Heterogeneous Catalytic Processes Research Articles

The influence of heterogeneous catalytic processes on the heat flux to the surface and the chemical composition of the shock layer at high-speed flow around blunt bodies

Numerical modeling of the high-speed flow of a multicomponent dissociated gas around a blunt body was carried out for the flow regime corresponding to the thermally stressed point of the gliding trajectory of entry into the Earth's atmosphere in the surface temperature range of 800–2000 K. As boundary conditions, a stage-by-stage model of heterogeneous catalysis of the interaction of dissociated air with the thermal protection material SiO2 was used, previously developed by the authors on the basis of transition state theory and quantum mechanical calculations. The dependence of the modes of heterogeneous chemical reactions on the surface temperature and the density of surface adsorption centers and their influence on the chemical composition of the shock layer and the convective heat flux to the streamlined surface are analyzed. The contributions of individual mechanisms of heterogeneous recombination to the total rate of formation of molecules on the surface are estimated. The possibility of using the density of adsorption sites as an effective parameter when setting boundary conditions on a real thermal protection surface in flow problems is shown.

Advances in Aluminophosphates for Catalytic Upgrading of Lignocellulose and Derived Compounds

Utilization of lignocellulosic biomass as a renewable resource to produce liquid fuels/fuel additives and commodity chemicals offer solutions to minimize the exhaustion of nonrenewable carbon‐based fossil resources and mitigate environmental problems. Cellulose and hemicellulose derived from lignocellulose can be converted into several important platform molecules like glucose, fructose, xylose, 5‐hydroxymethylfurfural, furfural, levulinic acid, etc., which subsequently can be transformed into fuels/fuel additives and value‐added chemicals using heterogeneous catalytic processes. Aluminophosphates (AlPO‐n) are zeotype materials with tunable physicochemical properties like acidity and porosity, and this have promoted their wide use as versatile catalysts for several acid‐catalyzed reactions, including hydrolysis, dehydration, isomerization, transfer hydrogenation, reductive etherification, acetalization and aldol condensation. This review summarizes the design and synthetic advances of AlPO‐n catalysts as well as their application in the valorization of lignocellulose and derivatives to platform chemicals and fuel compounds. Perspectives for future design strategies are finally outlined

A Bioinspired Copper-Pair Catalyst in Metal-Organic Frameworks for Molecular Dioxygen Activation and Aerobic Oxidative C-N Coupling.

Open Cu sites were loaded to the UiO-67 metal-organic framework (MOF) skeleton by introduction of flexible Cu-binding pyridylmethylamine (pyma) side chains to the biphenyldicarboxylate linkers. Distance between Cu centers in the MOF pores was tuned by controlling the density of metal-binding side chains. "Interacted" Cu-pair or "isolated" monomeric Cu sites were achieved with high and low (pyma)Cu side chain loading, respectively. Spectroscopic and theoretical studies indicate that "interacted" Cu pairs can effectively bind and activate molecular dioxygen to form Cu2O2 clusters, which showed high catalytic activity for aerobic oxidative C-N coupling. On the contrary, MOF catalyst bearing isolated monomeric Cu sites only showed modest catalytic activity. Enhancement in catalytic performance for the Cu-pair catalyst is attributed to the remote synergistic effect of the paired Cu site, which binds molecular dioxygen and cleaves the O═O bond in a collaborative manner. This work demonstrates that noncovalently interacted metal-pair sites can effectively activate inert small molecules and promote heterogeneous catalytic processes.

Generalized Linear Driving Force Formulas for Diffusion and Reaction in Porous Catalysts

Approximate models are a fast and most often precise tool for determining the effectiveness factor for heterogeneous catalysis processes that are realized in the real world. They are also frequently applied as robust transient models describing the work of a single catalyst pellet or as a part of a more complex model, for example, a reactor model, where mass balances for the gas phase and solid phase are necessary. So far, approximate models for diffusion and reaction processes have been presented for processes described by a single balance equation. In the present work, approximate models without the mentioned limitation are presented and discussed. In addition, simple rules are shown for the development of other complex approximate models without tedious derivation in the complex domain. The formulas considered in this work are typical long-time approximations of the transient process. The accuracy is good, especially in the range of small and intermediate Thiele modulus values.

