Bond Oxidation Research Articles

Photo-Induced Aerobic Oxidation of C–H Bonds

The photo-induced aerobic oxidation of C–H bonds has become an increasingly valuable strategy in organic synthesis, offering a green and efficient method for introducing oxygen into organic molecules. The utilization of molecular oxygen as an oxidant, coupled with visible-light photocatalysis, has gained significant attention due to its sustainability, atom economy, and environmentally benign nature. This review highlights the recent advancements in the field, focusing on the development of metal-free and transition-metal-based photocatalytic systems and novel photosensitizers capable of promoting selective C–H bond oxidation. The mechanistic pathways involved in various substrate oxidations, including benzylic, alkyl, alkene, and alkyne C–H bond transformations, are discussed. This review concludes with insights into the potential for integrating photocatalysis with renewable energy sources, positioning photo-induced aerobic oxidation as a cornerstone of sustainable chemical processes.

Spectroscopic Properties and Reactivity of a MnIII-Hydroperoxo Complex that is Stable at Room Temperature.

Manganese catalysts that activate hydrogen peroxide have seen increased use in organic transformations, such as olefin epoxidation and alkane C-H bond oxidation. Proposed mechanisms for these catalysts involve the formation and activation of MnIII-hydroperoxo intermediates. Examples of well-defined MnIII-hydroperoxo complexes are rare, and the properties of these species are often inferred from MnIII-alkylperoxo analogues. In this study, we show that the reaction of the MnIII-hydroxo complex [MnIII(OH)(6Medpaq)]+ (1) with hydrogen peroxide and acid results in the formation of a dark-green MnIII-hydroperoxo species [MnIII(OOH)(6Medpaq)]+ (2). The formulation of 2 is based on electronic absorption, 1H NMR, IR, and ESI-MS data. The thermal decay of 2 follows a first order process, and variable-temperature kinetic studies of the decay of 2 yielded activation parameters that could be compared with those of a MnIII-alkylperoxo analogue. Complex 2 reacts with the hydrogen-atom donor TEMPOH two-fold faster than the MnIII-hydroxo complex 1. Complex 2 also oxidizes PPh3, and this MnIII-hydroperoxo species is 600-fold more reactive with this substrate than its MnIII-alkylperoxo analogue [MnIII(OOtBu)(6Medpaq)]+. DFT and time-dependent (TD) DFT computations are used to compare the electronic structure of 2 with similar MnIII-hydroperoxo and MnIII-alkylperoxo complexes.

Ferrate(Ⅵ) oxidative degradation of capecitabine in aquatic matrices: Degradation performance, mechanisms, and toxicity assessment

The growing utilization of anticancer drugs in recent years has resulted in their presence in surface water and sewage, which could have ecological consequences. In this work, ferrate (Fe(VI)) was utilized to oxidize capecitabine (CAP), a frequently used anticancer drug that has gained attention lately. The experiments have demonstrated that Fe(VI) was quite reactive with CAP at pH 7. The addition of humic acid (0.1–10 mg L−1) significantly inhibited the oxidation process. Then, four reaction pathways, mainly including hydroxyl substitution, direct oxidation and cleavage of CO and CN bond were proposed based on twelve products detected by high-resolution hybrid quadrupole time-of-flight mass spectrometer. These pathways were further validated by theoretical calculations. Experiments conducted in water matrices assessed the applicability of Fe(VI) technology. Toxicity assessments of CAP and its intermediates were performed using the TEST program, and predictions indicated that the intermediates were generally less toxic than CAP. Overall, this work revealed that Fe(VI) has great potential to solve the environmental pollution problems associated with capecitabine in water.

Diverse Catalytic Applications of Phosphine Oxide‐Based Metal Complexes

AbstractPhosphine oxides are an interesting class of compounds possessing tetracoordinate and pentavalent phosphorus atoms and have been employed in a wide range of applications including reagents in organic synthesis, metal extractants, flame retardants, pharmaceuticals, and bioactivity studies. Among all, the degree of basicity of phosphoryl oxygen driven by the nature of substituents influences the electronic properties of the central metal in a complex toward the diversified catalytic processes. Further, the presence of heteroatoms adjacent to the central phosphorus atom enhances the nucleophilicity of the phosphoryl oxygen atom. In view of this, the present review covers the past two decades of remarkable catalytic versatility of P=O‐based metal complexes and describes the governing factors influencing the structural properties and the resultant coordination behavior. Interestingly, some of the P=O bond distances of metal complexes are either longer or shorter compared to their free ligands, indicating the catalytic activity. These complexes can effectively catalyze a wide range of chemical reactions including polymerizations, C−C and Si−C bond activations, oxidation, reduction, hydroformylation, hydrophosphination, hydrogenation and cyclization reactions. Furthermore, this review emphasizes the impact of substituents, solvents, additives, light, and temperature on the catalytic efficiency.

