Density functional theory (DFT) study of water autoionization in solvated clusters.

We have implemented a cluster-continuum method using density functional theory to model water clusters and various charged species derived from water. The two aims of this study are to determine the minimal basis required for proper modeling of water autoionization and to determine the minimum number of explicit water molecules required to properly model the energetics of solvation. The thermodynamics of water autoionization converge following a modified power law to deliver chemically accurate values of the Gibbs energy change for autoionization with tractably small clusters. Convergence is slower and not exponential as assumed in previous work. We identify the n = 21 set of clusters as the first effectively bulk water like clusters that can capture the energetic influence of both the first and second solvation shells. In this cluster, a water molecule is encapsulated in the center of a closed shell of other water molecules that hydrogen bond to form five-membered rings. The total energy change for clusters with n ≥ 21 calculated using both the RPBE-D3 and ωB97X-D exchange-correlation functionals with the 6-311+G** basis set is shown to deliver good approximations to the free energy change at 298 K. This is true even though neither functional models the individual enthalpy or entropy contributions particularly well.

Silica particles convert thiol-containing molecules to disulfides.

Synthetic amorphous silica is a common food additive and a popular cosmetic ingredient. Mesoporous silica particles are also widely studied for their potential use in drug delivery and imaging applications because of their unique properties, such as tunable pore sizes, large surfaces areas, and assumed biocompatibility. Such a nanomaterial, when consisting of pure silicon dioxide, is generally considered to be chemically inert, but in this study, we showed that oxidation yields for different compounds were facilitated by simply incubating aqueous solutions with pure silica particles. Three thiol-containing molecules, L-cysteine, glutathione, and D-penicillamine, were studied separately, and it was found that more than 95% of oxidation happened after incubating any of these compounds with mesoporous silica particles in the dark for a day at room temperature. Oxidation increased over incubation time, and more oxidation was found for particles having larger surface areas. For nonporous silica particles at submicron ranges, yields of oxidation were different based on the structures of molecules, correlating with steric hindrance while accessing surfaces. We propose that the silyloxy radical (SiO•) on silica surfaces is what facilitates oxidation. Density functional theory calculations were conducted for total energy changes for reactions between different aqueous species and silicon dioxide surfaces. These calculations identified two most plausible pathways of the lowest energy to generate SiO• radicals from water radical cations H2O•+ and hydroxyl radicals •OH, previously known to exist at water interfaces.

Direct Ink 3D Printing of Porous Carbon Monoliths for Gas Separations.

Additive manufacturing or 3D printing is the advanced method of manufacturing monolithic adsorbent materials. Unlike beads or pellets, 3D monolithic adsorbents possess the advantages of widespread structural varieties, low heat and mass transfer resistance, and low channeling of fluids. Despite a large volume of research on 3D printing of adsorbents having been reported, such studies on porous carbons are highly limited. In this work, we have reported direct ink 3D printing of porous carbon; the ink consisted of commercial activated carbon, a gel of poly(4-vinylphenol) and Pluronic F127 as plasticizer, and bentonite as the binder. The 3D printing was performed in a commercial 3D printer that has been extensively modified in the lab. Upon 3D printing and carbonization, the resultant 3D printed porous carbon demonstrated a stable structure with a BET area of 400 m2/g and a total pore volume of 0.27 cm3/g. The isotherms of six pure-component gases, CO2, CH4, C2H6, N2, CO, and H2, were measured on this carbon monolith at 298 K and pressure up to 1 bar. The selectivity of four gas pairs, C2H6/CH4, CH4/N2, CO/H2, and CO2/N2, was calculated by Ideally Adsorbed Solution Theory (IAST) and reported. Ten continuous cycles of adsorption and desorption of CO2 on this carbon confirmed no loss of working capacity of the adsorbent.

Metal-Assisted Catalytic Etching (MACE) for Nanofabrication of Semiconductor Powders.

