How Pt Influences H 2 Reactions on High Surface-Area Pt/CeO 2 Powder Catalyst Surfaces
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
SEARCH · Engineering Papers
Results for “surface reactions”
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Regulating the surface Pt coordination environment in the PtN overlayers on PtCuN hollow nanospheres for efficient oxygen reduction reaction
Engineering the surface Pt coordination environment is a promising strategy for promoting the kinetically sluggish oxygen reduction reaction (ORR) on Pt-based catalysts. Here, in this study, we achieve the compressive strain effect and electronic effect by Cu and N co-doping to synthesize the PtCuN hollow nanospheres with PtN overlayers (PtCuN@PtN HNSs) using a facile solvothermal synthesis. Electrochemical investigations show that the constructed disordered Pt–N coordination structures effectively facilitate the ORR and stabilize Pt atoms in the compressed lattice, whereas an excessive N-doping can lead to the formation of a structurally unstable Pt nitride phase. Theoretical analyses confirm that the oxygen reduction kinetics on the compressed PtN overlayers are regulated by a synergistic effect resulting from N-doping and lattice compression, circumventing the traditional linear scaling relationships (LSR). The optimized PtCuN@PtN HNSs, with the composition of PtCu 0.29 N 1.1 , demonstrate an area-specific activity of 1.98 mA cm –2 and a mass-specific activity of 1.81 A mg Pt –1 .
36 MATERIALS SCIENCE↗
Interfacial Hydrophilicity Controls Mineral Transformation Outcomes for Enstatite and Amorphous MgSiO 3
Subsurface injection of carbon dioxide (CO 2 ) into mafic-ultramafic rocks for permanent storage via mineralization is being studied to reduce emissions. Here, we investigated the carbonation products of enstatite (MgSiO 3 ) to assess its efficiency in sequestering CO 2 for safe and permanent storage as carbonate minerals. This was accomplished by conducting variable temperature carbonation reactions with samples of differing crystallinities and surface chemistries. Reaction progress was monitored utilizing in situ X-ray diffraction, and the presence of carbonate products was confirmed using additional techniques, such as thermogravimetric analysis coupled with mass spectrometry and scanning electron microscopy with energy dispersive spectrometry. Our results show that crystalline enstatite produces small amounts of the anhydrous form of MgCO 3 (magnesite), while amorphous MgSiO 3 , which was used to simulate mafic glass, more readily converts to the hydrated/hydroxylated hydromagnesite [Mg 5 (CO 3 ) 4 (OH) 2 ·4H 2 O]. These results, supplemented with dynamic vapor sorption experiments, suggest that surface properties play a significant role in the pathway and degree of carbonation. These developments concerning the reactivity of CO 2 with reactive mafic phases will help further our understanding of the reactivity of these mafic-ultramafic minerals with implications for permanent carbon storage and other subsurface engineering scenarios involving reactive reservoirs.
basalt↗
Atomic-Scale Structure of Chemically Distinct Surface Oxygens in Redox Reactions
During redox reactions, oxide-supported catalytic systems undergo structural and chemical changes. Improving subsequent catalytic properties requires an understanding of the atomic-scale structure with chemical state specificity under reaction conditions. For the case of 1/2 monolayer vanadia on α-TiO 2 (110), we use X-ray standing wave (XSW) excited X-ray photoelectron spectroscopy to follow the redox induced atomic positional and chemical state changes of this interface. Furthermore, while the resulting XSW 3D composite atomic maps include the Ti and O substrate atoms and V surface atoms, our focus in this report is on the previously unseen surface oxygen species with comparison to density functional theory predictions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Design and characterization of surface molecular assemblies for the preparation of solar fuels
A key issue in solar energy conversion is the utilization of solar energy for the preparation of solar fuels. In this area, artificial photosynthesis offers promising approaches for the conversion of H 2 O and CO 2 into usable solar fuels. This review highlights both the design and characterization of surface molecular assemblies for the preparation of solar fuels. It includes mechanistic summaries of the details of the underlying surface chemical reactions including water oxidation and proton/water reduction. The surface mechanisms are shown to integrate molecular reactivity with surface electron transfer in integrated assemblies that lead to impressive efficiencies for water oxidation and proton or CO 2 reduction.
catalysts and catalysis↗
Toward MBenes Battery Electrode Materials: Layered Molybdenum Borides for Li-Ion Batteries
Lithium-ion and sodium-ion batteries (LIBs and SIBs) are crucial in our shift toward sustainable technologies. In this work, the potential of layered boride materials (MoAlB and Mo 2 AlB 2 ) as novel, high-performance electrode materials for LIBs and SIBs, is explored. It is discovered that Mo 2 AlB 2 shows a higher specific capacity than MoAlB when used as an electrode material for LIBs, with a specific capacity of 593 mAh g -1 achieved after 500 cycles at 200 mA g -1 . It is also found that surface redox reactions are responsible for Li storage in Mo 2 AlB 2 , instead of intercalation or conversion. Moreover, the sodium hydroxide treatment of MoAlB leads to a porous morphology and higher specific capacities exceeding that of pristine MoAlB. When tested in SIBs, Mo 2 AlB 2 exhibits a specific capacity of 150 mAh g -1 at 20 mA g -1 . These findings suggest that layered borides have potential as electrode materials for both LIBs and SIBs, and highlight the importance of surface redox reactions in Li storage mechanisms.