Ethers as Building Blocks for the Synthesis and Modification of N‐Heterocycles

The use of C‐H compounds as reactive partners in a variety of transformations represents the state of the art in synthetic methodology. In this review, we have summarized the main achievements in using ethers as building blocks for the construction and modification of one of the basic platforms of organic chemistry, nitrogen‐containing heterocycles. Ethers, previously considered mainly as solvents, are excellent CH‐partners, capable of generating radical or cationic reactive species under the action of HAT agents and oxidants. The challenge in this field is the still limited number of heterocyclic systems and other starting reagents, with which the processes can be carried out selectively due to closer bond dissociation energies and oxidation potentials of heterocycles, reactive intermediates and ethers. However, the fine‐tuning of the reaction system using electro‐ and photochemical approaches and a deep understanding of the reaction pathways make the use of ethers as C‐H reagents a promising synthetic strategy.

Energy transfer-mediated multiphoton synergistic excitation for selective C(sp3)–H functionalization with coordination polymer

Activation and selective oxidation of inert C(sp3)–H bonds remain one of the most challenging tasks in current synthetic chemistry due to the inherent inertness of C(sp3)–H bonds. In this study, inspired by natural monooxygenases, we developed a coordination polymer with naphthalenediimide (NDI)-based ligands and binuclear iron nodes. The mixed-valence FeIIIFeII species and chlorine radicals (Cl•) are generated via ligand-to-metal charge transfer (LMCT) between FeIII and chlorine ions. These Cl• radicals abstract a hydrogen atom from the inert C(sp3)–H bond of alkanes via hydrogen atom transfer (HAT). In addition, NDI converts oxygen to 1O2 via energy transfer (EnT), which then coordinates to FeII, forming an FeIV = O intermediate for the selective oxidation of C(sp3)–H bonds. This synthetic platform, which combines photoinduced EnT, LMCT and HAT, provides a EnT-mediated parallel multiphoton excitation strategy with kinetic synergy effect for selective C(sp3)–H oxidation under mild conditions and a blueprint for designing coordination polymer-based photocatalysts for C(sp3)–H bond oxidation.

Polyoxometalate-embedded copper-organic network as dual-site synergetic catalyst for the selective oxidation of benzylic C−H bond

Selective activation and oxidization of inert C−H bonds into value-added chemicals affords attractively economic and ecological benefits, as well as central challenge in modern synthetic chemistry. Herein, by integrating the redox polyoxometalate (POM) centers and multinuclear copper sites in one system, four compounds were constructed with formulas of [Cu2(μ2-Cl)(H2O)2L3][PM12O40]·4H2O (M = Mo for 1, W for 2), and [Cu4(μ2-OH)4L2] [H3PM11CuO40]·12H2O (M = Mo for 3, W for 4, L = 1,4-di[4H-1,2,4-triazol-4-yl]-benzene). Both compounds 1–2 exhibited 3-D POM-embedded supramolecular networks constructed by discrete [PM12O40]3− clusters and binuclear {Cu2(μ2-Cl)(N–N)2} unit-based metal-organic sheets. While compounds 3–4 displayed 3-D POM-supported supramolecular networks composed of monosubstituted Keggin-type anions [H3PM11CuO40]4− and {Cu2(μ2-OH)(N–N)2} chain-based metal-organic layers. Four crystalline structures with distinct dual-active site distribution showed significant peroxidase-like activities owing to the collaborative catalysis of multinuclear copper units and polyanionic clusters, which can smoothly catalyze the C−H bond oxidation of diphenylmethane to benzophenone with ca. 97 % conversion and >98 % selectivity within 24 h. Notably, the monosubstituted [H3PM11CuO40]4−-based compounds 3−4 showed higher catalytic activities than [PM12O40]3−-based compounds 1−2 (88 % conversion and >97 % selectivity within 12 h). This kind of crystalline structures also showed good recoverability. The synergetic reaction mechanism was also explored. This work provides a new strategy to design robust heterogeneous POM-based synergetic catalysts for C−H bond functionalization.

