Epoxidation Of Styrene Research Articles

Localized surface plasmon resonance effect-mediated in-situ photochemical–formation of H2O2 for high epoxidation performance over LaSrCoNiO6 nanoparticles

Selective aerobic epoxidation of allylic alcohols and olefins presents a promising solution to the modern chemical industry. However, the development of non-noble metal catalysts with superior catalytic performance for this reaction remains a significant challenge. This study introduces a plasmonic photothermal-catalytic system centered around nano LaSrCoNiO6 (LSCNi-N) catalyst, enabling the epoxidation of cinnamyl alcohol and styrene mediated by LSPR effect under visible light illumination (>420 nm). This catalyst exhibits superior epoxidation catalytic performance, with selectivities of up to 72.3 % in a 93.4 % conversion of cinnamyl alcohol and 91.8 % selectivity of styrene oxide at almost 100 % conversion of styrene. Mechanistic studies reveal that the high selectivity derives from the in-situ photochemical formation of H2O2 mediated by the localized surface plasmon resonance effect of LSCNi-N and hole scavenger effect of cinnamyl alcohol. These findings highlight the potential of designing plasmonic transition-metal oxidic catalysts to overcome challenges in selectively synthesizing fine chemicals through visible light catalysis.

Catalytic performances of Ag/SiC catalysts for styrene epoxidation in O2 atmosphere

SiC supported Ag catalysts were prepared by an impregnation-reduction method for styrene epoxidation in O2 atmosphere. Under the condition of 100 °C, 0.5 MPa O2 and 4 h, 5 wt% Ag/SiC catalyst achieved styrene conversion of 98.5 % and styrene oxide selectivity of 69.7 %. Further studies show that O2 was activated on the Ag surface and then formed reactive oxygen species, 1O2 and •O2-. Based on the O2 adsorption results, the atomic ratio of O/Ag larger than 0.5 indicated that more oxygen species had spilled over to the SiC surface. In-situ diffuse reflectance Fourier transform infrared spectroscopy and Density Functional Theory calculation results showed that styrene was adsorbed on the SiC surface. The active oxygen species generated on the Ag surface could spill over to the SiC surface, reacting with the adsorbed styrene to produce styrene oxide or benzaldehyde. In addition, the catalyst exhibits good stability.

Efficient epoxidation of styrene over single-atomic copper-doped ordered mesoporous alumina (Cu-OMA) composited with carbon nitride

The present study assessed the catalytic performance in epoxidation of styrene using tert‑butyl hydroperoxide (TBHP) as an oxidant over single-atomic copper-doped Ordered mesoporous alumina (Cu-OMA) composited with g-C3N4 (CN). The thermal treatment at three temperatures (300, 500, 700 °C) provided a facile mean to modify the texture and electronic structure of the Cu-OMA@CN composite. The X-Ray absorption spectroscopy proved the single-atomic Cu-O-Al and Cu-O-C in Cu-OMA@CN-500 catalyst. Catalytic reaction parameters, namely temperature (60–80 °C), catalyst amount (10–70 mg), substrate/oxidant ratio (1:1–1:3), and solvents (acetone, ethanol, acetonitrile, N, N-dimethylacetamide) were optimized to obtain high conversion of styrene and selectivity to styrene epoxide. Under the optimized reaction conditions (75 °C, 30 mg of catalyst, 1:2 of styrene/TBHP and acetonitrile as solvent), the conversion decreased in the order of Cu-OMA@CN-500 > Cu-OMA@CN-300 > Cu-OMA@CN-700. This sequence was related to the formation of electron-rich single-atom copper sites, high surface area, medium alkaline environment and high content of graphic nitrogen species in Cu-OMA@CN-500. This structure differed from the blocky structure of C3N4 in Cu-OMA@CN-300 and the destroyed tri-s-triazine ring in Cu-OMA@CN-700. The most active Cu-OMA@CN-500 catalyst displayed a high styrene conversion (87.2 %) and striking selectivity to styrene oxide (90.0 %). Its catalytic activity was retained after five recyclability tests. The possible catalytic mechanism for epoxidation of styrene over this catalyst was tentatively proposed.

