Monolithic Catalysts Research Articles

Effects of Slurry Composition and Interfacial Adhesion of Monolithic Coatings on FeCrAl Honeycombs

Excellent coating adhesion is a crucial requirement for monolithic catalysts. Within this investigation, a Design of Experiments (DOEs) Taguchi approach was leveraged to construct a 9-factor-3-level matrix encompassing 27 parallel experiments. This framework was employed to scrutinize the pivotal elements influencing the adhesion of FeCrAl metal-based integral coatings, which were prepared using the slurry method. Moreover, an unprecedented endeavor was made to scrutinize the mechanism of coating delamination from the vantage points of macroscopic slurry, microscopic coatings, and nanoscale interfaces. The findings reveal the following: (1) The inclusion of a high-acidity additive (>5%) emerges as one of the pivotal factors in achieving superior adhesion, particularly when the boehmite content exceeds 1%. (2) The existence of binder-filled interstices within the coating, smaller by 1–2 orders of magnitude than the carrier particles, significantly contributes to heightened adhesion. (3) A bonding region of approximately 5 nm is present at the interfaces between carrier particles, resulting in augmented adhesion.

Producing a monolithic catalyst for the catalytic oxidization of dioxins by comparing extrusion and coating methods

Producing a monolithic catalyst for the catalytic oxidization of dioxins by comparing extrusion and coating methods

Development and performance evaluation of a novel solar mid-and-low temperature receiver/reactor with packed metal foam

Solar-driven hydrogen production from methanol decomposition (MD) is an important method of storing solar energy as clean fuels and improving the solar energy utilization efficiency. Catalyst preparation is one of the key steps, but conventional Cu-ZnO-Al2O3 particle catalysts lead to uneven reactor temperature, reducing the efficient conversion of solar energy into fuels. To alleviate this challenge, a monolithic catalyst utilizing packed foamy copper as a carrier is developed with exceptional thermal and mass transfer properties. The experimental results validate its excellent performance in hydrogen production using MD. The absolute conversion increases by an average of 12.11 % at 250 °C and further by 14.43 % at 270 °C compared to the particle catalyst. Based on these findings, a novel solar reactor is proposed, and a multi-field coupling model is built. The comparative results verify the performance advantage of the developed solar thermochemical receiver/reactor with packed metal foam-based catalyst. It maintains high conversion rates and solar-to-fuel energy efficiency, while alleviating overheating problems caused by traditional particle catalysts. Under the design conditions, the new reactor significantly improves the absolute conversion of methanol and the energy efficiency of solar-to-fuel conversion by 4.57 % and 3.00 %, respectively, resulting in 92.64 % and 67.56 %. This study provides a theoretical basis and technical solution for more stable and efficient use of mid-and-low temperature solar energy.

Ozone-Catalytic Treatment of Automotive Exhaust

In the paper, an original design of an ozone-catalytic device, in which the process of ozone formation occurs directly inside the catalyst monolith of the honeycomb structure, is proposed for solving the problem of exhaust gases purification at the "cold start" of an automobile engine. For the considered device, various regimes of operation were examined, and the equations allowing us to calculate the concentrations of ozone depending on time were obtained. The developed mathematical model shows a significant decrease in ozone concentration after the "cold start" is over and the temperature of the exhaust gases increases, because of changes in the balance of various chemical reactions. Thus, the ozone concentration is maximum during a cold start, precisely when the lower temperatures do not allow other reactions than those of oxidation of toxic gases with ozone, and decreases by the time the catalytic unit warms up, when effective neutralization of toxic impurities becomes possible without the participation of ozone. The results of the mathematical modeling were confirmed by testing this device for purifying exhaust gases of a YaMZ-238M2 engine. The test results show that the use of ozone-catalytic reactions significantly increases the efficiency of neutralizing toxic impurities under cold start conditions, compared to the case when only catalytic reactions with oxygen without the participation of ozone are used.

