Active Reaction Control of Cu Redox State Based on Real-Time Feedback from In Situ Synchrotron Measurements
Abstract not provided
Rakita, Yevgeny↗
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Concurrent measurement of strain and chemical reaction rates in a calcite grain pack undergoing pressure solution: Evidence for surface-reaction controlled dissolution
Pressure solution is inferred to be a significant contributor to sediment compaction and lithification, especially in carbonate sediments. For a sediment deforming primarily by pressure solution, the compaction rate should be directly related to the rate of calcite dissolution, transport along grain contacts, and calcite reprecipitation. Previous experimental work has shown that there is evidence that deformation in wet calcite grain packs is consistent with control by pressure solution, but considerable ambiguity remains regarding the rate limiting mechanism. We present the results of laboratory compaction experiments designed to directly measure calcite dissolution and precipitation rates (recrystallization rates) concurrently with strain rate to test whether measured rates are consistent with predicted rates both in absolute magnitude and time evolution. Recrystallization rates are measured using trace element chemistry (Sr/Ca, Mg/Ca) and isotopes (87Sr/86Sr) of fluids flowing slowly through a compacting grain pack as it is being triaxially compressed. Imaging techniques are used to characterize the grain contacts and strain effects in the post-experiment grain pack. Our data show that calcite recrystallization rates calculated from all three geochemical parameters are in approximate agreement and that the rates closely track strain rate. The geochemically inferred rates are close to predicted rates in absolute magnitude. Uncertainty in grain contact dimensions makes distinguishing between surface reaction control and diffusion control difficult. Measured reaction rates decrease faster than predicted from standard pressure solution creep flow laws. This inconsistency may indicate that calcite dissolution rates at grain contacts are more complex, and more time-dependent, than suggested by geometric models designed to predict grain contact stresses.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Controlling Reaction Pathways of Ethylene Hydroformylation Using Isolated Bimetallic Rhodium–Cobalt Sites
Designing efficient ligand-free heterogeneous catalysts for ethylene hydroformylation to produce C 3 oxygenates is of importance for both fundamental research and practical applications, but it is often hindered by insufficient catalytic activity and selectivity. Here, this work designs isolated rhodium–cobalt (Rh–Co) sites confined within a ZSM-5 zeolite to enhance ethylene hydroformylation rates and selectivity while maintaining catalyst stability. By adjusting the Co/Al ratio in Co-ZSM-5, different sizes of Co are formed; subsequent Rh introduction produces isolated Rh 1 Co x clusters with different Rh–Co coordination numbers (CNs). In-situ characterizations and density functional theory calculations reveal that a Rh–Co CN of 3, corresponding to an isolated Rh 1 Co 3 site, provides optimal bindings to reaction intermediates and thus achieves the highest hydroformylation rates among supported Rh-based catalysts. This study demonstrates the role of coordination-tuning via a secondary metal in effectively controlling the reaction pathway over single Rh atom catalysts.
03 NATURAL GAS↗
Controlling Reaction Routes in Noble‐Metal‐Catalyzed Conversion of Aryl Ethers
Abstract Hydrogenolysis and hydrolysis of aryl ethers in the liquid phase are important reactions for accessing functionalized cyclic compounds from renewable feedstocks. On supported noble metals, hydrogenolysis is initiated by a hydrogen addition to the aromatic ring followed by C−O bond cleavage. In water, hydrolysis and hydrogenolysis proceed by partial hydrogenation of the aromatic ring prior to water or hydrogen insertion. The mechanisms are common for the studied metals, but the selectivity to hydrogenolysis increases in the order Pd 2 pressure, thus, the selectivity to hydrogenolysis is maximized by increasing temperature and decreasing H 2 pressure. Selectivity to C−O bond cleavage reaches >95 % in water and alkaline conditions.
