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At least 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Print-Consistency and Process-Interaction for Inkjet-Printed Copper on Flexible Substrate

Printed electronics is a fastest growing and emerging technology that have shown much potential in several industries including automotive, wearables, healthcare, and aerospace. Its applications can be found not only in flexible but also in large area electronics. The technology provides an effective and convenient method to additively deposit conductive and insulating materials on any type of substrate. Comparing with traditional manufacturing processes, which involves chemical etching, this technology also comes to be relatively environmental friendly. Despite its status, it is not without its challenges. Starting from the material being compatible in the printer equipment to the point of achieving fine resolutions, and with excellent properties are some of the challenges that printed electronics face. Among the myriad of printing technologies such as Aerosol Jet, micro-dispensing, gravure printing, screen printing, Inkjet printing, Inkjet has gained much attention due to its low-cost, low material consumption, and roll-to-roll capability for mass manufacturing. The technology has been widely used in home and office, but recently gained interest in printed electronics in a research and development setting. Conductive materials used in Inkjet printing generally comprises of metal Nanoparticles that need to be thermally sintered for it to be conductive. The preferred metal of choice has been mostly silver due to its excellent electrical properties and ease in sintering. However, silver comes to be expensive than its counterpart copper. Since copper is prone to oxidation, much focus has been given towards photonic sintering that involves sudden burst of pulsed light at certain energy to sinter the copper Nanoparticles. With this technique, only the printed material gets sintered in a matter of seconds without having a great impact on its substrate, due to which it is also preferred in low temperature applications. With all the knowledge, there is still a large gap in the process side with copper where it is important to look how the print process affects the resolution of the print along with the effect of post-print processes on electrical and mechanical properties. In this paper, a copper Inkjet ink is utilized for understanding the effect of Inkjet print parameters on the ejected droplet and its resolution. Post-print process is also quantified using a photonic sintering equipment for excellent electrical and mechanical properties. To demonstrate the complete process, commercial-off-the-shelf components will also be mounted on the additively printed pads via Inkjet. Statistically, control charting technique will be utilized to understand the capability of the Inkjet process.

printed electronics↗
DOE OSTI2025

Tuning Cation (Dis)Order in Cr‐Based Li‐Excess Oxide Cathode Materials to Improve Li+ Transport Properties

Abstract Li‐excess disordered rocksalts (DRXs) hold promise as next‐generation cathodes for Li‐ion batteries due to their high capacity and energy density, along with the potential to eliminate the need for Co and Ni. However, due to their low Li + diffusivity, DRXs need to be pulverized into nanoparticles to achieve high performance. Herein, a new strategy for overcoming this limitation is demonstrated, involving the design of as‐synthesized partially disordered oxides with a structure that lies between ordered layered and fully disordered, exhibiting a varying degree of local (dis)order. This unique structure activates new Li + diffusion channels, improving percolation and transport properties. This strategy allows a large content of Li + to be accessed in material with large, micron‐sized particles through highly reversible Cr 3+/6+ and O redox, yielding a first discharge capacity of 286 mAh g −1 (881 Wh kg −1 ). The Li + percolation network is further improved by substituting Ti with a mixture of multiple metals, which appears to locally decrease the migration barrier through lattice distortion. Proper tuning of the chemical composition, especially the content of metals with empty d orbitals, is established as a crucial factor for controlling the degree of disorder and mitigating voltage fade and hysteresis growth upon cycling.

Moździerz, Maciej↗
DOE OSTI2021

Pt Catalysts Modified with Manganese Oxide through Atomic Layer Deposition for CO Oxidation: Establishing a Coating Layer above or below Pt

