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Abstract Modulating unique microenvironment including both oxidation and metallic states on sub-nanocluster metal catalysts remains challenging, since designing heterogeneous catalysis within controllable oxidation state is necessary for achieving optimum performance. Here we construct stable sub-nano-Co clusters, which shows different microenvironment with the reported sub-nanocluster catalysts and reported Co-based catalysts. The coexistence of both ionic bonds of Co-O and metallic bonds of Co-Co shows features of multiple oxidation and metallic states, which changes the electronic orbital configuration of the individual Co atom in clusters. The specific microenvironment within low oxidation state and high electron density promotes combination of empty and filled host orbitals to yield high electron transfer between metal and propane, which exhibits higher reactivity than the reported Co-based and other non-noble metals catalysts. The desired reactivity offers the possibility for the exploitation of highly efficient non-noble metal catalysts for propane dehydrogenation in industrial applications.

Volatile organic compounds (VOCs) have boiling points ranging from 50 ℃ to 260 ℃ at room temperature. These compounds are emitted from complex sources, including automobile manufacturing, fine chemicals, the pharmaceutical industry, interior decoration, and the plastics industry. VOCs serve as important precursors of secondary organic aerosols and ozone. However, some VOCs discharged into the atmosphere undergo photochemical reactions, resulting in the formation of photochemical smog. This byproduct is irritating, teratogenic, and carcinogenic, causing considerable harm to human health and posing a serious threat to the environment. Among VOCs, aromatic hydrocarbons originate from a wide range of sources relevant to human life. These compounds have been a constant hot spot in the field of VOC removal due to their unique aromatic ring structure, highly toxic effects, and challenging treatment. VOC removal mainly comprises source reduction, process management, and end–to–end treatment. End–to–end treatment methods involve adsorption, photocatalytic, plasma decomposition, membrane separation, and catalytic oxidation. Catalytic oxidation can effectively convert VOCs into carbon dioxide and water at relatively low temperatures, making it one of the most effective methods for VOC treatment. Efficient catalyst development is the key point for catalytic oxidation methods. This review highlights progress in catalyst development for the catalytic oxidation of toluene, focusing on the characteristics of noble-metal catalysts, such as noble-metal species, particle size, alloying systems, and support properties. While transition-metal oxide catalysts are abundant and inexpensive, they exhibit low catalytic performance for toluene oxidation. Therefore, discussions on transition-metal oxide catalysts include synthesis or calcination temperature, atomic substitution (isovalent and heterovalent substitutions), surface modification (noble- and transition-metal doping), and in situ surface treatment (chemical etching and surface modification). Although studies on toluene degradation using spinel- and perovskite-type oxide catalysts and metal-organic framework-based catalysts are limited, a brief summary of their characteristics during catalytic oxidation of toluene is provided, focusing on the relationship between the catalyst microstructure and performance. Furthermore, the kinetic model for the catalytic oxidation of toluene was briefly evaluated, and the corresponding reaction mechanism and kinetics were analyzed. This review aims to contribute to the development of efficient catalysts for the complete or selective oxidation of toluene.

Developing the alternative supported noble metal catalysts with low cost, high catalytic efficiency, and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds (VOCs). In this work, we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom (Co1Ni1/meso-Cr2O3) and bimetallic Co and Ni nanoparticle (CoNPNiNP/meso-Cr2O3) catalysts adopting the one-pot polyvinyl pyrrolidone (PVP)- and polyvinyl alcohol (PVA)-protecting approaches, respectively. The results indicate that the Co1Ni1/meso-Cr2O3 catalyst exhibited the best catalytic activity for n-hexane (C6H14) combustion (T50% and T90% were 239 and 263 °C at a space velocity of 40,000 mL g−1 h−1; apparent activation energy and specific reaction rate at 260 °C were 54.7 kJ mol−1 and 4.3 × 10−7 mol gcat−1 s−1, respectively), which was associated with its higher (Cr5+ + Cr6+) amount, large n-hexane adsorption capacity, and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane, in which Ni1 was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility, while Co1 preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane. n-Hexane combustion takes place via the Mars−van Krevelen (MvK) mechanism, and its reaction pathways are as follows: n-hexane → olefins or 3-hexyl hydroperoxide → 3-hexanone, 2-hexanone or 2,5-dimethyltetrahydrofuran → 2-methyloxirane or 2-ethyl-oxetane → acrylic acid → COx → CO2 and H2O.