Schmid, Julian↗
Controlling Reaction Routes in Noble‐Metal‐Catalyzed Conversion of Aryl Ethers
Abstract Hydrogenolysis and hydrolysis of aryl ethers in the liquid phase are important reactions for accessing functionalized cyclic compounds from renewable feedstocks. On supported noble metals, hydrogenolysis is initiated by a hydrogen addition to the aromatic ring followed by C−O bond cleavage. In water, hydrolysis and hydrogenolysis proceed by partial hydrogenation of the aromatic ring prior to water or hydrogen insertion. The mechanisms are common for the studied metals, but the selectivity to hydrogenolysis increases in the order Pd 2 pressure, thus, the selectivity to hydrogenolysis is maximized by increasing temperature and decreasing H 2 pressure. Selectivity to C−O bond cleavage reaches >95 % in water and alkaline conditions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Controlled Reaction Dynamics of Binary Hexafluorides to Explore New Chemical Signatures
Uranium hexafluoride (UF6 ) is a key compound in the nuclear fuel cycle. • Many enrichment technologies utilize UF6 due to its advantageous properties: • Fluorine (F) has only one isotope of major abundance. • UF6 is a solid at room temperature but has a high (~70 torr) vapor pressure. • There is significant knowledge regarding the chemical processing of UF6 . • UF6 readily hydrolyzes when released to the atmosphere. • Despite significant advances in UF6 processing, the fundamental chemistry governing reaction with UF6 is still poorly understood.
Dorris, Austin L. [Savannah River National Laborat↗
Controlled Reaction Dynamics of Binary Hexafluorides to Explore New Chemical Signatures
Conclusions • Successfully halted the UF6 hydrolysis reaction and trapped intermediate complexes • Simple alcohol instead of water leads to shifting of bands in UF6 likely from change in matrix effects • MoF6 reaction shows some potential for methyl group being present in structure of intermediates • Future work with bulkier R-groups will hopefully reveal further information as to the reaction pathway and intermediate structure via kinetics and peak shifting
Dorris, Austin L. [Savannah River National Laborat↗
Controlled Reaction Dynamics of Binary Hexafluorides to Explore New Chemical Signatures
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Dorris, Austin L. [Savannah River National Laborat↗
Catalytic resonance theory: parallel reaction pathway control
Branched catalytic reaction networks with oscillating chemical pathways perfectly select for reaction products at varying frequency.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Controlling a power output of a nuclear reaction without control rods
A nuclear power system includes a reactor vessel that includes a reactor core mounted therein. The reactor core includes nuclear fuel assemblies configured to generate a nuclear fission reaction. The reaction vessel does not include any control rod assemblies therein. The nuclear power system further includes a riser positioned above the reactor core, a primary coolant flow path, a primary coolant that circulates through the primary coolant flow path to receive heat from the nuclear fission reaction and release the received heat to generate electric power in a power generation, and a control system communicably coupled to the power generation system and configured to control a power output of the nuclear fission reaction independent of any control rod assemblies.
Callaway, Allyson↗
Controlling a power output of a nuclear reaction without control rods
A nuclear power system includes a reactor vessel that includes a reactor core that includes nuclear fuel assemblies configured to generate a nuclear fission reaction. A representative nuclear power system further includes a riser positioned above the reactor core and a primary coolant flow path that extends from a bottom portion of the reactor vessel, through the reactor core, and through an annulus between the riser and the reactor vessel. A primary coolant circulates through the primary coolant flow path to receive heat from the nuclear fission reaction and release the heat to a power generation system configured to generate electric power. The nuclear power system further includes a control rod assembly system positioned in the reactor vessel and configured to position control rods in only two discrete positions.
