Heterogeneous Catalytic Reactions Research Articles

Constructing Oxygen Vacancies in Anatase TiO2: Enhancing Acetylene Semi-Hydrogenation Performance through H2 Heterolytic Cleavage

Oxygen vacancies (OV) constitute significant defects in TiO2 and various other metal oxides, profoundly influencing heterogeneous catalytic reactions. In this investigation, anatase TiO2 samples with different OV concentrations were synthesized...

Modelling combined diffusion and surface resistances in adsorbent particles: zero length column for spherical and slab geometries

Mass transport in nanoporous materials is a key property that allows to improve the performance of many gas separation processes and design more efficient heterogeneous catalytic reactors. In many instances a combination of surface resistance and internal diffusion are present. The combined model for surface barrier and diffusion in a ZLC system is discussed in detail and the analytical solutions valid for the traditional and the partial loading experiments have been derived for the spherical and slab geometries. The model reduces to the limiting forms of pure diffusion when 100$$\\end{document}]]>, and pure surface barrier when . This study has shown that most literature studies have analysed ZLC responses incorrectly based on an effective combined dimensionless parameter. Two methods are described to obtain the parameters from the long-time asymptotic behaviour of the response curves. Both approaches have been demonstrated on curves generated from the full model solution and experimental data on an etched sample of Y zeolite. Both the analysis of the model and of the experimental results confirm that to characterize combined surface barriers and diffusion one should perform at least experiments at two different flowrates where the system is kinetically controlled, and crucially a partial loading experiment with a time to the switch which should be at least an order of magnitude smaller than the smallest of the diffusion and surface barrier times.

Irreversible Lattice Expansion Effects in Nanoscale Indium Oxide for CO2 Hydrogenation Catalysis.

Thermal energy has been considered the exclusive driving force in thermochemical catalysis, yet associated lattice expansion effects have been overlooked. To shed new light on this issue, variable temperature in situ high-resolution (scanning) transmission electron microscopy (HR-(S)TEM) and electron energy-loss spectroscopy (EELS) were employed to provide detailed information on the structural changes of an archetype nanoscale indium oxide materials and how these effects are manifest in reverse water gas shift heterogeneous catalytic reactivity. It is found that with increasing temperature and vacuum conditions, an irreversible surface lattice expansion is traced to the formation and migration of oxygen vacancies. Together, these changes are believed to be responsible for the decreased activation energy and improved reaction rate observed for the reverse water gas shift reaction. Studies of this kind provide new insight into how thermal energy affects thermochemical heterogeneous catalysis.

Fundamentals and Challenges of Ligand Modification in Heterogeneous Electrocatalysis

AbstractThe development of efficient catalytic materials in the energy field could promote the structural transformation from traditional fossil fuels to sustainable energy. In heterogeneous catalytic reactions, ligand modification is an effective way to regulate both electronic and steric structures of catalytic sites, thus paving a prospective avenue to design the interfacial structures of heterogeneous catalysts for energy conversion. Although great achievements have been obtained for the study and applications of heterogeneous ligand‐modified catalysts, the systematical refinements of ligand modification strategies are still lacking. Here, we reviewed the ligand modification strategy from both the mechanistic and applicable scenarios by focusing on heterogeneous electrocatalysis. We elucidated the ligand‐modified catalysts in detail from the perspectives of basic concepts, preparation, regulation of physicochemical properties of catalytic sites, and applications in different electrocatalysis. Notably, we bridged the electrocatalytic performance with the electronic/steric effects induced by ligand modification to gain intrinsic structure‐performance relations. We also discussed the challenges and future perspectives of ligand modification strategies in heterogeneous catalysis.

Fundamentals and Challenges of Ligand Modification in Heterogeneous Electrocatalysis.

