钴高度分散于还原氧化石墨烯用于高级氧化降解有机污染物

doi:10.11949/0438-1157.20240423

摘要/Abstract

摘要：

在废水处理技术中，基于过氧单硫酸盐（PMS）的高级氧化工艺被认为是降解有机污染物中最高效且绿色的方法之一。在激活PMS的方法中，负载过渡金属的催化剂由于金属离子溶出量低而广受关注，但却面临金属物种易团聚引发的降解活性低的问题。在本工作中，将Co负载在还原氧化石墨烯（rGO）上，经简单方法分别合成了Co高分散的QSCo-rGO和Co团聚的AGCo-rGO。XRD、HRTEM和元素分布研究表明，QSCo-rGO中的Co未发生金属团聚现象，实现了高度分散；而AGCo-rGO中的Co以CoO纳米颗粒的形式团聚。在激活PMS降解苯酚的反应中，QSCo-rGO可在30 min内完成100%的降解，而AGCo-rGO需要长达90 min。此外，QSCo-rGO展现出较好的可重复性和使用广泛性。机理研究表明，催化剂QSCo-rGO中的Co高度分散，暴露出更多活性金属位点，其通过激活PMS产生非自由基¹O₂从而高活性降解苯酚。本文为设计增强降解活性的高级氧化催化剂提供新思路。

关键词: 降解, 催化剂, 自由基, 还原氧化石墨烯, 过氧单硫酸盐

Abstract:

In wastewater treatment, the advanced oxidation process based on peroxymonosulfate (PMS) is considered to be one of the most efficient and green methods for degrading organic pollutants. Among the methods of activating PMS, transition metal-supported catalysts have attracted much attention due to the low dissolution of metal ions, but they face the problem of low degradation activity, which is caused by the easy aggregation of metal species. In this work, Co was loaded on reduced graphene oxide (rGO). Through a simple method, QSCo-rGO with highly dispersed Co and AGCo-rGO with agglomerated Co were synthesized, respectively. XRD, HRTEM and element mapping studies showed that Co in QSCo-rGO was highly dispersed without metal agglomeration. The Co in AGCo-rGO was aggregated in the form of CoO nanoparticles. In the reaction of activating PMS to degrade phenol, QSCo-rGO could complete 100% degradation efficiency within 30 min, while AGCo-rGO required up to 90 min. In addition, QSCo-rGO exhibited good reusability and versatility. The mechanism study indicated that Co in QSCo-rGO catalyst was highly dispersed, which exposed more active sites, and it generated non-free radical ¹O₂ by activating PMS to degrade phenol with high activity. This work provides a new idea for designing advanced oxidation catalysts with enhanced degradation activity.

Key words: degradation, catalyst, radical, reduced graphene oxide, peroxymonosulfate

中图分类号:

X 52

李文宁, 陆敏, 殷俞. 钴高度分散于还原氧化石墨烯用于高级氧化降解有机污染物[J]. 化工学报, DOI: 10.11949/0438-1157.20240423.

Wenning LI, Min LU, Yu YIN. High dispersion of cobalt on the reduced graphene oxide for advanced oxidation degradation of organic pollutants[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240423.

图/表 9

图1 样品1.5QSCo-rGO（a）、1.5AGCo-rGO（b）的TEM图; 样品1.5QSCo-rGO的（c）HRTEM和（d）HAADF-STEM 图像以及对应元素O、C、Co的分布图

Fig.1 TEM images of 1.5QSCo-rGO(a), 1.5AGCo-rGO(b); (c) HRTEM and (d) HAADF-STEM images of sample 1.5QSCo-rGO and element mapping of corresponding O, C and Co elements

图2 催化剂（a）QSCo-rGO和（b）AGCo-rGO的XRD图注:(a) 样品QSCo-rGO的XRD图 (b) 样品rGO和AGCo-rGO的XRD图

Fig.2 XRD patterns of (a) QSCo-rGO and (b) AGCo-rGO catalysts

图3 样品rGO和1.5QSCo-rGO的XPS总谱图（a），以及Co 2p（b）、C 1s（c，e）、O 1s（d，f）分谱图

Fig.3 XPS spectra (a) and Co 2p (b), C 1s (c, e), O 1s (d, f) regions of rGO and 1.5QSCo-rGO samples

