Structural Design of π–d Conjugated TM_xB₃N₃S₆ (x=2, 3) Monolayer Toward Electrocatalytic Ammonia Synthesis

Abstract

Single–atom catalysts (SACs) have attracted wide attention to be acted as potential electrocatalysts for nitrogen reduction reaction (NRR). However, the coordination environment of the single transition metal (TM) atoms is essential to the catalytic activity for NRR. Herein, we proposed four types of 3‐, 4‐coordinated and π–d conjugated TMxB3N3S6 (x=2, 3, TM=Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Tc, Ru, Hf, Ta, W, Re and Os) monolayers for SACs. Based on density functional theory (DFT) calculations, I‐TM2B3N3S6 and III‐TM3B3N3S6 are the reasonable 3‐coordinated and 4‐coordinated structures screening by structure stable optimizations, respectively. Next, the structural configurations, electronic properties and catalytic performances of 30 kinds of the 3‐coordinated I‐TM2B3N3S6 and 4‐coordinated III‐TM3B3N3S6 monolayers with different single transition metal atoms were systematically investigated. The results reveal that B3N3S6 ligand is an ideal support for TM atoms due to existence of strong TM‐S bonds. The 3‐coordinated I‐V2B3N3S6 is the best SAC with the low limiting potential (UL) of −0.01 V, excellent stability (Ef=−0.32 eV, Udiss=0.02 V) and remarkable selectivity characteristics. This work not only provides novel π–d conjugated SACs, but also gives theoretical insights into their catalytic activities and offers reference for experimental synthesis.

Delving into the Variability of Supramolecular Affinity: Self‐Ion Pairing as a Central Player in Aqueous Host‐Guest Chemistry

“…This aspect gains even greater significance when considering the wide range of scenarios where these macrocycles can be employed. Concerning this issue, host concentrations can vary widely in terms of applications, ranging from minute quantities in supramolecular catalysis [52] to large‐scale amounts as water pollutant adsorbents [53] . Hence, to ensure an optimal performance in all the different settings, understanding how the host affinities are influenced by the operational concentrations becomes imperative.…”

Single-atom catalysts supported on a hybrid structure of boron nitride/graphene for efficient nitrogen fixation via synergistic interfacial interactions

“…Single-atom catalysts (SACs), 9–21 a new type of heterogeneous catalyst, show promise as an alternative to scarce noble-based catalysts by maximizing atom utilization efficiency and inhibiting the undesired HER. Hexagonal boron nitride (BN)-based catalysts have demonstrated promising catalytic activity in the NRR while suppressing the HER.…”