Synthesis Method and Principle of Octahedral Hierarchical LTA Zeolite and Its Application to Enhance Catalytic Activity in Styrene Epoxidation.

A 4 Å zeolite prepared under the synergistic effect of intense ultrasound and a high-voltage electrostatic field had an octahedral structure rather than a conventional hexahedral structure. XPS and XRD analyses showed that the ratio of silicon to aluminum, 2θ peak position, and the corresponding crystal planes were the same as those in traditional hexahedral 4 Å zeolite, but some crystal planes were more prominent. SEM imaging showed that the octahedral zeolites had a larger particle size. Porosimetry (BET surface area and BJH analysis) showed that the octahedral zeolite had become a mesoporous zeolite, and its specific surface area increased and its pore size expanded, which was conducive to loading catalytically active materials and thus improving its catalytic performance. In this paper, the mechanism of formation of hierarchical LTA zeolite is discussed, and the octahedral hierarchical LTA zeolite is used to catalyze the epoxidation of styrene, giving very good results. It is concluded that the (600), (622), (642), and (644) crystal planes played a decisive role in the styrene epoxidation reaction, providing a realistic basis for explaining the crystal plane catalysis effect of the 4 Å zeolite. This new zeolite prepared under the synergistic effect of intense ultrasound and a high-voltage electrostatic field, being the first time to prepare the octahedral hierarchical LTA zeolite, is simple to produce, green, and environmentally friendly and has good economic development prospects compared to the use of templating agents, which not only provides ideas and simpler methods for optimizing the performance of traditional zeolites and developing new zeolites with better performance but also enhances the theoretical basis for preparing new zeolites.

Uniform nanorhombic α-Fe2O3 on g-C3N4 nanosheet: 2D/2D lattice matched S-scheme heterojunction towards efficient styrene oxidation and H2 evolution

The design and modification of heterojunction photocatalysts to enhance efficient interfacial charge transfer and superior photocatalytic performance are fundamental objectives in the field of solar-light-driven energy conversion and production. This study presents a novel S-scheme heterojunction which features lattice-matched morphological hetero-nanostructures, composing of two-dimensional (2D) graphitic carbon nitride (CN) loaded with uniformly distributed and size-consistent 2D nano-rhombohedral α-Fe2O3 (Fe2O3 NR/CN). The directional charge transfer in the lattice-matched S-scheme heterojunction was confirmed using a combination of in situ irradiated X-ray photoelectron spectroscopy, metal deposition experiments, electron paramagnetic resonance, and density functional theory calculations. The optimized heterojunction demonstrates exceptional photocatalytic activity, achieving a hydrogen generation rate that surpasses those of g-C3N4 and α-Fe2O3 alone by factors of 2.1 and 7, respectively. Additionally, this heterojunction exhibits an excellent styrene conversion rate of 94.1 % and a styrene epoxidation selectivity of 95.3 % under light irradiation at 80 °C using tert-butyl hydroperoxide (TBHP) as the oxidant. The incorporation of uniformly distributed nano-rhombohedral α-Fe2O3 particles with g-C3N4 successfully constructs an unobstructed interfacial pathway to form the lattice-matched S-scheme heterojunction, enabling efficient separation of photogenerated carriers. This unique structure provides a valuable reference for dual-functional photocatalytic reactions.

Stereocomplementary Unspecific Peroxygenases for Asymmetric Anti-Markovnikov Wacker-Type Oxidation and Epoxidation of Styrenes

Stereocomplementary Unspecific Peroxygenases for Asymmetric Anti-Markovnikov Wacker-Type Oxidation and Epoxidation of Styrenes

Titanium metal-organic frameworks for photocatalytic CO2 conversion through a cycloaddition reaction.

