Catalytic Activity For Oxidation Research Articles

Co single atoms/nanoparticles over carbon nanotubes for synergistic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

The preparation of high-value 2,5-furandicarboxylic acid (FDCA) from biomass-based platform compound 5-hydroxymethylfurfural (HMF) is an important synthetic reaction, as the resulting FDCA holds promise to replace terephthalic acid to produce environmentally friendly polyester materials. However, due to the complex tandem nature of the oxidation of HMF to FDCA, which involves several stable intermediates, efficient conversion of HMF and achieving a high FDCA yield remain challenging. Herein, a catalyst of Co SAs/NPs@N-CNTs comprising Co single atoms (Co SAs) alongside Co nanoparticles (Co NPs) supported on carbon nanotubes (CNTs) was synthesized. Co SAs/NPs@N-CNTs exhibited outstanding catalytic activity for the selective oxidation of HMF to FDCA, achieving 100% HMF conversion and 94.2% FDCA yield. This remarkable performance was attributed to the synergistic effect between Co SAs and Co NPs. Poisoning and acid treatment experiments indicated that Co SAs served as the active sites, while Co NPs did not directly act as active sites. Instead, Co NPs merely assisted the Co SAs on the sidelines, facilitating the efficient conversion of HMF into various intermediates and promoting the further conversion of these intermediates into FDCA, thereby achieving high FDCA productivity. This strategy offers new insights for designing efficient catalysts for complex tandem reactions.

Revealing the essence of anion ligands in regulating amorphous MnOx to activate peracetic acid for micropollutant removal

How the anion ligands of manganese precursors affect the catalytic activity of amorphous manganese oxides (MnOx) in Fenton-like process is poorly understood. Here, five amorphous MnOx synthesized by Mn(II) precursors with different ligands were characterized and adopted to activate peracetic acid (PAA) for bisphenol A (BPA) degradation. Although > 90 % BPA removal was achieved in the five MnOx/PAA processes via both adsorption and oxidation, the oxidation kobs greatly differentiates by the ligands types with the order of MnOx-N > MnOx-S > MnOx-Cl > MnOx-AA > MnOx-OA. Ligands types would affect the specific surface area of MnOx and their ability to adsorb BPA, however which is not the decisive factor in determining the contaminant oxidation efficiency. Multiple experimental results indicate that the generation of oxygen vacancies induced by the ligands alters the Mn(III)/Mn(IV) ratio, ultimately contributing to the different efficiency of BPA oxidation driven by the direct electron transfer mechanism. Moreover, amorphous MnOx holds the promise of practical applications in catalytic PAA of various micropollutants with good stability. This study advances the fundamental understanding of ligand-regulated amorphous MnOx-catalyzed PAA process.

Simultaneous Catalytic Oxidation of Benzene and Toluene over Pd-CeZrOx Catalysts

Since actual industrial emissions contain a wide range of volatile organic compounds, studies into the simultaneous catalytic degradation of multi-component VOCs are essential. This work developed Pd-CeZrOx samples for the simultaneous elimination of benzene and toluene. Firstly, CeZrOx supports were synthesized using several methods (co-precipitation, CTAB template co-precipitation, and sol–gel method). Pd active species were then added into the 1.0Pd-CeZrOx samples using the impregnation procedure. XRD, BET, NH3-TPD, Raman, EPR, XPS, and H2-TPR were utilized to analyze the as-prepared Pd-CeZrOx samples. The catalytic performance tests reveal that the performance of 1.0Pd-CeZrOx-CTAB outperforms that of 1.0Pd-CeZrOx-PM and 1.0Pd-CeZrOx-CASG, and 1.0Pd-CeZrOx-CTAB displays superior catalytic activity for both benzene and toluene oxidation. The improved redox properties, the abundant surface oxygen vacancies, and the surface Pd2+ species of the 1.0Pd-CeZrOx-CTAB sample may be responsible for the simultaneous degradation activity of benzene and toluene.

Selective Oxidation of p-Cymene over Mesoporous LaCoO3 by Introducing Oxygen Vacancies.

