High dispersion of cobalt on the reduced graphene oxide for advanced oxidation degradation of organic pollutants

doi:10.11949/0438-1157.20240423

Abstract

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), and Co highly dispersed QSCo-rGO and Co agglomerated AGCo-rGO were synthesized by a simple method. 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

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。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。本文可为设计增强降解活性的高级氧化催化剂提供思路。

关键词: 降解, 催化剂, 自由基, 还原氧化石墨烯, 过氧单硫酸盐

CLC Number:

X 52

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, 2024, 75(10): 3793-3803.

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, 2024, 75(10): 3793-3803.

Figures/Tables 9

Fig.1 TEM images of 1.5QSCo-rGO, and 1.5AGCo-rGO; HRTEM and HAADF-STEM images and element mapping of corresponding O, C and Co elements of 1.5QSCo-rGO

Fig.2 XRD patterns of QSCo-rGO and AGCo-rGO

Fig.3 XPS spectra and Co 2p, C 1s, O 1s regions of rGO and 1.5QSCo-rGO

Fig.4 Degradation of phenol by different catalysts, degradation activity of leaching Co ions and removal efficiency of TOC

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

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

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

Fig.6 Inhibitory effects of different dosages of quenching agents TBA, EtOH, L-histidine, and KI on the degradation of phenol

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

Fig.8 EPR spectra of the reaction system at different time

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