Chlorinated volatile organic compounds (CVOCs) are persistent pollutants and harmful to the atmosphere, environment, and human health. The catalytic elimination of CVOCs has become a hotspot of interest due to their self-toxicity, the secondary generation of chlorinated by-products, and the Cl poisoning of catalysts. The development of high-performance, highly selective, and anti-poisoning catalysts is a critical issue. Bimetallic catalysts exhibit an improved dechlorination performance, poisoning resistance, and product selectivity through the modulation of geometrical and electronic structures. The present review article gives a brief overview of the recent advancements in the preparation of bimetallic catalysts and their catalytic CVOC elimination activities. In addition, representative case studies are provided to investigate the physicochemical properties, CVOC conversion, COx and inorganic chlorine species selectivities, and by-product control so that the structure–performance relationships of bimetallic catalysts can be established. Furthermore, this review article provides a fundamental understanding of designing bimetallic catalysts with specific active components and the desired physicochemical properties for target reactions. In the end, related perspectives for future work are proposed.

Intermetallic compounds (IMCs) have attracted significant attention in recent years due to their unique properties and potential applications in various fields, particularly in catalysis. This review aims to provide an in-depth understanding of IMCs, including their synthesis methods, structural characteristics, and diverse catalytic applications. The review begins with an introduction to IMCs, highlighting their distinct features and advantages over traditional catalyst materials. It then delves into the synthesis techniques employed to prepare IMCs and explores their structural properties. Subsequently, catalytic applications of the IMCs are introduced, focusing on the key reactions and highlighting their superior catalytic performance compared to conventional catalysts. Future perspectives for, and challenges to, the catalysis of IMCs are then proposed.

Xylene is one of the main components of volatile organic compounds (VOCs), the catalytic oxidation of xylene has been studied. In this work, the manganese-cobalt mixed oxide catalysts for the xylene removal have been prepared by one step direct decomposition method with the aid of glucose. The physicochemical properties of the catalysts were characterized by TG, XRD, TEM, BET, TPR and XPS. The catalytic experiments results show that the Mn-Co catalysts are composite oxides composed of Mn2O3 and Co3O4. The Mn1Co1.4Ox catalyst with the molar ratio of Mn to Co of 1:1.4 has excellent oxidation removal performance of xylene. At the space velocity of 20000 mL (g·h)−1 and the concentration xylene of 500 ppm, the temperature of complete conversion of xylene is 210 °C, which is related to the developed pore structure, high specific surface area, excellent reduction performance, abundant adsorbed oxygen species, coexistence and interaction of polyvalent species. The space structure and competitive adsorption of reactants make the oxidation performance of low polarity p-xylene better. The participation of water vapor reduced the catalytic performance of the reaction system by 12-19%, which is related to the ads-desorption of water molecules and the decomposition of active components.

The emission of methane leads to the increase in the methane concentration in the atmosphere, which not only wastes resources but also intensifies the greenhouse effect and brings about serious environmental problems. Catalytic combustion can completely convert methane into carbon dioxide and water at low temperatures. However, the catalytic activities of the conventional supported palladium catalysts (e.g., Pd/Al2O3 and Pd/ZrO2) are easy to decrease or the two catalysts can even be deactivated under actual harsh reaction conditions (high temperatures, steam- and sulfur dioxide-containing atmospheres, etc.). Recently, noble metal catalysts supported on zeolites with ordered pores and good thermal stability have attracted much attention. This review article summarizes the recent progress on the development and characteristics of zeolite-supported noble metal catalysts for the combustion of methane. The effects of framework structures, silica/alumina ratios, acidity, doping of alkali metals or transition metals, particle sizes and distributions, and their locations of/in the zeolites on methane combustion activity are discussed. The importance of developing high-performance catalysts under realistic operation conditions is highlighted. In addition, the related research work on catalytic methane combustion in the future is also envisioned.

