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At least 127 records · Page 7

Hydroxyls on CeO 2 Support Promoting CuO/CeO 2 Catalyst for Efficient CO Oxidation and NO Reduction by CO

Transition metal catalysts, such as copper oxide, are more attractive alternatives to noble metal catalysts for emission control due to their higher abundance, lower cost, and excellent catalytic activity. Here, in this study, we report the preparation and application of a novel CuO/CeO 2 catalyst using a hydroxyl-rich Ce(OH) x support for CO oxidation and NO reduction by CO. Compared to the catalyst prepared from a regular CeO 2 support, the new CuO/CeO 2 catalyst prepared from the OH-rich Ce(OH) x (CuO/CeO 2 –OH) showed significantly higher catalytic activity under different testing conditions. The effect of OH species in the CeO 2 support on the catalytic performance and physicochemical properties of the CuO/CeO 2 catalyst was characterized in detail. It is demonstrated that the abundant OH species enhanced the CuO x dispersion on CeO 2 , increased the CuO x –CeO 2 interfaces and surface defects, promoted the oxygen activation and mobility, and boosted the NO adsorption and dissociation on CuO/CeO 2 –OH, thus contributing to its superior catalytic activity for both CO oxidation and NO reduction by CO. These results suggest that the OH-rich Ce(OH) x is a superior support for the preparation of highly efficient metal catalysts for different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fine-Tuning of Pt Dispersion on Al 2 O 3 and Understanding the Nature of Active Pt Sites for Efficient CO and NH 3 Oxidation Reactions

Fine-tuning the dispersion of active metal species on widely used supports is a research hotspot in the catalysis community, which is vital for achieving a balance between the atomic utilization efficiency and the intrinsic activity of active sites. In this work, using bayerite Al(OH) 3 as support directly or after precalcination at 200 or 550 °C, Pt/Al 2 O 3 catalysts with distinct Pt dispersions from single atoms to clusters (ca. 2 nm) were prepared and evaluated for CO and NH 3 removal. Richer surface hydroxyl groups on AlO x (OH) y support were proved to better facilitate the dispersion of Pt. However, Pt/Al 2 O 3 with relatively lower Pt dispersion could exhibit better activity in CO/NH 3 oxidation reactions. Further reaction mechanism study revealed that the Pt sites on Pt/Al 2 O 3 with lower Pt dispersion could be activated to Pt 0 species much easier under the CO oxidation condition, on which a higher CO adsorption capacity and more efficient O 2 activation were achieved simultaneously. Compared to Pt single atoms, PtO x clusters could also better activate NH 3 into –NH 2 and –HNO species. The higher CO adsorption capacity and the more efficient NH 3 /O 2 activation ability on Pt/Al 2 O 3 with relatively lower Pt dispersion well explained its higher CO/NH 3 oxidation activity. This study emphasizes the importance of avoiding a singular pursuit of single-atom catalyst synthesis and instead focusing on achieving the most effective Pt species on Al 2 O 3 support for targeted reactions. Finally, this approach avoids unnecessary limitations and enables a more practical and efficient strategy for Pt catalyst fabrication in emission control applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling the Intermediate Reaction Complexes and Critical Role of Support-Derived Oxygen Atoms in CO Oxidation on Single-Atom Pt/CeO 2