Pd-Co Supported on Anodized Aluminium for VOCs Abatement: Reaction Mechanism, Kinetics and Applicability as Monolithic Catalyst

It has been found out that Pd-Co-based catalyst, supported on anodized aluminum, possesses very high activity in combustion reactions of C1–C6 alkanes and toluene. The catalyst characterization has been made by N2-pysisorption, XRD, SEM, XPS, FTIR, TEM, and EPR methods. In view of the great interest, methane combustion was investigated in detail. It is ascertained that the complete oxidation of methane proceeds by dissociative adsorption on PdO and formation of hydroxyl and methyl groups, the former being highly reactive, and it undergoes further reaction to oxygen-containing intermediates, whereupon HCHO is one of them. The presence of Co2+ cations promotes greatly oxygen adsorption. The dissociative adsorption is favored on neighboring Co2+ cations, leading to the formation of bridging peroxides. Further, the oxygen dissociates on the nearest Pd2+ cations. According to the results from the experimental data, instrumental methods, and the observed kinetics and DFT model calculations, it can be concluded that the reaction pathway over Pd+Co/anodic alumina support (AAS) catalyst proceeds most probably through Mars–van Krevelen. The obtained data on the kinetics were used for simulation of the methane combustion in a full-scale adiabatic reactor.

Foam Ti Supported Pd Catalysts for the Selective Hydrogenation of Nitroaromatics.

The selective hydrogenation of nitroaromatics plays an essential role in the chemical industry for the synthesis of anilines and their derivatives, which are known as crucial fine chemicals and pharmaceuticals. In this study, we demonstrate the preparation of Pd/Ti monolith catalyst containing well-isolated metallic Pd sites on Ti substrate through a simple impregnation method, showing remarkable catalytic properties in the selective hydrogenation of nitroaromatics containing various functional groups. Kinetic analyses reveal an apparent activation energy of 61 kJ/mol and the kinetic isotope effect (KH2/KD2) of ~1.7 in the hydrogenation of 3-chloronitrobenzene over Pd/Ti-200 ppm catalyst, indicating the facile dissociation of dihydrogen and the subsequent efficient hydrogenation. The Pd/Ti-200 ppm catalyst also demonstrates good stability and recyclability, maintaining its performance over multiple cycles. This simple but innovative approach not only enhances the efficiency of Pd catalysts in the selective hydrogenation of nitroaromatics but also offers significant potential for industrial applications in aniline production.

Topology optimization and numerical validation for heat transfer improvement in a packed-bed reactor with monolithic catalyst

This study focuses on optimizing heat transfer in packed-bed reactors by simplifying the problem to a two-dimensional steady-state heat conduction scenario. The objective is to efficiently arrange a limited volume of high-conductivity material to transport heat from the source to the low-conductivity heat-absorbing materials, representing the reacting fluid phase. The topology optimization problem is tackled using a density-based method that relies on a gradient-based algorithm. The optimized design is extruded and compared to a honeycomb internal structure using high-fidelity simulations for steam methane reforming. Results show a 6.04 % improvement in CH4 conversion for the optimized structure, highlighting the potential of this method to enhance monolithic catalysts, particularly in cases where heat transfer critically influences the reaction.

Ni/Al2O3 PROMOTED BY CeO2, CeO2-La2O3, AND CeO2-ZrO2 SUPPORTED ON CORDIERITE MONOLITHS FOR METHANE STEAM REFORMING

Promotion of Ni-based catalysts supported on cordierite monoliths was investigated for methane steam reforming. First, cordierite was coated by ɣ-Al2O3, and then the catalyst components were deposited by successive wet impregnation, obtaining: NiAl/cordierite; NiCeAl/cordierite; NiCeLaAl/cordierite and NiCeZrAl/cordierite. The monolithic catalysts were characterized by adherence test, Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDX), N2 physisorption, Temperature-Programmed Reduction (TPR), CO chemisorption, as well as by in situ and operando Raman spectroscopy. The catalyst layer showed very good adherence and distribution of the components over the cordierite surface. The catalysts presented high activity between 600 and 800 °C at a H2O/CH4 molar ratio=1.5, except for NiCeAl/cordierite, which obtained lower methane conversion, associated with its lower nickel dispersion. The catalysts showed high stability under extreme conditions for carbon deposition (600 °C and H2O/CH4=1), over 90h on stream. Raman spectroscopy revealed the presence of oxygen vacancies, which may be increased during ceria reduction, highlighting the potential of these catalysts to enhance the resistance to deactivation by carbon deposition in long-term tests.

