Phosphorus Induced Electron Localization of Single Iron Sites for Boosted CO₂ Electroreduction Reaction

Abstract

Electrochemical reduction of carbon dioxide (CO2) into chemicals and fuels has recently attracted much interest, but normally suffers from a high overpotential and low selectivity. In this work, single P atoms were introduced into a N‐doped carbon supported single Fe atom catalyst (Fe‐SAC/NPC) mainly in the form of P−C bonds for CO2 electroreduction to CO in an aqueous solution. This catalyst exhibited a CO Faradaic efficiency of ≈97 % at a low overpotential of 320 mV, and a Tafel slope of only 59 mV dec−1, comparable to state‐of‐the‐art gold catalysts. Experimental analysis combined with DFT calculations suggested that single P atom in high coordination shells (n≥3), in particular the third coordination shell of Fe center enhanced the electronic localization of Fe, which improved the stabilization of the key *COOH intermediate on Fe, leading to superior CO2 electrochemical reduction performance at low overpotentials.

Single-atom catalysts: stimulating electrochemical CO2 reduction reaction in the industrial era

“…Previous work showed that most carbon-supported SACs with abundant nitrogen-doped are stable activated single-metal ions to form the homogeneous microcosmic structure of M-N x -C y . The universal methods for synthesizing carbon-supported SACs include molecular skeleton encapsulation, [34][35][36][37][38] impregnation and pyrolysis, [39][40][41] coordination regulation, [42][43][44] and thermal dispersion.…”

High Performance 3D Self‐Supporting Cu−Bi Aerogels for Electrocatalytic Reduction of CO2 to Formate

“…Reasonable structures not only increase the exposure active site avoid aggregation, but also can regulate the interaction between the adsorbate and the catalyst, [17][18][19] which is why single-atom catalysts have been widely used in the field of carbon dioxide reduction in recent years. [20,21] Similar to this idea, self-supporting nanomaterials exhibit a three-dimensional (3D) structure, porosity and high specific surface area compared to bulk materials, which is ideal candidates for electrocatalytic reaction. [22] Various nanomaterials based on self-supporting have been used for CO 2 RR catalysts for decades, such as nanowires, [23] nanorods, [24] nanosheets, [25] nanotubes, [26] aerogels, [27,28] and graphene.…”

“…It is equivalent to adjusting the catalyst surface‘s geometry by designing the morphology and components rationally and reducing the size. Reasonable structures not only increase the exposure active site avoid aggregation, but also can regulate the interaction between the adsorbate and the catalyst, [17–19] which is why single‐atom catalysts have been widely used in the field of carbon dioxide reduction in recent years [20,21] . Similar to this idea, self‐supporting nanomaterials exhibit a three‐dimensional (3D) structure, porosity and high specific surface area compared to bulk materials, which is ideal candidates for electrocatalytic reaction [22] .…”

Hollow microstructural regulation of single-atom catalysts for optimized electrocatalytic performance

“…Among the wide variety of proposed technologies, electrochemical energy transformation technologies, such as water splitting, CO 2 reduction, fuel cells and metal-air batteries, are considered to be among the most effective substitutes for traditional fossil energy [10][11][12][13][14][15][16][17][18] . Previously reported electrocatalysts have shown high activity and superior stability, most of which are composed of precious transition-metal nanoparticles (NPs), such as Pt/C, RuO 2 and IrO 2 [19][20][21][22][23][24] . However, these precious metalbased catalysts have high costs and scarce reserves, which severely restrict their large-scale application [25][26][27][28][29][30][31] .…”