Nonmetal-to-Metal Transition of Magnesia Supported Au Clusters Affects the Ultrafast Dissociation Dynamics of Adsorbed CH3Br Molecules.

The detection of intermediate species and the correlation of their ultrafast dynamics with the morphology and electronic structure of a surface is crucial to fully understand and control heterogeneous photoinduced and photocatalytic reactions. In this work, the ultrafast photodissociation dynamics of CH3Br molecules adsorbed on variable-size Au clusters on MgO/Mo(100) is investigated by monitoring the CH3+ transient evolution using a pump-probe technique in conjunction with surface mass spectrometry. Furthermore, extreme-UV photoemission spectroscopy in combination with theoretical calculations is employed to study the electronic structure of the Au clusters on MgO/Mo(100). Changes in the ultrafast dynamics of the CH3+ fragment are correlated with the electronic structure of Au as it evolves from monomers to small nonmetallic clusters to larger nanoparticles with a metallic character. This work provides a new avenue to a detailed understanding of how surface-photoinduced chemical reactions are influenced by the composition and electronic structure of the surface.

Toward alcohol synthesis from CO hydrogenation on Cu(111)-supported MoS2 - predictions from DFT+KMC.

In the quest for cheap and efficient catalysts for alcohol synthesis from syngas, a material of interest is single-layer MoS2 owing to its low cost, abundancy, and flexible structure. Because of the inertness of its basal plane, however, it is essential to find ways that make it catalytically active. Herein, by means of density functional theory based calculations of reaction pathways and activation energy barriers and accompanying kinetic Monte Carlo simulations, we show that while S vacancy row structures activate the MoS2 basal plane, further enhancement of chemical activity and selectivity can be achieved by interfacing the MoS2 layer with a metallic support. When defect-laden MoS2 is grown on Cu(111), there is not only an increase in the active region (surface area of active sites) but also charge transfer from Cu to MoS2, resulting in a shift of the Fermi level such that the frontier states (d orbitals of the exposed Mo atoms) appear close to it, making the MoS2/Cu(111) system ready for catalytic activity. Our calculated thermodynamics of reaction pathways lead to the conclusion that the Cu(111) substrate promotes both methanol and ethanol as the products, while kinetic Monte Carlo simulations suggest a high selectivity toward the formation of ethanol.

Syngas molecules as probes for defects in 2D hexagonal boron nitride: their adsorption and vibrations.

Single-layer, defect-laden hexagonal boron nitride (dh-BN) is attracting a great deal of attention for its diverse applications: catalysis on the one hand, and single photon emission on the other. As possible probes for identifying some common defects in single-layer h-BN, we present results of ab initio calculations for the adsorption and vibrational characteristics of syngas molecules (H2, CO, CO2) on dh-BN containing one of four types of defects: nitrogen vacancy (VN), boron vacancy (VB), Stone-Wales defect (SW), and nitrogen substituted by boron (BN). Through a comparative examination of adsorption features, charge transfer, electronic structure, and vibrational spectrum, we obtain a deep understanding of the interaction of these molecules with dh-BN and the role of the defect states. We find that while CO, CO2 and atomic hydrogen chemisorb, molecular H2 physisorbs on dh-BN with the four considered defect types. VN and VB show strong affinity for CO and CO2 since the defect states induced by them lie close to the Fermi level. SW does not favor adsorption of these small molecules, as the process for each is endothermic. In the case of BN, CO adsorbs strongly but CO2 only weakly. Vibrational frequencies of notable modes localized at the adsorbed molecules are analyzed and suggested as measures for identification of the defect type. Through a simple comparison of adsorption characteristics of the molecules on these defects, we propose dh-BN with VN to be a good catalyst candidate for CO2 hydrogenation.

Methanol carbonylation to acetaldehyde on Au particles supported by single-layer MoS2grown on silica.

Homogenous single-layer MoS2films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS2films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2surface. A gas mixture of carbon monoxide (CO) and methanol (CH3OH) was partially converted to acetaldehyde (CH3CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C2species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS2facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. The formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.

Atomic-Scale Structure and Catalysis on Positively Charged Bimetallic Sites for Generation of H2.

