富氧空位铁锰催化剂活化过一硫酸盐降解RBK5的性能与机理

doi:10.19965/j.cnki.iwt.2024-0915

摘要/Abstract

摘要：

引入氧空位可显著提高催化剂中金属活性位点的电子转移效率，增强催化剂对过一硫酸盐（PMS）的活化能力。笔者通过氢气煅烧法制备富氧空位铁锰催化剂，用于活化PMS降解活性黑5（RBK5）。通过XRD、SEM及XPS等手段表征了催化剂的理化性质，证实了氧空位的成功引入，并揭示了催化剂的晶型结构和表观形貌。性能测试显示，在最佳条件（10 mg/L RBK5，0.2 g/L催化剂，3 mmol/L PMS）下，RBK5降解率可达98%，且催化剂具有优异的循环稳定性和抗干扰能力。机理分析表明，催化剂表面氧空位及Fe与Mn元素构成主要活性位点。催化反应体系中生成了SO₄ ^·-、·OH、O₂ ^·-和¹O₂等多种活性物质，其中SO₄ ^·-和·OH为RBK5降解的主要活性物质。RBK5的降解同时通过自由基途径和表面电子转移途径进行。研究为富氧空位金属催化剂的设计及高效水处理提供了理论依据和实践指导。

关键词: 活性黑5, 过一硫酸盐, 纳米级催化剂, 铁锰双金属

Abstract:

Introducing oxygen vacancies can significantly enhance the electron transfer efficiency of metal active sites and improve the activation of peroxymonosulfate (PMS). In this study, oxygen-vacancy-rich Fe-Mn catalysts were prepared via hydrogen calcination and applied to activate PMS for the degradation of Reactive Black 5 (RBK5). The physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). These analyses confirmed the successful introduction of oxygen vacancies and revealed their crystal structure and morphology of catalysts. Performance tests showed that under optimized conditions (10 mg/L RBK5,0.2 g/L catalyst,3 mmol/L PMS), RBK5 degradation reached 98%, with the catalyst exhibiting excellent re-usability and anti-interference ability. Mechanism analysis revealed that surface oxygen vacancies and Fe and Mn served as the primary active sites. The catalyst surface generated various reactive species, including SO₄ ^·-, ·OH, O₂ ^·-, and singlet oxygen (¹O₂), among which SO₄ ^·- and ·OH were the dominant contributors to RBK5 degradation. Degradation proceeded via both free-radical pathways and surface electron-transfer pathways. This work provides theoretical guidance and practical reference for the design of oxygen-vacancy-rich metal catalysts for efficient water treatment.

Key words: reactive black 5, peroxymonosulfate, nano-scale catalyst, Fe-Mn bimetal

中图分类号:

X703

林蓉, 田义德, 洪俊明. 富氧空位铁锰催化剂活化过一硫酸盐降解RBK5的性能与机理[J]. 工业水处理, 2025, 45(11): 188-197.

Rong LIN, Yide TIAN, Junming HONG. Performance and mechanism of an oxygen-vacancy-rich iron-manganese catalyst activating peroxymonosulfate for RBK5 degradation[J]. Industrial Water Treatment, 2025, 45(11): 188-197.

https://www.iwt.cn/CN/Y2025/V45/I11/188

图/表 11

图1 表观形貌分析（a）FeMn PBA的SEM图；（b）OV-FeMn-H300的SEM图；（c）~（d）OV-FeMn-H300的TEM图。

Fig.1 Analysis of apparent morphology

图2 催化剂的XRD谱图

Fig.2 XRD patterns of the catalysts

图3 催化剂的FTIR谱图

Fig.3 FTIR spectra of the catalysts

图4 Fe 2p（a）、Mn 2p（b）和O 1s（c）的XPS及FeMn PBA、OV-FeMn-H300的EPR（d）

Fig.4 XPS spectra of Fe 2p（a），Mn 2p（b），O 1s（c） and EPR spectra of FeMn PBA and OV-FeMn-H300（d）