Treatment of pharmaceutical wastewater by a sequential KMnO4/CoFe2O4-mediated catalytic ozonation process

Pharmaceutical compounds, which are of utmost concern, have found their way into natural water bodies, causing numerous problems for both human health and ecosystems. In this study, an integrated system including potassium permanganate (PM) pre-oxidation, followed by a heterogeneous catalytic ozonation process (HCOP) using CoFe2O4 magnetic nanoparticles (CF MNPs), and an activated sludge-based biological treatment (BT) was employed for the first time to treat pharmaceutical wastewater (PWW). In this regard, the effluent from PM pre-oxidation process was used as a batch for the HCOP, and the effluent was used as a batch for the BT process. The results showed that PM pre-treatment of PWW (PM dose = 1264 mg/L and pH = 8.0) reduced the COD content of the PWW from 900 ± 50 to 443 ± 10 mg/L within 120 min of reaction time. The application of HCOP for further treatment of PWW dramatically enhanced COD and TOC removal compared with the single ozonation process (SOP). Under optimum conditions (pH = 10, O3 = 4.0 mg/L, and CF MNPs = 1000 mg/L), HCOP successfully reduced the COD and TOC contents of PWW by 37 % and 46.1 %, respectively, after 120 min of treatment. The consecutive combination of PM pre-treatment followed by HCOP exhibited good potential and reduced COD by over 69 %, resulting in a residual COD of less than 280 mg/L. A biodegradability ratio of over 81 % and residual COD of 54 mg/L for the PWW treated by the PM/HCOP/BT integrated system indicated that biodegradability was enhanced, and a high fraction of refractory organic compounds was effectively removed. In conclusion, the PM/HCOP/BT integrated system is an efficient, synergistic, and easy-to-operate technique for enhancing the biodegradability of PWW.

Efficient degradation of sulfonamides by introducing sulfur to magnetic Prussian blue analog in photo-assisted persulfate oxidation system

The peroxynitrite photocatalytic degradation system was considered a green, convenient, and efficient water treatment process, but not satisfying against some antibiotics, e.g. sulfonamides (SAs). To improve the photocatalytic degradation efficiency of SAs, sulfur was introduced to a magnetic Fe-MOF (Fe-metal organic framework) Prussian blue analog to achieve a heteroatomic material CuFeO@S, which was applied in heterogeneous visible light photo-assisted catalytic process with persulfate (PS) as an oxidant. The characterization results of CuFeO@S by XRD and XPS confirmed the presence of Fe3O4 (for magnetic separation), Cu+ (for activation of PS) and S2− (for narrowing the energy band and prolonging the lifetime of photo-generated electronics). Through systematic optimization of reaction conditions in CuFeO@S + PS + hv system, efficient degradation of four tested SAs was achieved in 30 min (removal rate of 97–100% for the tested 4 SAs). Moreover, the material could be magnetically recycled and reused for over 7 cycles with a removal rate of >90% for sulfamerazine. Furthermore, the removal rate of sulfamerazine in pond water reached 99% at a mineralization rate of about 34% (decrease in total organic matter), demonstrating its potential in the treatment of antibiotic-containing wastewater.

