Catalysts For Selective Oxidation Research Articles

Impact of Ceria Support Morphology on Au Single‐Atom Catalysts for Benzyl Alcohol Selective Oxidation

AbstractAlcohol oxidations are a key industrial chemical transformation, with aldehydes and ketones finding use in an array of applications. Nobel metals are known for their activity towards this chemoselective transformation, however, sustainable catalyst synthesis requires optimal utilisation of these scarce elements. Here, we report Au catalytic systems based on the deposition of isolated Au sites on different morphologies of ceria in which different surface facets of the support are exposed. Through tailoring the support morphology and from extensive catalyst characterisation, it is shown that the exposed facet is critical for controlling the formation (or not) of isolated Au sites. Both the 110 and 111 facets are capable of this feat, yielding single‐atom sites for rod, octahedron, and polyhedron morphologies. In contrast, the 100 facet is not, resulting in Au nanoparticles on cubic ceria. This dictation over Au species is critical to benzyl alcohol oxidation capacity at mild conditions and in the absence of a soluble base, with only single‐atom catalyst (SAC) systems demonstrating activity. Furthermore, the exposed surface facet also governs the degree of surface oxygen vacancies, which is critical to catalyst activity due to their control over substrate adsorption strength, as revealed through T1/T2 NMR relaxation measurements.

Ammonia and toluene oxidation: Mutual activating effect of copper and cerium on catalytic efficiency

Copper and cerium containing hydrotalcite-like precursors Cux-Cey-Mg-Al were synthesized by mutual co-precipitation followed by calcination at 800 °C. The obtained mixed metal oxides were studied as catalysts for selective ammonia oxidation (NH3-SCO) and toluene combustion. Various techniques, such as temperature-programmed reduction with hydrogen, temperature-programmed desorption of toluene, scanning electron microscopy and reactive frontal chromatography were used to characterize the catalysts. Series 800-Cux-Ce2.5 showed the highest catalytic efficiency in both reactions, allowing complete NH3 and C7H8 conversion below 350 °C and 500 °C, respectively. CeO2 crystallites (12–18 nm), as well as dispersed CuO oxide forms were found in the most active samples. Both phases affect pollutants conversion, however, for ammonia oxidation the occurrence of Cu2+ is essential, while for toluene oxidation, the formation of Ce4+ is sufficient. Over the most active sample (800-Cu5-Ce2.5) the complete conversion in mutual oxidation of NH3 and toluene was achieved below 450 °C.

Hierarchical Porous N-Doped Carbon Particles Derived from ZIF-8 as Highly Efficient H2S Selective Oxidation Catalysts.

In the selective oxidation of H2S, the catalytic activity over N-doped carbon-based catalysts is significantly influenced by the accessibility of active sites and the mass transfer rates of reactant molecules (e.g., H2S and O2) as well as generated sulfur monomers. Therefore, it is crucial for enhancing the initial performance via the controlled synthesis of carbon-based catalysts with highly exposed active sites and unique porous structures. Herein, we reported on an efficient strategy to synthesize nanosized N-doped carbon particles with hierarchical porous structures by directly pyrolyzing an oversaturated NaCl-encapsulated ZIF-8 precursor mixture. The introduction of NaCl not only serves as a pollution-free template to promote the formation of graphitic carbon layers but also acts as an intercalating agent to guide the derivation of hierarchical porous structures, as well as enhances the amount of active nitrogen species in the catalysts. As a result, the as-prepared H-NC800 catalyst shows excellent H2S selective oxidation performance (sulfur formation rate is 794 gsulfur·kgcat-1·h-1), good stability (>80 h), and antiwater vapor properties. The characterization results and DFT calculations indicate the crucial role of pyridinic N in the adsorbing and activating reactant molecules (H2S, O2). Furthermore, nanoscale N-doped carbon particles accelerated the rapid transport of generated sulfur monomers under a hierarchical porous structure. This investigation introduces a distinctive strategy for synthesizing ZIF-8-derived N-doped carbon nanosized with a hierarchical porous structure, while its efficient and stable H2S selective oxidation performance highlights significant potential for practical implementation in the industrial desulfurization process.