Surfactants govern the fabrication of sulfur-enriched heterojunction catalysts for highly selective photocatalytic conversion of toluene

Photocatalytic selective oxidation of toluene represents a milder and more environmentally friendly strategy for the synthesis of benzaldehyde. In order to enhance catalytic performance, efficient carrier separation and transport are crucial in the photocatalytic process. This study focused on the preparation of ZnS@ZnIn2S4 with sulfur vacancies and heterostructures, combining the advantages properties of ZnS and ZnIn2S4 in photocatalysis. The effects of ZnS and surfactants on the catalytic properties of the composites were studied in depth. Characterization tests revealed that surfactant-modified ZnS@ZnIn2S4 exhibited a higher concentration of sulfur defects, which facilitated electron trapping and promoted photogenerated carrier separation and utilization. Additionally, the present study also demonstrated that the incorporation of ZnS and surfactants could reduce the crystal size of ZnIn2S4, thereby facilitating the exposure of additional active sites. The synergistic effect of the aforementioned advantages enabled toluene to undergo oxidation at a conversion rate of 39% in the presence of oxygen, resulting in the production of benzaldehyde with an exceptional selectivity of 92%. This finding offers valuable insights for future endeavors in designing photocatalytic C-H bond oxidation catalysts.

Highly catalytic performance for the selective C–H bond oxidation of p-chlorotoluene over Co, Cr co-doped OMS-2 catalyst

Using O2 as an oxidant, developing a non-noble metal catalyst for the selective catalytic C–H bond oxidation of p-chlorotoluene is desirable and challenging. In this work, a series of Co, Cr co-doped OMS-2 (Octahedral Molecular Sieve-2) catalysts were prepared by a conventional refluxing method. It was found that the incorporation of Co and Cr improved the catalytic activity for the selective oxidation of p-chlorotoluene to p-chlorobenzaldehyde. Among these catalysts, CoCr/OMS-2 (Co: Cr = 1: 1, mass ratio), the best catalyst, shows that the conversion and the selectivity of p-chlorobenzaldehyde is 94.8 % and 94.3 %, respectively. The enhanced catalytic activity was due to the larger specific surface area and even dispersion of active components. The characterization results also disclosed that the co-doping of Co and Cr increased the oxygen vacancy and enhanced the ability to activate the surface lattice oxygen. Additionally, density functional theory calculations demonstrated that co-doping of Co and Cr promoted the adsorption of p-chlorotoluene and O2, and decreased the energy barrier of rate-determining step (the conversion of p-chlorobenzyl alcohol to p-chlorobenzaldehyde). Besides, when H2O was added to the reaction system as the second solvent, the activation and dissociation of O2, and the formation of p-chlorobenzaldehyde were facilitated, in agreement with the experimental results. This work demonstrated the promotional effect of Co, Cr co-doped into OMS-2 catalyst and the role of H2O for the selective oxidation of p-chlorotoluene.

Efficient hole extraction to reactive oxidation sites over a Co3O4/Cs3Sb2Br9 p-n heterojunction for enhanced benzylic C(sp3)-H bond oxidation

Photocatalytic selective oxidation of aromatic hydrocarbons plays an important role in the production of value-added chemicals. A key step in this process is the activation of C(sp3)-H bond by photogenerated holes. However, the inadequate hole generation and lack of surface adsorption-activation sites severely hinders the improvement in photocatalytic C-H bond oxidation. In particular, the random charge migration to the surface impedes the effective capture of holes by surface active sites to dissociate the C(sp3)-H bond. Here, we design and fabricate a Co3O4/Cs3Sb2Br9 p-n heterojunction that effectively addresses these challenges. The p-n heterojunction forms strong built-in electric fields (BEF) facilitating spatial charge separation. Holes are accumulated on Co3O4, while electrons are accumulated on Cs3Sb2Br9, thereby offering abundant active holes and electrons. Moreover, Co3O4 shows stronger adsorption and activation capacity for the C(sp³)-H bond, enabling the C(sp3)-H bond dissociation with low reaction energy barrier. Consequently, the holes are directionally extracted from photoactive Cs3Sb2Br9 to catalytically active Co3O4 under visible light irradiation, thereby accelerating the toluene oxidation. The optimized 5 % Co3O4/Cs3Sb2Br9 exhibits a benzyl aldehyde (BAD) evolution rate of 5044 μmol g−1 h−1 and a benzyl alcohol (BA) production rate of 1820 μmol g−1 h−1, which are 12 and 17 times higher than that of blank Cs3Sb2Br9, respectively.