The elevated levels of CO2 in the atmosphere have been a major concern for environmental scientists. Capturing CO2 gas and its subsequent conversion to useful organic compounds is one of the avenues that have been extensively studied in the last decade. The photocatalytic cycloaddition of CO2 is a promising approach for effective CO2 capture and the production of value-added chemicals such as cyclic carbonates. MOF-901, a titanium-based metal-organic framework with hexagonal layers and imine linkages, was successfully oxidized in this study to MOF-997, incorporating amide linkages using Oxone. Both MOFs displayed remarkable photocatalytic activity in CO2 cycloaddition under mild conditions, including moderate temperatures and visible light exposure. Particularly noteworthy is MOF-997, exhibiting superior performance with donor-acceptor active sites, achieving a 99.9% yield in catalyzing CO2 conversion from styrene epoxide to styrene carbonate under solvent conditions.

Highly efficient aerobic epoxidation of styrene using mesoporous Co-Ni catalysts

This work reports the synthesis and characterization of mesoporous cobalt-nickel mixed metal oxide catalysts with varying Co:Ni ratios using an inverse micelle template self-assembly method. Their structural and morphological properties and catalytic performance in styrene epoxidation were evaluated. Among them, the 73CoNi-250 catalyst (Co: Ni70:30 mol/mol%, calcined 250°C) exhibited a unique flower-like morphology and the highest surface area, which XPS analysis linked to a higher concentration of oxygen vacancies. Notably,73CoNi-250 demonstrated exceptional catalytic activity for styrene epoxidation, achieving near-complete styrene conversion (>99 %) and high selectivity (94 %) for styrene epoxide under mild reaction conditions without the need for oxidants such as peroxides. Furthermore, the catalyst exhibited excellent reusability (≥ 4 cycles) without significant activity loss or changes in mesoporosity. Kinetic studies revealed a first-order reaction profile and a significantly enhanced rate constant compared to the best-reported values (fivefold) in the literature, further underlining the catalyst's efficiency, and emphasizing the environmentally friendly approaches in chemical synthesis.

New mixed ligand oxido-vanadium(V) complexes with O,O-donor and diimine ligands: Synthesis, crystal structure and catalytic activity in eco-friendly oxidation of olefins and phenol

The facile synthesis and structural characterization of a set of three new oxidovanadium(V) complexes of general formula [VO2(L)(diimine)], where L is ethyl-maltol(emal) (1), deferiprone(def) (2) or, maltol(mal) (3), and diimine is 5,6-dimethyl-1,10-phenanthroline(5,6-DMP) are described. The neutral complexes 1–3 have been comprehensively characterized by employing various analytical and spectroscopic techniques including single crystal X-ray diffraction analysis. The coordination geometry around the V(V) in each of the complexes was indicated by XRD-analysis to be distorted octahedral with equatorial plane being occupied by the deprotonated O,O-donor ligands. The complexes 1–3 could be successfully implemented in organic oxidations viz., hydroxylation of phenol (PH) and olefin epoxidation under environmentally clean organic-solvent-free conditions with aqueous H2O2 as oxidant. Phenol was selectively converted into dihydroxybenzene (DHB) products, catechol (CT) and hydroquinone (HQ) (HQ/CT=1.3:1) with aqueous H2O2 as oxidant at room temperature, with a TON value of 266. Moreover, the catalysts showed impressive activity in epoxidation of styrene and a range of cyclic olefins such as cyclohexene, cyclooctene, and norbornene in absence of organic solvent, to provide high conversion (up to 100 %) with excellent epoxide selectivity and good TON values. The catalysts are stable and afford recyclability for multiple cycles of epoxidation with virtually unaltered catalytic activity.

