Polarization Manipulation of NiO Nanosheets Engineered with Fe/Pt Single Atoms for High-Performance Electrocatalytic Overall Alkaline Seawater Splitting

Abstract

Regulating the metal–support interaction is recognized as an effective approach to modulating the electronic structure of single-atom catalysts. Here, we put forward a strategy to modulate the anchored metallic single atoms by manipulating the surface polarization of the support, which is demonstrated to be effective in designing alkaline seawater electrocatalysts. Specifically, we introduce Mn doping in weak-polarized NiO nanosheets to modulate its surface polarization and thereby regulate the electronic metal–support interaction between anchored Pt/Fe single atoms and NiO support. The optimized Pt1/Mn_NiO||Fe1/Mn_NiO electrode pair exhibits superior overall alkaline seawater-splitting performance, achieving an impressive low cell voltage of 1.44 V at a current density of 10 mA cm–2. The experimental characterizations and theoretical calculations highlight the significance of Mn doping in the surface polarization regulation of NiO. Moreover, the charge redistributions and the changes in coordination structure induced by Mn doping in Pt1/Mn_NiO and Fe1/Mn_NiO account for the decreased Gibbs free energy for the rate-determining steps in the HER and oxygen evolution reaction processes. This work demonstrates an effective method to design efficient alkaline seawater electrocatalysts by modulating electronic metal–support interaction over surface polarization regulation.

Catalysts for Direct Seawater Electrolysis: Current Status and Future Prospectives

“…For advanced HER catalysts, it is traditionally observed that the primary choice among the electrochemical community revolves around utilizing Pt. [76][77][78] However, there has been a joint effort to delve into cost-effective alternative sources that are abundantly available. Table 2 shows a comparison of the performance of the-state-of-art HER cathode catalysts, evaluated in direct seawater electrolysis.…”

Electrocatalysts for the oxygen evolution reaction: mechanism, innovative strategies, and beyond

“…In multiphase catalysts, various interesting structures often appear when metals are loaded on support leading to significant changes in catalytic activity and stability, which has received much attention from researchers. 124,132–139 With the rise of nanomaterials research, strong metal–support interaction (SMSI) was formally introduced in the 1970s. 140 The noble metal loaded on TiO 2 is reduced at 200 °C followed by uniform dispersion on the support.…”

Tailoring the Electronic Metal‐Support Interactions in Supported Silver Catalysts through Al modification for Efficient Ethylene Epoxidation

“…[5][6][7][8] By loading a decorating metal onto catalyst support and supported metal particles, the support might induce significant electronic perturbations of the supported metal particles, denoted as electronic metal-support interactions (EMSIs), which can modulate the d-band centers of the metal, leading to excellent catalytic performance. [9][10][11][12] However, undesigned metal modification often fails to significantly promote catalytic activity in a wide variety of catalytic systems, and the modification effect needs to be further studied under realistic reaction conditions. Therefore, it is significant and challenging to design well-defined metal-modified catalysts with excellent catalytic performance for heterogeneous catalytic reactions.…”