A monolithic self-supporting ZnFe2O4/ZnO/ZnNi foam photocatalyst and application in the decomposition of gaseous benzene

Volatile organic compounds (VOCs) are major air pollutants which seriously affect ecological environment and pose threats to human health. In this investigation, a monolithic self-supporting ZnFe2O4/ZnO/ZNF(ZFO/ZnO/ZNF) photocatalyst was developed by in-situ growing ZnFe2O4 and ZnO on ZnNi foam (ZNF). Using benzene as a representative of the target gaseous contaminants, the optimal 5ZFO/ZnO/ZNF achieved a 99.8 % removal efficiency and 99.7 % mineralization efficiency within 20 min at an initial benzene concentration of 600 ppm under simulated sunlight irradiation. Moreover, this catalyst presents the lower ullage during gas–solid reaction, and thus enables durable recycling reuse of the photocatalyst, which still retains a 95.8 % benzene decomposition after 30th consecutive run. The mechanism studies reveal that the metal-mediated Z-type heterostructure of ZFO/ZnO/ZNF enhances rapid transportation of the photo-generated electrons and promotes redox potential, leading to the excellent photocatalytic oxidation activity and mineralization efficiency. This study highlights the potential of self-supporting monolithic metal-mediated catalysts and provides a key strategy for effective VOCs degradation.

Robust palladium oxide nano-cluster catalysts using atomic ions and strong interactions for high-performance methane oxidation

Optimizing metal catalyst structures to achieve desired states is vital for efficient surface reactions, yet remains challenging due to the lack of well-defined precursor materials and weak metal-support interaction. Palladium-based catalysts, when not properly tailored for complete methane oxidation exhibit insufficient performance. Herein, we fabricate Pd oxide nano-clusters supported on SSZ-13 using atomic ions with strong metal-support interaction (SMSI). Steam treatment of Pd/SSZ-13 transforms Pd particles into ions and induces SMSI. Subsequently, CO reduction and O2 oxidation yield mildly sintered Pd oxide nano-clusters firmly anchored on extra-framework Alpenta sites of SSZ-13, facilitating superior activity. The robustness from SMSI prevents irreversible deactivation, and water-resistance by complete dehydration suppresses reversible degradation in wet conditions. This catalyst exhibits high performance in bench-scale reactions using monolith catalysts, ensuring applicability for industrial methane abatement. The results demonstrate that sequential treatment to Pd/SSZ-13 offers a promising approach for tailoring metal structures to enable high-performance methane oxidation.

Diverse Effects of SO2-Induced Pt-O-SO3 on the Catalytic Oxidation of C3H6 and C3H8.

The effects of sulfur dioxide (SO2) in the catalytic purification of short-chain hydrocarbons are still controversial, and the exact role of SO2 on adsorption and reaction pathways during the catalytic oxidation of different volatile organic compounds (VOCs) remains unclear. Herein, a three-dimensional ordered macroporous Ce0.8Zr0.2O2 supported Pt nanoparticle monolithic catalyst (Pt/OM CZO) was synthesized to investigate these effects. Our findings uncover the diverse effects of SO2: Upon SO2 treatment, the coupling between the S 3p and Pt 5d orbitals promotes the Pt-O-SO3 structure in situ formed on the catalyst surface. The propene (C3H6) molecule readily binds with the oxygen atom in Pt-O-SO3, resulting in the accumulation of acetone and carbon deposition, thereby hindering C3H6 oxidation. Conversely, a cleaved oxygen atom within the Pt-O-SO3 structure enhances propane (C3H8) adsorption and activates the C-H bond, facilitating C3H8 oxidation. These insights are pivotal for advancing the frontier of sulfur-tolerant catalysts, addressing both economic and environmental challenges.