Facile synthesis of nanoscale CuO and NiO via the PVA-assisted sol-gel method and their exploration in the catalytic epoxidation of styrene

The full-text of the article will be published in the English version of the journal "Catalysis in Industry" No. 4, 2024.Both nanoscale copper oxide and nickel oxides, with diameter 17 and 25 nm respectively, have been synthesized via an easy sol-gel method using polyvinyl alcohol. The method involves the simple dispersion of metal ions (M2+ = Cu or Ni) into the PVA gel and subsequent calcination of the dried gel at 400 °C for 3 h. The synthesized oxide materials are characterized by different physical tools like TGA, powder XRD, SEM, TEM and DRS UV-visible spectroscopic technique. The oxides are found to be very efficient catalysts in the epoxidation of styrene. CuO gives 87 % styrene conversion and 88 % SO selectivity while, NiO gives 69 % styrene conversion and 80 % with TBHP as an oxidant at the end of 6 h. Both the catalysts can suitably be reused for several successive runs without appreciable loss in activity and selectivity. The cost-effective synthesis, excellent catalytic performance and reusability make these oxides promising catalysts for the industrial use.

Synthesis, Crystal Structures and Catalytic Oxidation Property of Two Oxidovanadium(V) Complexes with Schiff bases.

Two new oxidovanadium(V) complexes, [VO2L1] (1) and [V2O2(μ-O)2L2)] (2), where L1 and L2 are the deprotonated form of 5-bromo-2-(((2-(pyrrolidin-1-yl)ethyl)imino)methyl)phenol (HL1) and 5-bromo-2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol (HL2), respectively, have been synthesized and structurally characterized by physico-chemical methods and single crystal X-ray determination. X-ray analysis indicates that the V atom in complex 1 is in square pyramidal coordination, and those in complex 2 are in octahedral coordination. Crystal structures of the complexes are stabilized by hydrogen bonds. The catalytic property for epoxidation of styrene by the complexes was evaluated.

Oxidovanadium(V) Schiff Base Complexes Derived from Chiral 3-amino-1,2-propanediol Enantiomers: Synthesis, Spectroscopic Studies, Catalytic and Biological Activity.

Oxidovanadium(V) complexes, [(+)VOL1-5] and [(-)VOL1-5], with chiral tetradentate Schiff bases, which are products of monocondensation of S(‒)-3-amino-1,2-propanediol or R(+)-3-amino-1,2-propanediol with salicylaldehyde derivatives, have been synthesized. Different spectroscopic methods, viz. 1H and 51V NMR, IR, UV-Vis, and circular dichroism, as well as elemental analysis, have been used for their detailed characterization. Furthermore, the epoxidation of styrene, cyclohexene, and two monoterpenes, S(‒)-limonene and (‒)-α-pinene, using two oxidants, aqueous 30% H2O2 or tert-butyl hydroperoxide (TBHP) in decane, has been studied with catalytic amounts of all complexes. Finally, biological cytotoxicity studies have also been performed with these oxidovanadium(V) compounds for comparison with cis-dioxidomolybdenum(VI) Schiff base complexes with the same chiral ligands, as well as to determine the cytoprotection against the oxidative damage caused by 30% H2O2 in the HT-22 hippocampal neuronal cells in the range of their 10-100 μM concentration.

Styrene epoxide: Unusual allergen in clinical practice.

Styrene epoxide: Unusual allergen in clinical practice.

