We present a systematic analysis of CO adsorption on Pt nanoclusters in the 0.2–1.5 nm size range with the aim of unraveling size-dependent trends and developing predictive models for site-specific adsorption behavior. Using an empirical-potential-based genetic algorithm and density functional theory (DFT) modeling, we show that there exists a size window (40–70 atoms) over which Pt nanoclusters bind CO weakly, the binding energies being comparable to those on (111) or (100) facets. The size-dependent adsorption energy trends are, however, distinctly nonmonotonic and are not readily captured using traditional descriptors such as d-band energies or (generalized) coordination numbers of the Pt binding sites. Instead, by applying machine-learning algorithms, we show that multiple descriptors, broadly categorized as structural and electronic descriptors, are essential for qualitatively capturing the CO adsorption trends. Nevertheless, attaining quantitative accuracy requires further refinement, and we propose...

Adsorption of CO on Low-Energy, Low-Symmetry Pt Nanoparticles: Energy Decomposition Analysis and Prediction via Machine-Learning Models

Direct selective catalytic conversion of CO to C2+ oxygenates with high performance and high stability is challenging. Generating dimethyl carbonate (DMC), a high added-value oxygenate, by CO direc...

Synthesis of High-Performance and High-Stability Pd(II)/NaY Catalyst for CO Direct Selective Conversion to Dimethyl Carbonate by Rational Design

Thirteen-atom metal clusters for genetic materials

Self-recoverable Pd–Ru/TiO2 nanocatalysts have been prepared by electrochemical stripping of Pd–Ru/TiO2 precursors. For the ethanol oxidation reaction (EOR), these Pd–Ru/TiO2 nanocatalysts are used as an anode catalyst. The characterization of catalysts via chronoamperometry has been repeated 15 times. After 15 stability tests, the Pd1Ru0.69/TiO2 nanocatalysts still achieve a factor of 9.4 enhancement at the residual current density (309.42 mA mgPd−1) for the EOR over commercial Pd/C catalysts (33.01 mA mgPd−1). From the 5th to 15th test, when each 10 000 s stability test is performed in a fresh ethanol electrolyte, the initial and residual current density of the catalysts could recover to the original or even better value in a few hours before performing another 10 000 s stability test. Herein, these Pd–Ru/TiO2 nanocatalysts with ultrastability towards ethanol electrooxidation are self-recoverable. Density functional theory calculations reveal that the introduction of oxophilic metal Ru and a TiO2 support into Pd-based catalysts and the synergistic effects between Ru and TiO2 have led to the ultrastability towards the EOR. The introduction of oxophilic metal Ru and a TiO2 support into catalysts can reduce the adsorption energy of OHads on the Pd–Ru/TiO2 nanocatalysts, and it will inhibit the COads produced and adsorbed on the Pd surface.

Self-recoverable Pd–Ru/TiO2 nanocatalysts with ultrastability towards ethanol electrooxidation

Water-soluble Au 13 clusters protected by binary thiolates: Structural accommodation and the use for chemosensing

A systematic study on the magnetic property variations of Pd13 particles as a function of particle sizes and structures, and of Pd13 interactions with the (100) TiO2 anatase surface, was carried out with standard density functional theory (DFT) based method with periodic boundary conditions. The biplanar Pd13 structure with the spin state quintet is obtained to be the ground state in the gas-phase and on the anatase surface, being more stable than the compact icosahedral configuration by 0.067 and 0.865 eV, respectively. The preferred particle nucleation on the anatase surface is that with the largest possible contacts between Pd13 and the oxide surface oxygens. The supported Pd13 particles are better stabilized by 0.3 eV compared to the isolated ones. The profiles of the relative energies as a function of the spin state reveal that the Pd13 magnetic isomers, belonging to the same cluster topology, become closer in energy and nearly degenerate on the anatase surface compared to their gas-phase counterpart...

Oussama Gantassi

Papers

Density Functional Study of Pd13 Magnetic Isomers in Gas-Phase and on (100)-TiO2 Anatase