The development of efficient and stable catalysts is of great importance for the elimination of volatile organic pollutants (VOCs). In this work, AuPdx nanoparticles (NPs) were loaded on TiO2 through the electrostatic adsorption approach to generate the yAuPdx/TiO2 (i.e., 0.35AuPd0.46/TiO2, 0.34AuPd2.09/TiO2, and 0.37AuPd2.72/TiO2; x and y are Pd/Au molar ratio and AuPdx loading, respectively; x = 0.46–2.72; and y = 0.34–0.37 wt%) catalysts, and their catalytic activities for the oxidation of ethyl acetate were determined. The results showed that the 0.37AuPd2.72/TiO2 sample exhibited the best activity (T50% = 217 °C and T90% = 239 °C at SV = 40,000 mL/(g h), Ea = 37 kJ/mol, specific reaction rate at 220 °C = 113.8 µmol/(gPd s), and turnover frequency (TOFNoble metal) at 220 °C = 109.7 × 10−3 s−1). The high catalytic performance of the 0.37AuPd2.72/TiO2 sample was attributed to the good dispersion of AuPd2.72 NPs, the strong redox ability, the large ethyl acetate adsorption capacity, and the strong interaction between AuPdx and TiO2. Acetaldehyde, ethanol, and acetic acid are the main intermediates in the oxidation of ethyl acetate, and the loading of AuPdx NPs effectively reduces the formation of the toxic by-product acetaldehyde. The oxidation of ethyl acetate over the 0.34AuPd2.09/TiO2 sample might occur via the pathway of ethyl acetate → ethanol → acetic acid → acetate → CO2 and H2O. We believe that the obtained results may provide a useful idea for the design of bimetallic catalysts under industrial conditions and for understanding the VOCs oxidation mechanisms.

Pt nanoparticles and a CeMnOx composite were loaded on the surface of the natural diatomite material to generate the Pt/CeMnOx/diatomite using the redox precipitation and impregnation methods. The physicochemical properties of the catalysts were characterized by means of various techniques. The catalytic properties and resistance to H2O and SO2 of the catalysts were measured for the oxidation of typical volatile organic compounds (i.e., toluene and ethyl acetate). Among all of the as-prepared samples, Pt/CeMnOx/diatomite exhibited the highest catalytic activity: the temperatures (T90%) at a toluene or ethyl acetate conversion of 90% were 230 and 210 °C at a space velocity (SV) of 20,000 mL g−1 h−1, respectively, and the turnover frequency (TOFPt) at 220 °C was 1.04 μmol/(gcat s) for ethyl acetate oxidation and 1.56 μmol/(gcat s) for toluene oxidation. In particular, this sample showed a superior catalytic activity for ethyl acetate oxidation at low temperatures, with its T50% being 185 °C at SV = 20,000 mL g−1 h−1. In addition, the Pt/CeMnOx/diatomite sample possessed good sulfur dioxide resistance during the toluene oxidation process. In the presence of SO2, some of the SO2 molecules were adsorbed on diatomite, which protected the active sites from being poisoned by SO2 to a certain extent. The pathways of ethyl acetate and toluene oxidation over Pt/CeMnOx/diatomite or Pt/CeMnOx were as follows: The C–C and C–O bonds in ethyl acetate are first broken to form the CH3CH2O* and CH3CO* species or toluene is first oxidized to benzaldehyde and benzoic acid, and all of these intermediates are then converted to CO2 and H2O. This work can provide a strategy to develop efficient catalysts with high catalytic activity, durability, low cost, and easy availability under actual working conditions.

