Catalysts For Decomposition Research Articles

Fe–Ce–Al Catalysts for Decomposition of Methane to High Purity Hydrogen and High-Value Carbon

Fe–Ce–Al Catalysts for Decomposition of Methane to High Purity Hydrogen and High-Value Carbon

Synergetic Effect of Ni‐CeO₂ Bimetallic Catalyst for an Effective Decomposition of Methane to Hydrogen and Filamentous Nanocarbons

AbstractThe work attempts to synthesis nickel‐ceria bimetallic catalysts supported on porous carbon template, thermally stable at 850 °C, for dehydrogenation of methane to hydrogen and carbon nanostructures. A series of bimetallic Ni catalysts were synthesized by varying the % ceria content (30Ni‐5CeO2/AC, 30Ni‐10CeO2/AC, and 30Ni‐15CeO2/AC) using the incipient wetness impregnation approach. Among the set of bimetallic catalysts, the 30Ni‐5CeO2/AC catalyst was found to offer highest methane conversion and stability. A maximum conversion of 90 % was achieved with 40 % methane feed concentration along with good catalyst stability. The promoter ceria at low concentration enhanced the dispersion of metal over the catalytic surface, resulting in adequate metal‐support interaction. The ability of the carbon support along with promoter ceria enhanced the thermal stability of the Ni catalyst up to 850 °C, offering high conversion and catalyst stability has been the highlight of the work. Advanced analytical techniques were used to characterize the catalyst's structural, textural, and morphological properties both before and after the reaction. The morphological study of the best‐performing catalyst demonstrated the formation of dense carbon nanotubes through tip‐growth mechanism exhibiting a high aspect ratio.

Effects of nitrogen vacancy sites of oxynitride support on the catalytic activity for ammonia decomposition

Nitrogen-containing compounds such as imides and amides have been reported as efficient materials that promote ammonia decomposition over nonnoble metal catalysts. However, these compounds decompose in an air atmosphere and become inactive, which leads to difficulty in handling. Here, we focused on perovskite oxynitrides as air-stable and efficient supports for ammonia decomposition catalysts. Ni-loaded oxynitrides exhibited 2.5–18 times greater catalytic activity than did the corresponding oxide-supported Ni catalysts, even without noticeable differences in the Ni particle size and surface area of the supports. The catalytic performance of the Ni-loaded oxynitrides is well correlated with the nitrogen desorption temperature during N2 temperature-programmed desorption, which suggests that the lattice nitrogen in the oxynitride support rather than the Ni surface is the active site for ammonia decomposition. Furthermore, NH3 temperature-programmed surface reactions and density functional theory (DFT) calculations revealed that NH3 molecules are preferentially adsorbed on the nitrogen vacancy sites on the support surface rather than on the Ni surface. Thus, the ammonia decomposition reaction is facilitated by a vacancy-mediated reaction mechanism.

The bimetallic 3,5-dinitrobenzoate composites: A flexible-synergistic catalysts for high-performance decomposition of ammonium perchlorate

Composites of metal complexes have catalytic effects on the thermal decomposition of ammonium perchlorate (AP), while the kinetics and mechanism studies of the processes are seldom mentioned. Here, composite microspheres of cupric 3,5-dinitrobenzoate and cobalt 3,5-dinitrobenzoate [(3,5-DNB)Cox•Cuy] were synthesized and employed to research the kinetics and mechanism of AP catalytic decomposition. The decomposition peak temperature of AP in the presence of the (3,5-DNB)Cox•Cuy microspheres decreased from 403 °C (pure AP) to 288 °C, and the released heat increased by 384.5–745.6 J/g. Notably, the (3,5-DNB)Cox•Cuy microspheres significantly improved the kinetic rate constant by 1.83–37.75 times. The (3,5-DNB)Cox•Cuy microspheres exhibited higher activity than their corresponding single components for the thermal decomposition of AP, indicating excellent synergistic effects and proposing a possible mechanism. Understanding the kinetics and mechanism of the catalytic process developed in this study could further improve the decomposition performance of AP.