The liquid-phase catalytic oxidation of p-cymene to 4-methylacetophenone is an industrially significant reaction. However, the targeted oxidation of a specific C-H bond of p-cymene is extremely difficult due to there being many branched chains in p-cymene. In here, we designed a simple method to synthesize mesoporous LaCoO3 catalysts with rich oxygen vacancy (Oov) sites. The as-prepared mesoporous LaCoO3 after 550 °C calcination (mLaCoO3) exhibits remarkable catalytic activity for solvent-free oxidation of the p-cymene reaction, with a selectivity of over 80.1% selectivity for 4-methylacetophenone and a conversion of 50.2% for p-cymene (120 °C, 3 MPa). Besides, recycling studies have demonstrated that the mLaCoO3 catalysts can be reused ten times in the aerobic oxidation of the p-cymene reaction without significant catalytic activity reduce. The experimental and characterization results indicated that the mesoporous structure of the catalyst is conducive to the generation of surface Oov, which can properly facilitate ion spread during the catalytic process and afford enough O2 for intermediate species, thus is beneficial for the generation of 4-methylacetophenone. This work demonstrates that the selectivity oxide p-cymene with an O2 employing mLaCoO3 catalyst is highly promising for chemical industrial applications.

Machine Learning Accelerated Discovery of Entropy-Stabilized Oxide Catalysts for Catalytic Oxidation.

The catalytic properties of unary to ternary metal oxides were already well experimentally explored, and the left space seems like only high entropy metal oxides (HEOs, element types ≥5). However, the countless element compositions make the trial-and-error method of discovering HEO catalysts impossible. Herein, based on the study of the crystal phase and catalytic performance of the ACr2Ox catalyst system, the strong correlation between the single spinel phase and good catalytic activity of CH4 oxidation was inferred owing to the similar element importance sequences, which were acquired by the corresponding high accuracy machine learning models (cross-validation score >0.7). Furthermore, searching for negative data and choosing the proper training data resulted in high-quality regression models to search for better catalysts. Finally, the screened irregular catalyst Ni0.04Co0.48Zn0.36V0.12Cr2Ox with outstanding sulfur and moisture resistance and long-term stability (>7000 h, T90 = 345 °C) envisions the potential of applying the machine learning method to discover HEOs for target processes.

Regulating oxygen vacancies to optimize the electronic structure and catalytic activity of tungsten oxides for hydrogen evolution reaction

The undesirable intrinsic activity of tungsten oxides derived from poor conductivity and adverse hydrogen absorption energy is insufficient for their practical application. Herein, the tungsten oxides with adjustable oxygen vacancies were synthesized by a facile pyrolysis of ammonium paratungstate hydrate in controllable atmospheres. The structural characterizations confirmed that oxygen vacancies and crystalline phases in tungsten oxides depend on the pyrolysis atmosphere. The electrochemical test indicated a strong dependence between catalytic activity and oxygen vacancies in tungsten oxides. Combining experimental results and density functional theory calculations verified that introducing oxygen vacancies into tungsten oxides effectively modulates the surface electronic structure. The enhanced electronic conductivity by reducing band gap accelerates the electron transfer from catalysts into the reactive species. The optimized hydrogen adsorption energy by electron migration from O into W promotes the activation of reactive species at W sites and the desorption from O sites, thereby accelerating the reaction kinetics.

Tuning the Active Oxygen Species of Two-Dimensional Borophene Oxide toward Advanced Metal-Free Catalysis.

Two-dimensional (2D) borophene materials are predicted to be ideal catalytic materials due to their structural analogy to graphene. However, the lack of chemical functionalization of borophene hinders its practical application in catalysis. Herein, we reported a massive production of freestanding few-layer 2D borophene oxide (BO) sheets with tunable active oxygen species by a moderate oxidation-assisted exfoliation method. State-of-the-art characterizations demonstrated the evolution of active oxygen species from surface B-O species at the initial stage to the intermediate BxOy (1.5 < x/y < 3) species and eventually to bulk B2O3 with an increasing oxidation duration. As a result, the 2D BO sheet with enhanced B-O species exhibited a strikingly high catalytic activity for the aerobic oxidation of benzylamine into N-benzylidenebenzylamine. The formation rate of imine reaches as high as 29.7 mmol gcatal-1 h-1 under mild reaction conditions, higher than that of pristine borophene, boron oxides, graphene oxide, and other metal/metal-free catalysts in the reported literature. Density functional theory calculations further revealed the critical role of surface B-O species, which favor the adsorption and N-H activation of benzylamine for high activity and suppress the deep dehydrogenation, yielding an outstanding imine selectivity (>90%). This work paves the route for a moderate and scalable synthesis of few-layer BO sheets with highly active B-O species toward advanced metal-free catalysis beyond graphene.