The development of efficient catalytic materials in the energy field could promote the structural transformation from traditional fossil fuels to sustainable energy. In heterogeneous catalytic reactions, ligand modification is an effective way to regulate both electronic and steric structures of catalytic sites, thus paving a prospective avenue to design the interfacial structures of heterogeneous catalysts for energy conversion. Although great achievements have been obtained for the study and applications of heterogeneous ligand-modified catalysts, the systematical refinements of ligand modification strategies are still lacking. Here, we reviewed the ligand modification strategy from both the mechanistic and applicable scenarios by focusing on heterogeneous electrocatalysis. We elucidated the ligand-modified catalysts in detail from the perspectives of basic concepts, preparation, regulation of physicochemical properties of catalytic sites, and applications in different electrocatalysis. Notably, we bridged the electrocatalytic performance with the electronic/steric effects induced by ligand modification to gain intrinsic structure-performance relations. We also discussed the challenges and future perspectives of ligand modification strategies in heterogeneous catalysis.

Supported phenylalanine on core-shell mesoporous microsphere as a catalyst for the synthesis of triazolo[1,2-a] indazole-triones and spiro triazolo[1,2-a] indazole-tetraones

In recent years, mesoporous silica materials have gained attention due to their unique properties, such as high surface area, pore volume, size, and chemical stability. These characteristics make them effective in various fields, particularly efficient supports in heterogeneous catalytic reactions. The present study developed a novel type of core-shell mesoporous microsphere material by anchoring phenylalanine on a core-shell SiO2@NiO@MS support. The catalyst support (SiO2@NiO@MS) was synthesized through homogeneous precipitation and sol-gel methods, with NiO encapsulated within the porous silica. The catalyst was characterized using various techniques, including Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS), Elemental mapping analysis, N2 adsorption-desorption, Transmission electron microscopy (TEM), Vibrating sample magnetometer (VSM), and Thermogravimetric analysis (TGA). It was then employed for the synthesis of triazolo[1,2-a]indazole-trione and spiro triazolo[1,2-a]indazole-tetraones compounds from 4-phenyl urazole, dimedone, and aromatic aldehydes or isatin derivatives. This synthetic approach offers multiple advantages, including high yields, faster reaction times, low catalyst requirements, and environmentally sustainable conditions.

Synthesis of 6- or 8-Carboxamido Derivatives of Imidazo[1,2-a]pyridines via a Heterogeneous Catalytic Aminocarbonylation Reaction.

Imidazo[1,2-a]pyridines and especially their amide derivatives exhibit a wide range of favourable pharmacological properties. In this work, Pd-catalysed carbonylation was used for the first time for the introduction of the carboxamide moiety into positions 6 or 8. A recyclable Pd catalyst, with palladium immobilised on a supported ionic liquid phase decorated with pyridinium ions, was used efficiently for the conversion of 6- or 8-iodo derivatives to the products. In the case of 6-iodo derivatives, a competing mono- and double carbonylation could be observed in the reactions of aliphatic amines as nucleophiles, but under the proper choice of reaction conditions, good-to-excellent selectivities could be achieved towards either the corresponding amides or α-ketomides. The heterogeneous catalyst showed excellent recyclability and low Pd-leaching.

DEVELOPMENT OF AN ENERGY-SAVING TECHNOLOGY FOR THE PRODUCTION OF SYNTHETIC METHANE FROM CARBON DIOXIDE. 1. RESEARCH OF KINETICS AND MACRO-KINETICS OF THE SABATIER REACTION ON MODIFICATIONS OF THE SERIAL NI/Α-AL2O3 CATALYST GIAP-3-6N