Photoelectrocatalytic allylic C–H oxidation to allylic alcohols coupled with hydrogen evolution

Allylic C–H bond oxidation of cycloolefins to allylic alcohols has attracted tremendous attention owing to its widespread application in pharmaceuticals production and natural synthesis. However, the production of allylic alcohols still suffers from the challenges of unsatisfactory selectivity and harsh conditions. Herein, we report the sustainable photoelectrocatalytic (PEC) allylic C–H oxidation to allylic alcohols, achieving the oxidation of cyclohexene to 2-cyclohexenol with a selectivity of 97.2 %. We reveal the reaction pathway wherein photogenerated holes and OH– synergistically activate cyclohexene to carbocation intermediates, and these intermediates combine with OH– to produce 2-cyclohexenol. Additionally, the mechanism by enriching OH– in local area of photoanode surface to enhance PEC performance is uncovered. Furthermore, we designed a self-powered PEC reaction system, attaining a 2-cyclohexenol productivity of 11.95 μmol h–1 (selectivity > 97 %) coupled with a H2 productivity of 1.44 mL h–1, demonstrating the application potential of this new strategy.

Degradation of tris(1,3-dichloro-2-propyl) phosphate (TDCPP) by ultraviolet activated hydrogen peroxide: Mechanisms, pathways and toxicity assessments

The ubiquity and ecotoxicity of tri (1,3-dichloro-2-propyl) phosphate (TDCPP) in aquatic environments make it essential to develop efficient related treatment techniques. The present research aims to systematically explore the mechanisms and toxicity changes of TDCPP degradation through UV-driven hydrogen peroxide process (UV/H2O2). The results revealed degradation efficiency of TDCPP attained 95 % with 0.5 mM H2O2, corresponding to a reaction rate constant (k) of 0.04919 min−1. Furthermore, three typical chlorinated OPEs (Cl-OPEs) were simultaneously degraded by the UV/H2O2 process, with different degradation efficiencies, according to the following order: TCEP<TDCPP<TCPP. The degradation efficiency was restricted under alkaline condition and the presence of humic acid (HA), nitrate (NO3–), chloride (Cl-), sulfate (SO42-), and dihydrogen phosphate (H2PO4-). A total of 12 intermediates were identified, which were generated through different pathways, including bond breaking, hydroxylation, and oxidation reactions. The Toxicity Estimation Software Tool (T.E.S.T) results demonstrated stronger mutagenicity and developmental toxicity of the TDCPP intermediates than parent compound. According to RNA sequencing results, UV/H2O2-based TDCPP degradation for 20 min and 60 min still had negative effects on Escherichia coli (E. coli). Indeed, the Gene Ontology (GO) enrichment and Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis results further suggested the stronger negative effect (e.g., damaging effects on the cell membrane, energy metabolism, and vitality) of the 20-min oxidation solution on E. coli, followed by those observed in without treatment and 60-min oxidation solution. Therefore, longer oxidation times are required in the UV/H2O2 process to decrease the toxicity of TDCPP.

Insights into the Synergistic Catalytic Effect of TiO2 Supported V-W Oxides for Selective C-H Bond Oxidation of Cyclohexane to KA Oil.

It is urgent to develop an efficient and stable non-noble metal catalyst for selective C-H bond oxidation of cyclohexane. Herein, a series of V-W oxides supported on TiO2catalysts (V-W/TiO2) were fabricated. The V-W/TiO2catalysts exhibited much higher catalytic activity for the selective oxidation of cyclohexane to KA oil, compared to that of V/TiO2and W/TiO2catalysts. The good distribution of active metals and the synergistic effect were responsible for the enhanced catalytic activity. H2-TPR results disclosed that the presence of V inV-W/TiO2 affected the reducibility of W6+species, and XPS verified that an electronic interaction was formed between them. Such results led to good catalytic reusability of V-W/TiO2catalyst during the reactions, and no obvious activity loss was found after six runs. The reaction mechanism was investigated, and the results verified that hydroxyl radicals generated from H2O2homolysis were the main active oxidative species. Theoretical study revealed that V dopant could regulate electronic structure of adjacent O atom, facilitating the adsorption of cyclohexane, and lower energy was needed for the rate-limiting step over V-W/TiO2during the whole oxidation reaction. This work developed an efficient V-W/TiO2catalyst for the selective oxidation of cyclohexane via a synergistic effect.