A combination of covalent and noncovalent restricted‐intramolecular‐rotation strategy for supramolecular AIE‐type photosensitizer toward photodynamic therapy

AbstractPhotodynamic therapy (PDT) is a promising noninvasive method for targeted cancer cell destruction. Still, its effectiveness is often hindered by the aggregation‐caused quenching effect of organic photosensitizer (PS) in aqueous environments. Here, we have employed a combination of covalent and noncovalent restricted‐intramolecular‐rotation strategies to develop supramolecular PSs with aggregation‐induced emission (AIE) characteristics. Firstly, a water‐soluble octacationic molecular cage (1) with a bilayer tetraphenylethene (TPE) structure has been designed and synthesized, which minimizes intramolecular rotation of TPE moieties and achieves the single‐molecule‐level aggregation by the covalent restriction of intramolecular rotation (RIR) via molecular engineering synthesis. Compared with its single‐layer TPE analog, 1 exhibits superior efficiency in generating reactive oxygen species (ROS) including superoxide radical (O2−•) and singlet oxygen (1O2) upon white‐light irradiation. Subsequently, by forming a 1:4 host–guest complex (1@CB[8]4) between 1 and cucurbit[8]uril (CB[8]), O2−• generation can be further enhanced by the noncovalent RIR via the host–guest assembly. Additionally, 1@CB[8]4 as a photocatalyst promotes rapid oxidation of nicotinamide adenine dinucleotide (NADH) in water. Given its Type‐I ROS generation and catalytic activity for NADH oxidation, 1@CB[8]4 acts as a supramolecular AIE‐type PS to exhibit strong photo‐induced cytotoxicity upon white‐light irradiation under hypoxic conditions, showcasing its potential for synergistic PDT.

Ceria-zirconia solid solution supported platinum catalysts for toluene oxidation: Studying the improved catalytic activity by tungsten addition

The catalytic oxidation of toluene at low temperatures is still an urgent issue to be solved. The key to addressing this issue is the preparation of a high-efficiency catalyst. Herein, ceria-zirconia (CZ) solid solution supported platinum (Pt) catalysts were prepared by citric acid (C)-assisted impregnation method. Surprisingly, the catalytic oxidation activity of the catalyst for toluene combustion significantly improved after introducing W into Pt-C/CZ. In addition, introducing W improved the redox property of the Pt-based catalyst, optimized the distribution of the oxygen vacancies, increased the average particle size of the catalyst particle, modulated the valence state and electronic structure of Pt, elevated the surface lattice oxygen activity, increased the number of surface moderate acidic sites and enhanced toluene adsorption capacity. In this study, the electronic structure of the Pt active site is modulated by introducing a W promoter, providing valuable guidance for the rational design of efficient noble metal catalysts.

Enhanced low-temperature methane oxidation over Pd supported Mn-doped NiO catalyst

This study introduces a novel catalyst system comprising Pd nanoparticles loaded onto Mn-doped NiO for the efficient oxidation of methane (CH4) at low temperatures. The loading of Pd nanoparticles onto the Mn-doped support has yielded a catalyst with exceptional activity and stability, as evidenced by the lowest T50 temperature of 276 °C and a CH4 conversion reaching 97% at 325 °C. The catalyst demonstrates optimized reaction kinetics with the lowest activation energy of 69.2 kJ mol–1. The catalyst's superior performance is attributed to the synergistic effects of the Pd/Mn-NiO composite, which include a higher Pd2+/Pd4+ ratio, increased adsorptive oxygen concentration (Oads/Ototal), and a reduced Ni3+/Ni2+ ratio. These characteristics collectively enhance the catalytic activity for CH4 oxidation. The Mars-van Krevelen mechanism underpins the oxidation process, with Pd2+ identified as the principal active site for CH4 adsorption and dissociation. Diffuse reflectance infrared Fourier transform spectroscopy coupled with mass spectrometry elucidates the pathway of surface reactive oxygen species in the formation of key intermediates, such as formates, and underscores the accelerated decomposition of carbonate facilitated by the Pd modification on the Mn-NiO surface. The findings signify a significant advancement in the development of catalysts for environmental and energy-related applications, particularly in the mitigation of CH4 emissions.

