Electrocatalytically Activating and Reducing N₂ Molecule by Tuning Activity of Local Hydrogen Radical

Abstract

Decarbonizing N2 conversion is particularly challenging, but essential for sustainable development of industry and agriculture. Herein, we achieve electrocatalytic activation/reduction of N2 on X/Fe−N−C (X=Pd, Ir and Pt) dual‐atom catalysts under ambient condition. We provide solid experimental evidence that local hydrogen radical (H*) generated on the X site of the X/Fe−N−C catalysts can participate in the activation/reduction of N2 adsorbed on the Fe site. More importantly, we reveal that the reactivity of X/Fe−N−C catalysts for N2 activation/reduction can be well adjusted by the activity of H* generated on the X site, i.e., the interaction between the X−H bond. Specifically, X/Fe−N−C catalyst with the weakest X−H bonding exhibits the highest H* activity, which is beneficial to the subsequent cleavage of X−H bond for N2 hydrogenation. With the most active H*, the Pd/Fe dual‐atom site promotes the turnover frequency of N2 reduction by up to 10 times compared with the pristine Fe site.

A Perspective on Cu‐Based Electrocatalysts for Nitrate Reduction for Ammonia Synthesis

“…Usually, the reaction pathway of alkaline HER is the Volmer Heyrovsky or Volmer Tafel step, and it is generally believed that the Volmer step (H 2 O + e − → H ads + OH − ) is the step that determines the entire HER rate. [ 27 ] The generation and consumption of *H need to reach a dynamic equilibrium state in order to achieve the highest FE and NH 3 yields of NO 3 RR, which has aroused researcher's interest in hydrogen radicals ( Figure a). [ 28 ] *H is usually formed in large quantities on the surface of metals (Pt, Pd, Ni, etc.)…”

Local structural environment of single-atom catalysts

“…5–8 Compared with traditional catalysts, the size of the active species of nanocatalysts is nanoscale, therefore nanocatalysts have higher specific surface areas with more exposed reaction sites. 9–11 Due to the unique physicochemical properties of catalysts at the nanoscale, such as crystal face effects, size effects and synergistic effects, nanocatalysts exhibit excellent catalytic performances in many chemical reactions. 12–14 Sub-nanoscale clusters outperform nanoscale particles in terms of catalytic activity and/or selectivity as demonstrated by theoretical and experimental findings.…”

Maximizing Thiophene–Sulfur Functional Groups in Carbon Catalysts for Highly Selective H2O2 Electrosynthesis

“…Advanced carbon materials are great promising electrocatalysts in sustainable energy conversion and storage devices − because of their large specific surface area, , high electrical conductivity, , and excellent stability under harsh electrochemical conditions. , Unfortunately, the pristine carbon skeleton is electrochemically inactive. Over the past few decades, research efforts have demonstrated that heteroatom doping can induce charge redistribution among carbon atoms, thereby greatly enhancing their electrocatalytic activity. − So far, various strategies, either through in situ doping during the synthesis of carbon materials or postdoping of presynthesized carbon nanomaterials in the presence of heteroatom-contained precursors, have been developed to incorporate heteroatoms to activate the carbon skeleton. , …”