25 ENERGY STORAGE↗
Single-Atom Doping at the Molecule–Metal Interface: How Rh Affects Surface Explosion Kinetics
Controlling chemical reactions at interfaces is central to many fields, including atmospheric, environmental, and biological chemistry as well as catalysis and corrosion. We performed a fundamental study of how catalytically active Rh atoms placed at and above a molecule-metal interface influence the surface reaction kinetics of tartaric acid (TA) decomposition. Specifically, TA decomposition on Cu(100) exhibits autocatalytic decomposition kinetics involving a slow initiation step followed by fast decomposition of the molecular layer. These so-called “surface explosions” are extremely sensitive to initial conditions, making it fundamentally interesting to study how the placement of reactive atoms affects the reaction rate. Temperature-programmed reaction (TPR) experiments reveal that Rh atoms embedded in the Cu(100) surface beneath TA (TA/Rh/Cu) or atop the TA layer (Rh/TA/Cu) reduce the decomposition temperature and modify the reaction rate constants. Isothermal TPR analysis reveals that Rh enhances both the initiation rate constant, k i , and the explosion rate constant, k e , facilitating explosive decomposition at lower temperatures. This result provides evidence that both the initiation and explosion steps occur at the metal-molecule interface and are accelerated by the presence of Rh at this interface. This study illustrates how small amounts of reactive elements may be used to control nonlinear kinetic processes at interfaces.
desorption↗
New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts
Abstract The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na 2 WO 4 /SiO 2 catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H 2 ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na 2 WO 4 active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO x sites are responsible for selectively activating CH 4 to C 2 H x and over‐oxidizing CH y to CO and ( ii ) molten Na 2 WO 4 phase is mainly responsible for over‐oxidation of CH 4 to CO 2 and also assists in oxidative dehydrogenation of C 2 H 6 to C 2 H 4 . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na 2 WO 4 /SiO 2 catalysts.
Sourav, Sagar↗
New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts
Abstract The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na 2 WO 4 /SiO 2 catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H 2 ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na 2 WO 4 active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO x sites are responsible for selectively activating CH 4 to C 2 H x and over‐oxidizing CH y to CO and ( ii ) molten Na 2 WO 4 phase is mainly responsible for over‐oxidation of CH 4 to CO 2 and also assists in oxidative dehydrogenation of C 2 H 6 to C 2 H 4 . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na 2 WO 4 /SiO 2 catalysts.
Sourav, Sagar↗
Enabling Structure/Interface Regulation for High Performance Ni-Rich Cathodes
Here, further commercialization of Ni-rich layered cathodes is hindered by severe structure/interface degradation and kinetic hindrance that occur during electrochemical operation, which leads to safety risks and reduced range in electric vehicles (EVs). Herein, by selecting elements with different solubility properties, a multifunctional strategy that synchronously fabricates perovskite-type SrZrO 3 coating and Sr/Zr co-doping is employed to strengthen the structure/interface stability and the Li + transport mobility of LiNi 0.85 Co 0.10 Mn 0.05 O 2 (NCM). Perovskite-type SrZrO 3 protective layers formed on the particle surface can substantially mitigate the unexpected interfacial side reactions and surface phase transitions. In addition, a robust crystal framework is constructed by optimizing local O coordination through the introduction of strong Zr-O bonds. Notably, Li + diffusion kinetics is effectively improved due to expanded cell parameters and O-Li-O slab spacing with the incorporation of large-diameter Sr pillar ions, as revealed by X-ray diffraction. As a result, the Sr/Zr-modified NCM achieves a remarkable capacity retention of 99.4% after 200 cycles at 1 C, and a high rate capacity of 168.9 mAh g -1 at 10 C. This work opens new avenues to develop high-performance NCM cathodes with high energy and high power for EVs with long calendar life.
