High‐Efficiency Electrosynthesis of Hydrogen Peroxide from Oxygen Reduction Enabled by a Tungsten Single Atom Catalyst with Unique Terdentate N₁O₂ Coordination

Abstract

Single-atom catalysts (SACs) have shown great potential in the electrochemical oxygen reduction reaction (ORR) toward hydrogen peroxide (H 2 O 2 ) production. However, current studies are mainly focused on 3d transition-metal SACs, and very little attention has been paid to 5d SACs. Here, a new kind of W SAC anchored on a porous O, N-doped carbon nanosheet (W 1 /NO-C) is designed and prepared via a simple coordination polymer-pyrolysis method. A unique local structure of W SAC, terdentate W 1 N 1 O 2 with the coordination of two O atoms and one N atom, is identified by the combination of aberrationcorrected scanning transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray absorption fine structure spectroscopy. Remarkably, the as-prepared W 1 /NO-C catalyzes the ORR via a 2epathway with high onset potential, high H 2 O 2 selectivity in the wide potential range, and excellent operation durability in 0.1 m KOH solution, superior to most of state-of-the-art H 2 O 2 electrocatalysts ever reported. Theoretical calculations reveal that the C atoms adjacent to O in the W 1 N 1 O 2 -C moiety are the most active sites for the 2e -ORR to H 2 O 2 with the optimal binding energy of the HOO* intermediate. This work opens up a new opportunity for the development of high-performance W-based catalysts for electrochemical H 2 O 2 production.

Oxygenated P/N co-doped carbon for efficient 2e−oxygen reduction to H2O2

“…According to the CHE model, the Δ G value was obtained using eqn (7). 4,41 Δ G = Δ E DFT + Δ E ZPE − T Δ S where Δ E DFT is the reaction energy, and Δ E ZPE and Δ S are the changes in zero-point energy and entropy at T = 298.15 K, respectively. The free energies of the H 2 O 2 molecule are determined using the equilibrium potential of the two-electron (0.70 V vs. RHE) ORR, which is estimated at 3.52 eV.…”

“…1–3 At present, the industrial production of H 2 O 2 mainly relies on the reactions of anthraquinone, which require tedious steps and involve high energy consumption. 4–7 Furthermore, transporting and storing anthraquinone may also pose safety hazards. The electrochemical oxygen reduction reaction (ORR) normally occurs in two pathways, giving rise to H 2 O 2 and H 2 O via sequential 2- and 4-electron (4e − ) pathways, respectively.…”

Tailoring the selectivity and activity of oxygen reduction by regulating the coordination environments of carbon-supported atomically dispersed metal sites

“…78 A new kind of 5d-metal tungsten (W) structure with the unique coordination of two O atoms and one N atom (W–O 2 N) was reported and it turned out to be an efficient catalytic site for high-efficiency electrosynthesis of H 2 O 2 . 44 The C atoms adjacent to O in the N, O coordinated W moiety were demonstrated to be the most active sites for adsorbing the *OOH with an optimal binding energy, consequently prompting the 2e − ORR process.…”

“…Nevertheless, the same metal atoms with different coordination environments may bring about distinctly different catalytic characteristics. 42–46 Thus, we emphatically focus on the coordination environment of the C-ADMSs, since the coordination atoms with central active metal atoms share strong electronic interactions and provide a direct way to optimize the catalytic properties. Here, three aspects are proposed regarding the coordination environment of C-ADMSs to investigate their electrocatalytic activity and selectivity for the ORR (Fig.…”

β-Arsenene Monolayer: A Promising Electrocatalyst for Anodic Chlorine Evolution Reaction

“…To date, two-dimensional (2D) layered nanostructures have attracted increasing attention using as electrocatalysts, since they expose more active sites and achieve much higher catalytic efficiency [20][21][22][23][24][25][26][27]. Recently, the successful fabrication of few-layer black phosphorus brings group-VA elements (P, As, Sb, and Bi) into the family of 2D materials and inspires research interest on other layered allotropes [28].…”