The Advanced Photon Source
a U.S. Department of Energy Office of Science User Facility

Chen of ChemMatCARS Wins DECTRIS Award 2020 for Work on In Situ Structural Analysis of Metal-Organic Frameworks

The original DECTRIS newsletter article Copyright © 2019 DECTRIS can be read here.

Yu-Sheng Chen, a research professor at the University of Chicago and Operations Manager for the ChemMatCARS Sector 15 x-ray beamllnes at the U.S. Department of Energy’s Advanced Photon Source (APS)  has been named the recipient of the 2020 DECTRIS Award sponsored by the DECTRIS detector manufacturer for studies of metal-organic frameworks carried out at ChemMatCARS. The awarded work was published in the journal Nature Chemistry and highlighted on the APS web site.

Rational design of functional materials is driven by tuning their structural properties in order to achieve a specific performance, such as gas separation or catalysis. In this quest, the stability of a material plays an important role. Under particular environmental conditions, materials may become instable, which hinders their functionality or their transfer to industry applications. As the instability of a material is usually demonstrated as a significant change of its crystal lattice, structural investigations of unstable materials provide information used in the design of materials with improved properties.   

Chen, co-author Krista S. Walton of the Georgia Institute of Technology, and their co-authors prove that a detailed analysis of stable materials is equally important. When exposed to non-lab conditions, stable materials may undergo very small structural changes. Investigating these changes in detail can help to understand their stability, paving a way for developing new design strategies for sorbent materials.

“In a time-resolved experiment, fine structural changes of a crystal can go under the radar for many reasons”, said Dubravka Šišak Jung, application scientist at DECTRIS. “This work presents a smart approach to the experimental challenges, and it involves careful data interpretation. Continuing this project brings a chance to provide a routine in situ analysis of functional materials.”

The DECTRIS Award was established with an aim to encourage researchers to share their findings at a scientific conference of their choice. Chen will use the award to support one of his students.

Below, Yu-Sheng Chen describes his award-winning work: 

Metal-organic frameworks (MOFs) are nanoporous materials, formed by linking inorganic nodes with organic molecules. The sheer size of this group of compounds provides a fruitful playground for the synthesis of crystals with various pore sizes, structures and properties. As these nanopores can serve as a host to molecules of specific chemico-physical properties, MOFs can find their applications in gas separation and storage, catalysis, chemical sensing, drug delivery, and more. One of the most relevant obstacles on the way to a successful technology transfer of MOFs is water. Present in industrial streams of gas separation and gas purification systems, water can be adsorbed in the material and cause two problems: (i) it can occupy active sites of the MOF (ii) it can cause degradation or defect formation of the MOF. Consequently, the effect of water on MOFs can cause significant changes of the crystal lattice. However, some MOFs are stable, that is, they are able to host water molecule without suffering major structural changes.

“Detailed structural analysis of stable MOFs during the water adsorption is often not investigated. In our work, we aimed to see these fine structural differences and relate them to the stability of the material,” said Chen. “This is particularly interesting in cases where two isostructural compounds exhibit different stabilities.”

The investigated MOF, DMOF-TM, proved to be stable under high relative humidity as opposed to its isostructural analogue that does not feature methyl groups on the terephthalate ligand. As the stability of the DMOF-TM could not be explained with the methylation of the ligand, the sample was investigated using dynamic in situ powder and single-crystal x-ray diffraction (SCXRD), as well as in situ infrared spectroscopy and molecular modeling.

In the dynamic in situ SCXRD experiment, designed/conducted by Ian M. Walton, the sample was exposed to a continuous range of relative humidity while data was collected. The results were used to examine the structural changes that are responsible for the observed stability throughout the course of the experiment. The rapid data collection was facilitated by a combination of the synchrotron radiation and the PILATUS3 X CdTe 1M detector. The experimental setup at the ChemMatCARS beamline 15-ID at the APS involved modifications to the existing in situ SCXRD system that would allow for the dynamic control of the relative humidity. (The APS is an Office of Science user facility at Argonne National Laboratory.) The data collected and the resulting structures were critical in the formulation of the proposed structural changes attributed to the stability of DMOF-TM. “The time resolution afforded by the combination of synchrotron radiation and the PILATUS detector enables us to examine fleeting meta-stable structures and gain a more accurate understanding of the dynamic adsorption process,” said article co-author Ian Walton. 

“The control over the environment around the sample and the impressive time resolution allowed for insights into the dynamic interactions within the crystal lattice”, said Chen. “This has enabled us to see that during the water absorption even stable compounds can exhibit small structural changes due to guest–host interactions such as water-induced bond rearrangements.”

See: Nicholas C. Burtch , Ian M. Walton, Julian T. Hungerford, Cody R. Morelock, Yang  Jiao , Jurn Heinen, Yu-Sheng Chen, Andrey A. Yakovenko, Wenqian Xu, David Dubbeldam , Krista S. Walton , “In situ visualization of loading-dependent water effects in a stable metal–organic framework,” Nat. Chem. 12, 186 (2020). DOI: 10.1038/s41557-019-0374-y

ChemMatCARS  is supported by the Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation, under grant number NSF/CHE- 1834750. The Pilatus 1M was funded by an NSF MRI grant (Major Research Instrument) NSF/DMR-1531283. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357.

The U.S. Department of Energy's APS is one of the world’s most productive x-ray light source facilities. Each year, the APS provides high-brightness x-ray beams to a diverse community of more than 5,000 researchers in materials science, chemistry, condensed matter physics, the life and environmental sciences, and applied research. Researchers using the APS produce over 2,000 publications each year detailing impactful discoveries, and solve more vital biological protein structures than users of any other x-ray light source research facility. APS x-rays are ideally suited for explorations of materials and biological structures; elemental distribution; chemical, magnetic, electronic states; and a wide range of technologically important engineering systems from batteries to fuel injector sprays, all of which are the foundations of our nation’s economic, technological, and physical well-being.  ― Stephen Taylor

Argonne National Laboratory seeks solutions to pressing national problems in science and technology. The nation's first national laboratory, Argonne conducts leading-edge basic and applied scientific research in virtually every scientific discipline. Argonne researchers work closely with researchers from hundreds of companies, universities, and federal, state and municipal agencies to help them solve their specific problems, advance America's scientific leadership and prepare the nation for a better future. With employees from more than 60 nations, Argonne is managed by UChicago Argonne, LLC, for the U.S. DOE Office of Science.

The U.S. Department of Energy's Office of Science is the single largest supporter of basic research in the physical sciences in the United States and is working to address some of the most pressing challenges of our time. For more information, visit the Office of Science website.

And see also the APS science highlight “Water Adsorption in Metal-Organic Frameworks,” by Dana Desonie

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