Diphenyl Carbonate: Recent Progress on Its Catalytic Synthesis by Transesterification

Diphenyl carbonate is one of the raw materials used for the synthesis of polycarbonate, and its green and clean production is of great importance to the non-phosgene process for polycarbonate. The production of diphenyl carbonate by transesterification is its representative process route and is considered to be one of the typical examples of a green and sustainable process for chemicals. Since the discovery of the transesterification catalyst for diphenyl carbonate in the 1970s, researchers have been committed to improving its catalytic activity and selectivity and, correspondingly, the reaction engineering process. However, thermodynamic limitations, low activity, low selectivity, and limited stability have been bottlenecks that the transesterification catalyst has not been able to completely overcome, and the improvement of the catalyst is still ongoing. Therefore, this review takes the transesterification reaction of dimethyl carbonate and phenol as a model reaction and, based on a review of the progress in catalyst research on catalytic reaction processes, tries to clarify the structure–activity relationship between catalytic active sites and catalytic performance in homogeneous and heterogeneous catalytic processes and provides an overview of the progress in catalyst synthesis and modification.

Structured Catalysts and Catalytic Processes: Transport and Reaction Perspectives.

The structure of catalysts determines the performance of catalytic processes. Intrinsically, the electronic and geometric structures influence the interaction between active species and the surface of the catalyst, which subsequently regulates the adsorption, reaction, and desorption behaviors. In recent decades, the development of catalysts with complex structures, including bulk, interfacial, encapsulated, and atomically dispersed structures, can potentially affect the electronic and geometric structures of catalysts and lead to further control of the transport and reaction of molecules. This review describes comprehensive understandings on the influence of electronic and geometric properties and complex catalyst structures on the performance of relevant heterogeneous catalytic processes, especially for the transport and reaction over structured catalysts for the conversions of light alkanes and small molecules. The recent research progress of the electronic and geometric properties over the active sites, specifically for theoretical descriptors developed in the recent decades, is discussed at the atomic level. The designs and properties of catalysts with specific structures are summarized. The transport phenomena and reactions over structured catalysts for the conversions of light alkanes and small molecules are analyzed. At the end of this review, we present our perspectives on the challenges for the further development of structured catalysts and heterogeneous catalytic processes.

Bimetallic PtPd Atomic Clusters as Apoptosis/Ferroptosis Inducers for Antineoplastic Therapy through Heterogeneous Catalytic Processes.

Active polymetallic atomic clusters can initiate heterogeneous catalytic reactions in the tumor microenvironment, and the products tend to cause manifold damage to cell metabolic functions. Herein, bimetallic PtPd atomic clusters (BAC) are constructed by the stripping of Pt and Pd nanoparticles on nitrogen-doped carbon and follow-up surface PEGylation, aiming at efficacious antineoplastic therapy through heterogeneous catalytic processes. After endocytosed by tumor cells, BAC with catalase-mimic activity can facilitate the decomposition of endogenous H2O2 into O2. The local oxygenation not only alleviates hypoxia to reduce the invasion ability of cancer cells but also enhances the yield of •O2- from O2 catalyzed by BAC. Meanwhile, BAC also exhibit peroxidase-mimic activity for •OH production from H2O2. The enrichment of reactive oxygen species (ROS), including the radicals of •OH and •O2-, causes significant oxidative cellular damage and triggers severe apoptosis. In another aspect, intrinsic glutathione (GSH) peroxidase-like activity of BAC can indirectly upregulate the level of lipid peroxides and promote ferroptosis. Such deleterious redox dyshomeostasis caused by ROS accumulation and GSH consumption also results in immunogenic cell death to stimulate antitumor immunity for metastasis suppression. Collectively, this paradigm is expected to inspire more facile designs of polymetallic atomic clusters in disease therapy.