图4 （a）（b）不同催化剂对苯酚的降解作用和（c）浸出Co离子的降解活性，以及（d）TOC的去除效率

Fig.4 (a),(b) Degradation of phenol by different catalysts, (c) degradation activity of leaching Co ions and (d) removal efficiency of TOC

表１已报道催化材料对苯酚降解的催化性能比较

Table 1 Comparison of catalytic properties of reported catalytic materials for phenol degradation

催化剂	反应条件				反应速率	速率常数k(min^-1)	文献
催化剂	温度	苯酚浓度	催化剂浓度	氧化剂浓度	反应速率	速率常数k(min^-1)	文献
1.5QSCo-rGO	25 ^oC	20 mg·L^-1	0.2 g·L^-1	PMS 6.5 mM	100% 30 min	0.131	this work
Co/CoO@NC-1%	25 ^oC	20 mg·L^-1	0.1 g·L^-1	PMS 1.63 mM	100% 20 min	0.324	[25]
CoNP@NC/Co-SA	25 ^oC	20 mg·L^-1	0.08 g·L^-1	PMS 0.49 mM	91.6% 3 min	0.696	[26]
Co@NG-900	25 ^oC	9.41 mg·L^-1	0.05 g·L^-1	PMS 3 mM	100% 12 min	0.397	[27]
Se@NC-900	25 ^oC	10 mg·L^-1	0.1 g·L^-1	PMS 0.25 mM	99.1% 30 min	0.169	[28]
CFGA	25 ^oC	20 mg·L^-1	0.2 g·L^-1	PMS 3.25 mM	100% 60 min	0.046	[18]
MnOOH-rGO	30 ^oC	23.5 mg·L^-1	0.5 g·L^-1	PMS 0.625 mM	100% 30 min	not provided	[29]
CNS6	25 ^oC	10 mg·L^-1	0.05 g·L^-1	PMS 3 mM	100% 60 min	0.089	[30]
CoOOH/GO	25 ^oC	10 mg·L^-1	0.2 g·L^-1	PMS 0.15 mM	41% 5 min	not provided	[12]
Co-30/KCC-1	25 ^oC	20 mg·L^-1	0.2 g·L^-1	PMS 7.8 mM	100% 9 min	not provided	[31]
Co₂MnO₄	25 ^oC	50 mg·L^-1	0.2 g·L^-1	PMS 6.5 mM	100% 30 min	0.076	[32]
10%Co₃O₄/CeO₂	20 ^oC	20 mg·L^-1	0.2 g·L^-1	PMS 6.5 mM	100% 50 min	0.0865	[33]
CoMgAl-LDH	30 ^oC	9.41 mg·L^-1	0.3 g·L^-1	PMS 3 mM	100% 60 min	0.051	[34]
2.5%MnOx/GO	25 ^oC	75 mg·L^-1	0.4 g·L^-1	PMS 6.5 mM	28% 30 min	not provided	[35]

图5 （a）不同温度对催化体系1.5QSCo-rGO/PMS的降解活性影响，以及（b）的稳定性与（c）普适性注:(a) 不同温度 (b) 再生实验 (c) 不同污染物的降解性能

Fig.5 (a) The effects of different temperatures on the degradation activity of catalytic system 1.5QSCo-rGO/PMS, and (b) the stability and (c) adaptability

图6 不同用量的淬灭剂（a）TBA、（b）EtOH、（c）L-histidine和（d）KI对降解苯酚的抑制效果

Fig.6 Inhibitory effects of different dosages of quenching agents (a) TBA, (b) EtOH, (c) L-histidine, and (d) KI on the degradation of phenol

图7 （a）不同淬灭剂L-histidine用量的速率常数k的变化，以及（b）活性物种1O2的探针实验注:(a) 不同L-histidine用量的速率常数 (b) 1O2探针实验的紫外谱图

Fig.7 (a) Change of rate constant k with different dosage of quenching agent L-histidine, and (b) probe experiments with active species 1O2

图8 反应体系不同时间的EPR光谱：（a）DMPO-OH、DMPO-SO4• ‾以及（b）TEMP-1O2注:(a) DMPO-OH和DMPO-SO4• ‾ (b) TEMP-1O2

Fig.8 EPR spectra of the reaction system at different times: (a) DMPO-OH, DMPO-SO4• ‾ and (b) TEMP-1O2

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