Reactions of pyrrole, imidazole, and pyrazole with ozone: kinetics and mechanisms

Tekle-Röttering, Agnes; Lim, Sungeun; Reisz, Erika; Lutze, Holger V.; Abdighahroudi, Mohammad Sajjad; Willach, Sarah; Schmidt, W.; Tentscher, Peter R.; Rentsch, Daniel; McArdell, Christa S.; Schmidt, Thorsten C.; Gunten, Urs von

doi:10.1039/c9ew01078e

Cited by 29 publications

(50 citation statements)

References 78 publications

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“…Although identification of all of the possible intermediates and end products is very difficult, several proposed products after the treatment time of 120 min have been confirmed, including formic acid, acetic acid, acetamide, and formamide, as well as formate, nitrate, and nitrite ions. By combining these results and pervious reports on oxidative degradation of imidazole-related molecules in homogeneous solutions, , the proposed destruction and conversion process is possible. On the other hand, the 2-methylimidazole ligand and its oxidized intermediates can make the solution weakly basic.…”

Section: Results and Discussionmentioning

confidence: 58%

“…For the instable MOFs, typically ZIF-67(Co), the possible destruction and ligand degradation process during the aqueous O 3 treatment is proposed (Scheme ). In homogeneous solutions, O 3 can rapidly oxidize imidazole . The high surface area and micropores of ZIF-67(Co) can make its ligand 2-methylimidazole easily accessible to O 3 (Scheme a).…”

Section: Results and Discussionmentioning

confidence: 99%

“…In homogeneous solutions, O 3 can rapidly oxidize imidazole. 47 The high surface area and micropores of ZIF-67(Co) can make its ligand 2methylimidazole easily accessible to O 3 (Scheme 2a). The C C double bond in 2-methylimidazole can be preferentially attacked by O 3 to form CO bonds (Scheme 2b), which can be validated by the FTIR spectra showing bands assigned to the CO groups (Figure 6B).…”

Section: Resultsmentioning

confidence: 99%

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Study on the Stability, Evolution of Physicochemical Properties, and Postsynthesis of Metal–Organic Frameworks in Bubbled Aqueous Ozone Solution

Yue

Lei

Lin

et al. 2021

ACS Appl. Mater. Interfaces

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Metal–organic frameworks (MOFs) are highly promising in many areas. Their application and postsynthesis under strong oxidative environments are emerging. However, the stability, physicochemical property evolution, and possible postmodification and postsynthesis of MOFs in strong oxidative solutions are largely unknown. In this paper, the behaviors of a series of MOFs in bubbled aqueous ozone (O3) solutions are studied. The chosen MOFs are categorized into trimesic type including MIL-101(Fe) and MIL-96(Al); terephthalic type including MOF-74(Co), UiO-66(Zr), MIL-53(Al), and MIL-101(Cr); and imidazole type including ZIF-67(Co) and ZIF-8(Zn), based on the ligand structure. The intrinsic stability and evolution of the physicochemical properties of these MOFs during aqueous O3 treatment are elucidated using structural, morphological, textural, thermal, and spectroscopic analyses. Several stable, metastable, and instable MOFs are identified. The critical parameters that determine the stability and capability for postsynthesis of these MOFs in aqueous O3 solutions are discussed. The stability follows the general order of trimesic-type > terephthalic-type ≫ imidazole-type MOFs because of the distinct antioxidation capability of the ligands. The effects of the ligand, metal cation, and their coordination number on stability are discussed. MIL-100(Fe), MIL-96(Al), and MOF-74(Co) are stable in aqueous O3. UiO-66(Zr), MIL-53(Al), and MIL-101(Cr) are metastable that their porosity, particle size, and crystallinity can be postmodified. ZIF-67(Co) and ZIF-8(Zn) are instable and can be gradually and completely disassembled. Their particle size and morphology and surface groups can be tuned by controlling the treatment time. Postsynthesis of metal hydroxides from ZIF-67(Co) and gradual release of dissolved zinc ion from ZIF-8(Zn) are achievable. The stable MIL-96(Al) shows promising performance in catalytic ozonation for degrading 4-nitrophenol, and the α-Co(OH)2 derived from treating ZIF-67(Co) shows highly promising performance in the electrocatalytic oxygen evolution reaction (OER).