Deciphering the structural origin for the remarkable CO oxidation activities of the CuO-based catalysts with diverse morphological CeO2 supports

In this work, octahedral, cubic, particle-like, spherical and rod-shaped nano-CeO2 supports were synthesized by hydrothermal method. CuO/CeO2 catalysts were then prepared via an ultrasonic-assisted impregnation method, employing these differently shaped CeO2 supports. The resulting catalysts were tested for their performance in CO oxidation. The findings revealed that the CuO active sites significantly influenced the oxygen storage and release capacity of CeO2, thereby improving its catalytic activity for low-temperature CO oxidation. The key factors affecting the CO oxidation performance of CuO/CeO2 catalysts with different CeO2 morphologies were investigated through various characterizations. It was found that the specific surface area was not the primary factor in determining catalytic activity. Instead, the exposed crystal planes played a crucial role. By adjusting the crystal plane exposure of CeO2, the supported 1CuO/CeO2 catalysts exhibited different crystal surface configurations. Notably, the 1CuO/CeO2-S catalyst, with exposed (100) and (110) crystal planes, and the 1CuO/CeO2-P catalyst, with exposed (111), (100), and (110) planes, exhibited higher surface defect concentrations. This increased defect concentration facilitated the formation of Cu+ species, enhancing the redox properties and further improving the overall catalytic performance of CO oxidation.

Nano-MnOx prepared by redox method for toluene oxidation removal from air

Catalytic oxidation is an efficient VOCs removal technology with great potential and development advantages. The key to the oxidative elimination of VOCs lies in the development and application of the catalyst with high efficiency. In this work, the nano-MnOx catalysts were prepared by redox method and the catalytic oxidation performance of toluene was studied. The calcination temperature could effectively change the surface chemical composition and the nano-MnOx catalyst structures, which could effectively regulate the number of active centers on the catalyst surface to improve the adsorption, activation, and oxidation ability of the nano-MnOx catalysts for toluene molecules. The nano-MnOx catalyst dominated by the MnO2 phase, which was prepared at the calcination temperature of 400 °C, had a high specific surface area, developed porosity, abundant reactive oxygen species, and oxygen vacancies. The structural characteristics are conducive to the adsorption, activation, and oxidation of toluene molecules, and thus exhibited excellent toluene catalytic oxidation activity. At the reaction temperature of 140 °C, the toluene oxidation conversion was as high as 99.4 %, and the toluene conversion remained above 96.6 % after experiencing a 690 min stability test.

Enhancing catalytic oxidation of benzene with Cu-Doped MnO2: Insights into structural defects and electronic modifications

The present research focuses on the role of copper (Cu) doping in enhancing the catalytic efficacy of manganese dioxide (α-MnO2) for benzene oxidation, a representative volatile organic compound (VOC). Despite the abundance and low cost of MnO2, its pristine form requires improvement for industrial VOC oxidation processes. Utilizing a range of characterization methods, the study reveals that Cu doping generates oxygen vacancies and increases the Mn3+ content within the catalyst structure, which are crucial for enhancing the adsorption and activation of reactants. The findings indicate that Cu-doped α-MnO2 exhibits superior catalytic activity and lower activation energy for benzene oxidation compared to the undoped counterpart. The electronic interactions induced by the doping of Cu and the effect on the catalytic process are demonstrated and discussed in depth. This work emphasizes the strategic importance of dopant optimization and contributes to the advancement of MnO2-based catalysts for environmental remediation, aligning with goals of environmental protection and human health safety.