Ultrathin 2D Porphyrin‐Based Zr‐MOF Nanosheets as Heterogeneous Catalysts for Styrene Epoxidation and Benzylic C‐H Oxidation

AbstractSelective oxidation of hydrocarbons using molecular oxygen as sole oxidant under mild conditions remains a challenging task. In this context, metal‐organic frameworks (MOFs) have been widely used in various oxidation reactions due to their porosity, high surface area and designability. However, the slow diffusion of substrates/products in micropores of three‐dimensional (3D) bulk MOFs hinders the efficient catalytic performance of such materials. Herein an ultrathin two‐dimensional (2D) porphyrin‐based Zr‐MOF nanosheet (Zr‐TCPP) is synthesized through modulator‐control strategy. Subsequently, various metal ions are anchored into the porphyrin ring by post synthesis modification to afford a series of 2D Zr‐TCPP(M) (M=Mn, Fe, Co, Ni, Cu and Zn). Various structural characterization techniques indicate Zr‐TCPP(M) is nanoflower structure with ultrathin nanoplate petals which provides fully exposed accessible active sites. Among them, Zr‐TCPP(Fe) shows excellent catalytic performance in styrene epoxidation reactions and benzylic C−H oxidation reactions using O2 as sole oxidant under ambient temperature and pressure. The remarkable activity arises from high density of exposed porphyrin‐Fe active sites, low diffusion barriers for substrates and products, as well as a similar homogeneous reaction space. Furthermore, Zr‐TCPP(Fe) nanosheet is easily recycled by centrifugation and reused at least five times without significant loss of catalytic activity.

New Cu(II) Schiff-base complex modified on magnetic nanoparticles: Oxidation and DFT investigation

A copper magnetic nanocatalyst was facilely synthesized by surface modification of silica magnetic nanoparticles (Fe3O4@SiO2) via reaction with 3-aminopropyltrimethoxysilane (Fe3O4@SiO2@APTMS), followed by a subsequent reaction with thiophene-2-carbaldehyde to form a Schiff base (Fe3O4@SiO2@SB). Sequentially, reaction with Cu(CH3COO)2·H2O in ethanol yielded Fe3O4@SiO2@[SB@Cu] (CH3COO)2. This nanomagnetic catalyst was comprehensively characterized using Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Thermogravimetric Analysis (TGA), and Vibrating Sample Magnetometry (VSM) techniques. The catalytic proficiency of these nanoparticles was evaluated through alkene and alcohol oxidation reactions. Under optimized conditions, the nanocatalyst exhibited significant efficacy in oxidizing styrene, cyclohexene, and benzyl alcohol, with notable selectivity values of 88 %, 100 %, and 100 % for the respective formation of styrene epoxide, 2-cyclohexene-1-one, and benzoic acid. The heterogeneous copper nanocatalyst offers advantages, including high conversion rates, facile separation, and exceptional selectivity in alkene and alcohol oxidation. Additionally, this study investigated density functional theory (DFT) methods, encompassing geometric optimization, natural charge analysis, molecular electrostatic potential maps, and vibrational normal modes of the chelating ligands.

Cobalt Supported on Ce-MOF-Derived CeO2 as a Catalyst for the Efficient Epoxidation of Styrene Under Aerobic Conditions

Cobalt Supported on Ce-MOF-Derived CeO2 as a Catalyst for the Efficient Epoxidation of Styrene Under Aerobic Conditions

Oxidovanadium(V) complexes with chiral tetradentate Schiff bases: Synthesis, spectroscopic characterization, catalytic and biological activity

New mononuclear oxidovanadium(V) complexes, [(−)VOL1–10] and [(+)VOL1–4], with chiral tetradentate Schiff bases have been obtained by monocondensation of salicylaldehyde derivatives and optically active amino alcohols, i.e. 1R,2R-(−)-2-amino-1-phenyl-1,3-propanediol or 1S,2S-(+)-2-amino-1-phenyl-1,3-propanediol. All complexes have been characterized by elemental analysis, circular dichroism, UV–vis, IR, 1D (1H, 51V) and 2D (COSY, NOESY) NMR spectroscopy. The catalytic activity studies have also been performed for all complexes in the epoxidation of styrene, cyclohexene and two monoterpenes, i.e. S(−)-limonene and (−)-α-pinene, using aqueous 30 % H2O2 or tert-butyl hydroperoxide (TBHP) as the terminal oxidant. In addition, biological properties of these chiral oxidovanadium(V) compounds, as well as cis-dioxidomolybdenum(VI) complexes with the same chiral Schiff bases, were studied in relation to their cytoprotective activity against the oxidative damage generated exogenously by 30 % hydrogen peroxide in the HT-22 hippocampal neuronal cells. The latter compounds have revealed distinct cytoprotective properties causing the highest increase in the viability of HT-22 cells. Concentration dependent effect in the range of 10-100 μM concentration of the investigated compounds has also been observed.