The effect of atomic layer deposition (ALD) of manganese oxide on CO oxidation over Pt/Al2O3 is investigated. Two types of catalysts with a thin MnOx layer coated on or under the Pt nanoparticles (NPs) are prepared, and a pristine Pt/Al2O3 catalyst is used as a reference sample. The addition of the ALD layers improves the catalyst durability and both catalysts with MnOx exhibit greater stability after thermal aging at 1073-K. Besides, MnOx promotes CO oxidation through active Pt-MnOx interfacial sites, showing a reaction rate up to 35-fold faster than that of unmodified Pt. Interestingly, the CO adsorption ability of the Pt catalysts with MnOx overcoats is greatly suppressed after the high-temperature calcination; however, the reaction rate of CO oxidation is still excellent. This phenomenon is because the uniformly covered MnOx with two atomic layers diminishes the exposed Pt surface, but the reaction near the Pt-MnOx interfacial site still occurs. Our results guide the effective use of ALD, which is actively applied to heterogeneous catalysis, and provide a novel direction to control metal-assisted interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Nanometre-resolved observation of electrochemical microenvironment formation at the nanoparticle–ligand interface

The dynamic response of surface ligands on nanoparticles (NPs) to external stimuli critically determines the functionality of NP–ligand systems. For example, in electrocatalysis the collective dissociation of ligands on NP surfaces can lead to the creation of an NP/ordered-ligand interlayer, a microenvironment that is highly active and selective for CO 2 -to-CO conversion. However, the lack of in situ characterization techniques with high spatial resolution hampers a comprehensive molecular-level understanding of the mechanism of interlayer formation. Here, in this work, we utilize in situ infrared nanospectroscopy and surface-enhanced Raman spectroscopy, unveiling an electrochemical bias-induced consecutive bond cleavage mechanism of surface ligands leading to formation of the NP/ordered-ligand interlayer. This real-time molecular insight could influence the design of confined localized fields in multiple catalytic systems. Moreover, the demonstrated capability of capturing nanometre-resolved, dynamic molecular-scale events holds promise for the advancement of using controlled local molecular behaviour to achieve desired functionalities across multiple research domains in nanoscience.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2006

pH Sensitive Microcapsules for Delivery of Corrosion Inhibitors

A considerable number of corrosion problems can be solved by coatings. However, even the best protective coatings can fail by allowing the slow diffusion of oxygen and moisture to the metal surface. Corrosion accelerates when a coating delaminates. Often, the problems start when microscopic nicks or pits on the surface develop during manufacturing or through wear and tear. This problem can be solved by the incorporation of a self-healing function into the coating. Several new concepts are currently under development to incorporate this function into a coating. Conductive polymers, nanoparticles, and microcapsules are used to release corrosion-inhibiting ions at a defect site. The objective of this investigation is to develop a smart coating for the early detection and inhibition of corrosion. The dual function of this new smart coating system is performed by pH-triggered release microcapsules. The microcapsules can be used to deliver healing agents to terminate the corrosion process at its early stage or as corrosion indicators by releasing dyes at the localized corrosion sites. The dyes can be color dyes or fluorescent dyes, with or without pH sensitivity. Microcapsules were formed through the interfacial polymerization process. The average size of the microcapsules can be adjusted from 1 to 100 micron by adjusting the emulsion formula and the microcapsule forming conditions. A typical microcapsule size is around 10 microns with a narrow size distribution. The pH sensitivity of the microcapsule can also be controlled by adjusting the emulsion formula and the polymerization reaction time. Both corrosion indicator (pH indicator) and corrosion inhibitor containing microcapsules were formed and incorporated into paint systems. Test panels of selected steels and aluminum alloys were painted using these paints. Testing of compatibility between the microcapsule system and different paint systems are in progress. Initial experiments with the microcapsule containing paint show visible color changes at induced corrosion sites and improvement of corrosion protection. Further investigation of the performance of the coating using electrochemical techniques and long term exposure are currently underway.

Li, Wenyan↗
DOE OSTI2026

Co-Design of Charge Transport Superhighways to Connect Catalytic Sites in Soft Photoelectrochemical Systems