Microstructure of highly effective platinum–iridium alloys as catalysts for hydrogen peroxide decomposition

Microstructure of highly effective platinum–iridium alloys as catalysts for hydrogen peroxide decomposition

Cation induced electrostatic adsorption driven self-assembly sandwich-like α-MnO2/MXene for efficient self-heating photothermal synergistic catalytic decomposition of carcinogenic gaseous formaldehyde

Realizing self-assembly between different nanoparticles is an important strategy for constructing novel nanostructures or excellent functional composites. Formaldehyde is the primary gaseous pollutant in indoor air, and achieving its ambient temperature decomposition is of great significance for improving indoor air quality. This research reports an electrostatic adsorption driven self-assembly strategy, constructing a sandwich structure α-MnO2/MXene for self-heating photothermal synergistic catalytic decomposition of formaldehyde. The self-assembly process and electrostatic adsorption driven mechanism were detailed. A comparative study was conducted on the performance and mechanisms of the self-assembled sandwich structure and mechanically mixed α-MnO2/MXene in the self-heating photothermal catalytic decomposition of formaldehyde. The sandwich structure α-MnO2/MXene with built-in electric field and Schottky barrier exhibited excellent self-heating photothermal catalytic activity for formaldehyde decomposition, realizing the 100% mineralization of formaldehyde under simulated solar-light irradiation at room temperature; even with the irradiation of visible light, the sandwich structure α-MnO2/MXene can still maintain 82.6% HCHO conversion. Furthermore, we elucidated the self-heating photothermal catalytic mechanism, shedding light on the distinct roles and contributions of photocatalysis and thermal catalysis. It was found that the photothermal catalytic mechanism of the sandwich structure α-MnO2/MXene-S composite involved a thermally assisted photocatalytic process. The advantages of the self-assembled sandwich structure and its mechanism for enhancing photothermal performance were fully revealed. This study reports an effective strategy for electrostatic adsorption self-assembly, offering a fresh perspective on developing non-noble metal catalysts for ambient-temperature formaldehyde decomposition

Innovative Design of anode materials for Li-ion batteries: Bismuth oxide/sodium bismuth molybdate nanocomposites

Novel bismuth oxide/sodium bismuth molybdate nanocomposites (NCs), Bi2O3@NaBi(MoO4)2, were developed successfully via simple methods. Advanced analyses revealed that the NCs were composed of Bi2O3 and NaBi(MoO4)2 particles at the nanoscale, below 10 nm, in a combination of amorphous and crystalline forms. In this work, these NCs were utilized as lithium-ion battery anode materials for the first time, demonstrating exceptional electrochemical performances, including high capacity, superior capacity retention, high coulombic efficiency, excellent rate capacity, and pseudo-capacitance behavior. For instance, Bi2O3@NaBi(MoO4)2 NCs prepared at 1 h and 3 h of reaction time delivered a reversible charge capacity of 1052 and 1034 mAh g−1 after 200 cycles at current densities of 0.1 A g−1 with a capacity retention of 110 and 129 %, respectively. Notably, all the NCs anodes exhibited an excellent initial coulombic efficiency of above 80 %. Materials characterizations and electrochemical analysis revealed that the improved electrochemical properties of the NCs were attributed to their unique architectures, which featured nanostructures, molybdate components, and a small amount of amorphous phase. In addition, the significant capacity increase could be due to the electrochemical milling effect, the in situ formation of metallic particles, and the role of Mo metal in the NCs anodes as the catalysts for Li2O decomposition during cycling. It concluded that Bi2O3@NaBi(MoO4)2 NCs have great potential as advanced anodes for Li-ion storages.

{Co4O4} Cubanes in a conducting polymer matrix as bio-inspired molecular oxygen evolution catalysts

Exploration of efficient molecular water oxidation catalysts for long-term application remains a key challenge for the conversion of renewable energy sources into fuels. Cuboidal {Co4O4} complexes keep attracting interest as molecular water oxidation catalysts as they combine features of both heterogeneous and homogeneous catalysis with bio-inspired motifs. However, the application of many cluster-based catalysts for the oxygen evolution reaction still requires new stabilization strategies. Drawing inspiration from the stabilizing effects of natural polymers, we introduce a conductive polymer-hybrid approach to covalently immobilize {Co4O4} cubane oxo clusters as oxygen evolution catalysts. Polypyrrole is applied as an efficient p-type conducting polymer that promotes hole transfer during the oxygen evolution reaction, resulting in higher turnover frequency compared to the pristine {Co4O4} oxo cluster and heterogeneous Co-oxide benchmarks. The asymmetric coordination of {Co4O4} not only mitigates catalyst decomposition pathways, but also increases the catalytic efficiency by exposing a directed cofacial dihydroxide motif during catalysis.