Interrogating site dependent kinetics over SiO2-supported Pt nanoparticles

A detailed knowledge of reaction kinetics is key to the development of new more efficient heterogeneous catalytic processes. However, the ability to resolve site dependent kinetics has been largely limited to surface science experiments on model systems. Herein, we can bypass the pressure, materials, and temperature gaps, resolving and quantifying two distinct pathways for CO oxidation over SiO2-supported 2 nm Pt nanoparticles using transient pressure pulse experiments. We find that the pathway distribution directly correlates with the distribution of well-coordinated (e.g., terrace) and under-coordinated (e.g., edge, vertex) CO adsorption sites on the 2 nm Pt nanoparticles as measured by in situ DRIFTS. We conclude that well-coordinated sites follow classic Langmuir-Hinshelwood kinetics, but under-coordinated sites follow non-standard kinetics with CO oxidation being barrierless but conversely also slow. This fundamental method of kinetic site deconvolution is broadly applicable to other catalytic systems, affording bridging of the complexity gap in heterogeneous catalysis.

Tracking Coordination Environment and Reaction Intermediates in Homogeneous and Heterogeneous Epoxidation Catalysts via Ti L2,3-Edge Near-Edge X-ray Absorption Fine Structures.

Ti-based molecules and materials are ubiquitous and play a major role in both homogeneous and heterogeneous catalytic processes. Understanding the electronic structures of their active sites (oxidation state, local symmetry, and ligand environment) is key to developing molecular-level structure-property relationships. In that context, X-ray absorption spectroscopy (XAS) offers a unique combination of elemental selectivity and sensitivity to local symmetry. Commonly, for early transition metals such as Ti, K-edge XAS is applied for in situ characterization and subsequent structural analysis with high sensitivity toward tetrahedral species. Ti L2,3-edge spectroscopy is in principle complementary and offers specific opportunities to interrogate the electronic structure of five-and six-coordinated species. It is, however, much more rarely implemented because the use of soft X-rays implies ultrahigh vacuum conditions. Furthermore, the interpretation of the data can be challenging. Here, we show how Ti L2,3-edge spectroscopy can help to obtain unique information about both homogeneous and heterogeneous epoxidation catalysts and develop a molecular-level relationship between spectroscopic signatures and electronic structures. Toward this goal, we first establish a spectral library of molecular Ti reference compounds, comprising various coordination environments with mono- and dimeric Ti species having O, N, and Cl ligands. We next implemented a computational methodology based on multiplet ligand field theory and maximally localized Wannier orbitals benchmarked on our library to understand Ti L2,3-edge spectroscopic signatures. We finally used this approach to track and predict the spectra of catalytically relevant intermediates, focusing on Ti-based olefin epoxidation catalysts.

Quantum-chemical calculations of thermodynamic characteristics of some heterogeneous catalytic processes with the use of multilayer cluster models

The approaches to estimating the changes in enthalpy, entropy, and Gibbs energy of adsorption processes and heterogeneous catalytic reactions on the basis of the quantum chemical calculation data were studied. By comparing with the experimental data on CO adsorption on the anatase (TiO2) surface, the applicability of the developed multilayer cluster model for calculation of the adsorption energy (enthalpy) was shown. The data on the calculation methods of the entropy change in heterogeneous processes were analyzed. The use of the theories of an ideal two-dimensional gas and an ideal two-dimensional lattice gas for estimating a configuration contribution to the entropy of a heterogeneous process was studied. The density of adsorption centers on the (101) anatase surface and the population corresponding to the standard state of an ideal two-dimensional gas were calculated. The consistency of the studied models at low populations was shown, and the limits of their applicability were established.

Performance boosting by induction heating for hydrolysis of carbonyl sulfide using magnetic ordered mesoporous alumina as catalyst

Hydrolysis of carbonyl sulfide (COS) has been recognized as an efficient way for COS removal, however, searching for an effective way of minimizing the catalyst deactivation is always the most important task to realize its industrial application. In this study, a high-performance alkali-free catalyst of magnetic ordered mesoporous Al2O3 has been synthesized for the COS hydrolysis. At the same time, induction heating has been introduced as a novel heating method to boost the performance of the catalyst. Results show that the inducting heating can boost the performance of COS hydrolysis, as well as minimize the catalyst deactivation compared to the joule heating under the same reaction conditions. The reaction performance under induction heating mode, in terms of COS conversion, is at least 7.0% on average higher than the joule heating mode. This is attributed to precise control of the localized temperature on active sites since the heat is generated directly from the catalyst under induction heating mode. While in the joule heating mode, the heat should be transferred to the catalyst from environments, which induces a huge temperature gradient. This study implies that induction heating can be used as a unique way of minimizing the side reactions over the gas-solid heterogeneous catalytic processes and boosting the catalyst performance.

