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At least 37 records · Page 2

Understanding the Deactivation of Ag–ZrO 2 /SiO 2 Catalysts for the Single-step Conversion of Ethanol to Butenes

Ag–ZrO 2 /SBA-16 has recently been found to be efficient for catalyzing the single-step conversion of ethanol to butene (1- and 2-butene mixtures) in the presence of H 2 . The reaction proceeds via a cascading sequence of reactions over mixed metal and Lewis sites, with the catalyst composition tuned to selectively favor butene formation. However, the catalyst slowly deactivates when evaluated over long reaction times. Here, we evaluated the lifetime of the Ag–ZrO 2 /SBA-16 catalyst system for ethanol-to-butene conversion at 325 °C for up to 800 hours on stream. Several characterization techniques were used to elucidate the mechanism(s) by which catalyst deactivation occurs. Coke deposition, Ag particle sintering, and Ag 0 -to-Ag + oxidation state change were identified to be the major causes of catalyst deactivation. Coke deposits cover primarily Lewis acid sites which are responsible for aldol condensation, Meerwein-Ponndorf-Verley (MPV) reduction, and dehydration reactions. Ag particle sintering and Ag oxidation state change leads to a reduction in the number of metallic Ag sites responsible for the dehydrogenation/hydrogenation steps. The fresh catalyst likely experiences hydrothermal sintering in the early stage of reaction and permanently loses some active Lewis acid sites before reaching a new structural steady state. The deactivation of Lewis acid sites leads to a decrease in overall ethanol conversion, whereas the deactivation of the metallic Ag sites decreases the butene selectivity. For catalyst regeneration, oxidative calcination (at 500 °C) followed by reduction (at 325 °C) successfully removes all the coke species on the catalyst surface and restores the metallic Ag particles of the 4Ag–4ZrO 2 /SBA-16 catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deactivation by Potassium Accumulation on a Pt/TiO 2 Bifunctional Catalyst for Biomass Catalytic Fast Pyrolysis

Biomass-derived feedstocks bring significant challenges to the longevity of the catalysts used for their conversion, and alkali metals, for example, K, in the feedstock have been widely ascribed as one of the important factors causing catalyst deactivation. To address this challenge, it is critical to understand the mechanism of catalyst deactivation caused by K accumulation to guide the improvement of catalysts and processes and the development of catalyst regeneration strategies. In this work, we report a deep understanding of the impact of K on a bifunctional Pt/TiO 2 catalyst, which is an efficient catalyst for the ex situ catalytic fast pyrolysis of biomass. We simulated the K-poisoning of Pt/TiO 2 catalysts by purposely loading different amounts of K (100-6000 ppm by weight) on the catalysts. A series of characterization approaches, including scanning transmission electron microscopy, Fourier transform infrared spectroscopy, and chemical titration, were combined with a kinetic assessment of multiple probe reactions to elucidate the mechanism of Pt/TiO 2 deactivation by K accumulation. At low K loadings (<800 ppm), K preferentially poisons the strong Lewis acid sites, leading to significantly reduced activity for acid-catalyzed alcohol dehydration. However, acetone condensation is less sensitive to the poisoning of strong Lewis acid sites. Reactions that occur on Pt sites or at the metal-support interface, including alkene hydrogenation, m-cresol hydrodeoxygenation (HDO), and CO oxidation, were not impacted. At high K loadings (>800 ppm), K starts to accumulate on the Pt-TiO 2 interfacial area, poisoning the interfacial active sites for HDO and CO oxidation reactions. We further found that the poisoning of the Pt/TiO 2 catalyst by K is reversible, and water washing can successfully remove the accumulated K and recover the activities for both alcohol dehydration and m-cresol HDO reactions.

09 BIOMASS FUELS↗

Visible Light Responsive Catalysts Using Quantum Dot-Modified Ti02 for Air and Water Purification

The method of photocatalysis utilizing titanium dioxide, TiO2, as the catalyst has been widely studied for trace contaminant control for both air and water applications because of its low energy consumption and use of a regenerable catalyst. Titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors and are a setback for the technology for space application due to the possibility of Hg contamination. The development of a visible light responsive (VLR) TiO2-based catalyst could lead to the use of solar energy in the visible region (approx.45% of the solar spectrum lies in the visible region; > 400 nm) or highly efficient LEDs (with wavelengths > 400 nm) to make PCO approaches more efficient, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts; those that are available still have poor activity in the visible region compared to that in the UV region. Thus, this study was aimed at the further development of VLR catalysts by a new method - coupling of quantum dots (QD) of a narrow band gap semiconductor (e.g., CdS, CdSe, PbS, ZnSe, etc.) to the TiO2 by two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications, using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems serve as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, type of quantum dots, and dosage of quantum dots.