Zeolites have ordered pore structures, good spatial constraints, and superior hydrothermal stability. In addition, the active metal elements inside and outside the zeolite framework provide the porous material with adjustable acid–base property and good redox performance. Thus, zeolites-based catalysts are more and more widely used in chemical industries. Combining the advantages of zeolites and active metal components, the zeolites-based materials are used to catalyze the oxidation of methane to produce various products, such as carbon dioxide, methanol, formaldehyde, formic acid, acetic acid, and etc. This multifunction, high selectivity, and good activity are the key factors that enable the zeolites-based catalysts to be used for methane activation and conversion. In this review article, we briefly introduce and discuss the effect of zeolite materials on the activation of C–H bonds in methane and the reaction mechanisms of complete methane oxidation and selective methane oxidation. Pd/zeolite is used for the complete oxidation of methane to carbon dioxide and water, and Fe- and Cu-zeolite catalysts are used for the partial oxidation of methane to methanol, formaldehyde, formic acid, and etc. The prospects and challenges of zeolite-based catalysts in the future research work and practical applications are also envisioned. We hope that the outcome of this review can stimulate more researchers to develop more effective zeolite-based catalysts for the complete or selective oxidation of methane.

Methane is the most stable hydrocarbon with a regular tetrahedral structure, which can be activated and oxidized above 1000 °C in conventional combustion. Catalytic oxidation is an effective way to eliminate lean methane under mild conditions, and the key issue is to develop the catalysts with high efficiencies, good stability, and high selectivities. Catalytic combustion of low-concentration methane can realize the light-off and deep conversion at low temperatures, thus achieving complete combustion with fewer byproducts below 500 °C. This review article summarizes the recent advances in preparation of ordered porous oxides and supported noble metal catalysts and their methane combustion applications. The results reveal that the superior performance (good hydrothermal stability and excellent moisture- or sulfur-resistant behavior) is associated with the well-ordered and developed three-dimensional porous structure, large surface area, ultrahigh component dispersion, fast mass transfer, low-temperature reducibility, reactant activation ability, and strong interaction between metal and support. In addition, the development trend of porous oxides for industrial applications in the future is also proposed.

Catalytic performance and moisture and sulfur dioxide resistance are important for a catalyst used for the oxidation of volatile organic compounds (VOCs). Supported noble metals are active for VOC oxidation, but they are easily deactivated by water and sulfur dioxide. Hence, it is highly desired to develop a catalyst with high performance and good moisture and sulfur dioxide resistance in the oxidation of VOCs. In this work, we first adopted the hydrothermal method to synthesize a V2O5-TiO2 composite support, and then employed the polyvinyl alcohol (PVA)-protecting NaBH4 reduction strategy to fabricate xPdPty/V2O5-TiO2 catalysts (x and y are the PdPty loading (0.41, 0.46, and 0.49 wt%) and Pt/Pd molar ratio (2.10, 0.85, and 0.44), respectively; the corresponding catalysts are denoted as 0.46PdPt2.10/V2O5-TiO2, 0.41PdPt0.85/V2O5-TiO2, and 0.49PdPt0.44/V2O5-TiO2). Among all the samples, 0.46PdPt2.10/V2O5-TiO2 exhibited the best catalytic activity for toluene oxidation (T50% = 220 °C and T90% = 245 °C at a space velocity of 40,000 mL/(g h), apparent activation energy (Ea) = 45 kJ/mol), specific reaction rate at 230 °C = 98.6 μmol/(gPt s), and turnover frequency (TOFNoble metal) at 230 °C = 142.2 × 10−3 s−1. The good catalytic performance of 0.46PdPt2.10/V2O5-TiO2 was associated with its well-dispersed PdPt2.10 nanoparticles, high adsorbed oxygen species concentration, good redox ability, large toluene adsorption capacity, and strong interaction between PdPty and V2O5-TiO2. No significant changes in toluene conversion were detected when 5.0 vol% H2O or 50 ppm SO2 was introduced to the reaction system. According to the characterization results, we can realize that vanadium is the main site for SO2 adsorption while PdO is the secondary site for SO2 adsorption, which protects the active Pt site from being poisoned by SO2, thus making the 0.46PdPt2.10/V2O5TiO2 catalyst show good sulfur dioxide resistance.

