Experimental and Theoretical Advances on Single Atom and Atomic Cluster‐Decorated Low‐Dimensional Platforms towards Superior Electrocatalysts

Abstract

The fundamental relationship between structure and properties, which is called “structure‐property”, plays a vital role in the rational designing of high‐performance catalysts for diverse electrocatalytic applications. Low‐dimensional (LD) nanomaterials, including 0D, 1D, 2D materials, combined with low‐nuclearity metal atoms, ranging from single atoms to subnanometer clusters, are currently emerging as rising star nanoarchitectures for heterogeneous catalysis due to their well‐defined active sites and unbeatable metal utilization efficiencies. In this work, a comprehensive experimental and theoretical review is provided on the recent development of single atom and atomic cluster‐decorated LD platforms towards some typical clean energy reactions, such as water‐splitting, nitrogen fixation, and carbon dioxide reduction reactions. The upmost attractive structural properties, advanced characterization techniques, and theoretical principles of these low‐nuclearity electrocatalysts as well as their applications in key electrochemical energy devices are also elegantly discussed.

Advances in the Electrocatalytic Hydrogen Evolution Reaction by Metal Nanoclusters‐based Materials

“…Compared with isolated atoms or sub-NPs, the MNCs tend to endow more satisfactory activity and selectivity for HER, attributing to their quantum size effect, surface geometric effect, and unique electronic properties. [35,36] Especially, the atomic level catalytic sites with abundant unsaturated and low coordination atoms are proved to be active centers in catalytic reactions (Figure 1). However, the MNCs tend to aggregate during the preparation owing to the high surface energy, which is a challenge in practical applications.…”

Insights into Heterogeneous Catalysts under Reaction Conditions by In Situ/Operando Electron Microscopy

“…This aspect is important considering the nanoscale-enhanced atomic diffusion, surface mobility, and surface interaction energies that contribute significantly to the low-temperature surface-mediated sintering of the nanoparticles or dispersion into clusters or single atoms. [282][283][284][285] Future development of the in situ/operando TEM and combined techniques will continue to play an increasingly important role not only in controlling or improving the existing catalysts for the various catalytic reactions, but also in designing or preparing new catalysts for advancing the cutting-edge areas of sustainable energy research and applications.…”

Recent Progress of Diatomic Catalysts: General Design Fundamentals and Diversified Catalytic Applications

“…The ONi 2 N 6 , Ni 2 N 6 , and NiN 4 structural models were constructed, respectively, and DFT calculations were performed. [ 40,145 ] The results showed that the ONi 2 N 6 structure participated in the reaction and the free energy for the generation of COOH* intermediate by activating CO 2 was significantly lower than that of the Ni 2 N 6 and NiN 4 structures. At the same time, compared with Ni 2 N 6 and NiN 4 , ONi 2 N 6 structure had the weakest adsorption capacity for CO, and the generated CO* intermediate was more easily desorbed to generate CO.…”

“…The ONi 2 N 6 , Ni 2 N 6 , and NiN 4 structural models were constructed, respectively, and DFT calculations were performed. [40,145] The results showed Small 2022, 18, 2203589 (a-g) Reproduced with permission. [135] Copyright 2022, Elsevier.…”