Metal-doped nanocages (Fe-Si76, Fe-C76, and Fe-Al38N38) as potential catalysts for ozone decomposition to oxygen molecules

Metal-doped nanocages (Fe-Si76, Fe-C76, and Fe-Al38N38) as potential catalysts for ozone decomposition to oxygen molecules

NiCoCr2O4 as a potential catalyst for the thermal decomposition of ammonium nitrate: a kinetic investigation

The thermal decomposition of high energetic materials plays an important role in their thermal performance. Use of the catalyst is one of the efficient ways improve the thermal performance of the high energetic materials. Therefore, in this work nickel cobalt chromite (NiCoCr2O4) prepared using precipitation approach was utilized as a catalyst for decreasing the thermal decomposition temperature and activation energy of high energetic material ammonium nitrate (AN). The results suggest that AN/NiCoCr2O4 decomposes at lower temperature (240 °C) within a short temperature range (Thermo gravimetry decomposition curve = 180–250 °C). The kinetic study was investigated using Kissinger-Akahira-Sunose (KAS) and Kissinger method (5, 10, and 15 °C min−1 heating rates). The activation energy of AN was reduced from 158.0 to 141.5 kJ mol−1 and decrease in the pre-exponential factor was observed upon addition of NiCoCr2O4. The outcome of the present work can be used to design AN based high energetic formulations containing NiCoCr2O4 catalyst with better thermal decomposition performance.

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.

Designing sulfide catalysts for H2S dissociation to H2 based on reaction descriptors and microkinetics

Molybdenum disulfide (MoS2) is a promising catalyst for the challenging transformation of hydrogen sulfide (H2S) into sulfur and hydrogen (H2). However, a detailed understanding of its structure-function correlation still needs to be provided. We used density functional theory calculations to extract relevant reaction indexes (binding energies and free energy barriers) over different MoS2 surfaces. We used these indexes as inspiration in developing new catalysts and a microkinetic model to compare the results, extracting insights into the reaction mechanisms and surface coverages. The turnover frequencies obtained experimentally and through microkinetic modeling are analogous, validating our approach. The findings pave the way for developing more efficient H2S decomposition catalysts and establish a descriptor-based design for other metal sulfide catalysts.

Enhancing CO2 conversion in a temperature-controlled DBD plasma reactor with HKUST-1 catalyst: Water removal and CuO/Cu2O-derived approach

Due to a synergy effect, using dielectric barrier discharge (DBD) plasma technology combined with catalysts for CO2 decomposition, a major contributor to global warming, is recognized as an effective approach to transforming CO2 into valuable products such as CO, which is a crucial feedstock for chemical synthesis. Herein, HKUST-1 was synthesized using the hydrothermal method for CO2 conversion in the DBD reactor. To enhance catalyst performance in the plasma region, HKUST-1 was treated with O2 plasma to increase its specific surface area. Additionally, HKUST-1 was calcined at 300 °C to produce the CuO/Cu2O catalyst. Since the recombination reaction in the CO2 conversion is increased at higher temperatures, the reactor heat is removed using fan cooling and a water circulation system. In the presence of the HKUST-1 catalyst, the CO2 conversion rate significantly increased by 132 %, 82 %, and 12 % in reactors operating without cooling, with fan cooling, and with water cooling circulation, respectively compared to the reactors without catalyst, at a flow rate of 50 ml/min and maximum input power. The catalysts have been characterized using a comprehensive suite of analytical techniques, including FTIR, XRD,TEM, SEM, EDS, and BET analysis. The BET analysis indicates that the specific surface area of HKUST-1 after O2 plasma treatment is increased by 52 %, which causes an increasing conversion rate of up to 18 %. The CuO/Cu2O catalyst demonstrated maximum CO2 conversion of 21 % at an input power of 140 W and achieved energy efficiency of 8.6 % at 40 W. The presence of oxygen vacancies within this catalyst enhances the process of CO2 decomposition.

Highly efficient Co-added Ni/CeO2 catalyst for co-production of hydrogen and carbon nanotubes by methane decomposition

