氮掺杂中空多孔碳材料活化过一硫酸盐催化降解双酚A

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摘要在高级氧化（AOPs）过程中，合理设计出环境友好、稳定高效的催化剂对水污染降解具有重要意义。使用原位聚合的方法合成了氮掺杂中空多孔碳材料（NHPC），并将其作为催化降解双酚A （BPA）的过一硫酸盐（PMS）活化剂；结合动力学分析与多种表征手段，探究了结构缺陷、sp²杂化碳、氧官能团和3种典型的N键构型（吡啶N、吡咯N和石墨N）等因素对催化氧化反应性能的影响。BPA的反应速率常数与石墨N含量呈线性相关，表明石墨N是主要活性位点。同时，热处理可以通过再生石墨N来恢复催化剂活性，再生后的催化剂性能优于未使用的催化剂。自由基猝灭实验和电化学测试分析确定了NHPC-800/PMS体系主要是通过超氧自由基（O₂^·-）介导的自由基过程降解双酚A （BPA）。加深了对氮掺杂碳基催化剂活化过硫酸盐的理解，对其在环境修复中的实际应用具有指导意义。

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	王清
	张凤宝
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	李阳

关键词：氮掺杂中空多孔碳材料过一硫酸盐石墨N 超氧自由基(O₂^· -)

Abstract： A rational design of economical, high-efficient and stable catalysts plays an important role in the degradation of water contaminants during advanced oxidations (AOPs). The N-doped hollow porous carbon materials (NHPC) are synthesized using an in-situ polymerization strategy, and then employed as peroxymonosulfate (PMS) activator for bisphenol A (BPA) degradation. Combined with kinetic analysis and various characterization methods, the effects of structural defects, sp²-hybridized carbon, oxygen functional groups and three typical N-bonding configurations (pyridinic N, pyrrolic N and graphitic N) on the catalytic oxidation ability are investigated. A positive linear correlation between reaction rate constants and the content of graphitic N in NHPC reveals that the graphitic N are the main active sites for PMS activation. Meanwhile, the activity of catalyst can be recovered through heat treatment by regenerating graphite N, and the recovered catalyst exhibits more excellent activation performance than fresh catalyst. Furthermore, the free radical quenching experiments and electrochemical experiments demonstrate that the NHPC-800/PMS system decompose the BPA via O₂^·--mediated radical processes. This study deepens the understanding of the N-doped carbon catalysts for PMS activation mechanism, providing guidance for the practical application of them in environmental remediation.

Keywords： N-doped hollow porous carbon materials peroxymonosulfate graphitic N superoxide radical (O₂^· -)

Received 2022-04-30;

Fund:国家自然科学基金（22078242）。

Corresponding Authors: 李阳,E-mail:liyang1895@tju.edu.cn。 Email: liyang1895@tju.edu.cn

About author: 王清(1995-),女,硕士研究生,现从事废水处理方面的研究。

引用本文:

王清, 张凤宝, 范晓彬, 李阳.氮掺杂中空多孔碳材料活化过一硫酸盐催化降解双酚A[J]. 化学工业与工程, 2022,39(6): 1-13

WANG Qing, ZHANG Fengbao, FAN Xiaobin, LI Yang.Activation of peroxymonosulfate for bisphenol A degradation by nitrogen-doped hollow porous carbon materials[J]. Chemcial Industry and Engineering, 2022,39(6): 1-13

