Wei Wan ◽

Faiz Rabbani ◽

Jie Su ◽

Hongyi Xu ◽

...

Keyword(s):

Electron Diffraction ◽

Structure Determination ◽

Structure Characterization ◽

Inorganic Crystal Structure Database ◽

Phase Identification ◽

X Ray Diffraction ◽

Crystalline Powder ◽

Unknown Compound ◽

X Ray ◽

Powder Samples

Phase identification and structure characterization are important in synthetic and materials science. It is difficult to characterize the individual phases from multiphase crystalline powder samples, especially if some of the phases are unknown. This problem can be solved by combining rotation electron diffraction (RED) and powder X-ray diffraction (PXRD). Four phases were identified on the same transmission electron microscopy grid from a multiphase sample in the Ni–Se–O–Cl system, and their structures were solved from the RED data. Phase 1 (NiSeO3) was found in the Inorganic Crystal Structure Database using the information from RED. Phase 2 (Ni3Se4O10Cl2) is an unknown compound, but it is isostructural to Co3Se4O10Cl2, which was recently solved by single-crystal X-ray diffraction. Phase 3 (Ni5Se6O16Cl4H2) and Phase 4 (Ni5Se4O12Cl2) are new compounds. The fact that there are at least four different compounds in the as-synthesized material explains why the phase identification and structure determination could not be done by PXRD alone. The RED method makes phase identification from such multiphase powder samples much easier than would be the case using powder X-ray diffraction. The RED method also makes structure determination of submicrometre-sized crystals from multiphase samples possible.

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Crystal structure analysis of a star-shaped triazine compound: a combination of single-crystal three-dimensional electron diffraction and powder X-ray diffraction

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520618006686 ◽

2018 ◽

Vol 74 (3) ◽

pp. 287-294 ◽

Cited By ~ 1

Author(s):

Tatiana E. Gorelik ◽

Jacco van de Streek ◽

Herbert Meier ◽

Lars Andernach ◽

Till Opatz

Keyword(s):

Crystal Structure ◽

Electron Diffraction ◽

Single Crystal ◽

Diffraction Data ◽

Three Dimensional ◽

Electron Diffraction Data ◽

Dimensional Electron ◽

X Ray Diffraction ◽

Diffraction Profile ◽

X Ray

The solid-state structure of star-shaped 2,4,6-tris{(E)-2-[4-(dimethylamino)-phenyl]ethenyl}-1,3,5-triazine is determined from a powder sample by exploiting the respective strengths of single-crystal three-dimensional electron diffraction and powder X-ray diffraction data. The unit-cell parameters were determined from single crystal electron diffraction data. Using this information, the powder X-ray diffraction data were indexed, and the crystal structure was determined from the powder diffraction profile. The compound crystallizes in a noncentrosymmetric space group,P212121. The molecular conformation in the crystal structure was used to calculate the molecular dipole moment of 3.22 Debye, which enables the material to show nonlinear optical effects.

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Diffraction

Microscopy Today ◽

10.1017/s1551929512000107 ◽

2012 ◽

Vol 20 (2) ◽

pp. 7-7

Author(s):

Charles Lyman

Keyword(s):

Electron Diffraction ◽

100Th Anniversary ◽

Primary Phase ◽

Phase Identification ◽

X Rays ◽

X Ray Diffraction ◽

Identification Methods ◽

X Ray ◽

Structure Of Matter

This year marks the 100th anniversary of the discovery of X-ray diffraction and the 85th anniversary of electron diffraction (see Microscopy Pioneers). For most of the time since their introduction, microscopists have known these two techniques as the primary phase identification methods used in conjunction with various microscopies. However, these two diffraction methods also have played enormous roles in understanding the structure of matter, as well as the nature of both X rays and electrons.

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