Chapter 2
Atomically Precise Nanoclusters
as Electrocatalysts
Site Li and Rongchao Jin
Abstract This chapter summaries recent advances in electrocatalytic application of
atomically precise metal nanoclusters (NCs). Metal nanoclusters with determined
structures can serve as new model catalysts for electrochemical catalytic study at the
atomic level and offer insights into the underlying mechanisms. In recent years, electrocatalysis by metal nanoclusters has been reported and shows promise in several
important reactions, including oxygen reduction reaction, water splitting, and CO 2
reduction reaction. By tuning the structure/ligand of the metal nanoclusters, it is
possible to achieve catalytic property modification at the atomic level. Overall,
the new material of atomically precise metal nanoclusters holds great promise in
precise control of catalytic properties and investigation of the fundamental catalytic
mechanism at the atomic level.
Keywords Metal nanocluster · Atomic precision · X-ray structure ·
Electrocatalysis · Doping
2.1 Introduction
2.1.1 Atomically Precise Metal NCs
Atomically precise metal nanoclusters have attracted broad interest due to the crystal
structure availability and unique properties in optical and catalysis applications [1–
3]. Compared with the traditional plasmonic metal nanoparticles, the ultra-small NCs
(<3 nm) show quantized electronic structures because of the quantum confinement
effect [4]. As a result, a single atom change can significantly alter the properties of
NCs. The UV-vis spectrum can be used as the “fingerprints” of NCs [5] because it
shows certain distinct peaks for each size of NCs, rather than similar plasmonic peaks
for regular nanoparticles. Similarly, the catalytic properties of various metal NCs can
be totally different because of the major change in surface and electronic structure of
S. Li · R. Jin (B)
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA
e-mail: rongchao@andrew.cmu.edu
© Springer Nature Switzerland AG 2020
P. W. N. M. van Leeuwen and C. Claver (eds.), Recent Advances in Nanoparticle Catalysis,
Molecular Catalysis 1, https://doi.org/10.1007/978-3-030-45823-2_2
39
Atomically Precise Nanoclusters
as Electrocatalysts
Site Li and Rongchao Jin
Abstract This chapter summaries recent advances in electrocatalytic application of
atomically precise metal nanoclusters (NCs). Metal nanoclusters with determined
structures can serve as new model catalysts for electrochemical catalytic study at the
atomic level and offer insights into the underlying mechanisms. In recent years, electrocatalysis by metal nanoclusters has been reported and shows promise in several
important reactions, including oxygen reduction reaction, water splitting, and CO 2
reduction reaction. By tuning the structure/ligand of the metal nanoclusters, it is
possible to achieve catalytic property modification at the atomic level. Overall,
the new material of atomically precise metal nanoclusters holds great promise in
precise control of catalytic properties and investigation of the fundamental catalytic
mechanism at the atomic level.
Keywords Metal nanocluster · Atomic precision · X-ray structure ·
Electrocatalysis · Doping
2.1 Introduction
2.1.1 Atomically Precise Metal NCs
Atomically precise metal nanoclusters have attracted broad interest due to the crystal
structure availability and unique properties in optical and catalysis applications [1–
3]. Compared with the traditional plasmonic metal nanoparticles, the ultra-small NCs
(<3 nm) show quantized electronic structures because of the quantum confinement
effect [4]. As a result, a single atom change can significantly alter the properties of
NCs. The UV-vis spectrum can be used as the “fingerprints” of NCs [5] because it
shows certain distinct peaks for each size of NCs, rather than similar plasmonic peaks
for regular nanoparticles. Similarly, the catalytic properties of various metal NCs can
be totally different because of the major change in surface and electronic structure of
S. Li · R. Jin (B)
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA
e-mail: rongchao@andrew.cmu.edu
© Springer Nature Switzerland AG 2020
P. W. N. M. van Leeuwen and C. Claver (eds.), Recent Advances in Nanoparticle Catalysis,
Molecular Catalysis 1, https://doi.org/10.1007/978-3-030-45823-2_2
39