The hydrogen evolution reaction (HER) has a key role in electrochemical water splitting. Recently lot of attention been dedicated to HER from single atom catalysts (SACs). activity SACs is usually rationalized or predicted using the original model proposed by Nørskov where free energy H adsorbed on an extended metal surface M (formation MH intermediate) used explain trends exchange current for HER. However, differ substantially surfaces and can be considered analogues coordination compounds....

One-pot three-component regioselective azide-alkyne cycloadditions are central reactions for synthesizing pharmaceuticals and fine chemicals also applied in vivo metabolic labeling biotechnology. Homogeneous catalysts based on copper species coordinated with ancillary ligands regularly used to perform this reaction, offering superior catalytic activity selectivity compared conventional heterogeneous counterparts supported nanoparticles. However, the challenge of catalyst recovery limits use...

One of the objectives electronic structure theory is to predict chemical and catalytic activities. This a challenging target due large number variables that determine performance heterogeneous catalyst. The complexity problem has reduced considerably with advent single atom catalysts (SACs) and, in particular, graphene-based SACs for electrocatalytic reactions such as oxygen reduction (ORR), evolution (OER), hydrogen (HER) reactions. In this context we assist rapidly growing theoretical...

The description of the band gap halide perovskites at level density functional theory (DFT) has been subject several studies but still presents significant problems and deviations from experimental values. Various approaches have proposed, including use system-specific hybrid functionals with a variable amount exact exchange or explicit inclusion spin–orbit coupling (SOC) effects. In this work, we present pragmatic recipe to compute minimum average error. is tested on set 36 type ABX3 [A =...

Electronic structure calculations represent an essential complement of experiments to characterize single-atom catalysts (SACs), consisting isolated metal atoms stabilized on a support, but also predict new catalysts. However, simulating SACs with quantum chemistry approaches is not as simple often assumed. In this work, the factors that reliable simulation activity are examined. The Perspective focuses importance precise atomistic characterization active site, since even small changes in...

The attention toward single-atom catalysts (SACs) for electrochemical processes is growing at an impressive pace. Electronic structure calculations play important role in this race by providing proposals of potentially relevant based on screening studies or the identification descriptors chemical activity. So far, almost all these predictions ignore a crucial aspect design catalyst: its stability. We propose simple yet general first-principles approach to predict stability SACs under working...

The surface functionalization of TiO2-based materials with alkylsilanes is attractive in several cutting-edge applications, such as photovoltaics, sensors, and nanocarriers for the controlled release bioactive molecules. (3-Aminopropyl)triethoxysilane (APTES) able to self-assemble form monolayers on TiO2 surfaces, but its adsorption geometry solar-induced photodegradation pathways are not well understood. We here employ advanced experimental (XPS, NEXAFS, AFM, HR-TEM, FT-IR) theoretical...

In this work, we demonstrate the essential role of formation superoxo and peroxo complexes on single-atom catalysts (SACs), an aspect that is often neglected in study these systems. By means density functional theory calculations, consider a representative set 11 transition metal atoms (Sc, V, Ti, Cr, Mn, Fe, Co, Ni, Cu, Pd, Pt) anchored nitrogen-doped graphene, show most them form stable intermediates when they react with molecular oxygen. Their has direct impact oxygen evolution reaction...

Abstract The most widely used approach to predict catalytic activity is density functional theory, whose results however depend on the adopted exchange‐correlation functional. In this work, role played by in predicting of single atom catalysts (SAC) hydrogen and oxygen evolution reactions (HER OER) studied. 16 transition metal (TM) atoms embedded N‐doped graphene are simulated performance Perdew–Burke–Ernzerhof (PBE) against hybrid PBE0 assessed. PBE+ U approach, a computationally less...

TiO2 is a relevant catalytic material, and its chemistry in aqueous environment challenging aspect to address. Also, the morphology of particles at nanoscale often complex, spanning from faceted spherical. In this work, we study pH- facet-dependent surface TiO2/water interfaces by performing ab initio molecular dynamics simulations with grand canonical formulation species solution. We first determined acid-base equilibrium constants interface, which allows us estimate pH point zero charge,...

The electrochemical reduction of CO2 on single atom catalysts (SAC) has emerged as a highly promising yet intricate process, requiring an in-depth understanding each elementary step the reaction. Most theoretical studies pertaining screening new efficient neglect important effects such capability catalytic site to bind and activate CO2, occurrence competing reaction paths via formation different isomers in intermediate steps, role water. In this work we will show that these are key aspects...

Impact of the adopted DFT functional on activation CO 2 a set single-atom catalysts.

This work evaluates the feasibility of alkaline hydrogen evolution reaction (HER) using Pt single-atoms (1.0 wt %) on defect-rich ceria (Pt

Abstract Composite polymer electrolytes are systems of choice for future solid‐state lithium metal batteries (LMBs). Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) is among the most interesting matrices to develop new generation quasi‐solid (QSEs). Here it reported on nanocomposites made PVDF‐HFP and pegylated SiO 2 nanoparticles. Silica‐based hybrid nanofillers obtained by grafting chains poly(ethylene glycol) methyl ether (PEG) with different molecular weight surface silica...

Reproduction of the band gaps semiconductors and insulators represents a well-known problem for standard DFT approaches based on semilocal functionals. The can be partly solved using hybrid functionals, in which given portion exact exchange is mixed with exchange. Recently, new class dielectric-dependent functionals has been introduced amount derived from static dielectric function compound. In this study we considered systematic way an equal footing set 24 nonmagnetic three-dimensional (3D)...

A new semiclassical ``divide-and-conquer'' method is presented with the aim of demonstrating that quantum dynamics simulations high dimensional molecular systems are doable. The first tested by calculating vibrational power spectra water, methane, and benzene---three molecules increasing dimensionality for which benchmark results available---and then applied to ${\mathrm{C}}_{60}$, a system characterized 174 degrees freedom. Results show approach can accurately account anharmonicities,...

Band gap variation in group III–V semiconductor slabs due to quantum size effects.

Abstract Single atom catalysts (SACs) consist of isolated metal atoms stabilized on a solid support. The name suggests that the catalytic activity is due to nature atom, but course interaction with substrate plays role as well. But what more important? or its surrounding? To answer this question, we have performed numerical experiments based density functional theory (DFT). 24 transition been incorporated in Nitrogen‐doped graphene, and hydrogen evolution reaction (HER) has studied changing...

We investigate the pH-dependent surface chemistry of three relevant and widely used oxides, MgO, TiO2, γ-Al2O3, from ab initio molecular dynamics simulations at level density functional theory (DFT). studied MgO (001), anatase TiO2 (101), γ-Al2O3 (001) low-index surfaces considered solvation effects by explicitly simulating solid/water interfaces. The analysis MgO/H2O, TiO2/H2O, γ-Al2O3/H2O interfaces allowed us to access atomistic details structure induced water on these surfaces. also...