Temperature-driven dynamic evolution process of Ag species on silver-loaded Zr0.2Sn0.8O2 catalyst for selective catalytic oxidation of ammonia

Silver-based catalysts are extensively utilized in the selective catalytic oxidation of ammonia (NH3-SCO). However, enhancing low-temperature activity often causes a decline in N2 selectivity, presenting a substantial challenge in balancing activity and N2 selectivity. In this work, we introduced zirconium into the SnO2 support, resulting in a significant enhancement of low-temperature activity by 200 °C for the Ag/Zr0.2Sn0.8O2 catalyst; yet, this also led to the formation of N2O at low temperatures and NOx at high temperatures. Characterizations such as XPS and in situ DRIFTS revealed that the dynamic changes of silver species driven by temperature had a profound impact on the reaction mechanism and guided the formation of different products. Below 200 °C, the predominance of Ag+ directed the imide mechanism, with the –HNO species being the key intermediate leading to the production of N2O. Above 300 °C, Ag0 became dominant, favoring the internal selective catalytic reduction (i-SCR) mechanism and the production of NOx. This work provides novel insights into improving N2 selectivity of Ag-based catalysts and contributes to a deeper understanding of the reaction mechanisms.

Cover Feature: Ionic liquid templated synthesis of cobalt‐substituted mesoporous aluminophosphates: A novel heterogeneous catalyst for selective oxidation of cyclohexane to cyclohexanol (ChemCatChem 8/2024)

Cover Feature: Ionic liquid templated synthesis of cobalt‐substituted mesoporous aluminophosphates: A novel heterogeneous catalyst for selective oxidation of cyclohexane to cyclohexanol (ChemCatChem 8/2024)

Correction to “Thermoresponsive Polymeric Nanoparticles as Efficient Pickering Interfacial Catalysts for Selective Oxidation of Sulfides”

Correction to “Thermoresponsive Polymeric Nanoparticles as Efficient Pickering Interfacial Catalysts for Selective Oxidation of Sulfides”

Roles of the A-Site Ca Dopant in Modifying Surface Properties of a Co-Based Perovskite Catalyst for Selective Oxidation of Cyclohexane

Roles of the A-Site Ca Dopant in Modifying Surface Properties of a Co-Based Perovskite Catalyst for Selective Oxidation of Cyclohexane

Rational Design of Cobalt Phthalocyanine (CoPc)‐Anchored TiO2 Nanorods for High‐Efficiency Selective Catalytic Oxidation

AbstractQuinclorac is important precursor for pharmaceutical, agricultural, and synthetic chemistry. The state‐of‐art synthesis of quinclorac via condensation, chlorination and oxidative hydrolysis often uses homogeneous catalysts and strong acid oxidant agents to promote the catalytic oxidation, which requires huge manpower input for the late‐stage purification process and is usually environmentally unfriendly. In this work, we successfully fabricated a stable cobalt phthalocyanine (CoPc) Co‐based composite (CoPc/TiO2) by anchoring CoPc on the surface of TiO2 nanorods for the selective oxidation of 3,7‐dichloro‐8‐dichloro methyl quinoline (3,7‐D‐8‐DMQ) into quinclorac. More impressively, CoPc/TiO2‐2.5 %‐Mn‐Br exhibits a high selectivity of 91.9 % for the catalytic oxidation of 3,7‐D‐8‐DMQ to quinclorac in acetic acid, with a quinclorac yield of 86.4 %, which is approximately 2.43 times higher than that of pristine CoPc‐Mn‐Br. The obtained heterogeneous catalytic system shows good reusability. Detailed mechanistic investigations reveal that the system works through a free radical mechanism via the formation of Co2+/Co3+ redox cycles. This work provides a new understanding for the stabilization of reaction intermediates and facilitates the designs of catalysts for selective catalytic oxidation.

Cobalt and nitrogen co-modified hollow periodic mesoporous organosilica spheres for selective oxidation of aryl alkanes

Hollow periodic mesoporous organosilica spheres (HPMOs) have stimulated great research interest owing to its unique organic–inorganic hybrid skeleton. In this work, HPMOs were synthesized by hydrothermal method, and then cobalt and nitrogen co-doped carbon catalyst was prepared by using HPMOs as supports. The optimal catalyst (Co-Nx/HPMOs-D) performed excellent activity in the selective oxidation reaction of aryl alkanes, with the conversion of ethylbenzene up to 97.0% and the selectivity of acetophenone was 98.9%, which was attributed to the Co-Nx active species and the unique HPMOs supports. The unique amphiphilic property of Co-Nx/HPMOs-D could better facilitate the adsorption and diffusion of organic substrates in the aqueous phase. The addition of dicyandiamide not only enhanced the nitrogen content in the catalyst, but also promoted the conversion of pyrrolic-N to pyridinic-N during the pyrolysis process, thus strengthened the interaction between the substrate and cobalt and improved the stability of the catalyst. This work presented a green and environmentally friendly method for the preparation of HPMOs and a facile strategy to obtain high performance catalysts for selective oxidation of aryl alkanes.

