Catalyst Particles Research Articles

Pristine and Nature‐Inspired Hematite (α‐Fe2O3) Nanoparticles and Search for their Photocatalytic Application

AbstractThe article describes synthesis of green‐mediated hematite nanoparticles (20–30 nm) using Polianthes tuberosa flower extract. Structural, microscopic, and magnetic studies confirm the synthesis of iron oxide nanoparticles of pure hematite phase. Spectroscopic techniques are employed to identify different electronic transitions and defect levels as well as to estimate the energy bandgap and Urbach energy. A correlation among the particle size, bandgap energy, and Urbach energy is noticed. These hematite nanoparticles act as visible light photocatalyst which degrade dye in aqueous medium without the addition of any additives. The catalyst particle size, catalyst quantity, pH of dye solution, and solution temperature have significant impact on the photodegradation process of dye molecules in aq. solution. All observations advocate that green synthesis of hematite nanoparticles with Polianthes tuberosa flower extract can significantly modulate their optical and photocatalytic properties. These materials may find potential uses in water splitting for hydrogen production and purification of water by removing organic pollutants. The study highlights that using commercially cheap starting materials and extract made from naturally available plant parts, materials having huge application potentials can be synthesized at low cost by the simple green synthesis approach.

Controlled Vapor-Liquid-Solid Growth of Long and Remarkably Thin Pb1-xSnxTe Nanowires with Strain-Tunable Ferroelectric Phase Transition.

The Pb1-xSnxTe family of compounds possess a wide range of intriguing and useful physical properties, including topologically protected surface states, robust ferroelectricity, remarkable thermoelectric properties, and potential topological superconductivity. Compared to bulk crystals, one-dimensional (1D) nanowires (NWs) offer a unique platform to enhance the functional properties and enable new capabilities, e.g., to realize 1D Majorana zero modes for quantum computations. However, it has been challenging to achieve controlled synthesis of ultrathin Pb1-xSnxTe (0 ≤ x ≤ 1) nanowires in the truly 1D region. In this work, we report on a Au-catalyzed vapor-liquid-solid (VLS) growth of remarkably thin (20-30 nm) and sufficiently long (several to tens of micrometers) Pb1-xSnxTe nanowires of high single-crystalline quality in a controlled fashion. This controlled growth was achieved by enhancing the incorporation of Te into the Au catalyst particle to facilitate the precipitation of the Sn/Pb species and suppress the enlargement of the particle, which we identified as a major challenge for the growth of ultrathin nanowires. Our growth strategy can be easily extended to other compound and alloy nanowires, where the constituent elements have different incorporation rates into the catalyst particle. Furthermore, the growth of thin Pb1-xSnxTe nanowires enabled strain-dependent electrical transport measurements, which shows an enhancement of electrical resistance and ferroelectric transition temperature induced by uniaxial tensile strain along the nanowire axial direction, consistent with density functional theory calculations of the structural phase stability.

A Tantalum-Rich Pt-Ta-Co Electrocatalyst for Polymer Electrolyte Fuel Cells

In polymer electrolyte fuel cells (PEFCs), Pt catalyst particle growth due to load fluctuation potential cycling, and oxidative corrosion of the carbon support due to start-stop potential cycling are important issues for cathode electrocatalysts affecting their durability. Here, we incorporate tantalum into the electrocatalyst to improve both the catalytic activity and durability. This is achieved via self-assembly of a nanocomposite electrocatalyst via dealloying to form Pt-Co alloy and TaOx support nanoparticles. Half-cell electrochemical measurements confirm that the catalytic activity and durability are significantly improved by the formation of this nanocomposite electrocatalyst.