表1 X射线光电子能谱分析

Table 1 Analyses of X-ray photoelectron spectroscopy

元素化合价和基团	FeMn PBA	OV-FeMn-H300	反应后OV-FeMn-H300
Fe²⁺	8.6%	82.9%	67.6%
Fe³⁺	91.4%	17.1%	31.4%
Mn²⁺	45.2%	54.0%	48.7%
Mn³⁺	22.7%	23.3%	24.7%
Mn⁴⁺	32.1%	22.7%	26.6%
表面H₂O	36.2%	—	—
O_L	—	28.2%	26.6%
O_V	—	28.3%	24.6%
O_ad	63.8%	43.5%	48.8%

图5 降解因素的影响

Fig.5 Influence of degradation factors

图6 OV-FeMn-H300的稳定性与适用性评价

Fig.6 Evaluation of the stability and applicability of OV-FeMn-H300

表2 其他催化剂活化降解RBK5效果对比

Table 2 Comparison with other catalysts in RBK5 degradation by activating persulfate

催化剂名称	污染物质量浓度/（mg·L^-1）	氧化剂浓度/ （mmol·L^-1）	降解效率	降解速率常数/min^-1	适用pH范围	主要活性物质	参考文献
Mn-Fe LDH	20	1	86.0%，90 min	0.026 6	≈7	SO₄ ^·-、·OH、	〔24〕
Fe₃O₄@α-MnO₂	30	4	91.0%，60 min	0.023	3~7	SO₄ ^·-	〔29〕
Mn₂O₃@α-Fe₃O₄	10	1	88.0%，90 min	0.027 2	≈3	·OH	〔30〕
c-CuFe₂O₄	100	8	92.9%，60 min	0.043 3	5~9	SO₄ ^·-、·OH	〔31〕
OV-FeMn-H300	10	3	98%，60 min	0.056 9	3~9	高价金属、SO₄ ^·-、·OH、O₂ ^·-和¹O₂	本研究

