An official website of the United States government
Robust multivalent ion interaction in electrodes is a grand challenge of next-generation battery research. In this manuscript, we design molecularly-precise nanographene cathodes that are coupled with metallic Zn anodes to create a new class of Zn-ion batteries. Our results indicate that while electrodes with graphite or flat nanographenes do not support Zn-ion intercalation, the larger intermolecular spacing in a twisted peropyrene enables peropyrene electrodes to facilitate reversible Zn-ion intercalation in an acetonitrile electrolyte. While most previous Zn-ion batteries utilize aqueous electrolytes, the finding that nonaqueous Zn electrolytes can support intercalation in nanographenes is important for expanding the design space of nonaqueous multivalent batteries, which often possess higher voltages than their aqueous counterparts. Furthermore, because these nanographenes can be synthesized using a bottom-up approach via alkyne benzannulation, this work paves the way for future battery electrodes that contain other molecularly-precise nanographenes with tailored electrochemical properties.
more »
« less
This content will become publicly available on March 28, 2026
Molecular Nanographenes: Synthesis, Properties, and Applications
“Redox Properties of Nanographenes”, Y. Zhu, M. A. Petrukhina. Chapter 20 in “Molecular Nanographenes: Synthesis, Properties and Applications”, Edited by N. Martín and C. Nuckols, Wiley-VCH, 2025, 449-482
more »
« less
- PAR ID:
- 10590540
- Editor(s):
- Martín, Nazario; Nuckolls, Colin P
- Publisher / Repository:
- Wiley
- Date Published:
- ISBN:
- 9783527353224
- Page Range / eLocation ID:
- 449 to 482
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
This manuscript describes a simple and effective method to cyclodehydrogenate arenes using liquid alkali metals. Direct reaction between molten potassium and arenes forms 6-membered rings and zigzag edged structures within polyarenes. The approach is extended to integration of pyridinic nitrogen and 5-membered rings to arene structures and synthesis of larger, open-shell nanographenes.more » « less
-
The synthesis of polycyclic aromatic hydrocarbons (PAHs) and related nanographenes requires the selective and efficient fusion of multiple aromatic rings. For this purpose, the Diels–Alder cycloaddition has proven especially useful; however, this approach currently faces significant limitations, including the lack of versatile strategies to access annulated dienes, the instability of the most commonly used dienes, and difficulties with aromatization of the [4 + 2] adduct. In this report we address these limitations via the marriage of two powerful cycloaddition strategies. First, a formal Cp 2 Zr-mediated [2 + 2 + 1] cycloaddition is used to generate a stannole-annulated PAH. Secondly, the stannoles are employed as diene components in a [4 + 2] cycloaddition/aromatization cascade with an aryne, enabling π-extension to afford a larger PAH. This discovery of stannoles as highly reactive – yet stable for handling – diene equivalents, and the development of a modular strategy for their synthesis, should significantly extend the structural scope of PAHs accessible by a [4 + 2] cycloaddition approach.more » « less
-
Abstract The stepwise chemical reduction of a molecular warped nanographene (WNG) having a negatively curved π‐surface and defined C80H30composition with Cs metal used as the reducing and complexing agent allowed the isolation of three different reduced states with one, two, and three electrons added to itsπ‐conjugated system. This provided a unique series of nanosized carbanions with increasing negative charge for in‐depth structural analysis of consequences of controlled electron charging of non‐planar nanographenes, using X‐ray crystallographic and computational tools. The 3D molecular electrostatic potential (MEP) maps identified the negative charge localization at the central part of the WNG surface where selective coordination of Cs+ions is confirmed crystallographically. In‐depth theoretical investigation revealed a complex response of the WNG to the stepwise electron acquisition. The extended and contorted π‐surface of the WNG undergoes subtle swinging distortions that are accompanied by notable changes in the electronic structure and site‐dependent aromaticity of the resulting carbanions.more » « less
-
Distributed consensus algorithms such as Paxos have been studied extensively. Many different liveness properties and assumptions have been stated for them, but there are no systematic comparisons for better understanding of these properties. This paper systematically studies and compares different liveness properties stated for over 30 prominent consensus algorithms and variants. We introduced a precise high-level language and formally specified these properties in the language. We then create a hierarchy of liveness properties combining two hierarchies of the assumptions used and a hierarchy of the assertions made, and compare the strengths and weaknesses of algorithms that ensure these properties. Our formal specifications and systematic comparisons led to the discovery of a range of problems in various stated liveness properties. We also developed TLA+ specifications of these liveness properties, and we used model checking of execution steps to illustrate liveness patterns for Paxos.more » « less