Coutts, Janelle L.↗

Effects of Water Vapor on the Reactivity of Aluminosilicates in Vapor-Phase Propanal Aldol Condensation

Aluminosilicate materials have been extensively studied as efficient aldol catalysts for C-C coupling reactions due to their acidic nature, high surface area, thermal stability, and porous structure. This work investigated the impact of water vapor pressure on the catalytic reactivity of aluminosilicates for the aldol condensation of propanal to 2-methyl-2-pentenal (MP). The catalytic performance of amorphous SiO2-Al2O3 (A-Si-Al) and aluminated MCM-41 (Al-MCM-41) for the vapor-phase aldol condensation of propanal was evaluated at 200 degrees C as a function of vapor-phase water content at atmospheric pressure. Our findings demonstrate that co-feeding low water vapor pressures (1-18 kPa) with propanal enhances the rates of MP production at 200 degrees C on A-Si-Al. Conversely, water vapor pressures of 25 kPa result in a decrease in aldol dimer formation rates. The rate of MP production evaluated on Al-MCM-41 also increased in the presence of 5 kPa water compared to anhydrous conditions. Propylamine temperature-programmed desorption analyses revealed an increase in Bronsted acid site density when both catalysts were exposed to water, which likely accounts for the observed enhancement in aldol condensation reactivity under hydrous conditions. Reversibility testing of the water vapor effect under reaction conditions, combined with X-ray diffraction analysis of fresh, spent, and regenerated catalysts, revealed no structural changes in either aluminosilicate upon exposure to water or reaction conditions. The rates of aldol condensation and the impact of water vapor were highly consistent across both materials, suggesting that zeolite crystallinity has minimal influence on the catalytic performance.

acid catalysts↗

Phosphate-passivated mordenite for tandem-catalytic conversion of syngas to ethanol or acetic acid

Selective and stable production of C 2 oxygenates from syngas is enabled by a phosphate-passivated mordenite catalyst used in tandem with a commercial Cu/ZnO/AlMgO x catalyst. Unmodified mordenite used in this arrangement is accompanied by substantial hydrocarbon formation and carbon deposition. Therefore, phosphate groups are used to remove or significantly reduce Brønsted acidity in mordenite by capping aluminum sites. Such groups are stable to calcination and catalyst regeneration. Here, trimethylphosphite is used as a phosphate precursor because it is able to enter the 12 membered-ring pores of mordenite where hydrocarbon formation occurs, but not enter the 8 membered-ring sidepockets, where methanol carbonylation occurs selectively. The catalyst was characterized using X-ray fluorescence, X-ray diffraction, and thermal gravimetric analysis. Optionally, a third bed of Cu/ZnO/AlMgO x catalyst is able to hydrodeoxygenate acetic acid to ethanol. The C 2 oxygenate selectivity is over 96% and among the best reported in a single reactor with a syngas feed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

H 2 Evolution at an Electrochemical “Underpotential” with an Iridium-Based Molecular Photoelectrocatalyst

Molecular platforms capable of both photochemical H 2 evolution and electrochemical catalyst regeneration hold promise for the efficient generation of solar fuels. Systems studied to date require a significant electrochemical overpotential (η), so no photon energy is being chemically stored. A detailed study of the parameters that govern the electrochemical overpotential of molecular photoelectrocatalysts is presented. By understanding how tuning the solvent, catalyst structure, and acid pK a affect the kinetics and thermodynamics of the potential- and light-driven H 2 evolution reaction, conditions were identified wherein the solvento complex [Cp*Ir(bpy)(NCCH 3 )][PF 6 ] 2 (Cp* is pentamethylcyclopentadienyl; bpy is 2,2'-bipyridine) mediates photoelectrocatalytic H 2 formation at an electrochemical “underpotential” (η < 0) driven by visible light. Under 460 nm illumination and in the presence of the weak organic acid H-PhTMG + (2-phenyl-1,1,3,3- tetramethylguanidinium), the catalyst facilitates H 2 evolution with Faradaic efficiencies up to 90% and overpotentials as low as –90 mV. As a result, mechanistic studies enabled the construction of graphical “maps” that can guide the choice of catalyst and conditions to minimize overpotential, applicable to both photoelectrocatalysts and dark electrocatalysts.