Regulating the valence and size of the active center of Co/Al2O3 catalyst improved the performance and selectivity of NH3-SCO

To improve the activity of Co/Al2O3 catalysts in selective catalytic oxidation of ammonia (NH3-SCO), valence state and size of active centers of Al2O3-supported Co catalysts were adjusted by conducting H2 reduction pretreatment. The NH3-SCO activity of the adjusted 2Co/Al2O3 catalyst was substantially improved, outperforming other catalysts with higher Co-loading. Fresh Co/Al2O3 catalysts exhibited multitemperature reduction processes, enabling the control of the valence state of the Co-active centers by adjusting the reduction temperature. Changes in the state of the Co-active centers also led to differences in redox capacity of the catalysts, resulting in different reaction mechanisms for NH3-SCO. However, in situ diffuse reflectance infrared Fourier transform spectra revealed that an excessive O2 activation capacity caused overoxidation of NH3 to NO and NO2. The NH3-SCO activity of the 2Co/Al2O3 catalyst with low redox capacity was successfully increased while controlling and optimizing the N2 selectivity by modulating the active centers via H2 pretreatment, which is a universal method used for enhancing the redox properties of catalysts. Thus, this method has great potential for application in the design of inexpensive and highly active catalysts.

Solvent Free, Selective Oxidation of Styrene Catalyzed by Cobalt Acylpyrazolone Supported onto Neutral Alumina: Synthesis and Spectral Characterization

AbstractThe present work describes the synthesis of the Cobalt acylpyrazolone complex supported over neutral alumina and its use as a heterogeneous catalyst for selective oxidation of styrene. The catalyst mentioned here was characterized by various physicochemical techniques such as FT‐IR, TGA, CV, SCXRD, PXRD and BET. This heterogeneous catalyst has successfully been used to oxidize styrene to benzaldehyde in a solvent‐free condition with good conversion (87 %) and high selectivity (90 %) using H2O2 and TBHP as oxidants. The effects of the reaction parameters (catalyst concentration, reaction duration, and temperature) have also been investigated. The existing complex was discovered to be recyclable and sustainable with no change in conversion or selectivity for benzaldehyde. FT‐IR spectra of the regenerated catalyst indicated that the catalyst was undegraded and stable after the reaction. The novel feature of the current work reported in this paper is the selective oxidation of styrene without the need for solvents under mild conditions. Single Crystal Analysis.

Streamlined synthesis of iron and cobalt loaded MCM-48: High-performance heterogeneous catalysts for selective liquid-phase oxidation of toluene to benzaldehyde

Hydrothermal synthesis of MCM-48 molecular sieves featuring the incorporation of both iron and cobalt with Si/M ratios of 20, 40 and 80 (where M represents either iron or cobalt) was performed using tetraethyl orthosilicate as the silica source and cetyltrimethylammonium bromide as a template. To gain a comprehensive understanding of the synthesized materials, these were thoroughly characterized using various techniques, including XRD, XPS, UV–Vis (DRS), FT-IR, N2 adsorption-desorption analysis, SEM with EDX, TEM, TGA and NH3-TPD analysis. XRD analysis revealed the presence of well-ordered MCM-48 structure in the metal-incorporated materials, while XPS and UV–Vis DRS confirmed the successful partial incorporation of metal ions precisely in their desired tetrahedral coordination within the framework. To assess their catalytic performance, we studied the activity and selectivity of these catalysts in liquid phase oxidation of toluene using tert-butyl hydroperoxide as the oxidant. Under optimized conditions, employing a 6% (w/w) Fe-MCM-48 (40) catalyst and maintaining a toluene to oxidant molar ratio of 1:3 at 353 K in a solvent-free environment for 8 h, the oxidation reaction resulted in the formation of benzaldehyde (88.1%) as the major product and benzyl alcohol (11.9%) as the minor product.