25 ENERGY STORAGE↗
Understanding the Role of Surface Heterogeneities in Electrosynthesis Reactions
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Gas-Phase Formation of 1,3,5,7-Cyclooctatetraene (C 8 H 8 ) through Ring Expansion via the Aromatic 1,3,5-Cyclooctatrien-7-yl Radical (C 8 H 9 • ) Transient
Gas-phase 1,3,5,7-cyclooctatetraene (C 8 H 8 ) and triplet aromatic 1,3,5,7-cyclooctatetraene (C 8 H 8 ) were formed for the first time through the bimolecular methylidyne radicals (CH) - 1,3,5-cycloheptatriene (C 7 H 8 ) reactions under single collision conditions on the doublet surface. The reaction involves methylidyne radical addition to the olefinic pi electron system of 1,3,5-cycloheptatriene followed by isomerization and ring expansion to aromatic 1,3,5-cyclooctatrien-7-yl radical (C 8 H 9 •). The chemically activated doublet radical intermediate undergoes unimolecular decomposition to 1,3,5,7-cyclooctatetraene. Substituted 1,3,5,7-cyclooctatetraene molecules can be prepared in the gas phase with hydrogen atom(s) in the 1,3,5-cycloheptatriene reactant being replaced by organic side groups. Furthermore, these findings are also of potential interest to organometallic chemists by expanding the synthesis of exotic transition metal complexes incorporating substituted 1,3,5,7-cyclooctatetraene dianion (C 8 H 8 2- ) ligands and to untangle the unimolecular decomposition of chemically activated and substituted 1,3,5-cyclooctatrien-7-yl radical eventually gaining a fundamental insight of their bonding chemistry, electronic structures, and stabilities.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Correction to How Pt Influences H 2 Reactions on High Surface-Area Pt/CeO 2 Powder Catalyst Surfaces
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
An Investigation of Variables Affecting Plutonium Hydriding (20210946DI): Surface Phase Transitions and Reactions
Tusas was originally developed for phase field simulation of solidification (see [33, 6, 32]) and evolution of polycrystalline solid mechanics (see [16]). Tusas is particularly developed for PDEs compatible with structured or unstructured Lagrange (nodal) finite element discretizations and explicit (Euler) or implicit (Euler, Trapezoid, BDF2) temporal discretizations.
97 MATHEMATICS AND COMPUTING↗
pynta: An automated workflow code for reaction path exploration on surfaces.
Abstract not provided.
Johnson, Matthew↗
Enhanced reactivity at the oil–water interface accelerates the synthesis of zymonic acid in microemulsions
Chemical reactions in microscale compartments, such as aerosols and emulsions, can exhibit significantly faster reaction rates relative to macroscale containers. This enhancement in chemistry is often due to the elevated importance of surfaces as reaction vessels are reduced to picoliter volumes. While most studies have focused on the air-water interface of droplets, there are comparably fewer studies of reactions in micron-scale aqueous solutions encapsulated by oil. Here we investigate the condensation reaction of pyruvic acid (PA) to form zymonic acid (ZA) and water. Using microfluidics and optical trapping, chemical kinetics are measured in monodisperse micron-sized emulsion droplets in situ via Raman spectroscopy. Relative to a macroscopic bulk solution, which exhibits little to no reaction over many days, we find efficient production of ZA over the same time period. A kinetic model is developed to elucidate the role of the interface in accelerating the microdroplet reaction kinetics. After quantifying the surface partitioning of PA from interfacial tension measurements, the rate coefficient for the condensation reaction at the oil-water interface is determined to be 1.8 × 10-2 M-1 s-1. This rate coefficient is estimated to be 105 larger than the reaction rate in bulk aqueous solutions. Compared to previous studies of accelerated ZA formation at the air-water interface on nanodroplets, we find that the reaction at the oil-water interface is 20 times more efficient. Despite this difference, the overall ZA formation rate in emulsions is significantly slower than in the same-sized aerosols, which arises from the weaker partitioning of PA to the oil-aqueous relative to air-water interface. These results highlight the interplay between interfacial partitioning and reactivity in accelerating chemistry in microcompartments and provides new insights into how interfacial composition influences condensation reactions.
Wallace, Brandon J↗
Concurrent Amorphization and Nanocatalyst Formation in Cu‐Substituted Perovskite Oxide Surface: Effects on Oxygen Reduction Reaction at Elevated Temperatures
Abstract The activity and durability of chemical/electrochemical catalysts are significantly influenced by their surface environments, highlighting the importance of thoroughly examining the catalyst surface. Here, Cu‐substituted La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3‐δ is selected, a state‐of‐the‐art material for oxygen reduction reaction (ORR), to explore the real‐time evolution of surface morphology and chemistry under a reducing atmosphere at elevated temperatures. Remarkably, in a pioneering observation, it is discovered that the perovskite surface starts to amorphize at an unusually low temperature of approximately 100 °C and multicomponent metal nanocatalysts additionally form on the amorphous surface as the temperature raises to 400 °C. Moreover, this investigation into the stability of the resulting amorphous layer under oxidizing conditions reveals that the amorphous structure can withstand a high‐temperature oxidizing atmosphere (≥650 °C) only when it has undergone sufficient reduction for an extended period. Therefore, the coexistence of the active nanocatalysts and defective amorphous surface leads to a nearly 100% enhancement in the electrode resistance for the ORR over 200 h without significant degradation. These observations provide a new catalytic design strategy for using redox‐dynamic perovskite oxide host materials.
Jeon, SungHyun↗