Heteronuclear coordination polymers with imidazole ligand: Synthesis, characterization and alcohol oxidation activities

Two new heteronuclear Cd(II)/Pd(II) coordination polymers, [Cd2(µ-im)2(Him)4Pd(µ-CN)4]n (1) and [Cd(Him)2Pd(µ-CN)4]n (2) (Him: imidazole), have been synthesized under different conditions and characterized using elemental analysis, thermal analysis, FT-IR and Raman spectroscopy, single-crystal and powder X-ray diffraction techniques.. In 1, the Cd(II) ions are bridged by imidazolate ligands to generate 1D chain structure. Neighbouring 1D chains were linked by [Pd(CN)4]2- ions to form 3D framework. In 2, the metal ions are bridged by cyanide ligands to generate 2D [Cd2Pd2(µ-CN)4]n network. Furthermore, catalytic peroxidative oxidation activity of catalysts 1 and 2 was examined on the oxidation of benzyl alcohol using tertiary-butyl hydroperoxide (t-BuOOH) as the oxygen source. The compound 1 exhibited over 90 % product conversion at 80 °C in 24-hour reaction time. In addition, the catalyst exhibited high selectivity towards benzaldehyde and no over-oxidation product (benzoic acid) was detected.

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.

Insight into the nonradical selective oxidation mechanism for versatile organic pollutants removal by perovskite activated peroxymonosulfate system

The heterogeneous catalysis of peroxymonosulfate (PMS) through nonradical pathway has shown many advantages in environmental remediation. It is necessary to unveil the factors affecting oxidation routes and selectivity toward different organic pollutants. Herein, a series of ABO3-type BiFexCo1-xO3 perovskite catalysts were fabricated via simple hydrothermal process to realize the changeover of catalytic activity and mechanism in PMS activation and pollutants oxidation. The as-prepared BiFe0.5Co0.5O3 (BFCO-3) achieved a 98 % removal efficiency of SMZ with a high kinetic constant (kobs = 0.334 min−1) in 10 min. The superior catalytic performance was ascribed to the introduction of bimetals at B-site, which enhanced electron donating capacity to PMS, confirming by d-band center calculations. Several parameters such as inorganic anions and humic acids affected the SMZ degradation slightly, owing that singlet oxygen was verified to be the primary reactive species in the BFCO-3/PMS system. Moreover, twelve organic pollutants including amoxicillin crystalline (AMX), cephalexin hydrate (CFX), ciprofloxacin (CIP), levofloxacin (LFX), Sulfadiazine (SDZ), sulfamethoxazole (SMZ), 4-acetamidophenol (ACP), benzoic acid (BA), bisphenol A (BPA), carbamazepine (CBZ), metronidazole (MNZ) and naproxen (NPX) were utilized to investigate the selective oxidation mechanism. A linear correlation between lnkobs and their half-wave potential (φ1/2) values (except for BA and MNZ) suggesting the dominant role of nonradical catalysis where phenolic compounds with lower anodic potential tend to lose electrons are more easily degraded. Furthermore, the reactive sites of representative SMZ for electrophilic species attack were precisely identified based on the Fukui index. And the degradation intermediates of SMZ were further determined by LC-MS/MS technology for proposing their degradation pathway and predicting ecotoxicity. This study not only provides an efficient advanced oxidation system for organic pollutants removal but also advances our understanding of the selective oxidation mechanism in nonradical-dominated catalytic process.

Cobalt and nitrogen co-doped hollow periodic mesoporous organosilica spheres activated by potassium chloride for selective oxidation of ethylbenzene.

Enhancing the exposure of metal active sites and maximizing metal atom utilization are critical challenges in heterogeneous catalysis. To solve these issues, heterogeneous catalysts are usually activated by chemicals. Herein, potassium chloride (KCl) was used as an activator to prepare cobalt-nitrogen co-doped (Co-Nx) hollow periodic mesoporous organosilica spheres (Co-Nx/HPMOs-KCl). Co-Nx/HPMOs-KCl showed outstanding catalytic activity for the selective oxidation of ethylbenzene to acetophenone, with a conversion of up to 94.0% for ethylbenzene and a high selectivity of 98.4% towards acetophenone. Additionally, Co-Nx/HPMOs-KCl maintained excellent catalytic performance for the oxidation of ethylbenzene after six cycles. The excellent performance of Co-Nx/HPMOs-KCl was attributed to the activation of KCl, which increased the specific surface area of the catalyst and thus facilitated the exposure of more metal active sites. After the removal of unstable metal species through further acid treatment, the remaining metal active sites were thus fully exposed and stably embedded in the framework of the hollow periodic mesoporous organosilica spheres (HMPOs). This work presents an efficient catalyst and offers new insights for the improvement of heterogeneous catalysts.