Facile fabrication of NF-loaded Co3O4 monolithic catalyst and its application in the reduction of P-nitrophenol

In this work, a foam nickel-loaded Co3O4 nanosheet featuring an integral structure (NF@Co3O4) was successfully fabricated by a facile hydrothermal-calcination strategy. The catalytic performance of the NF@Co3O4 was evaluated using the reduction of P-nitrophenol (PNP) to P-aminophenol (PAP) under NaBH4 as a model reaction. A reduction rate of 94.44% for PNP was achieved under the following reaction parameters over 25 min at 25∘C: two slices of NF@Co3O4 monolithic catalysts (3 × 4 cm2), a PNP concentration of 15 mg L[Formula: see text] (500 mL), and a NaBH4 dosage of 15 mmol L[Formula: see text]. Moreover, NF@Co3O4 presented a stable performance in PNP reduction, maintaining a reductive conversion above 91% over sixteen consecutive runs. This study suggested that NF-loaded Co3O4 is a promising monolithic catalyst for the treatment of phenol-containing wastewater, owe to its superb catalytic performance and ease of recovery.

Mechanism for airborne ozone decomposition on X-MIL-53(Fe) (X = H, NH2, NO2)

Ground−level ozone (O3) pollution poses a significant threat to both ecosystem sustainability and human health. The catalytic decomposition of O3 presents as a promising technology to address the issues of O3 pollution. This study undertook the synthesis of various functionalized metal−organic framework (MOF) catalysts (i.e., X-MIL-53(Fe) (X = H, NH2, NO3)) to delve into the influence of ligand functional groups on skeletal structure and catalytic efficacy, particularly focusing on unraveling the mechanism of O3 catalytic decomposition under humid conditions. NH2-MIL-53(Fe) catalyst achieved complete O3 decomposition under ambient temperature and high humidity conditions (RH=75 %), exhibiting a reaction rates (mol·m−2·s−1) 129 and 10.5 times greater than that of MIL-53(Fe) and NO2-MIL-53(Fe). The NH2 group promotes electron flow within the backbone towards the hydroxyl group (OH) linked to Fe atom. In humid O3, H2O molecules augment the interaction between O3 and NH2-MIL-53(Fe), and OH is converted to·O2− after deprotonation, promoting O3 decomposition. Additionally, leveraging three−dimensional (3D) printing technology, a monolithic catalyst for O3 decomposition was prepared for application. This study not only advances understanding of the mechanisms underlying O3 decomposition but also offers practical solutions for addressing O3 pollution at humid conditions.

Asymmetric oxygen vacancies of self-supporting Co3O4/CuOx on Cu foam boosts propane total oxidation

As a low-cost and environmentally friendly transition metal oxides material, the Co3O4 has good catalytic activity for volatile organic compounds (VOCs) oxidation. However, the active components of powder cobalt-based catalysts may present uneven distribution and aggregation, thus affecting the catalytic efficiency. Herein, the Co/Cu-CF monolithic catalyst with asymmetric oxygen vacancies was developed through in-situ growth of Cu(OH)2 nanoarrays on Cu foam, which exhibits excellent performance for propane oxidation (T90 at 215 ℃). It is impressive that the catalyst shows satisfactory stability in terms of long-term, cyclic and water resistance. The results indicate that the existence of nanoarrays can provide a rich load surface and better disperse the active components, which effectively facilitates the interface interaction between cobalt and copper, inducing the generation of asymmetric oxygen vacancies. And, the activity of catalyst was significantly improved owing to the double activation effect of asymmetric oxygen vacancy on molecular oxygen and lattice oxygen. Therefore, this research offers a novel approach for designing efficient nanoarray monolithic catalysts for VOCs oxidation and other environmental applications.

Catalytic oxidation of toluene-acetone mixture over MnOx/Cu foam monolithic catalyst: Strong Cu-Mn interaction and amorphous phase

Traditional powder catalysts are not suitable for industrial applications due to low utilization of active phase and easy sintering. Therefore, monolithic catalyst MCCF with good stability and water-resistance was designed for the catalytic oxidation of toluene-acetone mixture, in which amorphous MnOx derived via pyrolysis of Mn-MOFs loaded on copper foam (CF) and different transition layers were employed between MnOx and CF to regulate Cu-Mn interaction. The combined action of amorphous MnOx and the Cu-Mn strong interaction enhanced the catalytic degradation of toluene-acetone mixture. The existence of amorphous MnOx and the impacts of Cu-Mn interaction on weakening Mn-O bonds and stimulating reactive oxygen species were verified by various characterizations. Furthermore, the reaction pathways of toluene and acetone on catalyst MCCF were revealed as well as their interactions within the mixture.

