Computational Design of an Electro-Organocatalyst for Conversion of CO into Long Chain Aldehydes.

Density functional theory calculations employing a hybrid implicit/explicit solvation method were used to demonstrate that an electro-organocatalyst designed in our previous work for reducing CO to formaldehyde could also be capable of coupling formaldehyde to form long chain aldehydes. The catalytic activity is enabled by an electron-rich vicinal enediamine (>N-C═C-N<) backbone that activates formaldehyde by reversing the polarity on the carbon atom, enabling it to act as a nucleophile in the subsequent aldol addition step. The catalyst then enables reductive dehydroxylation of the aldol addition product by facilitating outer-sphere electron transfer.

Computational Design of an Electro-Organocatalyst for Conversion of CO into Formaldehyde.

Density functional theory calculations employing a hybrid implicit/explicit solvation method were used to explore a new strategy for electrochemical conversion of CO using an electro-organocatalyst. A particular structural motif is identified that consists of an electron-rich vicinal enediamine (>N-C═C-N<) backbone, which is capable of activating CO by the formation of a C-C bond while subsequently facilitating the transfer of electrons from a chemically inert cathode to ultimately produce formaldehyde. Unlike transition metal-based electrocatalysts, the electro-organocatalyst is not constrained by scaling relations between the formation energies of activated CO and adsorbed CO, nor is it expected to be active for the competing hydrogen evolution reaction.

An implicit electrolyte model for plane wave density functional theory exhibiting nonlinear response and a nonlocal cavity definition.

We have developed and implemented an implicit electrolyte model in the Vienna Ab initio Simulation Package (VASP) that includes nonlinear dielectric and ionic responses as well as a nonlocal definition of the cavities defining the spatial regions where these responses can occur. The implementation into the existing VASPsol code is numerically efficient and exhibits robust convergence, requiring computational effort only slightly higher than the original linear polarizable continuum model. The nonlinear + nonlocal model is able to reproduce the characteristic "double hump" shape observed experimentally for the differential capacitance of an electrified metal interface while preventing "leakage" of the electrolyte into regions of space too small to contain a single water molecule or solvated ion.

Modifying Metastable SrBO (B = Nb, Ta, and Mo) Perovskites for Electrode Materials.

The presence of surface/deep defects in 4d- and 5d-perovskite oxide (ABO, B = Nb, Ta, Mo, etc.) nanoparticles (NPs), originating from multivalent B-site cations, contributes to suppressing their metallic properties. These defect states can be removed using a H/Ar thermal treatment, enabling the recovery of their electronic properties (i.

Adsorption of Polarized Molecules for Interfacial Band Engineering of Doped TiO Thin Films.

Owing to their chemical and mechanical stability, metal-oxides have emerged as potential alternatives for conventional pure-metal and organic molecule-based solid-state electronic devices. Traditionally, band engineering of these metal-oxides has been performed to improve the efficiency of solar cells and transistors. However, recent advancements in the field of oxide-based electronic devices demand reversible band structure engineering for applications in next-generation adaptive electronics and memory devices.

Stabilizing the B-site oxidation state in ABO perovskite nanoparticles.

The stabilization of the B-site oxidation state in ABO3 perovskites using wet-chemical methods is a synthetic challenge, which is of fundamental and practical interest for energy storage and conversion devices. In this work, defect-controlled (Sr-deficiency and oxygen vacancies) strontium niobium(iv) oxide (Sr1-xNbO3-δ, SNO) metal oxide nanoparticles (NPs) were synthesized for the first time using a low-pressure wet-chemistry synthesis. The experiments were performed under reduced oxygen partial pressure to prevent by-product formation and with varying Sr/Nb molar ratio to favor the formation of Nb4+ pervoskites.

Lewis-Brønsted Acid Pairs in Ga/H-ZSM-5 To Catalyze Dehydrogenation of Light Alkanes.

The active sites for propane dehydrogenation in Ga/H-ZSM-5 with moderate concentrations of tetrahedral aluminum in the lattice were identified to be Lewis-Brønsted acid pairs. With increasing availability, Ga and Brønsted acid site concentrations changed inversely, as protons of Brønsted acid sites were exchanged with Ga. At a Ga/Al ratio of 1/2, the rate of propane dehydrogenation was 2 orders of magnitude higher than with the parent H-ZSM-5, highlighting the extraordinary activity of the Lewis-Brønsted acid pairs.