This study presents the results of laboratory research of kinetics and mechanisms of heterogeneous catalytic reactions of hydrogenation of carbon dioxide to carbon monoxide and methane through the Sabatier reaction on modifications of the serial Ni/α-Al2O3 catalyst GIAP-3-6N manufactured in Ukraine. The research was carried out on a laboratory bench using a classic glass gradientless reactor with internal piston stirring, which provides kinetic equations at the level of physicochemical constants of the reactions under consideration. A detailed analysis and review of the literature in the areas of kinetic research of our interest was carried out. A detailed comparison of the kinetic parameters obtained by us for the powder (kinetic) form of contact with a nickel content of 7.5 % (NiO = 7.5 %) with a similar and one of the best foreign analogs containing nickel, Katalco 57-4 (NiO = 15−18 %), produced by the British chemical and metallurgical company Johnson Matthey, was performed. The results of the research confirmed almost equal parameters of the kinetic activity of the compared catalysts in the reactions of hydrogenation of carbon dioxide with hydrogen, including the «Sabatier» reaction, which made it possible to propose a similar mechanism of the processes, calculate the reaction rate constants and their activation energy, propose (determine) kinetic equations for design of reactors and processes, both with the loading of a domestic catalyst and its replacement with a foreign analog. Kinetic equations will be used in the development of multi-ton synthesis gas plants for the production of methanol, ammonia, and synthetic methane, as well as carbon-free e-fuel for internal combustion engines that meet modern climate requirements. Bibl. 28, Fig. 4, Tab. 6.

Flipping Water Orientation at the Surface of Water-in-Salt and Salt-in-Water Solutions.

Salt-in-water and water-in-salt mixtures are promising for battery applications and fine-tuning of room-temperature ionic liquid (RTIL) properties. Although critical processes take place at interfaces of these systems, including charge transfer and heterogeneous catalytic reactions, the microscopic interfacial structures remain unclear. Here, we apply heterodyne-detected sum-frequency generation spectroscopy to aqueous solutions of imidazolium-based RTILs to unveil the microscopic structure of the interfaces of these solutions with air. Our results show that, under salt-in-water conditions, the orientation of the OH group hydrogen-bonded to the other water molecules flips from the OH group pointing down into the liquid for pure water to up due to the accumulation of anions in the cation-rich interfacial region. However, under the water-in-salt condition, the interfacial water molecules are confined by RTIL, and their orientation is down. Details of the water organization depend critically on the alkyl chain length of the imidazolium cation. Our results demonstrate that the surface structure can be tuned by altering the molecular structure and concentration of the RTIL.

An Enhanced YSZ Gas Sensor through Optimizing Electrode Thickness for ppb-level H2S Detection

Nowadays, there is uncertainty regarding the impact of sensing electrode thickness on the gas sensing performance of mixed potential gas sensors due to simultaneous competitive heterogeneous catalytic reaction and electrochemical reaction. In this study, yttrium oxide doped zirconia gas sensors with varying thickness of NiFe2O4 sensing electrode have been fabricated for H2S gas detection. The operating temperature of yttrium oxide doped zirconia gas sensors have been firstly optimized, followed by a systematic study of the effects of NiFe2O4 sensing electrode thickness on H2S sensing performance. The best sensing performance have been achieved for the yttrium oxide doped zirconia gas sensor with a 10 μm-thick sensing electrode (S-10 sensor). Sensitivities of −8.7 and −44.6 mV/decade have been attained for 10–100 ppb and 100–10000 ppb, respectively, with a lower limit of detection as low as 10 ppb at 510 °C for the S-10 sensor. Furthermore, the potential application of the S-10 sensor in halitosis detection was further evaluated using simulated exhaled breath from patient with halitosis and healthy volunteers. The significant change in human exhaled gas response values detect by the S-10 sensor at different times provide additional support for the prospect of diagnosing halitosis.

Unraveling the adsorption-limited hydrogen oxidation reaction at palladium surface via in situ electron microscopy