Properties analysis of catalyst particles during stripper distributor fault in industrial fluid catalytic cracking unit

Particle attrition is prevalent in fluid catalytic cracking (FCC) process, and severe particle attrition threatens the steady operation of FCC units. In this study, the processes of attrition and dealing in industrial FCC unit were investigated, and the relationship between particle physical properties and fault source was analyzed. The results showed that the most frequent particle sizes of the attrited equilibrium catalyst and the spent catalyst were 48.85 μm and 55.21 μm, respectively. The replacement of attrited catalyst by equilibrium catalyst with higher mechanical strength could alleviate the catalyst attrition problem, and the most frequent particle size of the catalyst remained at 75.81 μm after experiencing attrition. When the replacement rate reached 66.83 %, catalyst loss was reduced and the stability of FCC unit operation was significantly improved. This study would contribute to a deeper understanding of the particle abrasion and fragmentation behavior in different environments in industrial FCC units.

A Numerical Study on the Influence of Confining Walls on Drag and Heat Transfer Coefficients in Single‐Particle Lab‐Scale Reactors

AbstractSingle‐particle reactors in lab‐scale are a promising technology to gain an in‐depth understanding of the intricate reaction and transport processes that occur in catalyst particles under operando conditions. It is not described whether the effect of the bounding walls in such narrow flow channels influence the processes at the particle. Therefore, this work applies three‐dimensional (3D) computational fluid dynamics (CFD) simulations to analyze the drag coefficient CD alongside the local and average particle Nusselt number Nup as characteristic local and integral quantities in the range of particle Reynolds numbers 10 ≤ Rep ≤ 103. An equation is derived to correct for the wall effects on CD and Nup and assist the experimenter in the interpretation of measured results.

Modeling catalyst effectiveness factor with space-fractional derivative using Haar wavelet collocation method

Abstract Mass transfer limitations may considerably affect the rate of a heterogeneous catalytic process. The catalyst effectiveness factor is a quantitative measure of the impact of the diffusion process inside a catalyst particle. The effectiveness factor is derived from the solution of the steady-state reaction-diffusion problem. Herein, we simulate the steady-state reaction-diffusion equation with space-fractional derivative and linear reaction kinetics. The solution to the problem is obtained numerically using the Haar wavelet collocation method. The effect of the anomalous diffusion exponent on the catalyst effectiveness factor and process parameters, e.g. reactor volume and catalyst mass, is demonstrated. We anticipate that the process efficiency will be notably improved by changing the diffusion regime from standard to superdiffusive.

A Three–Dimensional Nanoscale View of Electrocatalyst Degradation in Hydrogen Fuel Cells

AbstractThe loss of platinum (Pt) electrochemically active surface area (ECSA) is a critical degradation mode that often becomes a limiting factor for heavy‐duty proton exchange membrane fuel cell vehicles. High surface area carbon supports have been shown to improve Pt dispersion and limit detrimental ionomer‐electrocatalyst interactions due to their large interior pore volume. In this work, using automated scanning transmission electron tomography, the degradation of nanoparticles located on the interior versus exterior surfaces of the carbon support is compared following a catalyst‐specific accelerated stress test (AST) of 90,000 voltage cycles between 0.6 V to 0.95 V. The results reveal a notable increase in median particle size for both interior and exterior Pt catalyst particles, with a slightly higher increase in particle size distribution and loss of specific surface area for the particles located on the exterior carbon surface. The fraction of Pt nanoparticles that reside within the interior of the carbon support also increased following the AST test, accompanied by evidence of an increase in average carbon mesopore size. The results shed light on the degradation mechanisms affecting electrochemical properties and the enhanced particle accessibility at lower relative humidity.

Fluidized-bed OCM reaction: A promising Mn2O3-Na2WO4/TiO2 catalyst and a numerical study