Electroless etching of semiconductors has been elevated to an advanced micromachining process by the addition of a structured metal catalyst. Patterning of the catalyst by lithographic techniques facilitated the patterning of crystalline and polycrystalline wafer substrates. Galvanic deposition of metals on semiconductors has a natural tendency to produce nanoparticles rather than flat uniform films. This characteristic makes possible the etching of wafers and particles with arbitrary shape and size. While it has been widely recognized that spontaneous deposition of metal nanoparticles can be used in connection with etching to porosify wafers, it is also possible to produced nanostructured powders. Metal-assisted catalytic etching (MACE) can be controlled to produce (1) etch track pores with shapes and sizes closely related to the shape and size of the metal nanoparticle, (2) hierarchically porosified substrates exhibiting combinations of large etch track pores and mesopores, and (3) nanowires with either solid or mesoporous cores. This review discussed the mechanisms of porosification, processing advances, and the properties of the etch product with special emphasis on the etching of silicon powders.

Low-Load Metal-Assisted Catalytic Etching Produces Scalable Porosity in Si Powders.

The recently discovered low-load metal-assisted catalytic etching (LL-MACE) creates nanostructured Si with controllable and variable characteristics that distinguish this technique from the conventional high-load variant. LL-MACE employs 150 times less metal catalyst and produces porous Si instead of Si nanowires. In this work, we demonstrate that some of the features of LL-MACE cannot be explained by the present understanding of MACE. With mechanistic insight derived from extensive experimentation, it is demonstrated that (1) the method allows the use of not only Ag, Pd, Pt, and Au as metal catalysts but also Cu and (2) judicious combinations of process parameters such as the type of metal, Si doping levels, and etching temperatures facilitate control over yield (0.065-88%), pore size (3-100 nm), specific surface area (20-310 m2·g-1), and specific pore volume (0.05-1.05 cm3·g-1). The porous structure of the product depends on the space-charge layer, which is controlled by the Si doping and the chemical identity of the deposited metal. The porous structure was also dependent on the dynamic structure of the deposited metal. A distinctive comet-like structure of metal nanoparticles was observed after etching with Cu, Ag, Pd, and, in some cases, Pt; this structure consisted of 10-50 nm main particles surrounded by smaller (<5 nm) nanoparticles. With good scalability and precise control of structural properties, LL-MACE facilitates Si applications in photovoltaics, energy storage, biomedicine, and water purification.

Controlling the Nature of Etched Si Nanostructures: High- versus Low-Load Metal-Assisted Catalytic Etching (MACE) of Si Powders.

Metal-assisted catalytic etching (MACE) involving Ag deposited on Si particles has been reported as a facile method for the production of Si nanowires (Si NWs). We show that the structure of Si particles subjected to MACE changes dramatically in response to changing the loading of the Ag catalyst. The use of acetic acid as a surfactant and controlled injection of AgNO3(aq) enhanced Ag deposition. The use of acetic acid and controlled injection of H2O2 not only facilitated optimization of the etching step but also allowed us to identify a previously unobserved etching regime that we denote as low-load MACE (LL-MACE). Material produced by LL-MACE exhibits dramatically different yield and structural characteristics as compared to conventionally produced material. We demonstrate the production of Si NWs as well as mesoporous Si nanoparticles from an inexpensive metallurgical-grade Si powder. High loading of Ag (HL-MACE) generates parallel etch track pores created by the correlated motion of Ag nanoparticles. The uniform size distribution (predominantly 70-100 nm) of the Ag nanoparticles is generated dynamically during etching. The walls of these etch track pores are cleaved readily by ultrasonic agitation to form Si NWs. Low loading of Ag (LL-MACE) creates 10-50 nm Ag nanoparticles that etch in an uncorrelated (randomly directed) fashion to generate a bimodal distribution of mesoporosity peaking at ∼4 and 13-21 nm. The use of a syringe pump to deliver the oxidant (H2O2) and Ag+ is essential for increased product uniformity and yield. Different process temperatures and grades of Si produced significantly different pore size distributions. These results facilitate the production of Si NWs and mesoporous nanoparticles with high yield, low cost, and controlled properties that are suitable for applications in, e.g., lithium-ion batteries, drug delivery, as well as biomedical imaging and contrast enhancement.