CeO 2 -supported Pt single-atom catalysts have been extensively studied due to their relevance in automobile emission control and for the fundamental understanding of CeO 2 -based catalysts. Though CeO 2 -supported Pt nanoparticles are often more active than their single-atom counterparts, the former could easily redisperse to Pt single atom under oxidizing diesel conditions. Therefore, to maximize the reactivity of every Pt atom, it is important to fully understand the reaction mechanism of CeO 2 -supported Pt single atoms. Here, we report a CO oxidation study on a Pt/CeO 2 single-atom catalyst, where we can account for all of the neighbors using in situ and operando spectroscopy techniques and microcalorimetric measurements. Coupled with density functional theory calculations, we present a comprehensive picture of the dynamics of the surface species, the role of surface intermediates, and explain the observed reaction kinetics. We started with a catalyst containing exclusively single atoms and used in situ/operando spectroscopy to provide evidence for their stability during the reaction and to identify the Pt 1 complexes before and during the reaction and their binding to CO. The results reveal that in the precatalyst, Pt is present as Pt(O) 4 on the CeO 2 (111) step edge sites, but during CO oxidation, we find that two Pt 1 complexes coexist, representing two states of the same active site in the reaction cycle. The dominant state/complex remains Pt(O) 4 , which adsorbs CO very weakly as shown by CO microcalorimetry. The second, minority state/complex, Pt(CO)(O) 3 is generated through the reaction of Pt(O) 4 with CO, and CO is bound strongly to Pt 1 . Labile oxygen adatoms from the CeO 2 surface play a major role in the regeneration of Pt(O) 4 either directly from Pt(O) 3 or by reaction with the strongly adsorbed CO in Pt(CO)(O) 3 . We show that the formation of an oxygen vacancy and generation of a labile O* are not barrierless, which explains the long lifetime of Pt(CO)(O) 3 and its detectability despite being a minority complex. The results help to develop a comprehensive view of the dynamic evolution of Pt 1 complexes along the reaction cycle and provide mechanistic insights to guide the design of Pt-based single-atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure-Activity Relationships of Hydrothermally Aged Titania-Supported Vanadium-Tungsten Oxide Catalysts for SCR of NOx Emissions with NH3

Supported V2O5-WO3/TiO2 materials employed as selective catalytic reduction (SCR) catalysts for NOx emission control from power plants. Fresh SCR catalysts usually receive exposure to harsh treatments in industry to accelerate catalyst activation (calcination in air at 650oC) and catalyst aging (hydrothermal aging at 650oC) in a way that represents various points in the catalyst/product lifetime. The present study investigates the catalyst structural and chemical changes occurring during such harsh treatments. Three series of supported V2O5-WO3/TiO2 catalysts were prepared by incipient-wetness impregnation of aqueous ammonium metavanadate and metatungstate precursors. The catalysts were subsequently dried and calcined at 550oC in O2, 650oC in O2, and hydrothermal conditions (10% O2, 8% H2O, 7% CO2 and 75% N2) at 650oC. The resulting catalysts were physically characterized by numerous techniques (in situ Raman, in situ IR, in situ High Field-High Spinning solid-state 51V MAS NMR, in situ EPR, XRD, BET surface area and ICP) and chemically probed with adsorbed ammonia, SCR-TPSR, and the SCR reaction. The surface WOx sites on the TiO2 support behave as a textural promoter that stabilizes the TiO2 (anatase) phase from sintering and transforming to the undesirable crystalline TiO2 (rutile) phase that can lead to formation of a Ti1-xVxO2 (rutile) solid solution with reduced V4+ cations (~7-15%). The surface VOx sites are mostly oligomerized as surface V+5Ox sites (~50-85% oligomers) and the extent of oligomerization tends to increase with surface WOx coverage and calcination temperature. A major difference between the calcined and hydrothermally treated catalysts was the low concentration of surface NH3* species on Lewis acid sites for the hydrothermally treated catalysts, yet the SCR activity was almost comparable for both catalysts. This finding suggests that surface NH4+*, primarily associated with the surface VOx sites, are able to efficiently perform the SCR reaction. Given that multiple catalyst parameters were simultaneously varying during these treatments, it was difficult to correlate the SCR activity with any single catalyst parameter. A correlation, however, was found between the SCR TOF/activity and the sum of the surface NH3* and NH4+* species, which is dominated by the surface NH4+* species.