Callaway, Allyson↗
Using molten salts to probe outer-coordination sphere effects on lanthanide( III )/( II ) electron-transfer reactions
Controlling structure and reactivity by manipulating the outer-coordination sphere around a given reagent represents a longstanding challenge in chemistry. Despite advances toward solving this problem, it remains difficult to experimentally interrogate and characterize outer-coordination sphere impact. Here, this work describes an alternative approach that quantifies outer-coordination sphere effects. It shows how molten salt metal chlorides (MCl n ; M = K, Na, n = 1; M = Ca, n = 2) provided excellent platforms for experimentally characterizing the influence of the outer-coordination sphere cations (M n+ ) on redox reactions accessible to lanthanide ions; Ln 3+ + e 1– → Ln 2+ (Ln = Eu, Yb, Sm; e 1– = electron). As a representative example, X-ray absorption spectroscopy and cyclic voltammetry results showed that Eu 2+ instantaneously formed when Eu 3+ dissolved in molten chloride salts that had strongly polarizing cations (like Ca 2+ from CaCl 2 ) via the Eu 3+ + Cl 1– → Eu 2+ + ½Cl 2 reaction. Conversely, molten salts with less polarizing outer-sphere M 1+ cations (e.g., K 1+ in KCl) stabilized Ln 3+ . For instance, the Eu 3+ /Eu 2+ reduction potential was >0.5 V more positive in CaCl 2 than in KCl. In accordance with first-principle molecular dynamics (FPMD) simulations, we postulated that hard M n+ cations (high polarization power) inductively removed electron density from Ln n+ across Ln–Cl···M n+ networks and stabilized electron-rich and low oxidation state Ln 2+ ions. Conversely, less polarizing M n+ cations (like K 1+ ) left electron density on Lnn+ and stabilized electron-deficient and high-oxidation state Ln 3+ ions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chemical diversity in angiosperms − monoterpene synthases control complex reactions that provide the precursors for ecologically and commercially important monoterpenoids
SUMMARY Monoterpene synthases (MTSs) catalyze the first committed step in the biosynthesis of monoterpenoids, a class of specialized metabolites with particularly high chemical diversity in angiosperms. In addition to accomplishing a rate enhancement, these enzymes manage the formation and turnover of highly reactive carbocation intermediates formed from a prenyl diphosphate substrate. At each step along the reaction path, a cationic intermediate can be subject to cyclization, migration of a proton, hydride, or alkyl group, or quenching to terminate the sequence. However, enzymatic control of ligand folding, stabilization of specific intermediates, and defined quenching chemistry can maintain the specificity for forming a signature product. This review article will discuss our current understanding of how angiosperm MTSs control the reaction environment. Such knowledge allows inferences about the origin and regulation of chemical diversity, which is pertinent for appreciating the role of monoterpenoids in plant ecology but also for aiding commercial efforts that harness the accumulation of these specialized metabolites for the food, cosmetic, and pharmaceutical industries.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Toward Spatial Control of Reaction Selectivity on Photocatalysts Using Area-Selective Atomic Layer Deposition on the Model Dual Site Electrocatalyst Platform
Photocatalytic water splitting is a promising route to low-cost, green H 2 . However, this approach is currently limited in its solar-to-hydrogen conversion efficiency. One major source of efficiency loss is attributed to the high rates of undesired side and back reactions, which are exacerbated by the proximity of neighboring oxidation and reduction sites. Nanoscopic oxide coatings have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as it cannot facilitate both half-reactions. In this work, area selective atomic layer deposition (AS-ALD) was used to selectively deposit semipermeable TiO 2 films onto model metallic cocatalysts for enhancing reaction selectivity while maintaining a high overall activity. Pt and Au were used as exemplary reduction and oxidation cocatalyst sites, respectively, where Au was deactivated toward ALD growth through self-assembled thiol monolayers while TiO 2 was coated onto Pt sites. Electroanalytical measurements of monometallic thin film electrodes showed that the TiO 2 -encapsulated Pt effectively suppressed undesired H 2 oxidation and Fe(II)/Fe(III) redox reactions while still permitting the desired hydrogen evolution reaction (HER). A planar model photocatalyst platform containing patterned interdigitated arrays of Au and Pt microelectrodes was further assessed using scanning electrochemical microscopy (SECM), demonstrating the successful use of AS-ALD to enable local reaction selectivity in a dual-reaction-site (photo)electrocatalytic system. Finally, interdigitated microelectrodes having independent potential control were used to show that selectively deposited TiO 2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared with uncoated control samples.