Palladium (Pd) catalysts have been extensively studied for the direct synthesis of H2O through the hydrogen oxidation reaction at ambient conditions. This heterogeneous catalytic reaction not only holds considerable practical significance but also serves as a classical model for investigating fundamental mechanisms, including adsorption and reactions between adsorbates. Nonetheless, the governing mechanisms and kinetics of its intermediate reaction stages under varying gas conditions remain elusive. This is attributed to the intricate interplay between adsorption, atomic diffusion, and concurrent phase transformation of catalyst. Herein, the Pd-catalyzed, water-forming hydrogen oxidation is studied in situ, to investigate intermediate reaction stages via gas cell transmission electron microscopy. The dynamic behaviors of water generation, associated with reversible palladium hydride formation, are captured in real time with a nanoscale spatial resolution. Our findings suggest that the hydrogen oxidation rate catalyzed by Pd is significantly affected by the sequence in which gases are introduced. Through direct evidence of electron diffraction and density functional theory calculation, we demonstrate that the hydrogen oxidation rate is limited by precursors' adsorption. These nanoscale insights help identify the optimal reaction conditions for Pd-catalyzed hydrogen oxidation, which has substantial implications for water production technologies. The developed understanding also advocates a broader exploration of analogous mechanisms in other metal-catalyzed reactions.

Basics of the reaction kinetics on metallic alloys.

Kinetics of heterogeneous catalytic reactions are often complicated by various factors, and from the perspective of statistical physics the development of the corresponding models is frequently challenging especially in the case of practically important alloy catalysts. To extend the basics in this area, I use a generic kinetic model of N_{2} formation inthe NO reaction with such species as CO or H_{2}. The focus is onthe reaction on the surface of a bimetallic alloy with low integral fraction of one of the metals so that the alloy is formed only at the surface. The main goal is to illustrate the specifics of the reaction kinetics and to clarify the accuracy of various approximations which are often inevitable for the analysis of such systems. The key results are as follows. (i) In the baseline one-metal case with the Langmuir-type equations, the model predicts the existence of the optimal adsorbate binding energy corresponding to the maximal reaction rate. (ii) With suitable substitution of the symbols, the equations employed for a uniform surface [item (i)] can be used for the mean-field description of reaction on the surface of a random alloy. In particular, the maximum in the dependence of the reaction rate on the binding energy is converted to the maximum with respect to the alloy composition. (iii) The reaction kinetics on the random-alloy surface have been described exactly. The corresponding maximum in the reaction rate is lower and somewhat smeared compared to that predicted in the mean-field approximation for an alloy or for the optimal monometallic catalyst. (iv) The reaction kinetics have been scrutinized also in the case of two-dimensional (2D) segregation of metal atoms at the surface in the limits of slow and rapid adsorbate diffusion between the spots. The kinetics are shown to be qualitatively different in these limits and also compared to the random-alloy case. (v) The thermodynamic criteria for 2D segregation of metal atoms at the surface have been derived as well.

Kinetics of continuously catalyzed peroxymonosulfate in a fixed-bed reactor

Most studies have been conducted in batch reactors. Therefore, understanding the catalytic reaction kinetics and mass transfer in continuous catalytic reactors is essential for the design of heterogeneous catalysts and optimisation of catalytic degradation processes in heterogeneous systems. In this research, granular catalysts (Co-600/AlSi-0.25/AP) is used to investigate the kinetic constants and mass transfer resistance for the continuous catalytic decomposition of peroxymonosulfate (PMS) and degradation of p-nitrophenol (PNP) in a fixed bed reactor. The flow rate is 5 mL/min and reaction temperature is 30 °C, intrinsic kinetic constants of PMS decomposition and PNP degradation are 48 and 195 kg−1·min−1·L, respectively, which are 20–30 times of the apparent kinetic constants of PMS decomposition and PNP degradation in fixed bed reactors, respectively. The decomposition rates of PMS and PNP are controlled by mass transfer, and the reaction takes place in the diffusion-controlled regime. The mass transfer kinetic model based on the plug-flow model shows a good agreement between the calculated data and the experimental data. Which indicate that PMS decomposition and pollutant degradation in a fixed-bed reactor can be predicted by mass transfer kinetic modelling, guide the design of catalysts and the optimisation of heterogeneous catalytic reaction system in a fixed-bed reactor.