A facile heterogeneous catalytic approach for one-pot synthesis of fused benzoxazinones using Cuβ zeolite and Evaluation of biological activities

A simple heterogeneous catalytic process has been established for the single-step synthesis of fused benzoxazinones, quinazolinones, and thiadazines through Markownikoff's hydroamination followed by intramolecular cyclization using Cuβ zeolite. The probability and limitations of this catalytic approach were explored using various substrates. The efficiency and feasibility of scaling up the current catalytic system were demonstrated through gram-scale experiments. Moreover, the catalyst was reused for up to five cycles with no noticeable decrease in its catalytic effectiveness. Furthermore, the synthesized compounds were subjected to in vitro assessment to determine their potential as anticancer agents against human cervical epithelioid carcinoma (HeLa), mouse breast cancer (4T-1), and human lung adenocarcinoma (A-549) cell lines. Cytotoxicity studies revealed that 3f, 3b′, 3d′, and 3g′ compounds exhibit anti-cancer activity against breast, cervical and lung cancer cells. Additionally, their antimicrobial activity against bacteria and yeast was also evaluated. The compound 3i exhibited superior antifungal activity against Candida albicans.

“Redox switches” of Fe species on zeolite catalysts: Modulating the acidity and the para-xylene yield from methanol

Molecular switches are widely studied in optical devices, computer science, DNA sensor systems, and chiral synthesis; however, their use in heterogeneous catalytic processes is rarely reported. Herein, we report a Fe-based redox switch for tuning the acidity of a ZSM-5-based catalyst in the methanol-to-aromatics reaction. In this reaction, the yield of the target product, para-xylene (PX), is low because various types of acids on the catalyst activate side reactions. Fe oxides and zeolite generate medium-strength Lewis acids, which activate the aromatization of methanol but suppress the dealkylation of xylene. Gradual reduction of Fe oxides during the reaction simultaneously decreases the conversion of methanol, the yield of aromatics, and the yield of PX. The oxidation state of the Fe species and the associated catalytic performance can be regenerated in the air at 550 °C. The redox switches caused regular fluctuation in the catalytic performance and remained stable throughout 16 regeneration cycles (up to 80 h). The employed strategy enabled a PX yield of up to 60% (carbon base) using a SiO₂-coated Zn/P/Fe/ZSM-5 catalyst, which is 3–6 times higher than previously reported values. The result showed a new mode of acidity modulation of the catalyst.

Preparation of catalyst of cobalt‐ and/or iron‐doped strontium zirconate and its performance in removal of m‐cresol using ozone as oxidant

AbstractBACKGROUNDWastewater containing m‐cresol has become a global water environmental problem because its degradation is difficult, and it is highly toxic to plants, animals, and humans. The heterogeneous catalytic ozonation process has been widely used in the treatment of environmental pollution, so it is very important to study efficient catalysts. Perovskite catalysts have been widely investigated and applied in catalytic ozonation processes. Among them, strontium zirconate is a promising perovskite catalyst owing to its high oxidation efficiency and environmental friendliness.RESULTSStrontium zirconate was successfully synthesized via the co‐precipitation method. To improve strontium zirconate catalytic performance, some methods such as changing the doping ratio of cobalt and iron, changing the amount of polyethylene glycol added, changing the calcination temperature, and changing the aging time were carried out during the synthesis process. Finally, the optimal conditions were determined. 0.4 g L−1 Sr2Co0.4Fe0.6ZrO6 prepared under the optimal conditions was used for catalytic ozonation of 100 ppm m‐cresol, which achieved the optimum degradation (0.136 min−1), m‐cresol conversion rate (92.2%) and total organic carbon removal rate (12.1%) within 20 min.CONCLUSIONThis work provides the best preparation conditions. The Sr2Co0.4Fe0.6ZrO6 catalyst, as prepared, is the optimal catalyst for catalytic ozonation of m‐cresol among the investigated Sr2CoxFe1−xZrO6 catalysts. © 2024 Society of Chemical Industry (SCI).