08 HYDROGEN↗
Controlling the corrosion resistance of multi-principal element alloys
Multi-principal element alloys (MPEAs) offer the possibility of many degrees of freedom in the choice of alloying elements to produce either single phase solid solutions or more complex multiphase microstructures. Large ranges of material properties have been observed for MPEAs and mastery of the selection of elements and their compositions can enable novel combinations of properties not possible in traditional alloys. From the aqueous corrosion perspective, optimization of phase stability, control of heterogeneities, passive film identity and its protectiveness, as well as substrate properties such as metal-metal bond strength and activation energy associated with dissolution, can all be controlling factors governed by alloy composition and structure. These factors can mediate the electrochemical reactions controlling spontaneous corrosion. The quest for superior properties based on well-informed element choice is suggested as a path forward guiding MPEA formulations for corrosion performance. However, gaps in fundamental knowledge exist regarding (a) the specific functions of each element, (b) the behavior of elements in unusual combinations, and (c) the formation of complex protective oxides. These issues currently hold back progress in optimization of corrosion properties.
Scully, John R.↗
Towards Spatial Control of Reaction Selectivity on Photocatalysts using Area Selective Atomic Layer Deposition on Model Dual Site Electrocatalyst Platform
Photocatalytic water splitting is a promising route to low-cost H2; however, this approach is currently limited by solar-to-hydrogen (STH) conversion efficiencies in the sub-10% range. Z-scheme water splitting, in which H2 and O2 evolving particles are operated in separate compartments and electronically coupled by a soluble redox mediator, offers improvements in STH efficiency but introduces high rates of undesired side and back reactions. Nanoscopic oxide coatings (e.g., CrOx, and SiOx) have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as the particle can no longer facilitate both half reactions. In contrast to photodeposition, which may produce non-uniform overlayers due to the difficulty of controlling local electrochemical reactivity on the surface, area-selective atomic layer deposition (AS-ALD) can be used to deposit conformal ultrathin oxide coatings while preserving access to non-growth areas of a substrate surface. To develop this technique for Z-scheme photocatalysts, we performed AS-ALD of TiO2 on a dual site planar electrocatalyst based on interdigitated arrays of Pt and Au. Self-assembled monolayers of 1-octadecanethiol (ODT) were used to block growth on the Au array, resulting in a patterned surface in which only the Pt sites were encapsulated with TiO2. These electrocatalysts demonstrated localized reaction selectivity for hydrogen evolution reaction (HER) over the TiO2/Pt sites, while the uncoated Au sites retained activity towards Fe(II)/Fe(III) redox (FeRR). Under independent potential control, these microelectrodes showed that selectively deposited TiO2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared to uncoated control samples.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
CO oxidation over a ligand coordinated single site Rh catalyst: identification of the active complex
Single atom catalysis has evolved as a promising strategy to enhance atom utilization efficiency, lower reaction temperatures, and control reaction pathways in heterogeneous catalytic reactions. An important challenge using supported single atom catalysts is the stability of metal single atoms during reactions. Here, we present an approach to stabilize single rhodium atoms on a titania support via a metal–ligand coordination strategy. We explore the reaction activity and mechanism of CO oxidation, as well as the stability under oxidative reaction conditions. Kinetic studies suggest that, with an excess of oxygen in the feed gas, oxygen activation is more facile on defective titania surfaces than on pristine titania surfaces. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis shows that on the pristine titania surface, the 1,10-phenanthroline-5,6-dione (PDO) coordinated Rh catalyst (Rh–PDO/TiO 2 ) catalyzes CO oxidation via the formation of carbonate-like species, which is similar to what occurs on Rh nanoparticle catalysts. However, on the defective titania surface, no carbonate species form for Rh–PDO/def-TiO 2 . The supported Rh–ligand catalysts are also shown to be very stable in such a reaction environment at elevated temperatures, potentially allowing for wide applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