Hierarchical Nanostructuring of Porous Silicon with Electrochemical and Regenerative Electroless Etching.

Hierarchically nanostructured silicon was produced by regenerative electroless etching (ReEtching) of Si powder made from pulverized anodized porous silicon. This material is characterized by ∼15 nm mesopores, into the walls of which tortuous 2-4 nm pores have been introduced. The walls are sufficiently narrow that they support quantum-confined crystallites that are photoluminescent. With suitable parameters, the ReEtching process also provides control over the emission color of the photoluminescence. Ball milling and hydrosilylation of this powder with undecylenic acid produces nanoparticles with hydrodynamic diameter of ∼220 nm that exhibit robust and bright luminescence that can be excited with either one ultraviolet/visible photon or two near-infrared photons. The long-lived, robust visible photoluminescence of these chemically passivated porous silicon nanoparticles is well-suited for bioimaging and theranostic applications.

Crystallographically Determined Etching and Its Relevance to the Metal-Assisted Catalytic Etching (MACE) of Silicon Powders.

Metal-assisted catalytic etching (MACE) using Ag nanoparticles as catalysts and H2O2 as oxidant has been performed on single-crystal Si wafers, single-crystal electronics grade Si powders, and polycrystalline metallurgical grade Si powders. The temperature dependence of the etch kinetics has been measured over the range 5-37°C. Etching is found to proceed preferentially in a 〈001〉 direction with an activation energy of ~0.4 eV on substrates with (001), (110), and (111) orientations. A quantitative model to explain the preference for etching in the 〈001〉 direction is developed and found to be consistent with the measured activation energies. Etching of metallurgical grade powders produces particles, the surfaces of which are covered primarily with porous silicon (por-Si) in the form of interconnected ridges. Silicon nanowires (SiNW) and bundles of SiNW can be harvested from these porous particles by ultrasonic agitation. Analysis of the forces acting between the metal nanoparticle catalyst and the Si particle demonstrates that strongly attractive electrostatic and van der Waals interactions ensure that the metal nanoparticles remain in intimate contact with the Si particles throughout the etch process. These attractive forces draw the catalyst toward the interior of the particle and explain why the powder particles are etched equivalently on all the exposed faces.

Regenerative Electroless Etching of Silicon.

Regenerative electroless etching (ReEtching), described herein for the first time, is a method of producing nanostructured semiconductors in which an oxidant (Ox1 ) is used as a catalytic agent to facilitate the reaction between a semiconductor and a second oxidant (Ox2 ) that would be unreactive in the primary reaction. Ox2 is used to regenerate Ox1 , which is capable of initiating etching by injecting holes into the semiconductor valence band. Therefore, the extent of reaction is controlled by the amount of Ox2 added, and the rate of reaction is controlled by the injection rate of Ox2 . This general strategy is demonstrated specifically for the production of highly luminescent, nanocrystalline porous Si from the reaction of V2 O5 in HF(aq) as Ox1 and H2 O2 (aq) as Ox2 with Si powder and wafers.

The mechanism of galvanic/metal-assisted etching of silicon.

Metal-assisted etching is initiated by hole injection from an oxidant catalyzed by a metal nanoparticle or film on a Si surface. It is shown that the electronic structure of the metal/Si interface, i.e., band bending, is not conducive to diffusion of the injected hole away from the metal in the case of Ag or away from the metal/Si interface in the cases of Au, Pd, and Pt. Since holes do not diffuse away from the metals, the electric field resulting from charging of the metal after hole injection must instead be the cause of metal-assisted etching.

The mechanism of photohydrosilylation on silicon and porous silicon surfaces.