图7 活性位点分析图

Fig.7 Diagram of active site analysis

图8 活性物种分析

Fig.8 Analysis of active species

图9 OV-FeMn-H300与RBK5、PMS之间的电子传递

Fig.9 Electron transfer between OV-FeMn-H300 and RBK5，PMS

参考文献 38

[1]	KAMAL I M， ABDELTAWAB N F， RAGAB Y M，et al. Biodegradation，decolorization，and detoxification of di-azo dye direct red 81 by halotolerant，alkali-thermo-tolerant bacterial mixed cultures［J］. Microorganisms，2022，10（5）：994. doi:10.3390/microorganisms10050994
[2]	LIU Zhongmou， ZHANG Pan， ZHAO Xiangyu. Combined treatment process of Fenton-like and peroxymonosulfate catalyzed by Fe（Ⅲ）-reduced graphene oxide for efficient removal of isoprothiolane：Fe（Ⅲ）/Fe（Ⅱ） cycle and mechanism study［J］. Journal of Environmental Chemical Engineering，2023，11（5）：110656. doi:10.1016/j.jece.2023.110656
[3]	ZHANG Hongmin， WANG Xudong， ZHAO Xiaochen，et al. Enhanced degradation of reactive black 5 via persulfate activation by natural bornite：Influencing parameters，mechanism and degradation pathway［J］. Environmental Technology，2024，45（20）：3961-3973. doi:10.1080/09593330.2023.2237660
[4]	CAI Yawen， HU Baowei， WANG Xiangke. Defect engineering on constructing surface active sites in catalysts for environment and energy applications［J］. Frontiers of Chemical Science and Engineering，2024，18（7）：74. doi:10.1007/s11705-024-2427-z
[5]	TAN Zicong， ZHANG Jieru， CHEN Yucheng，et al. Unravelling the role of structural geometry and chemical state of well-defined oxygen vacancies on pristine CeO₂ for H₂O₂ activation［J］. The Journal of Physical Chemistry Letters，2020，11（14）：5390-5396. doi:10.1021/acs.jpclett.0c01557
[6]	WANG Yanyong， QIAO Man， LI Yafei，et al. Tuning surface electronic configuration of NiFe LDHs nanosheets by introducing cation vacancies（Fe or Ni） as highly efficient electrocatalysts for oxygen evolution reaction［J］. Small，2018，14（17）：1800136. doi:10.1002/smll.201800136
[7]	HE Junyong， YANG Ya， HONG Peidong，et al. Oxygen Vacancies of Mn/CeO _x -H induced non-radical activation of peroxymonosulfate through electron mediation for bisphenol A degradation［J］. Journal of Environmental Chemical Engineering，2023，11（5）：111078. doi:10.1016/j.jece.2023.111078
[8]	SHAO Chunfeng， HUA Jiahui， LI Qiang，et al. Near-range modulation of single-atomic Fe sites by simultaneously integrating heteroatom and nanocluster for efficient oxygen reduction［J］. Nano Energy，2024，126：109668. doi:10.1016/j.nanoen.2024.109668
[9]	陆正义，王永全，蔡蓝燕，等. MOF衍生FeOOH-MnO _x 活化PMS降解盐酸四环素［J］. 中国环境科学，2024，44（12）：6935-6948.
	LU Zhengyi， WANG Yongquan， CAI Lanyan，et al. MOF-derived FeOOH-MnO _x activated permonosulfate to degrade tetracycline hydrochloride［J］. China Environmental Science，2024，44（12）：6935-6948.
[10]	WANG Na， LIU Yonglei， WU Can，et al. SnO₂ shells-induced rich Co²⁺ sites and oxygen vacancies in Fe _x Co_3- _x O₄ nanocubes：Enhanced peroxymonosulfate activation performance for water remediation［J］. Chemical Engineering Journal，2022，439：135682. doi:10.1016/j.cej.2022.135682
[11]	MA Quanyin， DONG Rui， LIU Heng，et al. Prussian blue analogue-derived Mn-Fe oxide nanocubes with controllable crystal structure and crystallinity as highly efficient OER electrocatalysts［J］. Journal of Alloys and Compounds，2020，820：153438. doi:10.1016/j.jallcom.2019.153438
[12]	XUE Fei， GUO Xinyang， MIN Boya，et al. Unconventional high-index facet of iridium boosts oxygen evolution reaction：How the facet matters［J］. ACS Catalysis，2021，11（13）：8239-8246. doi:10.1021/acscatal.1c01867
