Dopants in the Design of Noble Metal Nanoparticle Electrocatalysts and their Effect on Surface Energy and Coordination Chemistry at the Nanocrystal Surface

Abstract

Commercialization of energy conversion technologies, such as water electrolysis or fuel cells, has become a common prioritized goal in academia and industry due to the accelerated environmental crisis caused by the rapid increase in demand for fossil fuel‐based energy resources. However, these state‐of‐the‐art technologies require the use of expensive noble metal‐based electrocatalysts, which significantly undermine the feasibility of their commercial success. The introduction of less expensive elements into the noble metal‐based electrocatalysts, namely, doping, has become common in nanocatalysis research because of the lower catalyst preparation costs. Interestingly, recent studies have revealed additional roles of dopants in noble metal catalysts; doping can enhance the catalytic activity and selectivity by modulating the band structure, optimizing the surface energy of the catalysts, controlling the binding strength of adsorbates, and thus affecting the reaction kinetics. Dopants can also intervene in the nanocrystal growth mechanism, leading to shape‐ and phase‐controlled nanocrystals. This review discusses the great versatility of dopants in nanoparticle‐based catalysis in all aspects, from nanocrystal growth to nanocatalyst performance. The future challenges and outlook for dopants in nanocrystals and their applications are further discussed.

Sublayer Stable Fe Dopant in Porous Pd Metallene Boosts Oxygen Reduction Reaction

“…Apart from modifying the nanocrystal morphology, tuning the atomic and electronic structure of metallenes can further boost electrocatalytic activity by optimizing the activation energy gap of the reactant and the binding ability of intermediates during the ORR process. ,− Recently, the surface atomic doping of transition metals enables the precise electronic modulation of some already established ORR catalysts. − For example, Pt 3 Ni octahedra were doped with Fe, Co, Mo, and other metals. Among them, Mo-doped Pt 3 Ni nanocrystals induced a large change in the oxygen binding energy and hence significantly enriched the catalytic activity of the nanocrystals .…”

Facet Engineering of Advanced Electrocatalysts Toward Hydrogen/Oxygen Evolution Reactions

“…The traditional AEM followed by the scaling relationship between *OOH and *OH cannot surpass the limitation of minimal overpotential of 0.37 V [116,[128][129][130]. Fortunately, the emerged LOM can offer a unique reaction pathway for the occurrence of O-O bond coupling, wherein it would neither fully undergo reaction pathways of the AEM and nor restricted by the scaling relationship of the oxygenated intermediates [27,131,132]. As shown in Fig.…”

Surface Site-Specific Replacement for Catalysis Selectivity Switching

“…Surface site-specific modification (replacement, removal, adduction, etc.) with the other composition or structure still in place is important for describing relevant reaction mechanisms and surface-property correlations, and for tuning specific material functions. − Achieving modification with atomic precision lies at the frontier of materials and chemistry research and has attracted extensive interest in recent years while posing a major challenge in materials with unit sizes of not less than nanometers. , To our knowledge, the atomically precise modification (replacement, removement, etc.) of a nanocrystal surface has not been achieved with solution-based chemistry thus far. , The emergence of metal nanoclusters provides opportunities for such studies because their compositions and structures can be precisely determined by analytical techniques such as single crystal X-ray diffraction and mass spectrometry. − …”