Visible or UV light activates H-terminated Si surfaces because of the presence of a photogenerated hole in a Si-Si back-bond. Enhancing the lifetime of this hole at the surface increases reactivity. On the basis of photodynamics and electron transfer theory, the prevalence of two mechanisms of photoactivation (internal photoemission versus interband photoexcitation followed by electron transfer) are explored. To act as an effective trap, an acceptor state for the excited electron must either be populated directly by photoexcitation or the state must lie in a band gap (or both). It is predicted that oxidants with a properly positioned acceptor level will enhance the reactivity of porous silicon or silicon nanocrystals in a size selective manner.

Electroless etching of Si with IO3- and related species.

We have previously derived seven requirements for the formulation of effective stain etchants and have demonstrated that Fe3+, Ce4+, and VO2+ + HF solutions are highly effective at producing nanocrystalline porous silicon. Here, we show that Cl2, Br2, I2, ClO3-, BrO3-, IO3-, I-, and I3- induce etching of silicon when added to HF. However, using the strict definition that a pore is deeper than it is wide, we observe little evidence for porous layers of significant thickness but facile formation of pits. Iodate solutions are extremely reactive, and by the combined effects of IO3-, I3-, I2, and I-, these etchants roughen and restructure the substrate to form a variety of structures including (circular, rectangular, or triangular) pits, pyramids, or combinations of pits and pyramids without leaving a porous silicon layer of significant thickness.

Using effusive molecular beams and microcanonical unimolecular rate theory to characterize CH4 dissociation on Pt(111).

The dissociative sticking coefficient for CH4 on Pt(111) has been measured as a function of both gas temperature (Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated ambient gas dosing methods. The experimental results are used to optimize the three parameters of a microcanonical unimolecular rate theory (MURT) model of the reactive system. The MURT calculations allow us to extract transition state properties from the data as well as to compare our data directly to other molecular beam and thermal equilibrium sticking measurements. We find a threshold energy for dissociation of E0 = 52.5 +/- 3.5 kJ mol(-1). Furthermore, the MURT with an optimized parameter set provides for a predictive understanding of the kinetics of this C-H bond activation reaction, that is, it allows us to predict the dissociative sticking coefficient of CH4 on Pt(111) for any combination of Ts and Tg even if the two are not equal to one another, indeed, the distribution of molecular energy need not even be thermal. Comparison of our results to those from recent thermal equilibrium catalysis studies on CH4 reforming over Pt nanoclusters ( approximately 2 nm diam) dispersed on oxide substrates indicates that the reactivity of Pt(111) exceeds that of the Pt nanocatalysts by several orders of magnitude.

Effusive molecular beam study of C2H6 dissociation on Pt(111).

The dissociative sticking coefficient for C2H6 on Pt(111) has been measured as a function of both gas temperature (Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated ambient gas dosing methods. A microcanonical unimolecular rate theory (MURT) model of the reactive system is used to extract transition state properties from the data as well as to compare our data directly with supersonic molecular beam and thermal equilibrium sticking measurements. We report for the first time the threshold energy for dissociation, E0 = 26.5 +/- 3 kJ mol(-1). This value is only weakly dependent on the other two parameters of the model. A strong surface temperature dependence in the initial sticking coefficient is observed; however, the relatively weak dependence on gas temperature indicates some combination of the following (i) not all molecular excitations are contributing equally to the enhancement of sticking, (ii) that strong entropic effects in the dissociative transition state are leading to unusually high vibrational frequencies in the transition state, and (iii) energy transfer from gas-phase rovibrational modes to the surface is surprisingly efficient. In other words, it appears that vibrational mode-specific behavior and/or molecular rotations may play stronger roles in the dissociative adsorption of C2H6 than they do for CH4. The MURT with an optimized parameter set provides for a predictive understanding of the kinetics of this C-H bond activation reaction, that is, it allows us to predict the dissociative sticking coefficient of C2H6 on Pt(111) for any combination of Ts and Tg even if the two are not equal to one another.