Here, we report that a cationic bimetallic site consisting of one Pd and three Zn atoms (Pd1Zn3) supported on ZnO (Pd1Zn3/ZnO) exhibits an extraordinarily high catalytic activity for the generation of H2 through methanol partial oxidation (MPO) that is 2-3 orders of magnitude higher than that of a metallic Pd-Zn site on Pd-Zn nanoalloy (Pd-Zn/ZnO). Computational studies uncovered that the positively charged Pd atom of the subnanometer Pd1Zn3 bimetallic site largely decreases the activation barrier for dehydrogenation of methanol as compared to a metallic Pd atom of Pd-Zn alloy, thus switching the rate-determining step of MPO from methanol dehydrogenation over a Pd-Zn alloy with high barrier to the O2 dissociation step on a cationic Pd1Zn3 site with a low barrier, which is supported by our kinetics studies. The significantly higher catalytic activity and selectivity for H2 production over a cationic bimetallic site suggest a new approach to design bimetallic catalysts.

Deconstruction of biomass enabled by local demixing of cosolvents at cellulose and lignin surfaces.

A particularly promising approach to deconstructing and fractionating lignocellulosic biomass to produce green renewable fuels and high-value chemicals pretreats the biomass with organic solvents in aqueous solution. Here, neutron scattering and molecular-dynamics simulations reveal the temperature-dependent morphological changes in poplar wood biomass during tetrahydrofuran (THF):water pretreatment and provide a mechanism by which the solvent components drive efficient biomass breakdown. Whereas lignin dissociates over a wide temperature range (>25 °C) cellulose disruption occurs only above 150 °C. Neutron scattering with contrast variation provides direct evidence for the formation of THF-rich nanoclusters (Rg ∼ 0.5 nm) on the nonpolar cellulose surfaces and on hydrophobic lignin, and equivalent water-rich nanoclusters on polar cellulose surfaces. The disassembly of the amphiphilic biomass is thus enabled through the local demixing of highly functional cosolvents, THF and water, which preferentially solvate specific biomass surfaces so as to match the local solute polarity. A multiscale description of the efficiency of THF:water pretreatment is provided: matching polarity at the atomic scale prevents lignin aggregation and disrupts cellulose, leading to improvements in deconstruction at the macroscopic scale.

The relation between lignin sequence and its 3D structure.

BACKGROUND: Lignin, the second most abundant biopolymer on earth, plays a major structural role in plants, conferring mechanical strength and regulating water conduction. Understanding the three-dimensional structure of lignin is important for fundamental reasons as well as engineering plants towards lignin valorization. Lignin lacks a specific primary sequence, making its average chemical composition the focus of most recent studies. However, it remains unclear whether the 3D structure of lignin molecules depends on their sequence. METHODS: We performed all-atom molecular dynamics simulation of three S/G-lignin molecules with the same average composition but different sequence. RESULTS: A detailed statistical analysis of the radius of gyration and relative shape anisotropy reveals that the lignin sequence has no statistically significant effect on the global three-dimensional structure. We found however, that homopolymers of C-lignin with the same molecular weight have smaller radii of gyration than S/G-lignin. We attribute this to lower hydroxyl content of C-lignin, which makes it more compact and rigid. CONCLUSIONS: The 3D structure of lignin is influenced by the overall content of monomeric units and interunit linkages and not by its precise primary sequence. GENERAL SIGNIFICANCE: Lignin is assumed to not have a well-defined primary structure. The results presented here demonstrate there are no significant differences in the global 3D structure of lignin molecules with the same average composition but different primary sequence.

Antimicrobial Zn-Based "TSOL" for Citrus Greening Management: Insights from Spectroscopy and Molecular Simulation.

Huanglongbing (HLB), also known as citrus greening, is a bacterial disease that poses a devastating threat to the citrus industry worldwide. To manage this disease efficiently, we developed and characterized a ternary aqueous solution (TSOL) that contains zinc nitrate, urea, and hydrogen peroxide. We report that TSOL exhibits better antimicrobial activity than commercial bactericides for growers. X-ray fluorescence analysis demonstrates that zinc is delivered to citrus leaves, where the bacteria reside. FTIR and Raman spectroscopy, molecular dynamics simulations, and density functional theory calculations elucidate the solution structure of TSOL and reveal a water-mediated interaction between Zn2+ and H2O2, which may facilitate the generation of highly reactive hydroxyl radicals contributing to superior antimicrobial activity of TSOL. Our results not only suggest TSOL as a potent antimicrobial agent to suppress bacterial growth in HLB-infected trees, but also provide a structure-property relationship that explains the superior performance of TSOL.

