Chemical and physical transformations of carbon-based nanomaterials observed by liquid phase transmission electron microscopy

Abstract

This article addresses recent advances in liquid phase transmission electron microscopy (LPTEM) for studying nanoscale synthetic processes of carbon-based materials that are independent of the electron beam—those driven by nonradiolytic chemical or thermal reactions. In particular, we focus on chemical/physical formations and the assembly of nanostructures composed of organic monomers/polymers, peptides/DNA, and biominerals. The synthesis of carbon-based nanomaterials generally only occurs at specific conditions, which cannot be mimicked by aqueous solution radiolysis. Carbon-based structures themselves are also acutely sensitive to the damaging effects of the irradiating beam, which make studying their synthesis using LPTEM a unique challenge that is possible when beam effects can be quantified and mitigated. With new direct sensing, high frame-rate cameras, and advances in liquid cell holder designs, combined with a growing understanding of irradiation effects and proper experimental controls, microscopists have been able to make strides in observing traditionally problematic carbon-based materials under conditions where synthesis can be controlled, and imaged free from beam effects, or with beam effects quantified and accounted for. These materials systems and LPTEM experimental techniques are discussed, focusing on nonradiolytic chemical and physical transformations relevant to materials synthesis.

Appendix

Lucas Parent is a staff research scientist at the Innovation Partnership Building and the Center for Advanced Microscopy and Materials Analysis at the University of Connecticut. He received his BS degree in materials science from Rensselaer Polytechnic Institute in 2009, and his PhD degree in materials science from the University of California, Davis, in 2013. His research focuses on the development of in situ electron microscopy to study solution-phase formation, transition, and stimuli-response processes in carbon-based nanomaterials and biomaterials. Parent can be reached by email at lucas.parent@uconn.edu.

Maria Vratsanos is a doctoral candidate in materials science and engineering at Northwestern University. She received her undergraduate degree in polymer engineering with an emphasis on biomaterials at Case Western Reserve University in 2018. She is 2019 National Science Foundation Graduate Research Fellowship Program recipient. Her current research focuses on the investigation of soft-matter dynamics and transformations via liquid phase transmission electron microscopy. Vratsanos can be reached by email at mariavratsanos2023@u.northwestern.edu.

Biao Jin is a postdoctoral research associate at Pacific Northwest National Laboratory. He received his BE degree from Hainan University, China, in 2014, and his PhD degree in chemistry from Zhejiang University, China, in 2019. His current research focuses on nucleation and growth mechanisms of nanomaterials and in situ transmission electron microscopy techniques. Jin can be reached by email at biao.jin@pnnl.gov.

Jim De Yoreo is a chief scientist in materials science at the Physical and Computational Sciences Directorate at Pacific Northwest National Laboratory, and an affiliate professor of materials science and engineering and of chemistry at the University of Washington. He received his PhD degree in physics from Cornell University in 1985. His research focuses on interactions, assembly, and crystallization in inorganic, biomolecular, and biomineral systems. He served as president of the Materials Research Society (MRS) and is a Fellow of both MRS and the American Physical Society. De Yoreo can be reached by email at James.DeYoreo@pnnl.gov.

Nathan C. Gianneschi is the Jacob and Rosaline Cohn Professor of Chemistry, Materials Science and Engineering, Biomedical Engineering and Pharmacology at Northwestern University. He received his BSc degree from The University of Adelaide, Australia, in 1999, and his PhD degree from Northwestern University in 2005. He completed postdoctoral research at The Scripps Research Institute in 2008. He began his career at the University of California, San Diego. Gianneschi can be reached by email at nathan.gianneschi@northwestern.edu.