Fus-SMO: Kinetics, Biochemical Characterisation and In Silico Modelling of a Chimeric Styrene Monooxygenase Demonstrating Quantitative Coupling Efficiency.

The styrene monooxygenase, a two-component enzymatic system for styrene epoxidation, was characterised through the study of Fus-SMO - a chimera resulting from the fusion of StyA and StyB using a flexible linker. Notably, it remains debated whether the transfer of FADH2 from StyB to StyA occurs through diffusion, channeling, or a combination of both. Fus-SMO was identified as a trimer with one bound FAD molecule. In silico modelling revealed a well-distanced arrangement (45-50 Å) facilitated by the flexible linker's loopy structure. Pre-steady-state kinetics elucidated the FADox reduction intricacies (kred=110 s-1 for bound FADox), identifying free FADox binding as the rate-determining step. The aerobic oxidation of FADH2 (kox=90 s-1) and subsequent decomposition to FADox and H2O2 demonstrated StyA's protective effect on the bound hydroperoxoflavin (kdec=0.2 s-1) compared to free cofactor (kdec=1.8 s-1). At varied styrene concentrations, kox for FADH2 ranged from 80 to 120 s-1. Studies on NADH consumption vs. styrene epoxidation revealed Fus-SMO's ability to achieve quantitative coupling efficiency in solution, surpassing natural two-component SMOs. The results suggest that Fus-SMO exhibits enhanced FADH2 channelling between subunits. This work contributes to comprehending FADH2 transfer mechanisms in SMO and illustrates how protein fusion can elevate catalytic efficiency for biocatalytic applications.

Synthesis, Structural Characterization, Reactivity and Bioactivity Studies of Some Binuclear Salen Type Schiff Base Complexes of Manganese(III)

Four new phenoxy bridged binuclear Salen type Schiff base complexes of manganese(III), [MnLX]2 with tetradentate Schiff base, H2L [H2L = N,N′-O-phenylene bis(salicylaldimine)] containing anionic co-ligands, X (X = benzoate, p-hydroxy benzoate, p-aminobenzoate, 3,5-dinitrobenzoate) have been synthesized from manganese(II) acetate, Schiff base (H2L) and the corresponding co-ligands in methanol medium. Schiff base ligand (H2L) was obtained in situ by condensation of salicylaldehyde and o-phenylenediamine in aqueous methanol. Elemental analyses, FT-IR, molar conductance, UV-visible spectroscopic studies and magnetic moment measurements at room temperature were used to characterize the binuclear Schiff base complexes. The IR spectra of [MnLX]2 (X = benzoate, p-hydroxy benzoate, p-aminobenzoate, 3,5-dinitrobenzoate) complexes showed the characteristic absorptions due to coordinated azomethine nitrogen and phenolic oxygen atoms of the Schiff base. In addition, IR spectra of the compounds also suggest coordination of the co-ligands namely benzoate, p-hydroxy benzoate, p-aminobenzoate, 3,5-dinitrobenzoate in the respective complexes. A consistent presence of a band at ca. 755 cm-1 in all the binuclear complexes arises due to (Mn-O-Mn) moiety originated from interactions of phenoxy oxygen and manganese atoms, resulted in dimeric structure of the compounds. The magnetic moment values ranging from 4.74-4.91 B.M. per manganese centre for the complexes suggest presence of Mn(III) ion in the complexes. The overall coordination geometry around the manganese centres is distorted octahedral. Redox behaviour of the synthesized complexes was ascertained from cyclic voltametric studies. The Schiff base complexes, [Mn(L)X]2 (X = p-aminobenzoate, 3,5-dinitrobenzoate) have demonstrated their catalytic potentials in oxidizing selective organic substrates namely cyclohexene and styrene by hydrogen peroxide as oxidant. The oxidized products were characterized as trans-cyclohexane 1,2-diol and styrene epoxide, respectively. Complex 4 demonstrated a considerable level of effectiveness against a wide variety of pathogenic microorganisms.