Insight into the Hamilton and Crosser model for ternary hybrid nanofluid flow over a Riga wedge with heterogeneous catalytic reaction

Insight into the Hamilton and Crosser model for ternary hybrid nanofluid flow over a Riga wedge with heterogeneous catalytic reaction

Metal‐Supported Heterogeneous Catalysts for the Synthesis of Nitrogen‐Containing Heterocycles: A Comprehensive Review

AbstractThe use of metals in the preparation of heterocycles has become increasingly popular due to several key advantages of metals as catalysts. These include recycling capability, eco‐friendliness, simplicity of catalyst preparation and separation, longer lifespan, abundance, and higher yields. As a result of their novel applications in organic, inorganic, medicinal, industrial, polymer chemistry, material sciences, nanotechnology, and biological processes, the utilization of nitrogen‐containing heterocycles has rapidly increased in recent years. Various nitrogen‐containing organic moieties are used in therapeutic processes to enhance effectiveness against several bacterial and viral diseases. This review covers the preparation of imidazoles, triazoles, tetrazoles, pyridine derivatives, azo compounds, pyrimidines, quinoxalines, and quinolines using metals as heterogeneous catalysts. It provides an overview of current methodologies for metal‐assisted heterogeneous catalytic reactions, including product yield, operating temperature, and solvents, among other factors. Heterogeneous catalyst‐mediated organic synthetic reactions offer several advantages, particularly in medicinal chemistry, pharmaceuticals, and industrial applications, by reducing time and energy consumption. This review emphasizes recent advancements in the fabrication of nitrogen heterocycles utilizing heterogeneous catalysts, taking into account various economic, eco‐friendly, and user‐friendly considerations. Additionally, it discusses the benefits, reaction conditions, and yields reported in the literature over the past six years.

Water-Driven Surface Lattice Oxygen Activation in MnO2 for Promoted Low-Temperature NH3-SCR.

Water is ubiquitous in various heterogeneous catalytic reactions, where it can be easily adsorbed, chemically dissociated, and diffused on catalyst surfaces, inevitably influencing the catalytic process. However, the specific role of water in these reactions remains unclear. In this study, we innovatively propose that H2O-driven surface lattice oxygen activation in γ-MnO2 significantly enhances low-temperature NH3-SCR. The proton from water dissociation activates the surface lattice oxygen in γ-MnO2, giving rise to a doubling of catalytic activity (achieving 90% NO conversion at 100 °C) and remarkable stability. Comprehensive in situ characterizations and calculations reveal that spontaneous proton diffusion to the surface lattice oxygen reduces the orbital overlap between the protonated oxygen atom and its neighboring Mn atom. Consequently, the Mn-O bond is weakened and the surface lattice oxygen is effectively activated to provide excess oxygen vacancies available for converting O2 into O2-. Therefore, the redox property of Mn-H is improved, leading to enhanced NH3 oxidation-dehydrogenation and NO oxidation processes, which are crucial for low-temperature NH3-SCR. This work provides a deeper understanding and fresh perspectives on the water promotion mechanism in low-temperature NOx elimination.

Study on Ce-MOF-derived oxides as morphology-tunable catalyst supports for dry reforming of methane

Dry reforming of methane (DRM) using CH4 and CO2 as feedstocks to catalytically produce high-value synthesis gas products has great application prospects. However, as a high-temperature heterogeneous catalytic reaction, the challenge lies in preparing efficient and stable catalysts for long-term operation. To enhance the catalytic performance by optimizing support, this study proposed regulating the catalyst structure and properties using Ce-based metal-organic framework (MOF) derivatives. Compared with the conventional Ni/CeO2, Ni/CeO2-MOF catalysts performed better in DRM. Especially, Ni/CeO2-UiO-66 demonstrated significant improvement in both catalytic activity and stability. It was also noticed that the Ni/CeO2-MOF catalysts had a potential benefit in limiting the conversion of carbon species to inactive forms given the relatively lower carbon gasification temperatures at their surfaces. The advantage of Ni/CeO2-MOF catalysts was attributed to their better void structure and reduction characteristics, as well as higher oxygen vacancy concentration and improved CO2 adsorption activation capability after pre-activation. This study revealed that MOF-derived supports had distinctive structural characteristics, which were manifested as an important component in high-temperature catalyst systems.