[13]	WU Wenting， HUANG Zhi， LIU Yanying，et al. Boosted peroxymonosulfate activation by bimetallic organometallic frameworks via by-produced and dominated H₂O₂ generation［J］. Chemical Engineering Journal，2024，492：152235. doi:10.1016/j.cej.2024.152235
[14]	XIE Liangbo， WANG Pengfei， LI Yi，et al. Pauling-type adsorption of O₂ induced electrocatalytic singlet oxygen production on N-CuO for organic pollutants degradation［J］. Nature Communications，2022，13（1）：5560. doi:10.1038/s41467-022-33149-4
[15]	ZHANG Ruikang， NING Fanyu， XU Simin，et al. Oxygen vacancy engineering of WO₃ toward largely enhanced photoelectrochemical water splitting［J］. Electrochimica Acta，2018，274：217-223. doi:10.1016/j.electacta.2018.04.109
[16]	LI Jun， FANG Jia， GAO Long，et al. Graphitic carbon nitride induced activity enhancement of OMS-2 catalyst for pollutants degradation with peroxymonosulfate［J］. Applied Surface Science，2017，402：352-359. doi:10.1016/j.apsusc.2017.01.129
[17]	KHAN F， BAEK S H， KIM J H. Influence of oxygen vacancies on surface charge potential and transportation properties of Al-doped ZnO nanostructures produced via atomic layer deposition［J］. Journal of Alloys and Compounds，2017，709：819-828. doi:10.1016/j.jallcom.2017.03.133
[18]	朱紫琦，李立，徐铭骏，等. 菱形片状铁锰催化剂活化过硫酸盐降解四环素［J］. 中国环境科学，2021，41（11）：5142-5152.
	ZHU Ziqi， LI Li， XU Mingjun，et al. Rhombic sheet iron-manganese catalyst-activating peroxymonosulfate for tetracycline degradation［J］. China Environmental Science，2021，41（11）：5142-5152.
[19]	陈婧，宋炳皞，朱雷，等. 抗坏血酸改性Mn₃O₄活化过硫酸氢盐降解磺胺甲恶唑［J］. 中国环境科学，2024，44（1）：158-166. doi:10.1016/j.jece.2022.109230
	CHEN Jing， SONG Binghao， ZHU Lei，et al. Efficient degradation of sulfamethoxazole by ascorbic acid modified Mn₃O₄ via peroxymonosulfate activation［J］. China Environmental Science，2024，44（1）：158-166. doi:10.1016/j.jece.2022.109230
[20]	HU Xinyu， WANG Juntao， WANG Jing，et al. β particles induced directional inward migration of oxygen vacancies：Surface oxygen vacancies and interface oxygen vacancies synergistically activate PMS［J］. Applied Catalysis B：Environmental，2022，318：121879. doi:10.1016/j.apcatb.2022.121879
[21]	HUANG Zihang， LI Hao， LI Wenhan，et al. Electrical and structural dual function of oxygen vacancies for promoting electrochemical capacitance in tungsten oxide［J］. Small，2020，16（52）：2004709. doi:10.1002/smll.202004709
[22]	林双杰，王永全，曾静，等. 非自由基主导的FeMn纳米颗粒活化过一硫酸盐降解有机污染物［J］. 中国环境科学，2024，44（7）：3729-3740.
	LIN Shuangjie， WANG Yongquan， ZENG Jing，et al. Nonradical-dominated peroxymonosulfate activation by FeMn nanoparticles for the degradation of organic pollutants［J］. China Environmental Science，2024，44（7）：3729-3740.
[23]	李立，吴丽颖，董正玉，等. 高晶度Mn-Fe LDH催化剂活化过一硫酸盐降解偶氮染料RBK5［J］. 环境科学，2020，41（6）：2736-2745.
	LI Li， WU Liying， DONG Zhengyu，et al. Degradation of RBK5 by high crystallinity Mn-Fe LDH catalyst activating peroxymonosulfate［J］. Environmental Science，2020，41（6）：2736-2745.
[24]	TIAN Na， TIAN Xike， NIE Yulun，et al. Biogenic manganese oxide：An efficient peroxymonosulfate activation catalyst for tetracycline and phenol degradation in water［J］. Chemical Engineering Journal，2018，352：469-476. doi:10.1016/j.cej.2018.07.061
[25]	LI Wei， WANG Zeming， LIAO Huiyun，et al. Enhanced degradation of 2，4，6-trichlorophenol by activated peroxymonosulfate with sulfur doped copper manganese bimetallic oxides［J］. Chemical Engineering Journal，2021，417：128121. doi:10.1016/j.cej.2020.128121