Evolution, structure, and drug-metabolizing activity of mammalian prenylcysteine oxidases

Prenylcysteine oxidases (PCYOXs) metabolize prenylated cysteines produced by protein degradation. They utilize oxygen as a co-substrate to produce free cysteine, an aldehyde, and hydrogen peroxide through the unusual oxidation of a thioether bond. In this study, we explore the evolution, structure, and mechanism of the two mammalian PCYOXs. A gene duplication event in jawed vertebrates originated in these two paralogs. Both enzymes are active on farnesyl- and geranylgeranylcysteine, but inactive on molecules with shorter prenyl groups. Kinetics experiments outline a mechanism where flavin reduction and re-oxidation occur rapidly without any detectable intermediates, with the overall reaction rate limited by product release. The experimentally determined three-dimensional structure of PCYOX1 reveals long and wide tunnels leading from the surface to the flavin. They allow the isoprene substrate to curl up within the protein and position its reactive cysteine group close to the flavin. A hydrophobic patch on the surface mediates membrane association, enabling direct substrate and product exchange with the lipid bilayer. Leveraging established knowledge of flavoenzyme inhibition, we designed sub-micromolar PCYOX inhibitors. Additionally, we discovered that PCYOXs bind and slowly degrade salisirab, an anti-RAS compound. This activity suggests potential and previously unknown roles of PCYOXs in drug metabolism.

Photoredox Activation of Fluorinated Organozinc Reagents: Hydrofluoroalkylation of Unactivated and Electron Deficient Alkenes.

Hydrofluoroalkylation of alkenes with organozinc reagents under photocatalytic conditions is described. The fluorinated alkyl radicals were generated from organozincs by the single electron oxidation of the carbon-zinc bond. The radical addition step is followed either by hydrogen atom transfer for unactivated olefins or by a reduction/protonation sequence for strongly accepting arylidenemalononitriles.

Efficient C(sp3)-H Bond Oxidation on Perovskite Quantum Dots Based on Ce-Oxygen Affinity.

Perovskite quantum dots (QDs) have shown attractive prospects in the field of visible photocatalysis, especially in the synthesis of high value-added chemicals. However, under aerobic conditions, the stable operation of QD catalysts has been limited by the reactive oxygen species (ROS) generated by photoexcitation, especially superoxide species O2⋅-. Here, we propose a strategy of Ce3+ doping in perovskite QDs to guide superoxide species for photocatalytic oxidation reactions. In C(sp3)-H bond oxidation of hydrocarbons, superoxide species were rapidly generated and efficiently utilized on the surface of perovskite QDs, which achieves the stable operation of the catalytic system and obtains a high product conversion rate (15.3 mmol/g/h for benzaldehydes). The mechanism studies show that the strong Ce-oxygen affinity accelerates the relaxation process of photoinduced exciton transfer to superoxide species and inhibits the radiative recombination pathway. This work provides a new idea of utilizing oxygen species on perovskite surface and broadens the design strategy of high-performance QD photocatalysts.

Efficient C(sp3)−H Bond Oxidation on Perovskite Quantum Dots Based on Ce‐Oxygen Affinity

AbstractPerovskite quantum dots (QDs) have shown attractive prospects in the field of visible photocatalysis, especially in the synthesis of high value‐added chemicals. However, under aerobic conditions, the stable operation of QD catalysts has been limited by the reactive oxygen species (ROS) generated by photoexcitation, especially superoxide species O2⋅−. Here, we propose a strategy of Ce3+ doping in perovskite QDs to guide superoxide species for photocatalytic oxidation reactions. In C(sp3)−H bond oxidation of hydrocarbons, superoxide species were rapidly generated and efficiently utilized on the surface of perovskite QDs, which achieves the stable operation of the catalytic system and obtains a high product conversion rate (15.3 mmol/g/h for benzaldehydes). The mechanism studies show that the strong Ce‐oxygen affinity accelerates the relaxation process of photoinduced exciton transfer to superoxide species and inhibits the radiative recombination pathway. This work provides a new idea of utilizing oxygen species on perovskite surface and broadens the design strategy of high‐performance QD photocatalysts.

Anisotropic Effects in Local Anodic Oxidation Nanolithography on Silicon Surfaces: Insights from ReaxFF Molecular Dynamics.