Concentrated formate produced through co‐electrolysis of CO2 and methanol in a zero‐gap electrolyzer

AbstractRecent progresses have highlighted the enormous potentials of renewable electricities driven carbon dioxide (CO2) electrolysis in achieving carbon neutrality. However, its further industrial application is limited by low liquid product concentrations, which requires energy‐intensive downstream separation processing. Herein we report a CO2 and methanol co‐electrolysis strategy to produce formate at both electrodes and collect highly concentrated formate in zero‐gap CO2 electrolyzers. An anion exchange membrane was employed to enable formate product crossover from cathode to anode. A bismuth silicate derived nanofiber electrocatalyst with rich grain boundaries was synthesized and exhibited excellent formate selectivity (Faradaic efficiency >95%), high activity (partial current density >500 mA cm−2), as well as good stability (>120 h). Coupled with NiOX anode catalyst for methanol selective oxidation to formate in a zero‐gap electrolyzer, we demonstrate a ~180% of formate Faradaic efficiency and a full‐cell voltage of 2.43 V at an industrially relevant current density of 0.2 A cm−2. By decoupling product generation and collection, our electrolyzer produced a highly concentrated formate of 3.24 M, which could be directly used as anode fuel for fuel cells.

Ionic liquid templated synthesis of cobalt‐substituted mesoporous aluminophosphates: A novel heterogeneous catalyst for selective oxidation of cyclohexane to cyclohexanol

AbstractOrdered hexagonal mesoporous aluminophosphate and its cobalt‐substituted analogue were successfully synthesized using ionic liquid as a structure‐directing agent. The resulting materials were systematically characterized by various analytical, spectroscopic, and imaging methods, confirming the presence of divalent cobalt in the tetrahedral framework of the matrix. Further, the high surface area, pore volume, and thicker mesopore walls of these materials impart good thermal and hydrothermal stability. The mesoporous catalysts showed excellent activity towards the oxidation of cyclohexane reactions using hydrogen peroxide as an oxidant, with 98.5 % conversion and 90.4 % selectivity towards cyclohexanol.

Thermoresponsive Polymeric Nanoparticles as Efficient Pickering Interfacial Catalysts for Selective Oxidation of Sulfides

Thermoresponsive Polymeric Nanoparticles as Efficient Pickering Interfacial Catalysts for Selective Oxidation of Sulfides

Ru-modified Octahedral Manganese Oxide Molecular Sieve (Ru-OMS-2) as a Reusable Heterogeneous Catalyst in Selective Oxidation of Olanzapine and Other Polycyclic Compounds

Ru-modified Octahedral Manganese Oxide Molecular Sieve (Ru-OMS-2) as a Reusable Heterogeneous Catalyst in Selective Oxidation of Olanzapine and Other Polycyclic Compounds

Pd-Bi-Based Catalysts for Selective Oxidation of Glucose into Gluconic Acid: The Role of Local Environment of Nanoparticles in Dependence of Their Composition

Palladium–bismuth nanomaterials are used in various chemical applications such detectors, electrodes, and catalysts. Pd-Bi catalysts are attracting widespread interest because these catalysts enable the production of valuable products quickly and efficiently, and are environmentally friendly. However, the composition of the catalyst can have a significant impact on its catalytic performance. In this work, we identified a correlation between the composition of the catalyst and its efficiency in converting glucose into sodium gluconate. It was found that the conversion decreases with increasing bismuth content. The most active catalyst was the 0.35Bi:Pd sample with a lower bismuth content (glucose conversion of 57%). TEM, SEM, EXAFS, and XANES methods were used to describe, in detail, the surface properties of the xBi:Pd/Al2O3 catalyst samples. The increase in particle size with increasing bismuth content, observed in the TEM micrographs, was associated with the low melting point of bismuth (271 °C). The SEM method showed that palladium and bismuth particles were uniformly distributed over the surface of the support in close proximity to each other, which allowed us to conclude that an alloy of non-stoichiometric composition was formed. The EXAFS and XANES methods established that bismuth was located on the surface of the nanoparticle predominantly in an oxidized state.

Surface States Governing the Activity and Selectivity of Pt-Based Ammonia Slip Catalysts for Selective Ammonia Oxidation

Surface States Governing the Activity and Selectivity of Pt-Based Ammonia Slip Catalysts for Selective Ammonia Oxidation

Biotemplated heterostructure materials: opportunities for the elaboration of new photocatalysts and selective-oxidation catalysts

Natural biological materials display a large number of sophisticated nanostructures that are difficult to acquire even using the most technologically advanced synthetic methodologies.

Significant inhibition of secondary pollution in the catalytic oxidation of chloroaromatics over a bifunctional Ru1/CeO2 single-atom catalyst

Single atomic Ru supported CeO2 seems to be a more promising and selective catalyst for chlorobenzene oxidation than RuO2 NPs, which enables the inhibition of HCl conversion to Cl2 and stepwise formation of polychlorinated by-products.