[26]	卢嘉华，熊重铎，刘青，等. 磁性纳米复合物Fe₃ O4@C/MnCo ₂O₄ 活化PMS对 2，4-二氯苯酚的氧化降解［C］//中国化学会第30届学术年会摘要集-第二十六分会：环境化学. 大连，2016：76.
[27]	SHI Xiuding， HUANG Zhi， XU Jielong，et al. Co and N co-doped carbon nanotubes catalyst for PMS activation：Role of non-radicals［J］. Separation and Purification Technology，2025，353：128528. doi:10.1016/j.seppur.2024.128528
[28]	HONG Yuxiang， HUANG Zhi， XU Jielong，et al. Surging efficient PMS activation through a COF-MOF dual immobilized catalytic platform：Synergy of enhanced electron transfer and adsorption-PMS activation［J］. Separation and Purification Technology，2024，345：127376. doi:10.1016/j.seppur.2024.127376
[29]	董正玉，吴丽颖，王霁，等. 新型Fe₃O₄@α-MnO₂活化过一硫酸盐降解水中偶氮染料［J］. 中国环境科学，2018，38（8）：3003-3010.
	DONG Zhengyu， WU Liying， WANG Ji，et al. Novel Fe₃O₄@α-MnO₂ activated peroxymonosulfate degradation of azo dyes in aqueous solution［J］. China Environmental Science，2018，38（8）：3003-3010.
[30]	徐铭骏，郭兆春，李立，等. 纳米片状Mn₂O₃@α-Fe₃O₄活化过碳酸盐降解偶氮染料［J］. 化工进展，2022，41（2）：1043-1053.
	XU Mingjun， GUO Zhaochun， LI Li，et al. Degradation of azo dyes by sodium percarbonate activated with nanosheet Mn₂O₃@α-Fe₃O₄ ［J］. Chemical Industry and Engineering Progress，2022，41（2）：1043-1053.
[31]	王磊，成先雄，连军锋，等. 尖晶石型c-CuFe₂O₄催化过硫酸盐降解偶氮染料［J］. 精细化工，2021，38（10）：2117-2124.
	WANG Lei， CHENG Xianxiong， LIAN Junfeng，et al. Degradation of azo dye by catalyzed persulfate with spinel c-CuFe₂O₄ ［J］. Fine Chemicals，2021，38（10）：2117-2124.
[32]	佘月城，董正玉，吴丽颖，等. MnFe₂O₄活化过一硫酸盐降解废水中LAS［J］. 中国环境科学，2019，39（8）：3323-3331. doi:10.3969/j.issn.1000-6923.2019.08.025
	SHE Yuecheng， DONG Zhengyu， WU Liying，et al. Degradation of LAS in wastewater by peroxymonosulfate activated by MnFe₂O₄ ［J］. China Environmental Science，2019，39（8）：3323-3331. doi:10.3969/j.issn.1000-6923.2019.08.025
[33]	LIM J S， NAHM H H， CAMPANINI M，et al. Critical ionic transport across an oxygen-vacancy ordering transition［J］. Nature Communications，2022，13（1）：5130. doi:10.1038/s41467-022-32826-8
[34]	杨越，续可，马雪璐. 金属氧化物中氧空位缺陷的催化作用机制［J］. 化学进展，2023，35（4）：543-559.
	YANG Yue， XU Ke， MA Xuelu. Catalytic mechanism of oxygen vacancy defects in metal oxides［J］. Progress in Chemistry，2023，35（4）：543-559.
[35]	薛雨微，叶校圳，曾静，等. 纳米片层铁锰双金属催化剂活化过一硫酸盐预处理烟草糖香料废水［J］. 化工进展，2022，41（10）：5661-5668.
	XUE Yuwei， YE Xiaozhen， ZENG Jing，et al. Pretreatment of tobacco sugar flavoring wastewater by nano layered iron-manganese bimetallic catalysts activating peroxymonosulfate［J］. Chemical Industry and Engineering Progress，2022，41（10）：5661-5668.
[36]	钟晴，叶校圳，曾静，等. 八面体FMN-700活化过硫酸盐产生~¹O₂降解偶氮有机物［J］. 中国环境科学，2023，43（12）：6374-6385.
	ZHONG Qing， YE Xiaozhen， ZENG Jing，et al. Efficient decolorization of azo organics by singlet oxygen from activating PMS with octahedral structured FMN-700［J］. China Environmental Science，2023，43（12）：6374-6385.
[37]	LIN Shuangjie， NIU Bo， SHI Xiuding，et al. Non-destructive approach for upcycling the cathode of spent lithium-ion batteries：Combined with the efficient treatment of organic wastewater［J］. Separation and Purification Technology，2025，360：130917. doi:10.1016/j.seppur.2024.130917
[38]	ZHONG Qing， ZHANG Ting， HUANG Zhi，et al. In-situ immobilization of Fe PBA in the zeolite structure for efficient degradation of benzalkonium chloride：Towards compressed reaction site loss and promoted PMS utilization［J］. Chemical Engineering Journal，2024，501：157655. doi:10.1016/j.cej.2024.157655

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