Fully understanding the anisotropic effect of silicon surface orientations in local anodic oxidation (LAO) nanolithography processes is critical to the precise control of oxide quality and rate. This study used ReaxFF MD simulations to reveal the surface anisotropic effects in the LAO through the analysis of adsorbed species, atomic charge, and oxide growth. Our results show that the LAO behaves differently on silicon (100), (110), and (111) surfaces. Specifically, the application of an electric field significantly increases the quantity of surface-adsorbed -OH2 while reducing -OH on the (111) surface, and results in a higher charge on a greater number of Si atoms on the (100) surface. Moreover, the quantity of surface-adsorbed -OH plays a pivotal role in influencing the oxidation rate, as it directly correlates with an increased formation rate of Si-O-Si bonds. During bias-induced oxidation, the (111) surface appears with a high initial oxidation rate among three surfaces, while the (110) surface underwent increased oxidation at higher electric field strengths. This conclusion is based on the analysis of the evolution of Si-O-Si bond number, surface elevation, and oxide thickness. Our findings align well with prior theoretical and experimental studies, providing deeper insights and clear guidance for the fabrication of high-performance nanoinsulator gates using LAO nanolithography.

Photodegradation of the novel herbicide pyraclonil in aqueous solution: Kinetics, identification of photoproducts, mechanism, and toxicity assessment

Pyraclonil is a new type of pyrazole herbicide, whose photochemical fate in aqueous solution has not been reported yet. In this study, effects on the photolysis rate such as light source, pH, NO3−, Fe3+, fulvic acid (FA) and riboflavin (RF) were investigated. Pyraclonil photodegraded in pure water under both UV and simulated sunlight with half-lives of 32.29 min and 42.52 h, respectively. Under UV, the degradation rate of pyraclonil in pH 4 solution (0.0299 ± 0.0033 min−1) was about twice higher than that in pH 9 (0.0160 ± 0.0063 min−1). Under simulated sunlight, low concentration (0.1–1 mg/L) of FA, NO3−, Fe3+ and RF noticeably promoted the photodegradation of pyraclonil. Then, with the combination of experimental UPLC-Q-TOF/MS and computational calculation of density functional theory (DFT), fourteen transformation products (TPs) of pyraclonil were identified with possible mechanism of C–N bond cleavage, photorearrangement, demethylation, hydroxylation and oxidation. Additionally, acute toxicity assessment was conducted through ECOSAR prediction and laboratory bioassays. The prediction results indicated that toxicity of TP157 to daphnid and green algae was 1.3 and 1.4 times higher than that of the parent, respectively. The bioassay results indicated that toxicities of TP157 and TP263 to C. vulgaris were about 1.6 and 5.9 times higher than that of the parent, respectively. The results provided a reference for elucidating the potential hazards of pyraclonil to non-target organisms and promoting its rational use.

Effects of polymer matrix and temperature on pyrolysis of tetrabromobisphenol A: Product profiles and transformation pathways

Plastics are crucial constituents in electronic waste (e-waste) and part of the issue in e-waste recycling and environmental protection. However, previous studies have mostly focused on plastic recovery or thermal behavior of flame retardants, but not both simultaneously. The present study simulated the process of e-waste thermal treatment to explore tetrabromobisphenol A (TBBPA) pyrolysis at various temperatures using polystyrene (PS), polyvinyl chloride (PVC), and e-waste plastics as polymer matrices. Pyrolysis of TBBPA produced bromophenol, bromoacetophenone, bromobenzaldehyde, and bromobisphenol A. Co-pyrolysis with the polymer matrices increased emission factors by 1 − 2 orders of magnitude. The pyrolytic products of TBBPA, TBBPA+PS, and TBBPA+PVC were mainly low-brominated bisphenol A, while that of TBBPA in e-waste plastics was consistently bromophenol. Increasing temperature drove up the proportions of gaseous and particulate products, but lowered the relative abundances of inner wall adsorbed and residual products in pyrolysis of pure TBBPA. In co-pyrolysis of TBBPA with polymer matrix, the proportions of products in different phases were no longer governed solely by temperature, but also by polymer matrix. Co-pyrolysis of TBBPA with PS generated various bromophenols, while that with PVC produced chlorophenols and chlorobrominated bisphenol A. Transformation pathways, deduced by ab initio calculations, include hydrogenation-debromination, isopropylphenyl bond cleavage, oxidation, and chlorination.