SCR, NO, NH3, catalyst, V2O5, WO3, TiO2, promotion↗

CeO 2 Promoted CuO/MgO-Al 2 O 3 Catalyst with Enhanced Activity and Water-Resistance for CO Oxidation

Copper (Cu)-based catalysts have emerged as cost-effective and sustainable alternatives to noble metal systems (e.g., Pt, Pd) for catalytic CO oxidation. However, their practical application is hindered by insufficient low-temperature activity and rapid deactivation under wet conditions containing moisture. To address these challenges, this work introduces CeO 2 -modified CuO/MgO-Al 2 O 3 (Cu-Ce/MA) catalysts, strategically designed to enhance the catalytic performance and water resistance simultaneously. These catalytic materials were evaluated for CO oxidation under both dry and humid conditions, revealing that CeO 2 modification significantly improves the low-temperature activity. Specifically, the optimal catalyst, Cu-30Ce/MA, achieved a 50% CO conversion temperature (T 50 ) of 151 °C, a marked reduction from 218 °C on Cu/MA reference catalyst. Furthermore, the water resistance improves in a CeO 2 content-dependent manner, with higher CeO 2 loadings imparting greater stability in humid environments. Detailed characterizations demonstrate that CeO 2 promotes the dispersion of CuO and stabilizes Cu sites, while also enhancing the low-temperature reducibility and CO adsorption capacity. Crucially, CeO 2 modification suppresses the competitive H 2 O adsorption, mitigating water-induced deactivation. These synergistic effects collectively rationalize the superior activity and durability of Cu-Ce/MA catalysts. By elucidating the dual role of CeO 2 in optimizing Cu-based systems, this study advances the rational design of cost-effective catalysts for real-world CO emission control, particularly under water-rich industrial conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sintering Mechanism of Pt/Al 2 O 3 in Complex Emission Gases Elucidated via In Situ Environmental STEM

Emission control catalysts are crucial for protecting human health by preventing the release of harmful gases and unburnt fuel into the atmosphere. These catalysts often face deactivation through sintering processes in high-temperature, chemically reactive environments containing multiple gas species. Here, we use in situ environmental scanning transmission electron microscopy to monitor the sintering behavior and transient morphologies of Pt/Al 2 O 3 in various relevant gas environments through controlled experiments. Our results reveal the particle migration and atomic ripening behavior of Pt/Al 2 O 3 at the atomic scale in the presence of water vapor and oxygen, which differs from behaviors observed in single gas environments. We identify an atomic ripening mechanism involving the dissociation and migration of Pt adatom chains from Pt nanoparticles, observed only in combinational gases. Finally, these findings provide valuable insights into catalyst degradation behavior in complex gas environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal Platinum–Copper Nanocrystal Alloy Catalysts Surpass Platinum in Low-Temperature Propene Combustion

Low-temperature removal of noxious environmental emissions plays a critical role in minimizing the harmful effects of hydrocarbon fuels. Emission-control catalysts typically consist of large quantities of rare, noble metals (e.g., platinum and palladium), which are expensive and environmentally damaging metals to extract. Alloying with cheaper base metals offers the potential to boost catalytic activity while optimizing the use of noble metals. In this work, we show that Pt x Cu 100–x catalysts prepared from colloidal nanocrystals are more active than the corresponding Pt catalysts for complete propene oxidation. By carefully controlling their composition while maintaining nanocrystal size, alloys with dilute Cu concentrations (15–30% atomic fraction) demonstrate promoted activity compared to pure Pt. Complete propene oxidation was observed at temperatures as low as 150 °C in the presence of steam, and five to ten times higher turnover frequencies were found compared to monometallic Pt catalysts. Additionally, through DFT studies and structural and catalytic characterization, the remarkable activity of dilute Pt x Cu 100–x alloys was related to the tuning of the electronic structure of Pt to reach optimal binding energies of C* and O* intermediates. This work provides a general approach toward investigation of structure–property relationships of alloyed catalysts with efficient and optimized use of noble metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffusion Model-Guided Inverse Design of Bimetallic Catalysts for Ammonia Decomposition

In the past decade, artificial intelligence and deep learning have played increasingly prominent roles in materials design and discovery. Among these, generative AI models, known for their ability to create unique and complex structures, have emerged as state-of-the-art tools for materials screening due to their high efficiency and low computational cost. In catalysis, one of the major challenges is identifying promising material candidates within an immense chemical space. This challenge can be addressed using generative approaches, such as diffusion-based inverse design models. In this study, we present a machine learning-guided workflow that employed a diffusion model for the inverse design of bimetallic alloy catalysts for low-carbon ammonia decomposition, a key reaction for ammonia emission control and sustainable hydrogen production. Catalyst candidates were evaluated using nitrogen adsorption energy as the key descriptor, inspired by multiscale modeling. The proposed workflow identified low-cost, environmentally friendly catalysts with excellent catalytic performance, which have been validated theoretically and experimentally. Our framework decoupled the generative and property-prediction components, enhancing both flexibility and accuracy in the catalytic material design process.