The fluidized-bed reactor with excellent heat and mass transfer features has great appeal for application in the oxidative coupling of methane (FB-OCM), whereas qualified fluid catalysts represent a grand challenge. Herein, we report a high-performance Mn2O3-Na2WO4/TiO2 fluid catalyst (5.4 wt% Mn2O3 and 2 wt% Na2WO4), which was obtained by the incipient-wetness impregnation method and examined in the OCM reaction in an electric-heating quartz fluidized-bed reactor (i.d., 2 cm). The standard normalization method on the basis of carbon atom was used for calculating the CH4 conversion and C2-C3 selectivity. This catalyst achieves 35.5 % CH4 conversion, 66 % C2-C3 selectivity and particularly 15.1 % single-pass yield of C2H4 for a feed of CH4/O2/H2O=3/1/1 with a catalyst dosage of 20 mL at 700 °C and a total GHSV of 7200 h−1. Such catalyst is stable for at least 50 h without signs of deactivation and agglomeration/defluidization. The catalyst particle size is crucial for the FB-OCM reaction with respect to the reaction light-off and catalyst fluidization. The catalyst with preferable particle size of 450–600 μm can not only trigger the OCM reaction at a relatively low temperature of 630 °C but also warrant active bubbling fluidization. Furthermore, thanks to the low amount of Na2WO4 and interpenetrating structure of TiO2-nanorod, such catalyst achieves good anti-aggregation and robust mechanical strength (with a low attrition index of 1.9 %). The effects of water-adding amount in feedstock and catalyst particle size distribution on the hydrodynamics behaviour were investigated in a laboratory-scale fluidized-bed OCM reactor by using numerical simulation method.

Study on the arrangement of CO2 sorbent and catalyst for integrated CO2 capture and methanation

Integrated CO2 capture and utilization (ICCU) is an emerging technology to reduce CO2 emissions by greatly simplifying the processes of conventional CO2 capture and utilization. In particular, ICCU-methanation could directly convert the low-concentration CO2 into CH4 using hydrogen from new energy electricity, representing an efficient Power-to-Gas route. CO2 adsorption/catalytic materials play a crucial role for the operation of ICCU-methanation, and it is more feasible to scale up material production and avoid components interference by directly combining the sorbent and catalyst. However, it is necessary to reveal the effect of different arrangements of sorbent and catalyst on reaction characteristics of ICCU-methanation. In the work, the matching of K2CO3-doped Li4SiO4 sorbent with various supported Ni-based catalyst was tested and four arrangements of sorbent and catalyst particles in a fixed-bed were investigated to understand the influences on ICCU-methanation. Results show that the presence of catalyst accelerates CO2 supply by sorbent and achieves quicker methanation, and the promotion effect becomes more obvious with a closer contact between the sorbent and catalyst. Under optimized conditions, ICCU-methanation of uniformly mixed K-Li4SiO4 and Ni/Al2O3 shows an excellent performance with very stable CO2 conversion of 95.58% and CH4 selectivity of 93.29% during cyclic reactions.

Highly Stable Ni-B/Honeycomb-Structural Al2O3 Catalysts for Dry Reforming of Methane.

Two-component catalysts have garnered significant attention in the field of catalysis due to their ability to inhibit Ni sintering. In the present work, honeycomb-structuralstructured Al2O3-supported Ni and B were prepared to enhance coke tolerance during dry reforming of methane (DRM). Transmission electron microscopy (TEM) results revealed that the average particle sizes on Ni/Al2O3 and Ni-0.16B/Al2O3 were 7.6 nm and 4.2 nm, respectively, indicating that B can effectively inhibit Ni sintering. After a 100-hour reaction, the conversion of CH4 and CO2 on Ni/Al2O3 decreased by approximately 5 %, whereas on Ni-0.16B/Al2O3, there was no significant decrease in CH4 and CO2 conversion, with values of approximately 81.6 % and 87.2 %, respectively. In situ DRIFT spectra demonstrated that Ni-0.16B/Al2O3 enhanced the activation of CO2, thus improving the catalyst's stability. A Langmuir-Hinshelwood-Hougen-Watson (LHHW) model was developed for intrinsic kinetics, and the resulting kinetic expressions were well-fitted fit to the experimental data, with R2 values exceeding 0.9. ActivationThe activation energies were also calculated. The outstanding stability of Ni-0.16B/Al2O3 can be attributed to its stable honeycomb structure and B's ability to significantly inhibit Ni sintering, reduce catalyst particle size, and enhance coke tolerance.