Emerging Strategies for Modifying Cytochrome P450 Monooxygenases into Peroxizymes.

ConspectusCytochrome P450 monooxygenase is a versatile oxidizing enzyme with great potential in synthetic chemistry and biology. However, the dependence of its catalytic function on the nicotinamide cofactor NAD(P)H and redox partner proteins limits the practical catalytic application of P450 in vitro. An alternative to expensive cofactors is low-cost H2O2, which can be used directly to exploit the catalytic potential of P450s. However, the peroxide shunt pathway is generally inefficient at driving P450 catalysis compared to normal NAD(P)H-dependent activity. Over the last few decades, the scientific community has made continuous efforts to use directed evolution or site-directed mutagenesis to modify P450 monooxygenases into their peroxizyme modes─peroxygenase and peroxidase. Despite significant progress, obtaining efficient P450 peroxizymes remains a huge challenge. Here, we summarize our efforts to modulate peroxizyme activity in P450 monooxygenases and exploit their catalytic applications in challenging selective C-H oxidation, oxygenation, and oxyfunctionalization over the past seven years. We first developed a dual-functional small molecule (DFSM) strategy for transforming P450BM3 monooxygenase into peroxygenase. In this strategy, the typical DFSM, such as N-(ω-imidazolyl)-hexanoyl-l-phenylalanine (Im-C6-Phe), binds to the P450BM3 protein with an anchoring group at one end and plays a general acid-base catalytic role in the activation of H2O2 with an imidazolyl group at the other end. Compared with the O-O homolysis mechanism in the absence of DFSM, the addition of DFSM efficiently enables the heterolytic O-O cleavage of the adduct Fe-O-OH, thus being favored for the formation of active species compound I, which has been demonstrated by combining crystallographic and theoretical calculations. Furthermore, protein engineering showed the unique catalytic performance of DFSM-facilitated P450 peroxygenase for the highly difficult selective oxidation of C-H bonds. This catalytic performance was demonstrated during the chemoselective hydroxylation of gaseous alkanes, regioselective O-demethylation of aryl ethers, highly (R)-enantioselective epoxidation of styrene, and regio- and enantiomerically diverse hydroxylation of alkylbenzenes. Second, we demonstrated that DFSM-facilitated P450BM3 peroxygenase could be effectively switched to an efficient peroxidase mode through mechanism-guided protein engineering of redox-sensitive residues. Utilizing the peroxidase function of P450 enabled the direct nitration of unsaturated hydrocarbons including phenols, aromatic amines, and styrene derivatives, which was not only the P450-catalyzed direct nitration of phenols and aromatic amines for the first time but also the first example of the direct biological nitration of olefins. Finally, we report an H2O2 tunnel engineering strategy to enable peroxygenase activity in several different P450 monooxygenases for the first time, providing a general approach for accessing engineered P450 peroxygenases. In this Account, we highlight the emerging strategies we have developed for producing practical P450 peroxizyme biocatalysts. Although the DFSM strategy is primarily applied to P450BM3 to date, both strategies of redox-sensitive residue engineering and H2O2 tunnel engineering show great potential to extend to other P450s. These strategies have expanded the scope of applications of P450 chemistry and catalysis. Additionally, they provide a unique solution to the challenging selective oxidation of inert C-H bonds in synthetic chemistry.