Towards Sustainable Production of Polybutylene Adipate Terephthalate: Non-Biological Catalytic Syntheses of Biomass-Derived Constituents.

Renewable chemicals, which are made from renewable resources such as biomass, have attracted significant interest as substitutes for natural gas- or petroleum-derived chemicals to enhance the sustainability of the chemical and petrochemical industries. Polybutylene adipate terephthalate (PBAT), which is a copolyester of 1,4-butanediol (1,4-BDO), adipic acid (AA), and dimethyl terephthalate (DMT) or terephthalic acid (TPA), has garnered significant interest as a biodegradable polymer. This study assesses the non-biological production of PBAT monomers from biomass feedstocks via heterogeneous catalytic reactions. The biomass-based catalytic routes to each monomer are analyzed and compared to conventional routes. Although no fully commercialized catalytic processes for direct conversion of biomass into 1,4-BDO, AA, DMT, and TPA are available, emerging and promising catalytic routes have been proposed. The proposed biomass-based catalytic pathways toward 1,4-BDO, AA, DMT, and TPA are not yet fully competitive with conventional fossil fuel-based pathways mainly due to high feedstock prices and the existence of other alternatives. However, given continuous technological advances in the renewable production of PBAT monomers, bio-based PBAT should be economically viable in the near future.

Catalytic and non-catalytic reactions of methane pyrolysis for hydrogen production in screening and electromagnetic levitation reactors using computational fluid dynamics

Molten metal (MM)-based methane (CH4) pyrolysis is a promising technology for clean hydrogen production with a minimal carbon footprint. Electromagnetic levitation (EMLR) and screening reactors (SR) were used to investigate the intrinsic catalytic reaction kinetics of MM-based CH4 pyrolysis. Heterogeneous catalytic reactions in the SR and EMLR occurred on the surfaces of the MM crucible and droplet, respectively. However, a homogenous non-catalytic reaction may occur just above the surface because the CH4 gas is preheated by the high-temperature MM. This study presents three-dimensional (3D) computational fluid dynamics (CFD) model coupled with chemical reactions to assess the extent to which non-catalytic reactions intervene in CH4 pyrolysis in both the SR and EMLR, which is difficult to measure experimentally. The CFD model validated against experimental data revealed that the non-catalytic reaction accounted for 4.0 % of CH4 pyrolysis in the CH4-Ni0.27Bi0.73 SR at 1045 °C, whereas it represented 0.02 % in the CH4-Sn EMLR at 1021 °C. This result highlights that the EMLR is suitable for studying the intrinsic catalytic reaction kinetics of MM-based CH4 pyrolysis because the non-catalytic reaction occurs to a lesser extent.

The role of carboxylic acid contents in calcium-based metal-organic frameworks for the enhancement of Biginelli reaction

Metal-organic frameworks (MOFs) can carry different functional groups such as COOH, NH2, and SO3H. The most commonly used functional group was COOH due to its Brønsted acidity, polarity, and ability to bond with organic compounds and metals through various interactions. Here, calcium-based MOFs (Ca-MOFs) with different carboxylic arms were successfully prepared and used in heterogeneous Biginelli catalytic reactions. The prepared materials (Ca-BDC-H, Ca-BDC-COOH, and Ca-BDC-(COOH)2) were characterized using different spectroscopic techniques and the morphological structures were determined using microscopic analysis. Besides elucidating the fine form of MOFs, the role of the carboxylic content was tested in multicomponent reaction catalysis in different kinetics and thermodynamic studies, the formation of catalytic products was determined using NMR analysis, and the proposed mechanism was investigated. The results obtained showed that as the carboxylic content in the network increases, the catalytic reaction yield increases which can support the possibility of using the COOH group present in the network with acidic properties in heterogeneous catalysts giving high product yield.