Efficient photon-to-electron-to-molecule conversion requires multi-length scale control over charge transport pathways, where electronic charges are delivered to catalytic sites under high mass transport flux. A fundamental question is how can we co-design charge transport pathways to promote efficient charge transfer to/from catalytic sites in complex three-dimensional architectures? Soft conducting polymer systems offer exceptional promise to provide three-dimensional charge transport networks, where electrolyte (ion and solvent) can interdiffuse to promote long-lived charge carriers and the molecular nature allows for strategic synthetic design of catalytic sites. Herein we combine theoretical and experimental approaches to investigate the earliest stages of photoelectrochemical deposition of near-surface catalytic sites (Pt) on soft bulk heterojunction polymeric semiconductors composed of a prototype donor (PTB7-Th) and a prototype acceptor (N2200) as a model system towards better understanding molecular catalyst-polymer site interactions. We focus initially on photoelectrochemical deposition of low Pt loadings, nanoparticle sizes (formed by progressive nucleation) below 20 nm, for both density functional theory (DFT) modeling studies and for spectroscopic characterization using surface-sensitive X-ray and UV-photoemission (XPS/UPS). DFT modeling of “n-type” N2200 slabs reveal for the first time that sulfur atoms in the thiophene units serve as the lowest-energy adsorption sites for single Pt atoms, while larger Pt clusters engage more complexly with both thiophene and naphthalene diimide (NDI) core sites. Changes in chemical composition observed by X-ray photoelectron spectroscopy (XPS) support the DFT predictions, and the angle-resolved measurements reveal that Pt nucleation initiates at subsurface sites which appear to be localized active domains that promote charge transport/transfer and enable vertical growth toward the surface. These results suggest that light-activated Pt nanoparticle deposition decorates energetically distinct sites, where photoactivity is dictated by the local energetics of those sites, and the fact that they represent the termini of charge transport “super-highways” – a small percentage of the total volume of the donor/acceptor polymeric active layer which carries most of the photocurrent generated during both Pt deposition and photoelectrochemical HER. We posit that these initial studies provide a foundational strategy for design of catalytic sites in the near surface regions of complex polymeric materials and advancing soft semiconductor-based photoelectrochemical systems. Achieving a nanometer-scale understanding of catalyst deposition and the impact of local composition and energetics on that placement, should ultimately provide the design guidelines (co-design) for a broad array of catalysts at sites that optimize that efficiency and maximize platform durability.

14 SOLAR ENERGY↗
NASA NTRS2010

Field Testing of High Current Electrokinetic Nanoparticle Treatment for Corrosion Mitigation in Reinforced Concrete

Electrokinetic Nanoparticle (EN) treatment was used as a rapid repair measure to mitigate chloride induced corrosion of reinforced concrete in the field. EN treatment uses an electric field to transport positively charged nanoparticles to the reinforcement through the concrete capillary pores. Cylindrical reinforced concrete specimens were batched with 4.5 wt % salt content (based on cement mass). Three distinct electrokinetic treatments were conducted using high current density (up to 5 A/m2) to form a chloride penetration barrier that was established in 5 days, as opposed to the traditional 6-8 weeks, generally required for electrochemical chloride extraction (ECE). These treatments included basic EN treatment, EN with additional calcium treatment, and basic ECE treatment. Field exposures were conducted at the NASA Beachside Corrosion Test Site, Kennedy Space Center, Florida, USA. The specimens were subjected to sea water immersion at the test site as a posttreatment exposure. Following a 30-day post-treatment exposure period, the specimens were subjected to indirect tensile testing to evaluate treatment impact. The EN treated specimens exhibited 60% and 30% increases in tensile strength as compared to the untreated controls and ECE treated specimens respectively. The surfaces of the reinforcement bars of the control specimens were 67% covered by corrosion products. In contrast, the EN treated specimens exhibited corrosion coverage of only 4%. Scanning electron microscopy (SEM) revealed a dense concrete microstructure adjacent to the bars of the treated specimens as compared to the control and ECE specimens. Energy dispersive spectroscopic (EDS) analysis of the polished EN treated specimens showed a reduction in chloride content by a factor of 20 adjacent to the bars. This study demonstrated that EN treatment was successful in forming a chloride penetration barrier rapidly. This work also showed that the chloride barrier was effective when samples were exposed to field conditions at one of the most severely corrosive environments in North America.