The catalytic decomposition of methane (CDM) is a hydrogen and nanostructured carbon production process with minimal CO2 emission. Among the transition metal-based catalysts (e.g. Ni, Fe, Co, etc.), Ni-based catalysts are most widely studied due to the higher catalytic activity in decomposing methane. However, the limited lifespan of the catalyst makes it unsuitable for practical applications. Effective methane decomposition catalysts should be designed to optimize both reaction efficiency and catalyst lifetime. A Ni/CeO2 catalyst, developed in previous studies, Co was added to promote low-temperature (< 700 °C) activity manipulating the redox property of Co. Among the prepared catalysts with varying Ni:Co ratio, the methane conversion rate of the Ni8Co2/CeO2 catalyst was approximately twice that of the Ni10/CeO2 catalyst, confirming its excellent low-temperature activity. The reaction rate of Ni8Co2/CeO2 catalyst was 4.38 mmol/min∙gcat at 600 °C with WHSV of 36 L/gcat∙h. In terms of characteristics of carbon products, Raman spectroscopy analysis revealed that the carbon grown on the catalyst surface exhibited high crystallinity, with D-G band ratio (ID/IG) of 1.01. The fresh and used catalyst samples were characterized by TEM, XPS, XAS, and other methods to analyze the parameters affecting catalytic activity.

Highly effective direct conversion of H2S into COx-free H2 and S at low temperature over novel MoxC@ZrO2 microwave catalysts

Direct decomposition of H2S into H2 and S is an attractive alternative to the Claus process, because COx-free H2 and S can be simultaneously recovered from an abundant and toxic waste gas, which has huge social economic and ecological environmental benefits. However, it is still a great challenge to achieve the direct H2S decomposition reaction with high efficiency due to the thermal equilibrium limitation. Herein, a core-shell structured MoxC@ZrO2 was developed as novel microwave catalyst for microwave catalytic H2S decomposition. More specifically, the H2S conversion over MoxC@ZrO2 catalyst is as high as 99.9% at 650 °C, which immensely surpasses the H2S equilibrium conversion (6.1% at 650 °C). This study provides an effective strategy for the design of highly active microwave catalysts, and supplies a strategy for efficiently catalytic decomposition of H2S waste and recovering high-value hydrogen and sulfur at lower reaction temperatures.

Hemilabile and Redox-Active Quinone Ligands Unlock sp3-Rich Couplings in Nickel-Catalyzed Olefin Carbosulfenylation.

A three-component coupling approach toward structurally complex dialkylsulfides is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and alkylsulfenamide (N-S) electrophiles. Efficient catalytic turnover is facilitated using a tailored N-S electrophile containing an N-methyl methanesulfonamide leaving group, allowing catalyst loadings as low as 1 mol%. Regioselectivity is controlled by a collection of monodentate, weakly coordinating native directing groups, including sulfonamides, amides, sulfinamides, phosphoramides, and carbamates. Key to the development of this transformation is the identification of quinones as a family of hemilabile and redox-active ligands that tune the steric and electron properties of the metal throughout the catalytic cycle. DFT calculations show that the duroquinone (DQ) ligand adopts different coordination modes in different stages of the Ni-catalyzed 1,2-carbosulfenylation-binding as an η6 capping ligand to stabilize the precatalyst/resting state and prevent catalyst decomposition, binding as an X-type redox-active durosemiquinone radical anion to promote alkene migratory insertion with a less distorted square planar Ni(II) center, while binding as an η1 L-type ligand to promote N-S oxidative addition at a relatively more electron-rich and sterically less crowded Ni(I) center.

Hemilabile and Redox‐Active Quinone Ligands Unlock sp3‐Rich Couplings in Nickel‐Catalyzed Olefin Carbosulfenylation

A three‐component coupling approach toward structurally complex dialkylsulfides is described via the nickel‐catalyzed 1,2‐carbosulfenylation of unactivated alkenes with organoboron nucleophiles and alkylsulfenamide (N–S) electrophiles. Efficient catalytic turnover is facilitated using a tailored N–S electrophile containing an N‐methyl methanesulfonamide leaving group, allowing catalyst loadings as low as 1 mol%. Regioselectivity is controlled by a collection of monodentate, weakly coordinating native directing groups, including sulfonamides, amides, sulfinamides, phosphoramides, and carbamates. Key to the development of this transformation is the identification of quinones as a family of hemilabile and redox‐active ligands that tune the steric and electron properties of the metal throughout the catalytic cycle. DFT calculations show that the duroquinone (DQ) ligand adopts different coordination modes in different stages of the Ni‐catalyzed 1,2‐carbosulfenylation—binding as an η6 capping ligand to stabilize the precatalyst/resting state and prevent catalyst decomposition, binding as an X‐type redox‐active durosemiquinone radical anion to promote alkene migratory insertion with a less distorted square planar Ni(II) center, while binding as an η1 L‐type ligand to promote N–S oxidative addition at a relatively more electron‐rich and sterically less crowded Ni(I) center.