MoS2-supported gold nanoparticle for CO hydrogenation.

Employing dispersion-corrected density functional theory, we examine the geometry, electronic structure, and reactivity of 13-atom Au nanoparticle supported on defect-laden single-layer MoS2. The planar structure of Au13 favored in isolated phase, transforms into the three-dimensional structure when supported on MoS2. We find that charge is transferred from MoS2 to Au13, and that the electron density is also distributed away from the Au13/MoS2 interfacial region-making Au sites away from the interface catalytically active. Owing to effect of the support, the Au d states become narrower, and the frontier states appear close to the Fermi level. Consequently, in contrast to the reactivity of Au13/TiO2 toward methanol decomposition, Au13/MoS2 offers excellent activity toward methanol synthesis, as demonstrated here, via CO hydrogenation.

Adatom Extraction from Pristine Metal Terraces by Dissociative Oxygen Adsorption: Combined STM and Density Functional Theory Investigation of O/Ag(110).

The reconstruction and modification of metal surfaces upon O_{2} adsorption plays an important role in oxidation processes and in gauging their catalytic activity. Here, we show by employing scanning tunneling microscopy and the ab initio density functional theory that Ag atoms are extracted from pristine (110) terraces upon O_{2} dissociation, resulting in vacancies and in Ag-O complexes. The substrate roughening generates undercoordinated atoms and opens pathways to the Ag subsurface layer. With increasing O coverage, multiple vacancies give rise to remarkable structures. The mechanism is expected to be very general depending on the delicate interplay of energy and entropy, so that it may be active for other materials at different temperatures.

The symmetry-resolved electronic structure of 2H-WSe2(0 0 0 1).

The orbital symmetry of the band structure of 2H-WSe2(0 0 0 1) has been investigated by means of angle-resolved photoelectron spectroscopy (ARPES) and density functional theory (DFT). The WSe2(0 0 0 1) experimental band structure is found, by ARPES, to be significantly different for states of even and odd reflection parities along both the [Formula: see text]-[Formula: see text] and [Formula: see text]-[Formula: see text] lines, in good agreement with results obtained from DFT. The light polarization dependence of the photoemission intensities from the top of the valence band for bulk WSe2(0 0 0 1) is explained by the dominance of W 5[Formula: see text] states around the [Formula: see text]-point and W 5d xy states around the [Formula: see text]-point, thus dominated, respectively, by states of even and odd symmetry, with respect to the [Formula: see text]-[Formula: see text] line. The splitting of the topmost valence band at [Formula: see text], due to spin-orbit coupling, is measured to be 0.49 ± 0.01 eV, in agreement with the 0.48 eV value from DFT, and prior measurements for the bulk single crystal WSe2(0 0 0 1), albeit slightly smaller than the 0.513 ± 0.01 eV observed for monolayer WSe2.

Complementary roles of benzylpiperazine and iodine 'vapor' in the strong enhancement of orange photoluminescence from CuI(1 1 1) thin film.

We have employed density functional theory, corrected by the on-site electron-electron repulsion energy U, to clarify the mechanism behind the enhanced orange photoluminescence (PL) of a CuI(1 1 1) thin film conjugated with a benzylpiperazine (BZP) molecule in the presence of an iodine 'vapor' atom. Our results demonstrated that the adsorbed molecule and the 'vapor' atom play complementary roles in producing the PL. The latter, in attaching to the film surface, creates a hole-trapping surface state located ~0.25 eV above the valence band-edge of the film, in good agreement with ~0.2 eV reported in experiments. Upon photo-excitation of the BZP/CuI(1 1 1) system in the presence of surface iodine 'vapor' atoms, excited electrons are transferred into the conduction band of CuI, and holes are trapped by the 'vapor' atoms. These holes, in turn, quickly relax into the HOMO state of the BZP molecule, owing to the fact that the molecule adsorbs on the film surface in the immediate vicinity of a 'vapor' atom. Relaxed holes subsequently recombine with excited electrons in the conduction band of the CuI film, thereby producing a luminescence peak at ~2.1 eV, in qualitative agreement with experimental findings.