Enhanced Catalytic Ozonation for Eliminating CH₃SH via Graphene-Supported Positively Charged Atomic Pt Undergoing Pt²⁺/Pt⁴⁺ Redox Cycle

Abstract

Constructing catalysts with electronic metal–support interaction (EMSI) is promising for catalytic reactions. Herein, graphene-supported positively charged (Pt2+/Pt4+) atomically dispersed Pt catalysts (AD-Pt-G) with Pt x C3 (x = 1, 2, and 4)-based EMSI coordination structures are achieved for boosting the catalytic ozonation for odorous CH3SH removal. A CH3SH removal efficiency of 91.5% can be obtained during catalytic ozonation using optimum 0.5AD-Pt-G within 12 h under a gas hourly space velocity of 60,000 mL h–1 g–1, whereas that of pure graphene is 40.4%. Proton transfer reaction time-of-flight mass spectrometry, in situ diffuse reflectance infrared Fourier transform spectroscopy/Raman, and electron spin resonance verify that the Pt x C3 coordination structure with atomic Pt2+ sites on AD-Pt-G can activate O2 to generate peroxide species (*O2) for partial oxidation of CH3SH during the adsorption period and trigger O3 into surface atomic oxygen (*Oad), *O2, and superoxide radicals (·O2 –) to accomplish a stable, high-efficiency, and deeper oxidation of CH3SH during the catalytic ozonation stage. Moreover, the results of XPS and DFT calculation imply the occurrence of Pt2+ → Pt4+ → Pt2+ recirculation on Pt x C3 for AD-Pt-G to maintain the continuous catalytic ozonation for 12 h, i.e., Pt2+ species devote electrons in 5d-orbitals to activate O3, while Pt4+ species can be reduced back to Pt2+ via capturing electrons from CH3SH. This study can provide novel insights into the development of atomically dispersed Pt catalysts with a strong EMSI effect to realize excellent catalytic ozonation for air purification.

Evaluation of the Flexibility for Catalytic Ozonation of Dichloromethane over Urchin-Like CuMnOx in Flue Gas with Complicated Components

“…The active oxygen radicals and hydroxyl radicals generated from ozone activation play a dominant role for the further oxidation of Cl-VOCs. It should be noted that O 3 activation differs from O 3 decomposition, as the former needs to participate in the next oxidation cycle instead of being converted into O 2 directly . Therefore, O 3 activation, adsorption of active radicals, and cracking of Cl-VOC molecules are equally important to screen catalysts.…”

“…It should be noted that O 3 activation differs from O 3 decomposition, as the former needs to participate in the next oxidation cycle instead of being converted into O 2 directly. 12 Therefore, O 3 activation, adsorption of active radicals, and cracking of Cl-VOC molecules are equally important to screen catalysts. Manganese oxides with multiple valence states have been demonstrated to be the excellent candidates for Cl-VOC catalytic ozonation.…”

Self-Accelerating Interfacial Catalytic Elimination of Gaseous Sulfur-Containing Volatile Organic Compounds as Microbubbles in a Facet-Engineered Three-Dimensional BiOCl Sponge Fenton-Like Process

“…Meanwhile, formate (HCOO – ) was also detected, with formation amounts of 0.30 and 0.61 μmol within 60 min in 1BiOCl-001 sponge/MiB/H 2 O 2 and 1BiOCl-010 sponge/MiB/H 2 O 2 systems, respectively (Figure S32). The generation amount of HCOO – increased rapidly at first and then increased slowly, indicating that HCOO – is an intermediate product, which will be oxidized to CO 2 with the prolonging of the reaction. , This also indicates that the 1BiOCl-001 sponge has a stronger mineralization ability for HCOO – .…”

“…Our recent studies show that the construction of dualreaction-centers on BiOI surfaces can greatly induce surface electron transfer and achieve the selective reduction of H 2 O 2 by reducing activation energy demand and ignoring the pH limit. 14 The electrons of pollutants are captured via the interfacial reaction of dual-reaction-centers and are finally converted into 1 of pollutants is realized. These studies reveal the interfacial reactions between pollutants/DO and catalysts that may be activated by establishing electron-rich/poor sites on their surface.…”

“…Sulfur-containing volatile organic compounds (S-VOCs) are organic pollutants that boil below 260 °C at room temperature and atmospheric pressure. , S-VOCs have been widely used in the chemical industry and are inevitably discharged in a gaseous state, which seriously harms the environment and human health. − Recently, the Fenton-like process is considered to be a promising approach for S-VOC removal under mild conditions because of its advantages in producing strong oxidation active substances such as hydroxyl radicals (•OH), super oxygen radicals (•O 2 – ), and singlet oxygen ( 1 O 2 ). − Specifically, H 2 O 2 , as an electron acceptor, can be reduced to •OH in the Fenton-like process, while it can also be oxidized to •O 2 – and O 2 as electron donors . To overcome the rate-limiting step of Fe 3+ reduction, excessive consumption of H 2 O 2 is inevitable.…”