Design of electrochemical active boron (B) site at solid materials to understand the relationships between the localized structure, charge state at the B site and electrocatalytic activity plays a crucial role in boosting the green electrochemical synthesis of hydrogen peroxide (H₂O₂) via two-electron oxygen reduction (2eORR) pathway. Herein, we demonstrate a carbon (C) and nitrogen (N) localized bonding microenvironment to modulate the charge state of B site at the boron-carbon nitride solid (BCNs) to realize the efficient selective electrocatalytic H₂O₂ production. The localized chemical structure of N-B-N, N-B-C and C-B-C bonds at B site can be regulated through solid-state reaction between boron nitride (BN) and porous carbon (C) at variable temperatures. The optimized BCN-1100 achieves an outstanding H₂O₂ selectivity of 89% and electron transfer number of 2.2 (at 0.55 V vs. RHE), with the production of 10.55 mmol/L during 2.5 h and the catalytic stability duration for 15000 cycles. Further first-principles calculations identified the dependency of localized bonding microenvironment on the OOH* adsorption energies and relevant charge states at the boron site. The localized structure of B site with BNC₂-Gr configuration is predicted to be the highest 2eORR activity.

设计固体材料中的电化学活性硼 (B) 位点以了解局部结构、B 位点的电荷状态和电催化活性之间的关系对于促进过氧化氢 (H 2 O 2 ) 的绿色电化学合成_具有至关重要_的作用双电子氧还原 (2eORR) 途径。在此，我们展示了碳 (C) 和氮 (N) 局部键合微环境来调节硼-碳氮化物固体 (BCN) 上 B 位点的电荷状态，以实现高效的选择性电催化 H ₂ O ₂生产。NBN、NBC 和 CBC 键在 B 位点的局部化学结构可以通过氮化硼 (BN) 和多孔碳 (C) 在可变温度下的固态反应来调节。优化后的 BCN-1100 实现了 89% 的出色 H ₂ O ₂选择性和 2.2 的电子转移数（在 0.55 V相对于RHE），2.5 小时内的产量为 10.55 mmol/L，催化稳定性持续时间为 15000 个循环. 进一步的第一性原理计算确定了局部键合微环境对 OOH* 吸附能和硼位点相关电荷状态的依赖性。_{具有 BNC 2} -Gr 配置的 B 站点的本地化结构预计是最高的 2eORR 活动。