Cardenas, Henry↗
DOE OSTI2021

Photocatalytic Oxidation of Dissolved Mn 2+ by TiO 2 and the Formation of Tunnel Structured Manganese Oxides

The redox reaction of manganese (Mn) is of great environmental, geological, and public health significance, as Mn oxides control the distribution and electron flow of numerous nutrients and contaminants in natural and engineered environments. Current understanding on the oxidation pathways of Mn(II) to Mn(III/IV) mainly focuses on biotic processes due to their much higher oxidation rates than those of abiotic processes. This study demonstrates rapid photocatalytic oxidation of Mn 2+ (aq) under circumneutral conditions catalyzed by naturally abundant semiconducting TiO 2 minerals. Notably, the photocatalytic oxidation rates are comparable to or even higher than those of reported biotic/abiotic processes. In addition, the rapid photocatalytic oxidation leads to the formation of large tunnel structured Mn oxides (todorokite and romanechite) on the surface of TiO 2 . These findings suggest that photocatalytic oxidation of Mn 2+ (aq) by natural semiconducting minerals is likely an important yet previously overlooked pathway for understanding the occurrence of natural Mn oxide coatings on rock surfaces. In addition, considering the increasing input of photoreactive engineered nanoparticles into environmental systems, this work shows the potential impacts of nanoparticles on influencing natural redox cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Blocking Ion Migration Stabilizes the High Thermoelectric Performance in Cu 2 Se Composites

The applications of mixed ionic–electronic conductors are limited due to phase instability under a high direct current and large temperature difference. Here, it is shown that Cu 2 Se is stabilized through regulating the behaviors of Cu + ions and electrons in a Schottky heterojunction between the Cu 2 Se host matrix and in-situ-formed BiCuSeO nanoparticles. The accumulation of Cu + ions via an ionic capacitive effect at the Schottky junction under the direct current modifies the space-charge distribution in the electric double layer, which blocks the long-range migration of Cu + and produces a drastic reduction of Cu + ion migration by nearly two orders of magnitude. Moreover, this heterojunction impedes electrons transferring from BiCuSeO to Cu 2 Se, obstructing the reduction reaction of Cu + into Cu metal at the interface and hence stabilizes the β-Cu 2 Se phase. Furthermore, incorporation of BiCuSeO in Cu 2 Se optimizes the carrier concentration and intensifies phonon scattering, contributing to the peak figure of merit ZT value of ≈2.7 at 973 K and high average ZT value of ≈1.5 between 400 and 973 K for the Cu 2 Se/ BiCuSeO composites. Here, this discovery provides a new avenue for stabilizing mixed ionic–electronic conduction thermoelectrics, and gives fresh insights into controlling ion migration in these ionic-transport-dominated materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A Rapid, Sustainable, One‐step Mechanochemical Strategy for Synthesizing Gold Nanoparticle‐Doped Covalent Organic Frameworks

Doping gold nanoparticles within covalent organic frameworks (AuNPs@COFs) has garnered enormous momentum due to their unique properties and broad applications. Nevertheless, prevailing multi-step synthesis is plagued with low time efficiency, eco-unfriendliness, and tedious protocols. Herein, we introduce a rapid, sustainable, scalable, one-step mechanochemical strategy for synthesizing up to four AuNPs-doped COFs via steel ball milling within an hour under ambient conditions. This approach overcomes the synthetic barriers of conventional multi-step solution-based methods, such as extended reaction times (5 days), milligram scale, the use of toxic solvents, elevated temperatures, and reliance on external reducing agents. One exemplary AuNPs@COF (AuNPs@DMTP-TPB) exhibits high crystallinity, porosity, small AuNP size, and uniform dispersion (5.4±0.6 nm), surpassing its counterpart synthesized via multi-step solution-based methods (6.4±1.1 nm). Notably, the gram-scale synthesis of AuNPs@DMTP-TPB can be successfully achieved. Control experiments suggest that the in situ formation of AuNPs is attributed to the galvanic reduction of gold precursor by stainless steel apparatus. As a proof-of-concept catalytic application, AuNPs@DMTP-TPB demonstrates remarkable catalytic activity and recyclability for the aqueous reduction of 4-nitrophenol under ambient conditions. This study provides an environmentally benign and fast pathway to synthesize AuNPs@COFs via mechanochemistry for the first time, opening tremendous possibilities for heterogeneous catalysis and beyond.