Due to the expensive price and the low reserve of noble metals in nature, much attention has been paid to single-atom catalysts (SACs)—especially single-atom noble metal catalysts—owing to their maximum atomic utilization and dispersion. The emergence of SACs greatly decreases the amount of precious metals, improves the catalytic activity, and makes the catalytic process progressively economic and sustainable. However, the most remarkable challenge is the active sites and their stability against migration and aggregation under practical conditions. This review article summarizes the preparation strategies of SACs and their catalytic applications for the oxidation of methane, carbon monoxide, and volatile organic compounds (VOCs) and the reduction of nitrogen oxides. Furthermore, the perspectives and challenges of SACs in future research and practical applications are proposed. It is envisioned that the results summarized in this review will stimulate the interest of more researchers in developing SACs that are effective in catalyzing the reactions related to the environmental pollution control.

Herein we fabricated the supported single-atom silver catalysts using an in situ molten salt method. The Mn2O3 nanowires supported single-atom silver catalyst (i.e., 0.06 wt% Ag/Mn2O3) exhibited excellent catalytic activity for toluene combustion, with the temperatures required for 50 and 90% of toluene conversions being 170 and 205 °C, respectively, at a space velocity of 40,000 mL/(g h). However, the toluene conversion at 205 °C quickly decreased from 90 to 30% within 2.5 h of on-stream reaction. Based on the various characterization results, we found that there were no aggregation of Ag particles, no change in crystal structure of the Mn2O3 nanowire support, and no carbon deposition on the catalyst surface, and the quick deactivation of 0.06 wt% Ag/Mn2O3 was mainly associated with the low oxygen activation ability. The proper CeO2 addition to the 0.06 wt% Ag/Mn2O3 catalyst was found to not only improve the catalytic activity but also significantly enhance the stability of the catalyst. Toluene conversion at 195 °C over 0.63 wt% CeO2-0.06 wt% Ag/Mn2O3 decreased by only 10% in 50 h of on-stream reaction. Because Ag and CeO2 particles were highly dispersed on the Mn2O3 nanowire support, the oxygen species formed at the surface oxygen vacancies of CeO2 could efficiently migrate to the active sites (i.e., the interface of Ag-Mn2O3) and replenish the surface reactive lattice oxygen species. Thus, the present single-atom silver catalyst is an alternative for commercial noble metal catalysts for the removal of VOCs. Keywords: Volatile organic compounds, Catalytic oxidation, Single-atom silver catalyst, In-situ molten salt method

Chlorinated volatile organic compounds (CVOCs), even in small quantities, can cause Pt-based catalyst poisoning. Improving the low-temperature chlorine resistance of catalysts is of vital importance for industrial application, although it remains challenging. Considering actual industrial production, a TiO2-supported ternary metal catalyst was prepared in this work to study the catalytic oxidation of multicomponent VOCs (toluene and trichloroethylene (TCE)). Among all of the samples, PtWRu/TiO2 and PtWCr/TiO2 exhibited the best catalytic performance for toluene oxidation. In the mixed VOC oxidation, the PtWCr/TiO2 sample showed the best catalytic activity for toluene combustion (a toluene conversion of 90% was achieved at 258 °C and a space velocity of 40,000 mL g−1 h−1, and the specific reaction rate and turnover frequency at 215 °C were 44.9 × 10−6 mol gPt−1 s−1 and 26.2 × 10−5 s−1). The PtWRu/TiO2 sample showed the best catalytic activity for TCE combustion (a TCE conversion of 90% was achieved at 305 °C and a space velocity of 40,000 mL g−1 h−1, and the specific reaction rate and turnover frequency at 270 °C were 9.0 × 10−6 mol gPt−1 s−1 and 7.3 × 10–5 s−1). We concluded that the ternary metal catalysts could greatly improve chlorine desorption by increasing the active lattice oxygen mobility and surface acidity, thus reducing chlorinated byproducts and other serious environmental pollutants. This work may serve as a reasonable design reference for solving more practical industrial production emissions of multicomponent VOCs.