Water-retaining slurry washcoat for high-loading and robust CuMnOx structured catalyst toward durable monoxide oxide purification from real flue gas

Structured catalysts play key roles in many industries with the advantages of low pressure drop and efficient mass transfer. The copper-manganese oxide (CuMnOx) as a cost-effective catalyst has been widely applied in gas purification, but still lack efficient structured catalyst due to the challenge in controlling its slurry and coating quality. In this work, this challenge was addressed by introducing the water-retaining agent (WRA) into slurry with sophisticatedly designed conditions. The effects of the type and dosage of WRA, pH value, and temperature on slurry properties including viscosity, stability, and water-retention were systematically studied, and the slurry property-coating quality relationship was correlated. The preferred slurry and coated layer could be segregated into sub-millimeter-sized water-retaining regions where catalyst and binder particles were well dispersed and connected. After slow release of water and organic during drying and calcination, the CuMnOx structured catalyst with uniform, defect-free and dense coating was obtained, showing high loading (>160 kg/m3), great mechanical strength (powder shedding rate < 1 wt%), and no blockage for practical use. The robustness of the structured catalysts was validated by a scale-up preparation of 2 m3 volume amount for CO purification from real ore-sintering flue gas in a steel plant, which achieved the CO catalytic efficiency maintaining over 90 % for more than 1440 h. This work showcases an efficient strategy for structured catalyst preparation and expands the gas purification application of the industrially-favored CuMnOx.

The Coking of a Solid Catalyst Rationalized with Combined Raman and Fluorescence Lifetime Microscopy.

The formation of carbon deposits is a major deactivation pathway for solid catalysts. Studying coking on industrially relevant catalysts is, however, often challenging due to the sample heterogeneity. That is especially true for zeolite-containing catalysts where fluorescence often hampers their characterization with Raman spectroscopy. We turned this disadvantage into an advantage and combined Raman and fluorescence (lifetime) microscopy to study the coking behavior of an equilibrium catalyst material used for fluid catalytic cracking of hydrocarbons. The results presented illustrate that this approach can yield new insights in the physicochemical processes occurring within zeolite-containing catalyst particles during their coking process. Ex situ analyses of single catalyst particles revealed considerable intra-sample heterogeneities. The sample-averaged Raman spectra showed a higher degree of graphitization when the sample was exposed to more hexane, while the sample-averaged fluorescence lifetime showed no significant trend. Simultaneous in situ Raman and fluorescence (lifetime) microscopy, used to follow the coking and the regeneration of single particles, gave more insights in the changing fluorescence dynamics. During the coking, the rise and decline of the average fluorescence lifetime suggested the prolonged presence of smaller coke species that are quenched more and more by adjacent larger polyaromatics acting as Förster-resonance-energy-transfer acceptors.

Reaction-Driven Migration Dynamics of Nano-Metal Particles Unraveled by Quantitative Electron Microscopies.

The stability of supported nano-metal catalysts holds significant importance in both scientific and economic practice, beyond the long pursuit of enhanced activity. While previous efforts have concentrated on augmenting the interaction between nano-metals and carriers, in the thermodynamic macro-perspective, to achieve optimized repression upon particle migration coalescence and Ostwald ripening, nevertheless, the microscale kinetics of migrating catalyst particles driven by the reaction remains unknown. In this work, the migration of nano-copper particles is investigated during hydrogen oxidation reaction by utilizing high spatiotemporal resolution of environmental transmission electron microscopy. It is shown that there exists a delicate correlation between the migration dynamics of nano-copper particles and the evolution of asymmetrically distributed Cu and Cu2O phases over the particle surface. It is found that the interplay of reduction and oxidation near the surface areas filled with Cu and Cu2O phases can facilitate the pressure gradient, which drives the migration of nano-particles. A driving force model is therefore established which is capable of qualitatively explaining the influences of reaction conditions such as temperature and hydrogen-to-oxygen ratio on the reaction-driven particle migration. This work adds a potential yet critical perspective to understanding particle migration and thus the nano-metal catalyst particle sintering in heterogeneous catalysis.