Adsorption↗

Strategizing emission cuts in China to mitigate short-term warming from clean air policies

Aerosol-cloud interactions remain one of the largest sources of uncertainty in estimates of anthropogenic climate forcing. Reducing aerosols to achieve air quality improvement and climate goals can cause unintended warming due to the weakening of aerosol cooling. Here we investigate the climate impacts of spatially optimized sulfur dioxide (SO 2 ) emission reduction under a carbon-neutral pathway in China. We find that targeting reduction in highly polluted regions in China significantly suppresses the rise in effective radiative forcing due to aerosol-cloud interactions (ERF aci ) during 2020–2060. Owing to the nonlinear aerosol-cloud interaction, the optimized emission reduction strategy limits the regional average increase in ERF aci of more than 0.89 W m −2 to less than 0.13 W m −2 in the short-term future during 2020–2040 and weakens the ERF aci increase by two-thirds in 2060 over China. These findings demonstrate the critical role of targeted emission control in mitigating short-term climate risks while pursuing air quality goals.

Zhu, Yitong [Nanjing Univ. of Information Science ↗

Dephasingless two-color terahertz generation

A laser pulse composed of a fundamental and an appropriately phased second harmonic can drive a time-dependent current of photoionized electrons that generates broadband THz radiation. Over the propagation distances relevant to many experiments, dispersion causes the relative phase between the harmonics to evolve. This “dephasing” slows the accumulation of THz energy and results in a multi-cycle THz pulse with significant angular dispersion. Here, we introduce a novel optical configuration that compensates the relative phase evolution, allowing for the formation of a half-cycle THz pulse with almost no angular dispersion. The configuration uses the spherical aberration of an axilens to map a prescribed radial phase variation in the near field to a desired longitudinal phase variation in the far field. Simulations that combine this configuration with an ultrashort flying focus demonstrate the formation of a half-cycle THz pulse with a controlled emission angle and 1/4 the angular divergence of the multi-cycle pulse created by a conventional optical configuration.

47 OTHER INSTRUMENTATION↗

Nanocluster and single-atom catalysts for thermocatalytic conversion of CO and CO 2

In this Minireview, we discuss recent advances in understanding nanocluster and single-atom catalysts for CO and CO 2 emissions control applications. Through analyzing thermocatalytic CO oxidation and CO 2 reduction, two fundamentally and industrially important reactions, we compare representative nanocluster and single-atom catalytic systems from perspectives of intrinsic chemistry and reaction engineering. Generally, nanoclusters and single atoms display different catalytic performances (i.e., activity, selectivity, and stability) for these reactions depending on the synthesis methods, support materials, and reaction conditions. Key observations of activity and selectivity tradeoffs between nanoclusters and single-atom catalysts are highlighted. Here, the dynamic structural responses of these catalytic species under CO oxidation or CO 2 reduction reaction conditions are also discussed. Synthetic control and detailed experimental and computational characterization of single-atom and nanocluster catalysts for CO and CO 2 conversion have led to exciting progress over the past decade. Still, more efforts are needed to understand and develop catalysts that meet the environmental, energy, and technical requirements to power a sustainable global economy.

