Tailoring the interfacial reaction pathway and low consumption strategy for the high efficiency Fenton-like processes is environmentally desirable but still challenging. Herein, single Co atom-doped g-C3N4 was prepared for peroxymonosulfate (PMS) activation to reveal the interfacial reaction of high-valent cobalt-oxo species [Co(IV) = O] to singlet oxygen (1O2) and construct an energy efficient Fenton-like system. Experimental results showed that the system could achieve 99.6% carbamazepine removal with kobs of 0.355 min−1, while the decomposition of PMS was mild (0.0988 and 0.00917 min−1 in 0–2 and 2–30 min, respectively). Mechanistic studies revealed the reaction of Co(IV) = O to 1O2, which moderated the reduction of Co sites, thus slowing the decomposition rate of PMS. But the synergistic effect of 1O2 and Co(IV) = O maintained the high activity of the system. Combined with first-principles calculations, the optimal evolution path of PMS was PMS → OH*→Co(IV) = O → OO*→1O2, accompanied by the Co(II)/Co(III)/Co(IV) redox cycle. The work proposed a new interfacial reaction in term of Co(IV) = O triggered 1O2 generation, resulting in the construction of an energy-efficient Fenton-like system and provided a novel idea for the development of efficient and low consumption water purification technology.

中文翻译：

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高价钴-氧代物质触发单线态氧，在单个 Co 原子掺杂 g-C3N4 中触发单线态氧快速降解污染物以及温和的过氧一硫酸盐分解


为高效 Fenton 类过程定制界面反应途径和低消耗策略是环境可取的，但仍然具有挑战性。在此，制备了用于过氧一硫酸盐 （PMS） 活化的单个 Co 原子掺杂 g-C3N4，以揭示高价钴氧基物质 [Co（IV） = O] 与单线态氧 （1O2） 的界面反应，并构建一个节能的 Fenton 样系统。实验结果表明，该系统可以用 0.355 min-1 的 kobs 实现 99.6% 的卡马西平去除，而 PMS 的分解是温和的（0.0988 和 0.00917 min-1 分别在 0-2 和 2-30 分钟内）。机理研究揭示了 Co（IV） = O 对 1O2 的反应，这调节了 Co 位点的减少，从而减慢了 PMS 的分解速率。但 1O2 和 Co（IV） = O 的协同作用维持了系统的高活性。结合第一性原理计算，PMS 的最佳演变路径为 PMS → OH*→Co（IV） = O → OO*→1O2，伴随着 Co（II）/Co（III）/Co（IV） 氧化还原循环。该工作提出了一种新的界面反应，即 Co（IV） = O 触发 1O2 生成，从而构建了一种节能的 Fenton 样系统，并为开发高效、低消耗的净水技术提供了新思路。