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Three-Dimensional Lanthanide-Based Nanoporous Metal−Organic

Frameworks for High-Performance Supercapacitors
Deep Lata Singh, Tapan Kumar Ghosh, Vineet Mishra, Shanmugam Ramasamy, Malaya K. Sahoo,
and Ranga Rao Gangavarapu*
Cite This: ACS Appl. Nano Mater. 2022, 5, 15237−15249 Read Online

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ABSTRACT: Lanthanides have been proved to be unprecedented

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when it comes to organized nanoporous materials with high

coordination environment. In the quest to enhance the
applications for energy-storage materials, three lanthanide-based
metal−organic frameworks (MOFs) have been synthesized by
facile hydrothermal conditions using 5-nitroisophthalic acid (H2L)
as a ligand, namely, Ce−H2L, Sm−H2L, and Eu−H2L. These
nanoporous MOFs consist of nine coordination sites around the
lanthanide metal ion giving rise to distorted monocapped square
antiprism geometry and 3D crystal structures. The electrochemical
measurements demonstrate that charge storage in these MOFs
occurs through faradaic redox reactions. The charge−discharge
studies show that these nanoporous MOF materials deliver high
specific capacity. Ce−H2L, Sm−H2L, and Eu−H2L deliver specific capacities of 625, 356, and 252 C g−1 (1389, 791, and 560 F g−1),
respectively, at a current density of 1 A g−1. A symmetric supercapacitor Swagelok device has been fabricated using Ce−H2L as an
electrode to further demonstrate the advantage of as-synthesized MOF. The developed symmetric supercapacitor gives a maximum
specific energy of 13.6 Wh kg−1 and a maximum specific power of 7110 W kg−1 in the voltage window of 1.425 V. The energy
storage trend in these nanoporous materials is Ce−H2L > Sm−H2L > Eu−H2L, which is further supported by the DFT calculations.
KEYWORDS: density functional theory (DFT), hydrothermal synthesis, lanthanides, metal−organic frameworks (MOFs),
nanoporous materials, supercapacitor (SC) and symmetrical supercapacitor (SSC)

1. INTRODUCTION densities but suffer with low electrical conductivity and

Global energy demand and storage of renewable energy have restricted ion diffusion characteristics in the bulk of the
been the driving factors to design novel materials for energy electrode material. On the other hand, carbon-based materials
have good conductivity but deliver low specific capaci-
storage applications. The new materials are required to store
tance.16,18 Nanoporous transition metal and rare-earth-metal-
energy from renewable sources such as solar energy as an
based MOFs can be tuned to overcome these limitations by
alternate to fossil fuels. So far, a variety of electrochemical
altering the design and composition incorporating the redox-
devices and materials have been designed for the purpose of
active sites in pores.9,13,19,20
energy storage.1−4 The rapidly emerging energy-storage
Metal−organic frameworks (MOFs) are inorganic−organic
devices are supercapacitors (SC), which are considered as
materials which have recently been proved as promising
one of the most pragmatic and efficient technologies for
electrode materials because of their high porosity, high surface
advanced electrochemical energy storage systems.1,5−7 Super-
area, excellent chemical stability, adjustable pore size, and
capacitors have attracted significant research interest for their
unique morphology.8,19−22 MOFs consist of functional organic
use in hybrid vehicles and mobile communications, attributable
ligands that link with inorganic metal centers/clusters. The
to rapid charge and discharge times, long cycle life, and high
organic linkers (ligands) act as struts, creating voids in the
power and energy density.8−10 These are classified into electric
double-layer capacitors (EDLCs) and pseudocapacitors. At the
current time, many advanced materials including metal oxides, Received: July 30, 2022
porous carbonaceous materials, graphene, and polymer Accepted: September 30, 2022
composites have been investigated as supercapacitor electrode Published: October 12, 2022
materials.11−17 However, these materials have certain limi-
tations in charge-storage applications. The metal oxides
provide relatively higher specific capacitances and energy

© 2022 American Chemical Society https://doi.org/10.1021/acsanm.2c03347

15237 ACS Appl. Nano Mater. 2022, 5, 15237−15249