Boosting the Performance of Pt-Based Honeycomb Monolithic Catalysts for CO Preferential Oxidation in Hydrogen-Rich Streams via the Channel Rotation

Boosting the Performance of Pt-Based Honeycomb Monolithic Catalysts for CO Preferential Oxidation in Hydrogen-Rich Streams via the Channel Rotation

Computational Fluid Dynamics, Transport, and Chemical Kinetics-Based Monolith Catalyst Dimensioning Methodology for Cost-Effective Performance

The newly developed computational fluid dynamics, transport, and chemical kinetics-based monolith catalyst dimensioning methodology consists of the following steps: (i) initial calculations, which generate some of the data, e.g., average inlet fluid velocity used in the (ii) computational fluid dynamics (CFD) modelling, which uses the laminar flow interface and the transport of diluted species interface while the user has to provide the kinetics of the reactions; (iii) the model order reduction uses a modified version of the plug flow reactor model and the linear pressure variation model; and (iv) the dimensioning optimization algorithm extracts the optimal monolith catalyst’s channel geometry, which satisfies the user’s performance constraints and reduces material consumption. Therefore, the methodology enables chemical engineers to quickly and efficiently design and dimension monolith catalysts for many different applications in an environmentally friendly way, which enables them to reduce both the material and operating costs while maintaining sufficient catalyst performance and, therefore, achieve its cost-effective performance.

Enhancing Oxygen Activation Ability by Composite Interface Construction over a 2D Co3O4-Based Monolithic Catalyst for Toluene Oxidation.

Developing robust metal-based monolithic catalysts with efficient oxygen activation capacity is crucial for thermal catalytic treatment of volatile organic compound (VOC) pollution. Two-dimensional (2D) metal oxides are alternative thermal catalysts, but their traditional loading strategies on carriers still face challenges in practical applications. Herein, we propose a novel in situ molten salt-loading strategy that synchronously enables the construction of 2D Co3O4 and its growth on Fe foam for the first time to yield a unique monolithic catalyst named Co3O4/Fe-S. Compared to the Co3O4 nanocube-loaded Fe foam, Co3O4/Fe-S exhibits a significantly improved catalytic performance with a temperature reduction of 44 °C at 90% toluene conversion. Aberration-corrected scanning transmission electron microscopy and theoretical calculation suggest that Co3O4/Fe-S possesses abundant 2D Co3O4/Fe3O4 composite interfaces, which promote the construction of active sites (oxygen vacancy and Co3+) to boost oxygen activation and toluene chemisorption, thereby accelerating the transformation of reaction intermediates through Langmuir-Hinshelwood (L-H) and Mars-van Krevelen (MvK) mechanisms. Moreover, the growth mechanism reveals that 2D Co3O4/Fe3O4 composite interfaces are generated in situ in molten salt, inducing the growth of 2D Co3O4 onto the surface lattice of 2D Fe3O4. This study provides new insights into enhancing oxygen activation and opens an unprecedented avenue in preparing efficient monolithic catalysts for VOC oxidation.

Co3O4@SiO2 3D Monolith Catalysts, Additive Manufactured Structures for Propane Oxidation Reaction

AbstractIn this study, we successfully fabricated a three‐dimensional Co3O4@SiO2 3D Monolith catalyst. This process allowed for the effective and straightforward anchoring of Co3O4 nanoparticles onto SiO2 3D Monoliths. The active Co3O4 phase was primarily identified through XRD and XPS analyses, complemented by Co3O4 loading measurements (1.7 %). This innovative catalyst displayed remarkable proficiency in selectively converting propane to carbon dioxide. Additionally, it was demonstrated that the catalytic activity remained unimpaired even upon the catalyst's reuse in 5 successive reaction cycles. This performance was observed across various heating ramps, showcasing the catalyst's stability over time.

Understanding the Relationship between Internal Diffusion Resistance and Catalytic Degradation of Chlorobenzene by the Coated Monolithic Catalyst

Understanding the Relationship between Internal Diffusion Resistance and Catalytic Degradation of Chlorobenzene by the Coated Monolithic Catalyst