Three-dimensionally ordered macroporous (3DOM) TiO2-supported AuPd alloy (xAuyPd/3DOM TiO2 (x = 0.87⁻0.91 wt%; y = 0.51⁻1.86)) catalysts for trichloroethylene (TCE) oxidation were prepared using the polymethyl methacrylate-templating and polyvinyl alcohol-protected reduction methods. The as-prepared materials possessed a good-quality 3DOM structure and a surface area of 49⁻53 m2/g. The noble metal nanoparticles (NPs) with a size of 3⁻4 nm were uniformly dispersed on the surface of 3DOM TiO2. The 0.91Au0.51Pd/3DOM TiO2 sample showed the highest catalytic activity with the temperature at a TCE conversion of 90% being 400 °C at a space velocity of 20,000 mL/(g h). Furthermore, the 0.91Au0.51Pd/3DOM TiO2 sample possessed better catalytic stability and moisture-resistant ability than the supported Au or Pd sample. The partial deactivation induced by H2O introduction of 0.91Au0.51Pd/3DOM TiO2 was reversible, while that induced by CO2 addition was irreversible. No significant influence on TCE conversion was observed after introduction of 100 ppm HCl to the reaction system over 0.91Au0.51Pd/3DOM TiO2. The lowest apparent activation energy (51.7 kJ/mol) was obtained over the 0.91Au0.51Pd/3DOM TiO2 sample. The doping of Au to Pd changed the TCE oxidation pathway, thus reducing formation of perchloroethylene. It is concluded that the high adsorbed oxygen species concentration, good low-temperature reducibility, and strong interaction between AuPd NPs and 3DOM TiO2 as well as more amount of strong acid sites were responsible for the good catalytic activity, stability, and water- and HCl-resistant ability of 0.91Au0.51Pd/3DOM TiO2. We believe that 0.91Au0.51Pd/3DOM TiO2 may be a promising catalyst for the oxidative elimination of chlorine-containing volatile organics.

In the title compound, {[Ca3Eu2(C7H3NO4)6(H2O)12]·10.5H2O}n, the EuIII ion is nine-coordinated by three tridentate pyridine-2,6-dicarboxylate (PDA) ligands, forming a [Eu(PDA)3]3− building block. The Ca2+ ions adopt two types of coordination geometries. One Ca2+ ion, lying on a twofold rotation axis, is eight-coordinated by four carboxylate O atoms from four PDA ligands and four water molecules, and the other two Ca2+ ions, each lying on an inversion center, are six-coordinated by two carboxylate O atoms from two PDA ligands and four water molecules. The carboxylate groups bridge the EuIII and Ca2+ ions into a three-dimensional porous framework, with channels extending along [010] and [001] in which lattice water molecules are located. Two of the lattice water molecules are disordered over two sets of sites with equal occupancy and one water molecule is 0.25-occupied. Numerous O—H...O hydrogen bonds involving the water molecules and carboxylate O atoms are present.

In the title compound, [Cu(C6H3N2O5)2(H2O)2], the CuII ion, lying on an inversion center, is coordinated by two pyridine N atoms and two carboxylate O atoms from symmetry-related two 4-hydroxy-5-nitropyridine-2-carboxylate ligands, and two water molecules, forming a distorted octahedral geometry. In the crystal, O—H...O hydrogen bonds link the complex molecules. One of the H atoms of the water molecule is disordered over two sites of equal occupancy.