03 NATURAL GAS↗

Unveiling the support effect in Pt-based catalysts for the selective catalytic oxidation of NH 3 under realistic diesel engine conditions

Pt catalysts have been widely used for the selective catalytic oxidation of NH 3 (NH 3 -SCO) in practical applications due to their high activity at low temperatures. However, more stringent regulations require further enhancement of low-temperature NH 3 -SCO activity. In this study, we investigated the influence of different supports, including aluminum oxide (Al 2 O 3 ), silica (SiO 2 ), and chabazite (CHA), on the NH 3 -SCO performance of Pt catalysts. Furthermore, our findings demonstrate that the Pt/CHA catalyst exhibited superior NH 3 -SCO performance under realistic diesel engine conditions, characterized by high space velocity and the presence of water vapor. Notably, the Pt/CHA catalyst achieved a significantly lower T 50 (temperature at which 50% NH 3 conversion is achieved) of 218 °C under conditions with both CO 2 and H 2 O, with a 56 °C reduction compared to the state-of-the-art Pt/Al 2 O 3 catalyst. The exceptional NH 3 -SCO performance is attributed to the high abundance of metallic Pt 0 species and the presence of rich and stable acid sites that facilitate NH 3 adsorption and activation. Furthermore, these results highlight CHA as a promising support for the Pt catalyst in NH 3 -SCO applications for diesel engine emission control.

36 MATERIALS SCIENCE↗

Steering CO 2 hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces

The conversion of CO 2 into fuels and chemicals is an attractive option for mitigating CO 2 emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C–C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a strategy to favor C–C coupling on a supported Ru/TiO 2 catalyst by encapsulating it within the polymer layers of an imine-based porous organic polymer that controls its selectivity. Such polymer confinement modifies the CO 2 hydrogenation behavior of the Ru surface, significantly enhancing the C 2+ production turnover frequency by 10-fold. We demonstrate that the polymer layers affect the adsorption of reactants and intermediates while being stable under the demanding reaction conditions. Our findings highlight the promising opportunity of using polymer/metal interfaces for the rational engineering of active sites and as a general tool for controlling selective transformations in supported catalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling batch melting: Roles of heat transfer and reaction kinetics

Development of mathematical models of heat and mass transfer in glass-melting furnaces began in the 1970s and progressed rapidly with advances in sophisticated experimental/numerical techniques and increasing computational power. Today, practically all newly built or rebuilt furnaces are optimized with these models to meet stringent quality requirements, reduce the unit costs of manufacturing, or control emissions. One remaining hurdle is to model the batch-to-glass conversion accurately enough to reliably assess the glass production rate. This article summarizes two key aspects of the batch-conversion modeling—the heat transfer and the kinetics of conversion—and reviews the current state-of-the-art approaches to simulating them. We critically examine the advantages of the commonly used heat transfer approach, but also explain that its predictive capabilities are significantly restricted by the dependence of batch thermal properties on the time-temperature history. We argue that kinetic approaches to the batch-conversion modeling would offer a significant improvement when coupled with the heat transfer approach. Finally, we summarize key areas requiring further research on the way toward a realistic model of the batch blanket.

Pokorny, Richard↗

Coupled Air Quality and Boundary-Layer Meteorology in Western U.S. Basins during Winter: Design and Rationale for a Comprehensive Study

The wintertime episodes of high aerosol concentrations occur frequently in urban and agricultural basins and valleys worldwide. These episodes often arise following development of persistent cold-air pools (PCAPs) that limit mixing and modify chemistry. While field campaigns targeting either basin meteorology or wintertime pollution chemistry have been conducted, coupling between interconnected chemical and meteorological processes remains an insufficiently studied research area. Gaps in understanding the coupled chemical–meteorological interactions that drive high-pollution events make identification of the most effective air-basin specific emission control strategies challenging. To address this, a September 2019 workshop occurred with the goal of planning a future research campaign to investigate air quality in western U.S. basins. Approximately 120 people participated, representing 50 institutions and five countries. Workshop participants outlined the rationale and design for a comprehensive wintertime study that would couple atmospheric chemistry and boundary layer and complex-terrain meteorology within western U.S. basins. Participants concluded the study should focus on two regions with contrasting aerosol chemistry: three populated valleys within Utah (Salt Lake, Utah, and Cache Valleys) and the San Joaquin Valley in California. This paper describes the scientific rationale for a campaign that will acquire chemical and meteorological datasets using airborne platforms with extensive range, coupled to surface-based measurements focusing on sampling within the near-surface boundary layer, and transport and mixing processes within this layer, with high vertical resolution at a number of representative sites. No prior wintertime basin-focused campaign has provided the breadth of observations necessary to characterize the meteorological–chemical linkages outlined here, nor to validate complex processes within coupled atmosphere–chemistry models.