[1] ZHU S, HUANG X, MA F, et al. Catalytic removal of aqueous contaminants on N-doped graphitic biochars:Inherent roles of adsorption and nonradical mechanisms[J]. Environmental Science & Technology, 2018, 52(15):8649-8658
[2] LI X, HUANG X, XI S, et al. Single cobalt atoms anchored on porous N-doped graphene with dual reaction sites for efficient Fenton-like catalysis[J]. Journal of the American Chemical Society, 2018, 140(39):12469-12475
[3] QIAN K, CHEN H, LI W, et al. Single-atom Fe catalyst outperforms its homogeneous counterpart for activating peroxymonosulfate to achieve effective degradation of organic contaminants[J]. Environmental Science & Technology, 2021, 55(10):7034-7043
[4] HAN Q, WANG H, DONG W, et al. Degradation of bisphenol A by ferrate(VI) oxidation:Kinetics, products and toxicity assessment[J]. Chemical Engineering Journal, 2015, 262:34-40
[5] LUO H, ZENG Y, HE D, et al. Application of iron-based materials in heterogeneous advanced oxidation processes for wastewater treatment:A review[J]. Chemical Engineering Journal, 2021, doi:10.1016/j.cej.2020.127191
[6] WANG J, LI B, LI Y, et al. Facile synthesis of atomic Fe-N-C materials and dual roles investigation of Fe-N₄ sites in Fenton-like reactions[J]. Advanced Science (Weinheim, Baden-Wurttemberg, Germany), 2021, doi:10.1002/advs.202101824
[7] CHEN X, OH W D, HU Z, et al. Enhancing sulfacetamide degradation by peroxymonosulfate activation with N-doped graphene produced through delicately-controlled nitrogen functionalization via tweaking thermal annealing processes[J]. Applied Catalysis B:Environmental, 2018, 225:243-257
[8] LI X, WANG J, DUAN X, et al. Fine-tuning radical/nonradical pathways on graphene by porous engineering and doping strategies[J]. ACS Catalysis, 2021, 11(8):4848-4861
[9] KOHANTORABI M, MOUSSAVI G, GIANNAKIS S. A review of the innovations in metal- and carbon-based catalysts explored for heterogeneous peroxymonosulfate (PMS) activation, with focus on radical vs. non-radical degradation pathways of organic contaminants[J]. Chemical Engineering Journal, 2021, doi:10.1016/j.cej.2020.127957
[10] HE Y, ZHANG J, ZHOU H, et al. Synergistic multiple active species for the degradation of sulfamethoxazole by peroxymonosulfate in the presence of CuO@FeO_x@Fe₀[J]. Chemical Engineering Journal, 2020, doi:10.1016/j.cej.2019.122568
[11] 张笑丛, 王琮, 吴松海. 不同形貌氧化钴活化过一硫酸盐降解硝基酚[J]. 化学工业与工程, 2020, 37(6):38-47 ZHANG Xiaocong, WANG Cong, WU Songhai. Degradation of nitrophenols in wastewater by peroxymonosulfate activated by cobalt oxide with different morphologies[J]. Chemical Industry and Engineering, 2020, 37(6):38-47(in Chinese)
[12] JIANG N, XU H, WANG L, et al. Nonradical oxidation of pollutants with single-atom-Fe(Ⅲ)-activated persulfate:Fe(V) being the possible intermediate oxidant[J]. Environmental Science & Technology, 2020, 54(21):14057-14065
[13] LIU N, LU N, YU H, et al. Degradation of aqueous bisphenol A in the CoCN/Vis/PMS system:Catalyst design, reaction kinetic and mechanism analysis[J]. Chemical Engineering Journal, 2021, doi:10.1016/j.cej.2020.127228
[14] 马晓, 王燕, 李国兵, 等. CoCo-PBA@CuFe-LDH活化过一硫酸盐降解阿特拉津[J]. 化学工业与工程, 2021, 38(2):9-18 MA Xiao, WANG Yan, LI Guobing, et al. Activation peroxymonosulfate by CoCo-PBA@CuFe-LDH for the degradation of atrazine[J]. Chemical Industry and Engineering, 2021, 38(2):9-18(in Chinese)
[15] DUAN X, SUN H, WANG Y, et al. N-doping-induced nonradical reaction on single-walled carbon nanotubes for catalytic phenol oxidation[J]. ACS Catalysis, 2015, 5(2):553-559
[16] ZHANG M, HAN C, CHEN W, et al. Active sites and reaction mechanism for N-doped carbocatalysis of phenol removal[J]. Green Energy & Environment, 2020, 5(4):444-452
[17] GAO Y, ZHU Y, LI T, et al. Unraveling the high-activity origin of single-atom iron catalysts for organic pollutant oxidation via peroxymonosulfate activation[J]. Environmental Science & Technology, 2021, 55(12):8318-8328
[18] REN W, NIE G, ZHOU P, et al. The intrinsic nature of persulfate activation and N-doping in carbocatalysis[J]. Environmental Science & Technology, 2020, 54(10):6438-6447
[19] NOONAN O, ZHANG H, SONG H, et al. In situ Stöber templating:Facile synthesis of hollow mesoporous carbon spheres from silica-polymer composites for ultra-high level in-cavity adsorption[J]. Journal of Materials Chemistry A, 2016, 4(23):9063-9071