Performance of supported Co3O4 catalysts in the preferential oxidation of carbon monoxide: Effect of support type and synthesis method

This study investigated the performance of supported Co3O4 catalysts during the preferential oxidation of carbon monoxide (CO-PrOx) in a H2-rich environment, focusing on the effects of different catalyst synthesis methods, namely, wetness impregnation (WI) and solution combustion synthesis (SCS), and different support materials, namely, Al2O3 and SiC. During CO-PrOx, the SiC-supported Co3O4 catalysts attained higher CO2 yields when compared with the Al2O3-supported Co3O4 catalysts possibly because of the existence of weaker interactions between Co3O4 and SiC. Moreover, the catalysts prepared via SCS achieved higher CO2 yields than the catalysts prepared via WI likely due to the presence of smaller and well-dispersed Co3O4 particles in the SCS-prepared catalysts. Significantly high amounts of unwanted CH4 were produced over the SiC-supported catalysts between 225 and 250 °C. The high CO methanation activity was also attributed to the weaker Co3O4-SiC interactions, which enabled the easier reduction of Co3O4 to methanation active metallic Co.

Non-thermal plasma-catalytic ammonia synthesis over alumina-supported iron catalyst: Insights into the effect of alumina calcination temperature

Non-thermal plasma-catalytic ammonia synthesis (NTPCAS) has been regarded as a promising route to store hydrogen by utilizing renewable electricity. Alumina is a suitable support of the catalysts in NTPCAS and its properties can influence the performance of catalysts remarkably. In this study, the influence of the alumina calcination temperatures (Tc) on the catalytic performance of Fe-Al-x (x represents the value of Tc) was analyzed in a dielectric barrier discharge (DBD) reactor for NTPCAS. The results suggested that an increase in Tc transforms the alumina crystalline from γ phase to α phase. The best performance with a synthesized ammonia concentration of 11833 ppm was achieved over Fe-Al-900 with coexisting γ and θ phases of alumina under N2: H2 = 1:1 and SEI = 37.05 kJ/L conditions, which was 37 % higher than that of Fe-Al-800 with only γ phase. In addition, the larger Tc (i.e. 1100 and 1200 °C) decreased the specific surface area, increased the mean catalyst particle size, and led to the non-uniform dispersion of Fe species. The NH3-TPD and XPS studies suggested that an increase in Tc could influence the surface acidity and oxygen vacancy concentration of Fe catalysts, which were crucial to adjusting the catalytic activity for NTPCAS. This study clarifies the value of a suitable design of support of catalysts for improving NTPCAS.

Hydro-co-processing Jatropha oil and crude oil blend with Ni-Mo-supported Al2O3 catalyst to produce hybrid fuels: the effect of catalyst particle size

Hydro-co-processing Jatropha oil and crude oil blend with Ni-Mo-supported Al2O3 catalyst to produce hybrid fuels: the effect of catalyst particle size

A Fe-NC electrocatalyst boosted by trace bromide ions with high performance in proton exchange membrane fuel cells

Replacement of expensive and rare platinum with metal–nitrogen–carbon catalysts for oxygen reduction reactions in proton exchange membrane fuel cells is hindered by their inferior activity. Herein, we report a highly active iron-nitrogen-carbon catalyst by optimizing the carbon structure and coordination environments of Fe-N4 sites. A critical high-temperature treatment with ammonium chloride and ammonium bromide not only enhances the intrinsic activity and density of Fe-N4 sites, but also introduces numerous defects, trace Br ions and creates mesopores in the carbon framework. Notably, surface Br ions significantly improve the interaction between the ionomer and catalyst particles, promoting ionomer infiltration and optimizing the O2 transport and charge transfer at triple-phase boundary. This catalyst delivers a high peak power density of 1.86 W cm−2 and 54 mA cm−2 at 0.9 ViR-free in a H2-O2 fuel cells at 80 °C. Our findings highlight the critical role of interface microenvironment regulation.

