Construction of structurally stable and highly porous materials, like hexagonal boron nitride (h-BN), is a prerequisite for achieving efficient adsorptive desulfurization (ADS). Nevertheless, the present constraints in precisely adjusting the pore structure parameters of BN impede its further utilization in the field of adsorption. In this study, highly porous boron carbon oxynitride (BCNO) adsorbents were synthesized via a straightforward, one-step solvent-free reaction. By modifying the composition of nitrogen (N) precursors, it was possible to finer tuning the micropore ratio thereby leading to a substantial increase in micropore surface area. Moreover, the fitting coefficients (R²) between S_micropore, V_micropore, and adsorption capacity are 0.81959 and 0.80547, indicating a strong correlation between the microporous structure and the ADS performance. The prepared BCNO-UM6:4 adsorbent showed excellent adsorption performance with a capacity of 47.2 mg S/g adsorbent, surpassing the adsorbents synthesized using solvent-based methods (39.4 mg S/g adsorbent) and single-source N synthesis (BCNO-U18 32.1 mg S/g adsorbent, BCNO-M6 12.1 mg S/g adsorbent). Experimental results revealed that the main adsorption mechanism is multi-layer adsorption by the micropore filling. Density functional theory (DFT) revealed that the newly formed S-N covalent bonds and C-H···N hydrogen bonds are the main driving forces. In summary, this synthetic method expands the production pathway of porous BCNO and has potential application in various research fields.

构建结构稳定且高度多孔的材料，例如六方氮化硼（h-BN），是实现高效吸附脱硫（ADS）的先决条件。然而，目前精确调节BN孔结构参数的限制阻碍了其在吸附领域的进一步应用。在这项研究中，通过一种简单的一步无溶剂反应合成了高度多孔的硼碳氮氧化物 (BCNO) 吸附剂。通过改变氮（N）前体的组成，可以更精细地调节微孔比率，从而导致微孔表面积的显着增加。此外， S_微孔、V_微孔与吸附容量之间的拟合系数(R ² )分别为0.81959和0.80547，表明微孔结构与ADS性能之间存在很强的相关性。所制备的BCNO-UM6:4吸附剂表现出优异的吸附性能，容量为47.2 mg S/g吸附剂，超过了溶剂法合成的吸附剂（39.4 mg S/g吸附剂）和单一来源N合成（BCNO-U18） 32.1 mg S/g 吸附剂，BCNO-M6 12.1 mg S/g 吸附剂）。实验结果表明，主要吸附机制是微孔填充的多层吸附。密度泛函理论（DFT）揭示了新形成的SN共价键和CH·N氢键是主要驱动力。综上所述，该合成方法拓展了多孔BCNO的生产途径，在各个研究领域具有潜在的应用前景。