Key descriptors in hydrogenation catalysis are the nature of the active sites for H2 activation and the adsorption strength of H atoms to the surface. Using atomically resolved model systems of dilute Pd-Au surface alloys and density functional theory calculations, we determine key aspects of H2 activation, diffusion, and desorption. Pd monomers in a Au(111) surface catalyze the dissociative adsorption of H2 at temperatures as low as 85 K, a process previously expected to require contiguous Pd sites. H atoms preside at the Pd sites and desorb at temperatures significantly lower than those from pure Pd (175 versus 310 K). This facile H2 activation and weak adsorption of H atom intermediates are key requirements for active and selective hydrogenations. We also demonstrate weak adsorption of CO, a common catalyst poison, which is sufficient to force H atoms to spill over from Pd to Au sites, as evidenced by low-temperature H2 desorption.
Methanol steam reforming is a promising reaction for on-demand hydrogen production. Copper catalysts have excellent activity and selectivity for methanol conversion to hydrogen and carbon dioxide. This product balance is dictated by the formation and weak binding of formaldehyde, the key reaction intermediate. It is widely accepted that oxygen adatoms or oxidized copper are required to activate methanol. However, we show herein by studying a well-defined metallic copper surface that water alone is capable of catalyzing the conversion of methanol to formaldehyde. Our results indicate that six or more water molecules act in concert to deprotonate methanol to methoxy. Isolated palladium atoms in the copper surface further promote this reaction. This work reveals an unexpected role of water, which is typically considered a bystander in this key chemical transformation.
Atomic and molecular self-assembly are key phenomena that underpin many important technologies. Typically, thermally enabled diffusion allows a system to sample many areas of configurational space, and ordered assemblies evolve that optimize interactions between species. Herein we describe a system in which the diffusion is quantum tunneling in nature and report the self-assembly of H atoms on a Cu(111) surface into complex arrays based on local clustering followed by larger scale islanding of these clusters. By scanning tunneling microscope tip-induced scrambling of H atom assemblies, we are able to watch the atomic scale details of H atom self-assembly in real time. The ordered arrangements we observe are complex and very different from those formed by H on other metals that occur in much simpler geometries. We contrast the diffusion and assembly of H with D, which has a much slower tunneling rate and is not able to form the large islands observed with H over equivalent time scales. Using density functional theory, we examine the interaction of H atoms on Cu(111) by calculating the differential binding energy as a function of H coverage. At the temperature of the experiments (5 K), H(D) diffusion by quantum tunneling dominates. The quantum-tunneling-enabled H and D diffusion is studied using a semiclassically corrected transition state theory coupled with density functional theory. This system constitutes the first example of quantum-tunneling-enabled self-assembly, while simultaneously demonstrating the complex ordering of H on Cu(111), a catalytically relevant surface.
The dissociative adsorption of hydrogen on cobalt is central to a number of catalytic reactions, yet to date there are relatively few studies examining this important process. Here we utilize Co nanoparticles grown on Cu(111), instead of the traditional planar Co single crystals, to study a more catalytically relevant form of Co. We present scanning tunneling microscopy images of different phases of H on the close-packed Co nanoparticle surfaces with a range of densities. Our data reveal a so-far unreported high coverage phase of H with a (1 × 1) structure and elucidate the importance of spillover from step edges in H adsorption. We also illustrate that, in contrast to the low density phases, the H-(1 × 1) structure can only be formed at an intermediate temperature, indicating that compression to this higher-density phase is activated. Density functional theory calculations yield energies for each of the H overlayer structures, as well as their preferred geometries. This work is the first to report on higher coverage (>0.75 ML) phases of H on Co, which are undoubtedly important in catalytic systems at elevated pressure. Finally, through the use of epitaxial Co nanoparticle growth on Cu(111), we illustrate the importance of step edges in H 2 activation and the formation of dense H phases.
The chemistry of organoboron compounds has long been dominated by their high reactivity in synthetic organic chemistry. Recently, the incorporation of boron as a structural element in compounds has led to an increased diversity of organic compounds. A promising method of boron incorporation is BN/CC isosterism, where the replacement of a CC unit of the ubiquitous arene, benzene, with the isolectronic BN unit results in azaborine compounds whose properties are intermediate between benzene and borazine. These conjugated boron–nitrogen-containing heteroatom compounds show potential for use as charge transport materials in organic electronic devices in which the molecule–contact interface is a crucial factor of device performance. Therefore, to gain a fundamental understanding of the interaction of azaborines with two common metals, we examined 1,2-dihydro-1,2-azaborine and benzene desorption from Au(111) and Cu(111) by temperature-programmed desorption (TPD). Scanning tunneling microscopy imaging and theoretical calculations aided in the interpretation of the TPD results. Comparison between TPD spectra of 1,2-dihydro-1,2-azaborine and benzene allowed us to benchmark our experiments with literature values for benzene and to accurately quantify the magnitude of both molecule–molecule and molecule–surface interaction strengths. TPD spectra of 1,2-dihydro-1,2-azaborine show three well-defined adsorption states exist on each surface, assigned to mono-, bi-, and multilayers. The multilayer desorption energy of azaborine was found to be approximately 46 kJ/mol, about 4 kJ/mol larger than benzene and the increase is related to both dihydrogen bonding and dipole–dipole interactions. The bilayer formed by 1,2-dihydro-1,2-azaborine is less dense than that formed by benzene, with 0.7 molecules in the bilayer per each molecule in the monolayer on each surface. Importantly, in terms of application, azaborine did not decompose on either Cu or Au surfaces. Our data also reveal that a delicate balance of molecule–surface and molecule–molecule interactions dictate adsorption energetics in the submonolayer regime.
Pd bimetallic alloys are promising catalysts, especially for heterogeneous reactions involving hydrogen, as they exhibit increased activity and reduced demand for expensive precious metals. Using scanning tunneling microscopy, we examine the structure of Pd thin films on Cu(111) and Au(111) and demonstrate compression and expansion, respectively, of the bulk Pd lattice constant in the film. The relative binding strength of H to the two surfaces, inferred via tip-induced diffusion barriers, suggests that the strain in these systems may alter adsorbate binding and corroborates well-known trends in d-band shifts calculated by density functional theory. Modification to the topography and activity of Pd films based on the choice of substrate metal illustrates the value of bimetallic systems for designing less expensive, tunable catalysts.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.