Assessment of transport phenomena in catalyst effectiveness for chemical polyolefin recycling

Since the dawn of agitated brewing in the Paleolithic era, effective mixing has enabled efficient reactions. Emerging catalytic chemical polyolefin recycling processes present unique challenges, considering that the polymer melt has a viscosity three orders of magnitude higher than that of honey. The lack of protocols to achieve effective mixing may have resulted in suboptimal catalyst effectiveness. In this study, we have tackled the hydrogenolysis of commercial-grade high-density polyethylene and polypropylene to show how different stirring strategies can create differences of up to 85% and 40% in catalyst effectiveness and selectivity, respectively. The reaction develops near the H2–melt interface, with the extension of the interface and access to catalyst particles the main performance drivers. Leveraging computational fluid dynamics simulations, we have identified a power number of 15,000–40,000 to maximize the catalyst effectiveness factor and optimize stirring parameters. This temperature- and pressure-independent model holds across a viscosity range of 1–1,000 Pa s. Temperature gradients may quickly become relevant for reactor scale-up.

Regulation of surface oxygen vacancy of Cu-CeO2/TiO2 heterostructures via fast Joule heating method for enhanced CO2 electrochemical reduction

Strict control of carbon emissions is crucial for expediting the achievement of carbon neutrality. However, the current CO2RR electrocatalytic exhibits numerous shortcomings that impede the enhancement of catalytic activity. Issues such as lengthy catalyst preparation times, and high levels of precious metal content. Additionally, the aggregation of ultrafine nanoparticles contributes to a rapid deterioration in catalytic performance. Herein, a Joule-heating method is efficiently utilized to synthesize heterostructures nano-catalysts for CO2 electroreduction on carbon cloth substrates. This method takes advantage of the thermoelectric coupling of the carbon cloth to achieve carbothermal reduction, while also regulating phase composition and introduction of oxygen vacancies. The Cu-CeO2/TiO2/CC catalyst synthesized in this method showed a current density in CO2 of −32 mA·cm−2 at −1.0 V (vs. RHE). Notably, this catalyst demonstrated high CO selectivity and Faraday efficiency (FECO) of up to 82.5 % at a low potential of −0.3 V (vs. RHE). Optimal electrochemical performance is achieved at a power of 40 W. The ultra-fast temperature change process prevented the agglomeration of catalyst particles and facilitated the construction of a stable heterogeneous interface with a high oxygen vacancy concentration. In conclusion, this study presents a promising approach, particularly for the rapid preparation of low-cost, highly selective non-precious metal electrocatalysts.

Enhanced removal of antibiotic-resistant bacteria and resistance genes by three-dimensional electrochemical process using MgFe2O4-loaded biochar as both particle electrode and catalyst for peroxymonosulfate activation

In this study, MgFe2O4-loaded biochar (MFBC) was used as a three-dimensional particle electrode to active peroxymonosulfate (EC/MFBC/PMS) for the removal of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs). The results demonstrated that, under the conditions of 1.0 mM PMS concentration, 0.4 g/L material dosage, 5 V voltage intensity, and MFBC preparation temperature of 600 °C, the EC/MFBC600/PMS system achieved complete inactivation of E. coli DH5α within 5 min and the intracellular sul1 was reduced by 81.5 % after 30 min of the treatment. Compared to EC and PMS alone treatments, the conjugation transfer frequency of sul1 rapidly declined by 92.9 % within 2 min. The cell membrane, proteins, lipids, as well as intracellular and extracellular ARGs in E. coli DH5α were severely damaged by free radicals in solution and intracellular reactive oxygen species (ROS). Furthermore, up-regulation was observed in genes associated with oxidative stress, SOS response and cell membrane permeability in E. coli DH5α, however, no significant changes were observed in functional genes related to gene conjugation and transfer mechanisms. This study would contribute to the underlying of PMS activation by three-dimensional particle electrode, and provide novel insights into the mechanism of ARB inactivation and ARGs degradation under PMS advanced oxidation treatment.