Direct Electron-Transfer-Based Peroxymonosulfate Activation by Iron-Doped Manganese Oxide (δ-MnO<sub>2</sub>) and the Development of Galvanic Oxidation Processes (GOPs)

Huang, Kuan; Zhang, Huichun

doi:10.1021/acs.est.9b03648

Cited by 287 publications

(99 citation statements)

References 61 publications

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“…BPA decomposition was barely inhibited in the Cu-N 4 /C-B/PMS upon K 2 Cr 2 O 7 addition ( SI Appendix , Fig. S26 B ), suggesting that the system was likely based on direct electron transfer on the catalyst surface other than in solution phase ( 51 ). Moreover, chronoamperometry measurements were performed ( Fig.…”

Section: Resultsmentioning

confidence: 99%

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density

Zhou

Huang

et al. 2022

Proc. Natl. Acad. Sci. U.S.A.

192

142

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Developing heterogeneous catalysts with atomically dispersed active sites is vital to boost peroxymonosulfate (PMS) activation for Fenton-like activity, but how to controllably adjust the electronic configuration of metal centers to further improve the activation kinetics still remains a great challenge. Herein, we report a systematic investigation into heteroatom-doped engineering for tuning the electronic structure of Cu-N4 sites by integrating electron-deficient boron (B) or electron-rich phosphorus (P) heteroatoms into carbon substrate for PMS activation. The electron-depleted Cu-N4/C-B is found to exhibit the most active oxidation capacity among the prepared Cu-N4 single-atom catalysts, which is at the top rankings of the Cu-based catalysts and is superior to most of the state-of-the-art heterogeneous Fenton-like catalysts. Conversely, the electron-enriched Cu-N4/C-P induces a decrease in PMS activation. Both experimental results and theoretical simulations unravel that the long-range interaction with B atoms decreases the electronic density of Cu active sites and down-shifts the d-band center, and thereby optimizes the adsorption energy for PMS activation. This study provides an approach to finely control the electronic structure of Cu-N4 sites at the atomic level and is expected to guide the design of smart Fenton-like catalysts.

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Section: Resultsmentioning

confidence: 99%

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density

Zhou

Huang

et al. 2022

Proc. Natl. Acad. Sci. U.S.A.

192

142

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“…The first is the controversy regarding the catalytic mechanisms. Currently, four mechanisms of pollutant degradation and mineralization have been proposed, including sulfate/hydroxyl radicals, singlet oxygen, high-valent metals, and catalyst-mediated electron transfer 12 , 16 – 18 . However, solid evidence to support these mechanisms is still lacking.…”

Section: Introductionmentioning

confidence: 99%

Simultaneous nanocatalytic surface activation of pollutants and oxidants for highly efficient water decontamination

et al. 2022

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Removal of organic micropollutants from water through advanced oxidation processes (AOPs) is hampered by the excessive input of energy and/or chemicals as well as the large amounts of residuals resulting from incomplete mineralization. Herein, we report a new water purification paradigm, the direct oxidative transfer process (DOTP), which enables complete, highly efficient decontamination at very low dosage of oxidants. DOTP differs fundamentally from AOPs and adsorption in its pollutant removal behavior and mechanisms. In DOTP, the nanocatalyst can interact with persulfate to activate the pollutants by lowering their reductive potential energy, which triggers a non-decomposing oxidative transfer of pollutants from the bulk solution to the nanocatalyst surface. By leveraging the activation, stabilization, and accumulation functions of the heterogeneous catalyst, the DOTP can occur spontaneously on the nanocatalyst surface to enable complete removal of pollutants. The process is found to occur for diverse pollutants, oxidants, and nanocatalysts, including various low-cost catalysts. Significantly, DOTP requires no external energy input, has low oxidant consumption, produces no residual byproducts, and performs robustly in real environmental matrices. These favorable features render DOTP an extremely promising nanotechnology platform for water purification.

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“…45,46 As depicted in the Supporting Information (Figure S16a 47 Although the N-rGO-CoSA/IO 4 − system exhibited slightly lower reaction rates compared to that observed for the N-rGO-CoSA/PMS system, the Co leaching concentration in − consumed (Supporting Information, Figure S17a), indicating that the decomposition of 4-CP and IO 4 − occurred simultaneously; this was very different from the mechanism governing the conventional radical-based oxidation process. 49 The aforementioned result indicated that a nonradical mechanism might dominate the activities of the N-rGO-CoSA/IO 4 − system. Moreover, it was observed that the IO 4…”

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confidence: 95%

Atomically Dispersed Cobalt Sites on Graphene as Efficient Periodate Activators for Selective Organic Pollutant Degradation

Long

Dai

Zhao

et al. 2021

Environ. Sci. Technol.

188

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Pollutant degradation via periodate (IO 4 − )-based advanced oxidation processes (AOPs) provides an economical, energy-efficient way for sustainable pollution control. Although single-atomic metal activation (SMA) can be exploited to optimize the pollution degradation process and understand the associated mechanisms governing IO 4 − -based AOPs, studies on this topic are rare. Herein, we demonstrated the first instance of using SMA for IO 4 − analysis by employing atomically dispersed Co active sites supported by N-doped graphene (N-rGO-CoSA) activators. N-rGO-CoSA efficiently activated IO 4 − for organic pollutant degradation over a wide pH range without producing radical species. The IO 4 − species underwent stoichiometric decomposition to generate the iodate (IO 3 − ) species. Whereas Co 2+ and Co 3 O 4 could not drive IO 4− activation; the Co−N coordination sites exhibited high activation efficiency. The conductive graphene matrix reduced the contaminants/electron transport distance/resistance for these oxidation reactions and boosted the activation capacity by working in conjunction with metal centers. The N-rGO-CoSA/IO 4 − system exhibited a substrate-dependent reactivity that was not caused by iodyl (IO 3• ) radicals. Electrochemical experiments demonstrated that the N-rGO-CoSA/IO 4 − system decomposed organic pollutants via electron-transfer-mediated nonradical processes, where N-rGO-CoSA/periodate* metastable complexes were the predominant oxidants, thereby opening a new avenue for designing efficient IO 4 − activators for the selective oxidation of organic pollutants.

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Direct Electron-Transfer-Based Peroxymonosulfate Activation by Iron-Doped Manganese Oxide (δ-MnO₂) and the Development of Galvanic Oxidation Processes (GOPs)

Cited by 287 publications

References 61 publications

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density

Simultaneous nanocatalytic surface activation of pollutants and oxidants for highly efficient water decontamination

Atomically Dispersed Cobalt Sites on Graphene as Efficient Periodate Activators for Selective Organic Pollutant Degradation

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Direct Electron-Transfer-Based Peroxymonosulfate Activation by Iron-Doped Manganese Oxide (δ-MnO2) and the Development of Galvanic Oxidation Processes (GOPs)

Cited by 287 publications

References 61 publications

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density

Simultaneous nanocatalytic surface activation of pollutants and oxidants for highly efficient water decontamination

Atomically Dispersed Cobalt Sites on Graphene as Efficient Periodate Activators for Selective Organic Pollutant Degradation

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Product

Resources

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Direct Electron-Transfer-Based Peroxymonosulfate Activation by Iron-Doped Manganese Oxide (δ-MnO₂) and the Development of Galvanic Oxidation Processes (GOPs)