Role of MgO in Al2O3‐supported Fe catalysts for hydrogen and carbon nanotubes formation during catalytic methane decomposition

AbstractCatalytic methane decomposition is a promising technology for reducing the reliance on fossil fuels and mitigating the effects of climate change by producing clean hydrogen and value‐added carbon without the emission of greenhouse gases. The aim of the study was to investigate the use of Al2O3‐modified MgO doped iron‐based catalysts for the catalytic decomposition of methane. The catalysts were synthesized using the impregnation method and characterized using various analysis techniques, including Brunauer, Emmett, and Teller, temperature programmed reduction, temperature programmed oxidation, X‐ray diffraction, thermal gravimetric analysis, Raman, scanning electron microscopy, and transmission electron microscopy. The activity of the synthesized catalysts was tested in a packed‐bed reactor with a gas flow rate of 20 mL/min at a temperature of 800°C. The investigation focuses on the influence of incorporating magnesium into alumina catalysts with MgO concentration ranging from (20%–70%), where higher magnesium levels improve catalytic activity by creating more active sites, positively impacting methane decomposition. Enhanced catalyst reducibility and increased particle dispersion lead to improved catalytic properties despite the reduced surface area. The FA70M and FA63M catalysts exhibited almost the same catalytic characteristics and the highest stability and methane conversion among the catalysts investigated, reaching 87% and 85% at 800°C for 120 min. Moreover, both catalysts showed hydrogen yields of 86% and 85%, respectively. The introduction of MgO further increased the total carbon yield from 103% with FA and 39% for FM to 114% and 120% for the respective catalysts (FA70M and FA63M). During the methane decomposition reaction, carbon nanotubes of varying diameters were produced. Higher iron loading resulted in a positive trend.

Effect of promoters on the performance of CuNi catalysts for hydrogen production from methanol decomposition

Abstract Utilizing the exhaust heat from engines to decompose methanol for hydrogen production, and subsequently introducing this hydrogen into the combustion chamber, is one of the crucial approaches for achieving energy savings and emission reductions. The role of an efficient and stable catalyst for methanol decomposition is paramount in this application. Therefore, CuNi-based catalysts modified with promoters such as Zr, La, Mn, and Mg were prepared using a stepwise impregnation method. The developed catalysts were tested using various analytical methods and characterization techniques. The results indicate that the addition of the Zr enhances the dispersion of active components, improves the catalyst’s reducibility. This, in turn, enhances the catalyst’s activity and hydrogen selectivity. The hydrogen yield of the Zr modified catalyst increased by an average of 12% compared to the original catalyst. Furthermore, the Zr modified catalyst exhibits exceptional stability after prolonged use. La can enhance the low-temperature activity of the catalyst but performs poorly at high temperatures. The promoter Mn has a minimal impact on the overall performance of the catalyst. Conversely, the addition of Mg as a promoter inhibits the dispersion of active components, resulting in adverse effects on the catalyst.

Mechanisms of GTN-induced migraine: Role of NOS isoforms, sGC and peroxynitrite in a migraine relevant mouse model.

Migraine research has highlighted the pivotal role of nitric oxide (NO) in migraine pathophysiology. Nitric oxide donors such as glyceryl trinitrate (GTN) induce migraine attacks in humans, whereas spontaneous migraine attacks can be aborted by inhibiting NO production. The present study aimed to investigate how GTN triggers migraine through its three nitric oxide synthase (NOS) isoforms (neuronal NOS (nNOS), endothelial NOS (eNOS) and inducible NOS (iNOS)) via a suspected feed-forward phenomenon. Migraine-relevant hypersensitivity was induced by repeated injection of GTN in an in vivo mouse model. Cutaneous tactile sensitivity was assessed using von Frey filaments. Signaling pathways involved in this model were dissected using non-selective and selective NOS inhibitors, knockout mice lacking eNOS or nNOS and their wild-type control mice. Also, we tested a soluble guanylate cyclase inhibitor and a peroxynitrite decomposition catalyst (Ntotal = 312). Non-selective NOS inhibition blocked GTN-induced hypersensitivity. This response was partially associated with iNOS, and potentially nNOS and eNOS conjointly. Furthermore, we found that the GTN response was largely dependent on the generation of peroxynitrite and partly soluble guanylate cyclase. Migraine-relevant hypersensitivity induced by GTN is mediated by a possible feed-forward phenomenon of NO driven mainly by iNOS but with contributions from other isoforms. The involvement of peroxynitrite adds to the notion that oxidative stress reactions are also involved.