Addressing global uncertainty and sensitivity in first-principles based microkinetic models by an adaptive sparse grid approach.

In the last decade, first-principles-based microkinetic modeling has been developed into an important tool for a mechanistic understanding of heterogeneous catalysis. A commonly known, but hitherto barely analyzed issue in this kind of modeling is the presence of sizable errors from the use of approximate Density Functional Theory (DFT). We here address the propagation of these errors to the catalytic turnover frequency (TOF) by global sensitivity and uncertainty analysis.

Assessment of mean-field microkinetic models for CO methanation on stepped metal surfaces using accelerated kinetic Monte Carlo.

First-principles screening studies aimed at predicting the catalytic activity of transition metal (TM) catalysts have traditionally been based on mean-field (MF) microkinetic models, which neglect the effect of spatial correlations in the adsorbate layer. Here we critically assess the accuracy of such models for the specific case of CO methanation over stepped metals by comparing to spatially resolved kinetic Monte Carlo (kMC) simulations. We find that the typical low diffusion barriers offered by metal surfaces can be significantly increased at step sites, which results in persisting correlations in the adsorbate layer.

Constrained-Orbital Density Functional Theory. Computational Method and Applications to Surface Chemical Processes.

We present a method for performing density-functional theory (DFT) calculations in which one or more Kohn-Sham orbitals are constrained to be localized on individual atoms. This constrained-orbital DFT (CO-DFT) approach can be used to tackle two prevalent shortcomings of DFT: the lack of transparency with regard to the governing electronic structure in large (planewave based) DFT calculations and the limitations of semilocal DFT in describing systems with localized electrons or a large degree of static correlation. CO-DFT helps to address the first of these issues by decomposing complex orbital transformations occurring during elementary chemical processes into simpler and more intuitive transformations.

Generalized Temporal Acceleration Scheme for Kinetic Monte Carlo Simulations of Surface Catalytic Processes by Scaling the Rates of Fast Reactions.

A novel algorithm is presented that achieves temporal acceleration during kinetic Monte Carlo (KMC) simulations of surface catalytic processes. This algorithm allows for the direct simulation of reaction networks containing kinetic processes occurring on vastly disparate time scales which computationally overburden standard KMC methods. Previously developed methods for temporal acceleration in KMC were designed for specific systems and often require a priori information from the user such as identifying the fast and slow processes.

Perspective: On the active site model in computational catalyst screening.

First-principles screening approaches exploiting energy trends in surface adsorption represent an unparalleled success story in recent computational catalysis research. Here we argue that our still limited understanding of the structure of active sites is one of the major bottlenecks towards an ever extended and reliable use of such computational screening for catalyst discovery. For low-index transition metal surfaces, the prevalently chosen high-symmetry (terrace and step) sites offered by the nominal bulk-truncated crystal lattice might be justified.

Quantum chemistry of the oxygen evolution reaction on cobalt(ii,iii) oxide - implications for designing the optimal catalyst.

Density functional theory is used to examine the changes in electronic structure that occur during the oxygen evolution reaction (OER) catalyzed by active sites on three different surface terminations of Co3O4. These three active sites have reactive oxo species with differing degrees of coordination by Co cations - a μ(3)-oxo on the (311) surface, a μ(2)-oxo on the (110)-A surface, and an η-oxo on the (110)-B surface. The kinetically relevant step on all surfaces over a wide range of applied potentials is the nucleophilic addition of water to the oxo, which is responsible for formation of the O-O bond.

Structure Sensitivity of the Oxygen Evolution Reaction Catalyzed by Cobalt(II,III) Oxide.

Quantum chemical calculations and simulated kinetics were used to examine the structure sensitivity of the oxygen evolution reaction on several surface terminations of Co3O4. Active sites consisting of two adjacent Co(IV) cations connected by bridging oxos were identified on both the (001) and (311) surfaces. Formation of the O-O bond proceeds on these sites by nucleophilic attack of water on a bridging oxo.