Nailwal, Yogendra↗
DOE OSTI2023

Nanoparticle Diffusion in Miscible Polymer Nanocomposite Melts

X-ray photon correlation spectroscopy measurements were used to quantify the dynamics of bare and bimodal grafted silica nanoparticles mixed with PEO melts of different molecular weights. In dilute polymer nanocomposite (PNC) samples, we find diffusive NP behavior as described by the Stokes–Einstein relationship so long as the adsorbed PEO polymer layer is taken into account in determining both the effective NP size and its role on composite viscosity. The size of this bound layer was found to be approximately 2R g , where R g is the chain radius of gyration. We also expanded our system to investigate how the dynamics of grafted NPs differ from bare NPs with an adsorbed layer. We showed that the dynamics again can be determined by an effective NP radius at a scale smaller than the effective interparticle spacing; however, at larger length scales, the morphology and grafting parameters play a major role in the system dynamics. These results allow us to quantify NP ordering driven by polymer crystallization. It has previously been speculated that behavior is controlled by the relative ratio of time scale of crystal growth and the diffusive time scale of the NPs, a Peclet number. When the former time scale is longer, then the NPs are expected to be segregated into the interlamellar amorphous zones, while the NPs are too slow to be reorganized in the opposite case. We show here that this conjecture is quantitatively correct and the demarcation in behavior occurs for Pe = 1. Thus, we provide a way to estimate a critical spherulite growth rate for any semicrystalline PNC, at which a given NP can be ordered. Together, the results of this study permit us to tunably design PNCs through directed dispersion of NPs in a polymer matrix.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Direct measurement of thermal Knudsen forces in rarefied gas environments

At micro- and nanoscales, momentum transfer between surfaces is influenced by various physical mechanisms, including quantum fluctuations, electromagnetic interactions, electric charges, and the dynamics of (rarefied) gases. Under non-isothermal conditions, rarefied gases give rise to thermal Knudsen forces whose magnitudes strongly depend on the gas species and surface characteristics. Knudsen forces are particularly relevant in nanotechnology, optical manipulation, and aerospace systems, where gas rarefaction occurs due to highly confined geometries, sub-micrometer length scales, and reduced particle densities. Despite their significance, predictive modeling of Knudsen forces is limited by a lack of comprehensive experimental data across diverse materials and surface morphologies. Here, in this work, we present a highly sensitive and adaptable measurement platform capable of directly quantifying Knudsen forces using a suspended, interchangeable micro-cantilever within controlled rarefied helium and nitrogen environments. The system integrates optical fiber interferometry to precisely capture out-of-plane displacements at sub-micrometer resolution, driven by Knudsen forces. From the empirical data, we derive a robust correlation linking the magnitudes of Knudsen forces to energy accommodation coefficients, offering deeper insights into the underlying gas–surface interaction mechanisms.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Electrochemical Behavior of Cerium at an Indium Tin-Doped Oxide Electrode in Acidic Media

The redox behavior and speciation of cerium at mesoporous thin films composed of nanoparticles of indium tin-doped oxide (nITO) electrodes were characterized in pH 4.8, 0.1 M acetate buffer and both 0.1 and 1 M HNO 3 using electrochemical techniques and X-ray photoelectron spectroscopy. Anodic deposition of ceria species from Ce(III) to the nITO electrode was achieved under all solvent conditions via spontaneous condensation of electrochemically generated ceric hydroxide species. In 1 M nitric acid, the rate of CeO 2 dissolution is on the same order as CeO 2 deposition, resulting in negligible amounts of CeO 2 electrodeposited at the nITO surface. The cathodic stripping of CeO 2 from the nITO substrate deposited in 0.1 M nitric acid or pH 4.8 acetate buffer follows a 2-step process where Ce(IV)-oxide is initially reduced to an unstable Ce(III)-oxide species that rapidly undergoes acid catalyzed dissolution to yield soluble Ce(III) (aq) . These findings provide a foundation for the pH and anodic potential controlled deposition of CeO 2 thin films to ITO substrates, which can aid in the development of materials composed of ceria. As a result, they can also be used to infer likely analogous actinide redox behavior and speciation at these electrodes.

