Carbon-catalyzed persulfate activation is a metal-free advanced oxidation process for abating aqueous organic micropollutants. Recently, the electron-transfer mechanism in the activation of peroxydisulfate (PDS) has attracted tremendous interest due to its unknown nonradical reaction pathways. The conventionally used atomic-scale descriptors of adsorption energy (E_ads), O–O bond length (l_O–O) and S–O bond length (l_S–O) cannot accurately reflect the ability of the functionalities of PDS in its activation. In this work, a new descriptor, local electrophilicity index (ω), which represents the oxidative capacity of adsorbed S₂O₈²⁻, was included to identify the intrinsic active sites in carbocatalysts via density functional theory calculations. To verify the reliability of the proposed criteria, the catalytic performances of a series of highly boronated and nitrogenated carbon nanotube/nanosheet composites (BCN-NT/NS) with tailored physicochemical properties were comparatively studied for activating PDS to degrade phenol. By integrating the computational and experimental results, the catalytic activity of BCN-NT/NS was determined to not only be related to the contents of heteroatom dopants (B and N), but also the positions of B and N in the co-doping configurations. This study offers reliable criteria for determining the intrinsic catalytic sites in carbocatalysts for the activation of PDS based on an electron-transfer mechanism, which assists the rational design of nanocarbons as advanced catalysts for metal-free oxidation and water remediation.

中文翻译：

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综合实验和理论研究非自由基过硫酸盐活化过程中活性位的标准：以硼-氮共掺杂纳米碳为媒介的过氧二硫酸盐活化为例

碳催化的过硫酸盐活化是一种无金属的高级氧化工艺，用于消除水性有机微污染物。近来，过氧二硫酸盐（PDS）活化中的电子转移机理由于其未知的非自由基反应途径而引起了极大的兴趣。常规使用的吸附能的原子级描述子（E _ads），O-O键长（l _O-O）和S-O键长（l _S-O）不能准确地反映PDS的功能性。激活。在这项工作中，一个新的描述词，即局部亲电指数（ω），它代表被吸附的S ₂ O ₈ ^2-的氧化能力。，被列入识别carbocatalysts内在活性位点通过密度泛函理论计算。为了验证所提出标准的可靠性，比较研究了一系列具有特定理化性质的高硼化和氮化碳纳米管/纳米片复合材料（BCN-NT / NS）的催化性能，以活化PDS降解苯酚。综合计算和实验结果，确定了BCN-NT / NS的催化活性不仅与杂原子掺杂剂（B和N）的含量有关，而且还与B和N在共掺杂构型中的位置有关。 。这项研究为确定基于电子转移机理的PDS活化的碳催化剂中的固有催化位点提供了可靠的标准，这有助于合理设计纳米碳作为无金属氧化和水修复的高级催化剂。