Boosting Selective Nitrogen Reduction via Geometric Coordination Engineering on Single‐Tungsten‐Atom Catalysts

Abstract

Atomic interface regulation that can efficiently optimize the performance of single‐atom catalysts (SACs) is a worthwhile research topic. The challenge lies in deeply understanding the structure–properties correlation based on control of the coordination chemistry of individual atoms. Herein, a new kind of W SACs with oxygen and nitrogen coordination (W‐NO/NC) and a high metal loading over 10 wt% is facilely prepared by introducing an oxygen‐bridged [WO4] tetrahedron. The local structure and coordination environment of the W SACs are confirmed by high‐angle annular dark‐field scanning transmission electron microscopy, X‐ray photoelectron spectroscopy, and extended X‐ray absorption fine structure. The catalyst shows excellent selectivity and activity for the electrochemical nitrogen reduction reaction (NRR). Density functional theory calculation reveals that unique electronic structures of the N and O dual‐coordinated W sites optimize the binding energy of the NRR intermediate, resulting in facilitating the electrocatalytic NRR. This work opens an avenue toward exploring the correlation between coordination structure and properties.

Research Progress and Application of Single-Atom Catalysts: A Review

“…A new strategy reported the use of direct atoms emitting from bulk metals, and subsequent trapping on nitrogen-rich porous carbon to form appropriate interactions between the metal atoms and supports. The central atom forms a coordination structure with other atoms, which changes the electronic structure of the central atom to increase its activity [22,23].…”

Efficient modulation of the catalytic performance of electrocatalytic nitrogen reduction with transition metals anchored on N/O-codoped graphene by coordination engineering

“…Note that the structure models of experimental catalysts Mn–O 3 N 1 /PC 20 and W–N 2 O 2 /NC 21 were considered and excluded during the high throughput screening due to the rigid criteria (Δ G max < 0.5 eV) we set so as to obtain the eligible target catalysts with excellent performance.…”

“…After a comprehensive full reaction pathway search, we found that our calculated results on the structure models ( i.e. , Mn–O 3 N 1 @Gra and W–N 2 O 2 @Gra) of the experimental catalysts (Mn–O 3 N 1 /PC 20 and W–N 2 O 2 /NC 21 ) generally agree well with the experimental results even though the structure models (Mn–O 3 N 1 @Gra and W–N 2 O 2 @Gra) were excluded during high throughput screening under the rigid criteria of Δ G max < 0.5 eV. The detailed discussions, analyses, and comparisons between the experimental data and the calculated results on the structural models of experimental catalysts (Mn–O 3 N 1 /PC and W–N 2 O 2 /NC) are shown in the Appendix in last part of the supporting information.…”

“…20 Another experimental study demonstrated that the selectivity and NH 3 yield of W–N 2 O 2 /NC is much higher than that of W–N 4 /NC (NC is nitrogen doped carbon). 21 Actually, the coordination engineering was not just limited to the nitrogen reduction reaction, but could potentially be utilized for several crucial energy conversion electrochemical reactions. 22,23…”

Engineering Reductive Iron on a Layered Double Hydroxide Electrocatalyst for Facilitating Nitrogen Reduction Reaction

“…[5][6][7] Electrocatalytic reduction of N 2 to NH 3 under ambient conditions has been regarded as a potential alternative to the energy and resourceintensive Haber-Bosch process. [8][9][10] However, the strong NN bond impedes the reduction of N 2 , which relies on efficient nitrogen activation. [11,12] Albeit noble metals exhibit a favorable NRR activity, their scarcity, and high cost restrict their application in large-scale nitrogen fixation.…”