journal article·2023-10-11Open access

Elucidating the Mechanism of Large Phosphate Molecule Intercalation Through Graphene-Substrate Heterointerfaces

Jiayun Liang, Ke Ma, Xiao Zhao, Guanyu Lu, Jake Riffle, Carmen M. Andrei, Chengye Dong, Turker Furkan, Siavash Rajabpour, Rajiv Ramanujam Prabhakar, Joshua A. Robinson, Vasquez Magdaleno, Quang Thang Trinh, Joel W. Ager, Miquel Salmeron, Shaul Aloni, Joshua D. Caldwell, Shawna Hollen, Hans A. Bechtel, Nabil D. Bassim, Matthew P. Sherburne, Zakaria Y. Al Balushi

ACS Applied Materials & Interfaces· Volume 15· Issue 40

Abstract

High Resolution Image Download MS PowerPoint Slide Intercalation is the process of inserting chemical species into the heterointerfaces of two-dimensional (2D) layered materials. While much research has focused on the intercalation of metals and small gas molecules into graphene, the intercalation of larger molecules through the basal plane of graphene remains challenging. In this work, we present a new mechanism for intercalating large molecules through monolayer graphene to form confined oxide materials at the graphene-substrate heterointerface. We investigate the intercalation of phosphorus pentoxide (P 2 O 5 ) molecules directly from the vapor phase and confirm the formation of confined P 2 O 5 at the graphene-substrate heterointerface using various techniques. Density functional theory (DFT) corroborates the experimental results and reveals the intercalation mechanism, whereby P 2 O 5 dissociates into small fragments catalyzed by defects in the graphene that then permeates through lattice defects and reacts at the heterointerface to form P 2 O 5 . This process can also be used to form new confined metal phosphates (e.g., 2D InPO 4 ). While the focus of this study is on P 2 O 5 intercalation, the possibility of intercalation from predissociated molecules catalyzed by defects in graphene may exist for other types of molecules as well. This in-depth study advances our understanding of intercalation routes of large molecules via the basal plane of graphene as well as heterointerface chemical reactions leading to the formation of distinctive confined complex oxide compounds.
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Research context

OpenAlex topics: Graphene research and applications · 2D Materials and Applications · Advancements in Battery Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Materials Science and Engineering, University of California, Berkeley, Berkeley, California 94720, United States

Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

Department of Mechanical Engineering, Vanderbilt University, Nashville, Tennessee 37235, United States

Department of Physics and Astronomy, University of New Hampshire, Durham, New Hampshire 03824, United States

Canadian Centre for Electron Microscopy, McMaster University, Hamilton ,ON L8S 4L8, Canada

2D Crystal Consortium, The Pennsylvania State University, University Park, Pennsylvania 16802, United States

Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States

Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

Department of Mining, Metallurgy, and Materials Engineering, University of the Philippines, Diliman, Quezon City 1101, Philippines

Queensland Micro- and Nanotechnology Centre, Griffith University, Brisbane, 4111 Australia

The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

Department of Materials Science and Engineering, McMaster University, Hamilton ,ON L8S 4L8, Canada

Funding

Army Research Office · Basic Energy Sciences · Air Force Office of Scientific Research · Office of Naval Research · National Supercomputing Centre Singapore · Canadian Institute for Advanced Research · Division of Materials Research · Lawrence Berkeley National Laboratory

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