Constructing surface oxygen defects at CuO–Co3O4 interface to boost toluene oxidation over CuO/Co3O4 catalysts

As a typical heterogeneous catalytic process, the catalytic combustion of toluene over Co3O4-based catalysts is strongly depends on the surface properties of catalysts, especially the concentration of surface oxygen defects. Here, a novel way was proposed to construct chemically bonded CuO–Co3O4 interface by chemical deposition of CuO onto Co3O4 nanoflowers. The interfacial refinement effect between CuO and Co3O4 support disrupted the ordered atomic arrangement and created countless unsaturated coordination sites at CuO–Co3O4 interface, inducing a significant generation of surface oxygen defects. Surface-rich oxygen vacancies enhanced the capacity of 20%CuO/Co3O4–R to adsorb and activate oxygen species. Benefiting from this, 90 % toluene conversion was reached at 228 °C over 20%CuO/Co3O4–R, which was much lower than that over 20%CuO/Co3O4–S prepared by impregnation method and CuO/Co3O4-mix obtained by mechanically mixing way. In-situ DRIFTS analysis revealed that toluene could be directly decomposed into benzaldehyde at the highly defective CuO–Co3O4 interface, leading to toluene oxidation following the path of toluene → benzaldehyde → benzoate → maleic anhydride → water and carbon dioxide over 20%CuO/Co3O4–R, which was significantly different from decomposition mechanism over 20%CuO/Co3O4–S. Additionally, 20%CuO/Co3O4–R displayed terrific recyclability and outstanding stability, showing good application potential.

Theory-guided unraveling of the mechanism underlying Cu1.0/Mn1.0-ZnO with dual reaction centers for enhanced peroxymonosulfate activation

Developing efficient catalytic systems for water contamination removal is a topic of great interest. However, the use of heterogeneous catalysts faces challenges due to insufficient active sites and electron cycling. In this study, results from first-principles calculations demonstrate that dual reaction centers (DRCs) are produced around the Cu and Mn sites in Cu1.0/Mn1.0-ZnO due to the electronegativity difference. Experimental results reveal the material with DRCs greatly enhances electron transfer efficiency and significantly impacts the oxidation and reduction of peroxymonosulfate (PMS). In addition, the self-consistent potential correction (SCPC) method was introduced to correct the energy and charge of charged periodic systems simulating a catalytic process, resulting in more precise catalytic results. Specifically, the material exhibits a preference for adsorbing negatively charged PMS anions at electron-deficient Mn sites, facilitating PMS oxidation for the generation of 1O2, and PMS reduction around the electron-rich Cu for the formation of •OH and SO4•−. The major reactive oxygen species is 1O2, showcasing effective performance in various degradation systems. Overall, our work provides novel insights into the persulfate-based heterogeneous catalytic oxidation process, paving the way for the development of high-performance catalytic systems for water purification.

Pentachlorophenol degradation in the heterogeneous catalytic ozonation process using Al2O3 as a catalyst agent

Pentachlorophenol degradation in the heterogeneous catalytic ozonation process using Al2O3 as a catalyst agent

Homogeneous vs. heterogeneous catalysts for acceptorless dehydrogenation of biomass-derived glycerol and ethanol towards circular chemistry

Survey and comparison of homogeneous and heterogeneous catalytic processes for acceptorless dehydrogenation of glycerol and ethanol based on green metrics.