Cerium↗
DOE OSTI2021

Lanthanum-based double perovskite nanoscale motifs as support media for the methanol oxidation reaction

In this report we have not only analyzed the performance of perovskite oxides as support media for the methanol oxidation reaction (MOR) but also examined the impact and significance of various reaction parameters on their synthesis. Specifically, we have generated (a) La 2 NiMnO 6 , LaMnO 3 , and LaNiO 3 nanocubes with average sizes of ~200 nm, in addition to a series of La 2 NiMnO 6 (b) nanocubes possessing average sizes of ~70 and 400 nm and (c) anisotropic nanorods characterized by average diameters of 40-50 nm. All of these samples, when used as supports for Pt nanoparticles, exhibited activities which were at least twice that measured for Pt/C. We have investigated and correlated the effect of varying perovskite (i) composition, (ii) size, and (iii) morphology upon the measured MOR activity. (i) The Ni-containing perovskites yielded generally higher performance metrics than LaMnO 3 alone, suggesting that the presence of Ni is favorable for MOR, a finding supported by a shift in the Pt d-band in XPS. (ii) MOR activity is enhanced as the perovskite size increases in magnitude, suggesting that a growth in the perovskite particle size enables favorable, synergistic metal–support interactions. (iii) A comparison of the nanorods and nanocubes of a similar diameter implied that the one-dimensional morphology achieved a greater activity, a finding which can be attributed not only to the anisotropic structure but also to a desirable surface structure. Overall, these data yield key insights into the tuning of metal–support interactions via rational control over the composition, size, and morphology of the underlying catalyst support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Introducing dusty plasma particle growth of nanospherical titanium dioxide

In dusty plasma environments, spontaneous growth of nanoparticles from reactive gases has been extensively studied for over three decades, primarily focusing on hydrocarbons and silicate particles. Here, we introduce the growth of titanium dioxide, a wide bandgap semiconductor, as dusty plasma nanoparticles. The resultant particles exhibited a spherical morphology and reached a maximum monodisperse radius of 235 ± 20 nm after growing for 70 s. The particle grew linearly, and the growth displayed a cyclic behavior; that is, upon reaching their maximum radius, the largest particles fell out of the plasma, and the next growth cycle immediately followed. The particles were collected after being grown for different amounts of time and imaged using scanning electron microscopy. Further characterization was carried out using energy dispersive x-ray spectroscopy, x-ray diffraction, and Raman spectroscopy to elucidate the chemical composition and crystalline properties of the maximally sized particles. Initially, the as-grown particles exhibited an amorphous structure after 70 s. However, annealing treatments at temperatures of 400 and 800 °C induced crystallization, yielding anatase and rutile phases, respectively. Annealing at 600 °C resulted in a mixed phase of anatase and rutile. These findings open avenues for a rapid and controlled growth of titanium dioxide via dusty plasma.

Physics↗
DOE OSTI2024

Gas–Phase Preparation of the 14π Hückel Polycyclic Aromatic Anthracene and Phenanthrene Isomers (C 14 H 10 ) via the Propargyl Addition–BenzAnnulation (PABA) Mechanism

Polycyclic aromatic hydrocarbons (PAHs) imply the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles, commonly referred to as soot particles in combustion systems and interstellar grains in deep space. Whereas gas phase formation pathways to the simplest PAH – naphthalene (C 10 H 8 ) – are beginning to emerge, reaction pathways leading to the synthesis of the 14π Hückel aromatic PAHs anthracene and phenanthrene (C 14 H 10 ) are still incomplete. Here, by utilizing a chemical microreactor in conjunction with vacuum ultraviolet (VUV) photoionization (PI) of the products followed by detection of the ions in a reflectron time-of-flight mass spectrometer (ReTOF-MS), the reaction between the 1'- and 2'-methylnaphthyl radicals (C 11 H 9 •) with the propargyl radical (C 3 H 3 •) accesses anthracene (C 14 H 10 ) and phenanthrene (C 14 H 10 ) via the Propargyl Addition–BenzAnnulation (PABA) mechanism in conjunction with a hydrogen assisted isomerization. Furthermore, the preferential formation of the thermodynamically less stable anthracene isomer compared to phenanthrene suggests a kinetic, rather than a thermodynamics control of the reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