A single-atom Fe–N2 embedded in nitrogen-doped porous carbon as a bifunctional photocatalyst for efficient removal of marine petroleum pollutants

Xin Li , Yuwen Chen , Zhiyue Zhao , Yizhe Huang , Ke Zhu , Sitong Feng , Shaojuan Luo , Lei Wang , Kai Yan
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Abstract

Petroleum and its refined products enter the marine environment during the extraction process, causing serious pollution. Herein, a bifunctional Fe–N2 single-atom embedded in nitrogen-doped porous carbon photocatalyst (FC) was fabricated for the efficient removal of marine petroleum pollutants. The combination of highly dispersed Fe–N2 active sites, large surface area, high porosity, and good conductivity results in excellent photocatalytic activities. The FC catalyst exhibited a 96.7% degradation rate in the oxidative removal of bisphenol A (BPA) and a 63.4% reduction of Cr(VI) within 1 ​h, whereas the reaction equilibrium rate constants of 0.0132 ​min−1 and 0.0505 ​min−1 were reached, respectively. FC with good stability and reusability could reach 88.3% and 53.5% removal rate of BPA and Cr(VI) after 5 cycles. Radical quenching experiments and electron spin resonance (ESR) confirmed that ‧OH and e were the most driving active species for photo-oxidation and reduction, respectively. Besides, the FC catalyst was applied to an actual seawater system and the simulation results showed a good removal rate (82.7% of BPA and 50.9% of Cr(VI) within 1 ​h). The BPA oxidation pathway in the system was proposed and the toxicity of each intermediate was accessed. This work offers a new way to construct single-atom functionalized carbon-based catalysts for marine pollution control.

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单原子Fe-N2包埋于氮掺杂多孔碳中作为双功能光催化剂高效去除海洋石油污染物
石油及其精炼产品在开采过程中进入海洋环境,造成严重污染。本文制备了一种双功能Fe-N2单原子包埋在氮掺杂多孔碳光催化剂(FC)中,用于高效去除海洋石油污染物。高度分散的Fe-N2活性位点、大表面积、高孔隙率和良好的导电性使其具有优异的光催化活性。该催化剂在1 h内氧化去除双酚a (BPA)的降解率为96.7%,Cr(VI)的还原率为63.4%,反应平衡速率常数分别为0.0132 min−1和0.0505 min−1。经过5次循环后,对BPA和Cr(VI)的去除率分别达到88.3%和53.5%,具有良好的稳定性和可重复使用性。自由基猝灭实验和电子自旋共振(ESR)证实,o和e−分别是光氧化和还原最具驱动活性的物质。此外,将该催化剂应用于实际的海水系统中,模拟结果表明,该催化剂在1 h内对BPA的去除率为82.7%,对Cr(VI)的去除率为50.9%。提出了双酚a在体系中的氧化途径,并对各中间体的毒性进行了分析。本研究为构建用于海洋污染治理的单原子功能化碳基催化剂提供了一条新途径。
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