CO Oxidation at Low Temperatures over the Au Cluster Supported on Crystalline Silicotitanate.

Crystalline silicotitanate (CST) with a sitinakite structure has attracted considerable attention as an ion exchanger because of its anionic surface owing to SiO4 tetrahedral and TiO6 octahedral linked structures. In particular, the anionic surface of CST is advantageous in immobilizing single Au atoms derived from a cationic precursor such as Au(en)2Cl3 (en = ethylenediamine). In this study, a Au/CST catalyst was prepared and evaluated for CO oxidation. The transmission electron microscopy and X-ray photoelectron spectroscopy results suggest that Au single atoms and clusters (Auδ+, 0 < δ < 1) were supported on Na+-CST particles. The 1.0 wt % Au/CST catalyst yielded high catalytic activity for CO oxidation, where 50% CO oxidation was achieved at a low temperature of -13 °C. In the low-temperature region (from -84 to 20 °C), CO oxidation over Au/CST may progress through the well-known Langmuir-Hinshelwood mechanism. Conversely, the experimental results of CO oxidation without O2 confirmed that the reaction proceeded according to the Au-assisted Mars-van Krevelen mechanism using the lattice oxygens of the CST particles at temperatures above 20 °C. Therefore, this work contributes to the design of highly dispersed single-atom or cluster catalysts using the anionic surface of the microporous CST.

Cu(II) Coordination Polymers for the Selective Oxidation of Biomass-Derived Veratryl Alcohol in Green Solvents: A Sustainable Catalytic Approach.

Four air-stable one-dimensional copper(II) coordination polymers (CP1-CP4) with azide linkers were synthesized using tridentate NNS and NNN ligands. Single-crystal X-ray diffraction (XRD) analysis confirmed the molecular structures of CP1, CP3, and CP4. In the presence of TEMPO, all four coordination polymers demonstrated effective catalytic activity for the selective aerobic oxidation of veratryl alcohol, a biomass model compound, under base-free conditions. CP4 exhibited the best catalytic efficiency. Oxidations were conducted at ambient temperature (40 °C) utilizing air as a sustainable oxidant. Selective oxidation of veratryl alcohol to veratraldehyde was also conducted in the presence of a catalytic amount of base (5 mol %), and enhanced reactivity was observed. The green solvents, acetone, and water, were used to maximize sustainability. The optimized reaction conditions were applied to broaden the substrate scope of various lignin model alcohols and substituted benzylic alcohols with wide electronic variability. CP4 exhibited high recyclability, consistently providing quantitative yields even after ten consecutive runs. The catalytic protocol demonstrated sustainability and environmental compatibility, as evidenced by a low E-factor (4.29) and a high Eco-scale score (90). Based on experimental evidence and theoretical calculations, a plausible catalytic cycle was proposed. Finally, the sustainability credentials of the different optimized reaction protocols were evaluated using the CHEM21 green metrics toolkit.

Revealing the promotional effect of Zr and phosphate Co-decorated on δ-MnO2 catalysts for highly efficient catalytic elimination of chlorinated VOCs: An experimental and theoretical study

The development of advanced catalysts for catalytic oxidation of CVOCs still presents challenges in terms of low activity, chlorination poisoning and the formation of toxic byproducts. In this study, a series of nP-MnxZry catalysts with exceptional catalytic oxidation activity were developed for the removal of CVOCs in industry. Among them, 15P‐MZ exhibited the optimal catalytic activity and stability for CB degradation, achieving a T90 of 180 ℃. Notably, the CB oxidation rate of 15P‐MZ was found to be 5.76 times higher than that of MnO2 at 155 °C. Structure and properties analysis combining with DFT calculations revealed that the dual modification strategy involved Zr doping and phosphate loading induced the formation of high concentration of oxygen vacancy over 15P‐MZ, which enhanced oxygen mobility, facilitating the breakage of the aromatic ring. Meanwhile, this strategy introduced more Brønsted acid sites, promoting the dissociation of Cl in the form of HCl, thereby inhibiting the formation of polychlorinated byproducts. Moreover, the activation effect of phosphate on the dissociation of H2O further promoted the Cl dissociation, thereby regenerating more active sites and improving catalytic activity and stability in humid environment, making it more promising for industrial applications.