14 SOLAR ENERGY↗

Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, nature of the quantum dots, and dosage of quantum dots.

visible light↗

Visible-Light Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure.

visible light↗

Vacuum-assisted carbon molecular sieve membrane reactor for non-oxidative ethane dehydrogenation

Non-oxidative ethane dehydrogenation (EDH) is equilibrium-limited and endothermic. Selective hydrogen removal using a gas-permeable membrane within the EDH reaction zone can overcome the thermodynamic equilibrium, enabling higher ethane conversions. Employing vacuum as the permeation driving force, rather than a sweep gas, enhances the industrial viability of membrane reactors by eliminating additional post-reaction separation units. This study presents a membrane reactor that integrates H 2 -permeable carbon molecular sieve (CMS) hollow fiber membranes embedded in a fixed bed of cobalt in a dealuminated beta zeolite (Co@DeAl-BEA) catalyst, utilizing a vacuum to remove hydrogen efficiently. The CMS membrane exhibits high hydrogen permeance and an excellent H 2 /C 2 H 6 separation factor. The membrane reactor significantly enhanced the ethane conversion under reaction conditions comparable to those reported in the literature. A Langmuir-Hinshelwood kinetic rate expression was developed and incorporated into a one-dimensional steady-state reactor model. The experimentally validated model indicates that increasing the number of hollow fibers improves ethane conversion, although ethane loss to the permeate limits the benefit. The contact area between the catalyst and the membrane limits the reactor performance more than the catalytic throughput. Furthermore, we find that the location of the catalyst packing relative to the hollow fiber membranes influences ethane loss and conversion. Higher reactor pressures and inlet ethane flow rates improve space-time yield at the expense of lower ethane conversion. Increasing reactor temperature or packing length promotes both performance metrics. The EDH membrane reactor demonstrated durability over 200 h of continuous operation, maintaining record-low deactivation rates and high ethylene selectivity. Protocols for catalyst regeneration were developed.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Highly crystalline, low-ash, graphite from coal using an Fe 2 O 3 -based catalytic process with recovery and reuse of catalyst and process acid

This study presents a sustainable process for producing highly crystalline, low-ash graphite from sub-bituminous coal using an Fe 2 O 3 -based catalytic method. The process integrates coal mineral removal, catalyst regeneration, and reagent recycling into a closed-loop system. Acid-soluble Fe-residue and mineral impurities are eliminated from the solid graphite through HCl treatment, followed by hydrolytic distillation to regenerate Fe 2 O 3 and recover HCl for reuse. Coal-derived silica is removed with a KOH rinse, yielding low-ash graphite suitable for high-performance applications. The closed-loop catalytic graphitization, where the recovered Fe 2 O 3 and HCl are used in subsequent graphitization runs, produces graphite with a degree of graphitization exceeding 95%. The L a and L c crystallite sizes reach 65–78 nm and 44–48 nm, respectively, with BET surface areas of 4–10 m 2 /g and an ash content below 0.1 wt.%. Lithium-ion battery testing reveals that anodes fabricated with this graphite deliver an initial discharge capacity between 384.5 and 421.2 mAh/g, averaging 395.0 ± 19.1 mAh/g, along with initial coulombic efficiencies of 85.0–89.1%. After 100 discharge–charge cycles at 0.25C, reversible capacities remain between 358.8 and 369.7 mAh/g, while coulombic efficiency stays above 99.9%. The findings highlight that coal can serve as a viable precursor for high-quality graphite production under relatively mild conditions, avoiding the need for extreme temperatures or aggressive reagents such as hydrofluoric acid, commonly employed in conventional processes. This work demonstrates both technical feasibility and environmental benefits, emphasizing its potential to support large-scale, sustainable graphite production for applications such as lithium-ion batteries.