[20] CAI A, HE H, ZHANG Q, et al. Synergistic effect of N-doped sp² carbon and porous structure in graphene gels toward selective oxidation of C-H bond[J]. ACS Applied Materials & Interfaces, 2021, 13(11):13087-13096
[21] ZHANG H, NOONAN O, HUANG X, et al. Surfactant-free assembly of mesoporous carbon hollow spheres with large tunable pore sizes[J]. ACS Nano, 2016, 10(4):4579-4586
[22] CHEN Y, LI Z, ZHU Y, et al. Atomic Fe dispersed on N-doped carbon hollow nanospheres for high-efficiency electrocatalytic oxygen reduction[J]. Advanced Materials, 2019, doi:10.1002/adma.201806312
[23] CHEN J, LI H, FAN C, et al. Dual single-atomic Ni-N₄ and Fe-N₄ sites constructing Janus hollow graphene for selective oxygen electrocatalysis[J]. Advanced Materials, 2020, doi:10.1002/adma.202003134
[24] QIN L, DING R, WANG H, et al. Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction[J]. Nano Research, 2017, 10(1):305-319
[25] ZHAO T, KUMAR A, XIONG X, et al. Assisting atomic dispersion of Fe in N-doped carbon by aerosil for high-efficiency oxygen reduction[J]. ACS Applied Materials & Interfaces, 2020, 12(23):25832-25842
[26] DUAN X, SU C, ZHOU L, et al. Surface controlled generation of reactive radicals from persulfate by carbocatalysis on nanodiamonds[J]. Applied Catalysis B:Environmental, 2016, 194:7-15
[27] DU N, LIU Y, LI Q, et al. Peroxydisulfate activation by atomically-dispersed Fe-N_x on N-doped carbon:Mechanism of singlet oxygen evolution for nonradical degradation of aqueous contaminants[J]. Chemical Engineering Journal, 2021, doi:10.1016/j.cej.2020.127545
[28] LIU Y, MIAO W, FANG X, et al. MOF-derived metal-free N-doped porous carbon mediated peroxydisulfate activation via radical and non-radical pathways:Role of graphitic N and CO[J]. Chemical Engineering Journal, 2020, doi:10.1016/j.cej.2019.122584
[29] WANG J, DUAN X, GAO J, et al. Roles of structure defect, oxygen groups and heteroatom doping on carbon in nonradical oxidation of water contaminants[J]. Water Research, 2020, doi:10.1016/j.watres.2020.116244
[30] WANG H, GUO W, LIU B, et al. Edge-nitrogenated biochar for efficient peroxydisulfate activation:An electron transfer mechanism[J]. Water Research, 2019, 160:405-414
[31] ZHANG W, LI Y, FAN X, et al. Synergy of nitrogen doping and structural defects on hierarchically porous carbons toward catalytic oxidation via a non-radical pathway[J]. Carbon, 2019, 155:268-278
[32] WANG L, LAN X, PENG W, et al. Uncertainty and misinterpretation over identification, quantification and transformation of reactive species generated in catalytic oxidation processes:A review[J]. Journal of Hazardous Materials, 2021, doi:10.1016/j.jhazmat.2020.124436
[33] LI H, SHAN C, PAN B. Fe(Ⅲ)-doped g-C₃N₄ mediated peroxymonosulfate activation for selective degradation of phenolic compounds via high-valent iron-oxo species[J]. Environmental Science & Technology, 2018, 52(4):2197-2205
[34] PAN J, GAO B, DUAN P, et al. Improving peroxymonosulfate activation by copper ion-saturated adsorbent-based single atom catalysts for the degradation of organic contaminants:Electron-transfer mechanism and the key role of Cu single atoms[J]. Journal of Materials Chemistry A, 2021, 9(19):11604-11613
[35] LONG Y, DAI J, ZHAO S, et al. Atomically dispersed cobalt sites on graphene as efficient periodate activators for selective organic pollutant degradation[J]. Environmental Science & Technology, 2021, 55(8):5357-5370
[36] PENG L, DUAN X, SHANG Y, et al. Engineered carbon supported single iron atom sites and iron clusters from Fe-rich Enteromorpha for Fenton-like reactions via nonradical pathways[J]. Applied Catalysis B:Environmental, 2021, doi:10.1016/j.apcatb.2021.119963
[37] QI Y, LI J, ZHANG Y, et al. Novel lignin-based single atom catalysts as peroxymonosulfate activator for pollutants degradation:Role of single cobalt and electron transfer pathway[J]. Applied Catalysis B:Environmental, 2021, doi:10.1016/j.apcatb.2021.119910
[38] CHU C, YANG J, ZHOU X, et al. Cobalt single atoms on tetrapyridomacrocyclic support for efficient peroxymonosulfate activation[J]. Environmental Science & Technology, 2021, 55(2):1242-1250
[39] LI Y, YANG T, QIU S, et al. Uniform N-coordinated single-atomic iron sites dispersed in porous carbon framework to activate PMS for efficient BPA degradation via high-valent iron-oxo species[J]. Chemical Engineering Journal, 2020, doi:10.1016/j.cej.2020.124382