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Section: Results and Discussionmentioning

confidence: 58%

Section: Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Study on the Stability, Evolution of Physicochemical Properties, and Postsynthesis of Metal–Organic Frameworks in Bubbled Aqueous Ozone Solution

Yue

Lei

Lin

et al. 2021

ACS Appl. Mater. Interfaces

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“…Gas-phase product compounds exhibiting O/N values of ≤2 are detected in both ESI– and ESI+ mode, indicating that these compounds cannot have organic nitrate functionality but instead contain reduced nitrogen-containing functional groups (e.g., amines and imides) (Figure ). ,, …”

Section: Resultsmentioning

confidence: 99%

“…In fact, most of the CHON compounds detected in ESI+ mode have more reduced N atoms (O/N = 1), such as formamide (HCONH 2 ) and cyanic acid (CHNO), which could be produced by O 3 oxidation of N-heterocyclic compounds (azoles), such as pyrrole, imidazole, and pyrazole, , although these kinds of compounds could be also formed through ozonolysis of amines such as monoethanolamine, diethylamine, and trimethylamine. , The existence of CHON+ product compounds with an O/N ratio of 0.5 suggests the presence of nitrosamine (H 2 N 2 O), which also could be formed by O 3 oxidation of azoles. Interestingly, the compounds with the highest intensity, detected in ESI– and ESI+ modes, have O/N ratios of 0, confirming the presence of CHN compounds. , …”

Section: Resultsmentioning

confidence: 99%

Interfacial Ozone Oxidation Chemistry at a Riverine Surface Microlayer as a Source of Nitrogen Organic Compounds

Wang

Deng

et al. 2022

Environ. Sci. Technol. Lett.

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Nitrogen (N)-containing organic compounds, including “brown carbon” (BrC), represent an important fraction of organic aerosols. However, little is known about the processes of formation of the secondarily formed N-containing organics in the atmosphere. Here, we investigated the formation of gas-phase organic compounds, including N-containing organics, through interfacial oxidation chemistry of gaseous O3 with an authentic riverine surface microlayer (SML) by using a high-resolution quadrupole Orbitrap mass spectrometer coupled to a commercial secondary electrospray ionization source. The resulting hierarchical cluster diagram obtained for real-time observation for 60 min shows the occurrence of 677 ions in positive mode. The level of N-containing organics, including BrC compounds (e.g., imidazoles), formed during the heterogeneous processing of O3 on the SML in the dark and under ultraviolet–visible light irradiation, was on average 20.7% among all samples. Many of the detected N-containing compounds comprise a CN bond, suggesting that they are potentially toxic compounds that also affect urban air quality. Overall, this study provides evidence that interfacial ozone oxidation chemistry at the riverine SML plays an important role as an additional source of air pollution in urban environments, which can affect both human health and the absorption properties of urban aerosols.

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Unusual Post Modulation of Pore Size, Nanostructure, and Composition of Metal–Organic Frameworks via Cooperative Ozone/Water Co‐Etching

Mao

Huang

et al. 2023

Adv Funct Materials

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Rational engineering of pore structure and size, nanostructure, and local composition of metal‐organic frameworks (MOFs) plays a crucial role for their applications. Herein, a facile O3/H2O co‐etching strategy is reported to treat ZIF‐67 to synthesize derivatives with novel and hard‐to‐acquire structures and properties, including mesoporous ZIF‐67 dodecahedra with variable mesopore sizes (3–30 nm), core–shell and core‐void‐shell mesoporous ZIF‐67@amorphous cobalt hydroxide dodecahedra, and hollow dodecahedral frameworks. In the cooperative etching mechanism, O3 diffuses into the hydrophobic ZIF‐67 to progressively oxidize the ligand to create functional groups, mesopores and voids, while the enhanced hydrophilicity and pore size allow H2O to diffuse inside to hydrolyze the metal centers to form cobalt hydroxide shells. The co‐etching boosts the performance of ZIF‐67 in the electrocatalytic oxygen evolution reaction. The derived core‐void‐shell material possesses a highly attractive performance (an overpotential of 286 mV, a Tafel slope of 59.5 mV dec−1, and a stability of >20 h) because of the presence of amorphous cobalt species, large pores, hierarchal structure, and high hydrophilicity. This work provides a general approach for post engineering of MOFs to create novel structures and functionalities.

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Reactions of pyrrole, imidazole, and pyrazole with ozone: kinetics and mechanisms

Abstract: Kinetics and transformation products for the reactions of ozone with pyrrole, imidazole, and pyrazole were determined. For the imidazole–ozone reaction, all possible transformation products were identified, completing the mass balance.

Cited by 29 publications

References 78 publications

Study on the Stability, Evolution of Physicochemical Properties, and Postsynthesis of Metal–Organic Frameworks in Bubbled Aqueous Ozone Solution

Study on the Stability, Evolution of Physicochemical Properties, and Postsynthesis of Metal–Organic Frameworks in Bubbled Aqueous Ozone Solution

Interfacial Ozone Oxidation Chemistry at a Riverine Surface Microlayer as a Source of Nitrogen Organic Compounds

Unusual Post Modulation of Pore Size, Nanostructure, and Composition of Metal–Organic Frameworks via Cooperative Ozone/Water Co‐Etching

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