Catalytic graphitization↗

Elucidating the reversible exsolution–dissolution behaviour of high-entropy oxides in crystalline and amorphous phases

High-entropy oxides (HEOs), as a subclass of high-entropy materials (HEMs), offer a versatile platform for catalysis by leveraging entropy-stabilized solid solutions with tunable compositions, lattice structures, and electronic properties. While exsolution–dissolution of metal species in crystalline HEOs has emerged as a promising strategy for reversible active sites regeneration, the dynamic behaviour of HEOs possessing amorphous nature remains under-explored, particularly the difference with crystalline counterparts. In this work, we systematically investigate the architecture-dependent exsolution–dissolution behavior of HEOs by comparing a crystalline-phase HEO (c-HEO) and an amorphous-phase HEO (a-HEO), both comprising Ni, Mg, Cu, Zn, and Co as principal metal elements. Using a combination of in situ variable-temperature X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron microscopy, and in situ CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), the structural evolution of the two HEO phases under redox conditions was elucidated. Both materials exhibit reversible exsolution of metallic species or alloys in reducing environments, followed by re-incorporation into the host lattice upon oxidation. Remarkably, the a-HEO demonstrates more facile and dynamic self-healing behavior, with alloy exsolution and dissolution occurring under milder conditions because of its enhanced reducibility and structural disorder. This study provides critical insights into the design of next-generation regenerable catalysts based on amorphous HEOs, highlighting the role of phase structure in governing reversible metal-site formation dynamics and catalytic performance.

Wang, Qingju [Univ. of Tennessee, Knoxville, TN (U↗

Oxidant-assisted methane pyrolysis

Adding small amounts of CO 2 or H 2 O to methane pyrolysis boosts hydrogen and carbon yieldsviacyclic catalyst regeneration, enabling efficient low-carbon hydrogen and crystalline carbon production.

Chemistry↗

CFD Simulation of Biomass Pyrolysis Vapor Upgrading over a Pt/TiO 2 Catalyst in Fixed and Moving Beds

This report presents a comprehensive computational fluid dynamics (CFD) study of the biomass pyrolysis vapor phase upgrading and the catalyst regeneration in different reactors under various operational conditions. This study used the open-source software Multiphase Flow with Interphase eXchanges (MFiX), developed at National Energy Technology Laboratory (NETL) for simulating hydrodynamics, heat transfer, and chemical reactions in multiphase systems. This simulation solved the conservation of mass, momentum, energy, species for gas and solid phases with chemical reactions.

09 BIOMASS FUELS↗

Assessments of advanced reactor heat supply to high temperature industrial unit operations: Heat Engines and Heat Pumps

In this report, the feasibility of employing Advanced Nuclear Reactors to supply the necessary high-quality heat to Industrial Processes is investigated. As a first step, the most relevant industrial applications that could benefit from this coupling were identified. Four industries including petroleum refining (distillation, catalyst regeneration, hydro-steam cracking), chemical polymers, steel manufacturing (metals annealing/soaking) and cement manufacturing (calcination of limestone and dolomite industries) were considered. An overview of the heat duties, i.e., the temperatures and thermal powers required by representative plants of the different processes, was provided. Secondly, the thermodynamic conditions of the steam produced by representative designs of Advanced Reactor concepts (Liquid Metal Fast Breeder Reactors, Molten Salt Reactors, and High Temperature Gas-cooled Reactors) were summarized. The comparison between the requirements of the industrial processes and the capabilities of the candidate nuclear power plants showed that only a few processes could benefit from the coupling. Although Advanced Reactors operate at higher temperatures than Light Water Reactors, the thermodynamic conditions of the generated steam flow rates are generally not suitable for the selected applications. At the same time, data indicate that most of the processes can be suitably supplied if the temperature of steam is elevated to 900 °C. One possible solution to boost the quality of the steam from the nuclear island involves the use of a heat pump. Based on a technology similar to that found in refrigerators and air conditioners, heat pumps extract heat from a source, elevate its temperature and transfer it to where it is needed. A simple numerical example illustrating the viability of this method is described. Specifically, the energy conversion cycle of a conventional Pressurized Water Reactor was extended to incorporate a compressor to raise the heating value of the steam produced by the reactor. Two reference configurations, i.e., one where the industrial process coupled to the nuclear power plant exhausts saturated liquid and the other where it exhausts saturated steam, were considered. The thermal efficiencies achievable by increasing the heating value of the reactor steam in this way are significantly greater than by direct electric heating.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Advancing Catalytic Fast Pyrolysis Through Integrated Experimentation and Multi-Scale Computational Modeling

