4.7 Article

New insight into peroxymonosulfate activation by CoAl-LDH derived CoOOH: Oxygen vacancies rather than Co species redox pairs induced process

Journal

CHEMICAL ENGINEERING JOURNAL
Volume 442, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2022.136251

Keywords

Cobalt oxyhydroxide; Oxygen vacancies; Peroxymonosulfate; Activation mechanism

Funding

  1. Natural Science Foundation of Hunan Province [2021JJ40069]
  2. Hunan Science & Technology Innovation Program [2021RC3039]
  3. National Natural Science Foundation of China [51808206, 51878256, 51978618]

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This study presents a facile self-sacrifice method to synthesize highly effective hexagonal CoOOH microplate (B-CoOOH) for organics elimination. The B-CoOOH/PMS system achieved a high degradation rate and displayed satisfactory recyclability, excellent physicochemical stability, and high mineralization efficiency.
Cobalt oxyhydroxide (CoOOH) has received much attention as a environmental friendly mineral for activating peroxymonosulfate (PMS) for organics elimination in environment remediation. Yet, it suffered from unsatisfactory catalytic activity. This work presents a facile self-sacrifice method to synthesize highly effective hexagonal CoOOH microplate (B-CoOOH) from cobalt aluminum layered double hydroxide (CoAl-LDH). 40 mu M of sulfamethoxazole (SMX) was 100% eliminated in 6 min in the presence of 0.1 g/L B-CoOOH and 0.3 mM PMS. B-CoOOH/PMS system achieved a high degradation (0.60 min(-1)), which was 12 times higher than CoOOH/PMS system (0.05 min(-1)). Besides, B-CoOOH also displayed satisfactory recyclability during the repeating tests, excellent physicochemical stability with low cobalt ions leaching (0.05 mg/L), and high mineralization efficiency (97.5% of TOC removal). Quenching tests signified the dominant role of O-1(2) in SMX degradation. Mechanisms exploration revealed that the abundant oxygen vacancies (O-V) on B-CoOOH acted as the electron donator in PMS activation process, which differed from previous report, in which Co species redox pairs was responsible for activating PMS and producing reactive oxygen species. In the initial stage of PMS activation, the dissolved oxygen in solution contributed to the generation of O-1(2), while in the later stage PMS was regarded as the main precursor for the O-1(2) formation. This study provides a convenient approach for the synthesis of cobalt oxyhydroxide with excellent catalytic activity, and sheds a new insight into the indispensable role of O-V in heterogeneous catalysis.

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