54 ENVIRONMENTAL SCIENCES↗

Primer on the Cost of Marine Fuels Compliant with IMO 2020 Rule

This report aims to provide information for owners and operators of U.S. ocean-going marine cargo vessels on the cost of different approaches to compliance with the IMO mandate to reduce the sulfur content of marine fuels (outside emission control areas) to no more than 0.5%. The IMO 2020 rule came into effect on January 1, 2020. The report discusses a suite of options for compliance including low-sulfur petroleum-based fuels and alternative fuels. Since fuel prices are a primary factor in determining the cost of the various alternatives, the document also includes a discussion of the main drivers of marine fuel prices. The cost analysis compares the average annual costs (capital and fuel) out to 2050 of each compliance approach under alternative scenarios regarding fuel prices, policy, and technology innovation. The cost calculations focus on representative U.S. fleet vessels for containership and tanker types. Even though the analysis focuses on average cost of approaches to comply with IMO 2020, the comparison of approaches also acknowledges other benefits or risks including fuel price risk and the contribution of the approach to achieving other potential environmental performance objectives or regulations.

02 PETROLEUM↗

Elucidating Arsenic and Selenium Speciation in Coal Fly Ashes

Coal fly ash (CFA) is produced during the coal combustion process and contains trace elements (<100 ppm) including selenium (Se) and arsenic (As), both detrimental for environmental and human health. Existing management strategies for CFAs involve disposal in landfills and ash ponds, as well as beneficial usage in other applications such as in concrete. Both the direct disposal and beneficial usage of CFA raise concerns for environmental hazards due to the potential leaching of Se and As. CFAs were classified as reusable material by the U.S. Environmental Protection Agency (EPA) with the first federal regulation (Disposal of Coal Combustion Residuals from Electric Utilities, CCR) for its disposal established six years ago. During coal combustion process, parameters such as furnace firing type, emissions controls, coal rank, use of additives, and particulate matter controls, could contribute to significant variability in As/Se concentrations and their speciation. Although there have been a handful of studies on As/Se speciation on small sets of samples, they do not fully represent the current state of coal-fired electrical generating units. Little information exists on the detailed speciation (e.g. oxidation state, complexation state) of As/Se in large set of fly ash samples. To better investigate the role of the potential contributing parameters, a large-scale survey study with representative samples of typical coal source and combustion conditions is highly desired. The overall goal of this research is to systematically characterize As and Se speciation of representative coal fly ash samples using state-of-the-art synchrotron based spectroscopic and microscopic techniques, in order to develop a correlation between coal source/type, operation condition, As/Se speciation, and As/Se mobility. A detailed survey study was conducted documenting the current state-of-knowledge on fossil power generating units as a function of coal type/source, operating conditions, environmental control systems, additive use, and fly ash handling methods. Based on this survey, a matrix of fly ash samples representing a range of conditions were chosen and collected. The collected ash samples were analyzed for bulk characteristics such as elemental composition, microstructure, chemical and mineralogical composition, surface area, and particle size distribution. State-of-the-art synchrotron X-ray microscopy and spectroscopy techniques were applied to reveal the molecular scale speciation information of As and Se, such as oxidation state, association with other elements/minerals, and complexation states.

01 COAL, LIGNITE, AND PEAT↗

Support Effect Studied on Thin-Film Perovskites

Some functional oxides exhibit strong support effects but typically have low surface areas and stabilities that negate the promotional effects. The primary goal of our work in the past three years was to develop high-surface-area versions of these supports by Atomic Layer Deposition onto stable supports, then use these to understand how the oxide supports affect the metal catalytic properties. The primary application targeted for these materials was methane oxidation and related reactions for emissions control. Systems of particular interest were supported, precious metals on thin-film perovskites in order to develop “intelligent” catalysts in which the metal can reversibly ex-solve from perovskite lattices. This following report lists the papers that were published with the support of this DOE grant, together with a brief summary of the results from each paper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