This webinar will highlight recent results from a multi-disciplinary research effort in which integrated reaction testing was coupled with particle- and reactor-scale computational modeling to advance catalytic fast pyrolysis (CFP) for the production of renewable hydrocarbon fuels. Data will be presented from a series of ex situ CFP experiments in which a fixed bed of Pt/TiO2 was utilized with co-fed H2 to upgrade woody biomass pyrolysis vapors. Further discussion will include the application of these data towards the development of (1) a multiscale simulation framework to de-couple apparent kinetics from both intraparticle and reactor-scale transport phenomena and (2) a finite element computational model to understand and predict thermal excursions during catalyst regeneration. Throughout the presentation, the speakers will emphasize synergistic outcomes derived from the collaborative approach and highlight ongoing research efforts to accelerate technology maturation.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Structurally Regenerable High Entropy Aluminate Spinel Catalysts for Dry Reforming of Methane

The dry reforming of methane reaction is a promising means to convert two potent greenhouse gases, methane and carbon dioxide, into industrially valuable synthesis gas. However, the presence of reducing gases and high operating temperatures degrade conventional nickel catalysts via excessive coke formation and particle sintering. These catalysts are not readily regenerated because the oxidative heat treatments employed to remove coke further promote active particle sintering. In this work, we designed high entropy aluminate spinel oxides (MAl 2 O 4 where M = Co, Mg, Ni, and divalent site vacancies in nominal equimolar concentration) as selective and regenerable reforming catalysts. Under reaction conditions, reducible nickel and cobalt cations exsolved from the spinel lattice to form highly selective bimetallic particles on the oxide surface. Instead of sintering, these particles uniquely redissolved back into the aluminate lattice upon reoxidation and regained the original spinel structure. This phenomenon is ascribed to entropic stabilization, wherein an increase in configurational entropy creates a thermodynamic driving force for redispersing supported metal particles back into the multi‐cationic oxide structure. During the dry reforming reaction, nickel atoms similarly exsolved from a NiAl 2 O 4 sample and reduced to form metallic nickel particles. However, subsequent oxidation of this sample promoted sintering and oxidation of the nickel particles to an inactive state. High entropy materials thus provide a unique mechanism of regeneration, which is inaccessible in conventional catalysts.

coke deposition↗

In situ catalyst activation and regeneration enable energy-efficient high-current CO 2 reduction to ethanol-rich C 2+ mixtures

Electrochemical conversion of dissolved CO 2 in bicarbonate electrolytes, i.e., bicarbonate electrolysis, offers distinct advantages over gas diffusion electrode systems by enabling direct utilization of the CO 2 capture electrolyte while bypassing the energy-intensive CO 2 release step. However, bicarbonate electrolysis faces challenges such as CO 2 mass-transfer limitation, local pH-driven CO 2 depletion, and high cathodic potentials. The higher potential often causes catalyst surface reorganization, leading to a gradual loss of active sites and variations in selectivity during CO 2 reduction. Here, we report a directed, in situ activation and regeneration method that allows precatalysts to equilibrate under dynamic (pulsed) electrolysis conditions. We demonstrate in situ activation of a scalable Cu 2 O/Cu mesh that, under short-width (t = 4 s) pulsed electrolysis, provides stable mixed oxidation states of Cu, favoring the formation of an ethanol-rich crude mixture. The pulsed electrolysis waveform, consisting of six distinct segments, is tuned to form Cu + oxides, which are then reduced to generate local alkaline conditions favoring C–C coupling. This synergistic effect results in FEs of 73% for C2+ products and 39% for ethanol at an applied current density of −150 mA cm −2 and a cathodic potential of −1.45 V (vs. RHE). The overall half-cell energy efficiency is ∼30% for C 2+ products. The in situ Raman experiments confirm the role of pCO 2 R in dynamically regenerating Cu+-containing surface species during pulsed operation, thereby steering selectivity towards C 2+ products. A comprehensive multiscale, multiphysics model is developed to investigate the dynamic behavior of copper surface species (Cu, Cu + , and Cu 2+ ) and local microenvironmental conditions during the pCO 2 R. The results reveal that the coexistence of different copper oxidation states, especially the Cu+ intermediate, is critical in steering selectivity towards multicarbon (C 2+ ) products. The dynamic modulation of surface redox states via tailored pulsing strategies favors C–C coupling pathways by inducing localized alkaline conditions and stabilizing reactive intermediates. This work establishes a predictive modeling platform that links pulse waveform design with mechanistic insights into catalyst state evolution and product selectivity. Overall, this study provides valuable insights into the synergistic effect of in situ activation of pre-catalysts and pulsed electrolysis for higher selectivity towards C 2+ products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