Manipulating Interfaces of Electrocatalysts Down to Atomic Scales: Fundamentals, Strategies, and Electrocatalytic Applications

Abstract

Raising electrocatalysis by rationally devising catalysts plays a core role in almost all renewable energy conversion and storage systems. The principal catalytic properties can be controlled and improved well by manipulation of interfaces, ascribed to the interactions among different components/players at the interfaces. In particular, manipulating interfaces down to atomic scales is becoming increasingly attractive, not only because those atoms at around the interface are the key players during electrocatalysis, but also, understandings on the atomic level electrocatalysis allow one to gain deep insights into the reaction mechanism. With the feature down‐sizing to atomic scales, there is a timely need to redefine the interfaces, as some of them have gone beyond the conventionally perceived interfacial concept. In this overview, the key active players participating in the interfacial manipulation of electrocatalysts are examined, from a new angle of “atomic interface,” including those individual atoms, defects, and their interactions, together with the essential characterization techniques for them. The specific approaches and pathways to engineer better atomic interfaces are investigated, and thus to enable the unique electrocatalysis for targeted applications. Looking beyond recent progress, the challenges and prospects of the atomic level interfacial engineering are also briefly visited.

Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

“…Researchers have already developed various strategies to boost the intrinsic activity of specific active sites and to decouple the binding energetics of intermediates in primary reactions,s uch as heteroatom doping,d efect engineering, cation/anion regulation, surface/interface engineering,a lloying, tethering,and ligand stabilization. [1,8,15,36,45,46,[157][158][159][160] Based on these advances,h erein, we will introduce universal concepts for the design of materials that specifically target complex electrocatalytic reactions,m ainly involving 1) construction of multiple functional sites and 2) introduction of new degrees of freedom to manipulate the intermediate adsorption. Several promising strategies are highlighted below and schematically shown in Figure 8.…”

Recent Advances in Interface Engineering for Electrocatalytic CO2 Reduction Reaction

“…Recently, the researches on atomic scale have received more attention, which partly is ascribed to an essential role of atoms at (or around) the interface, and more importantly, it is conducive to deep insight about electrocatalysis mechanism [76]. Jiao [90].…”

“…Moreover, the features of high activity, low toxicity, and high abundance [ 90 ] enable the Cu to commercialize CO 2 RR. However, the present issues, such as low selectivity toward a specific product and low FE due to competition with HER and sluggish kinetics, still need to be addressed [ 76 , 81 , 84 , 85 , 90 , 91 ]. In recent years, various interface-related strategies have been devised to enhance its catalytic performance, such as intermetallic compounds [ 92 ], heteroatomic doping [ 68 , 93 ], single Cu atom catalysts [ 94 ], core–shell structures [ 86 ], and heterostructure [ 95 – 97 ].…”

“…Recently, the researches on atomic scale have received more attention, which partly is ascribed to an essential role of atoms at (or around) the interface, and more importantly, it is conducive to deep insight about electrocatalysis mechanism [ 76 ]. Jiao et al for the first time, proposed atom-pair catalyst for CO 2 RR with FE of CO up to 92% and almost completely suppressed HER [ 94 ] and offered a novel and efficient method to construct functional atomic interface at atomic level.…”

“…In recent years, interface engineering has brought novel and exciting possibilities, such as confinement, electronic, and synergistic effects, to improve catalytic properties through intense interactions between different components [ 76 ]. An interface is the boundary between two domains that facilitates interactions and synergistic effects among various active actors, resulting in remarkable ability in modulating intermediate adsorption/desorption, managing electron transmission, and mass movement [ 76 , 77 ]. With the fast advancement of nanotechnology, it is believed that interface engineering would develop into a successful technique to address the important issues and thus to improve catalytic activity, selectivity, and stability.…”