Aliphatic Ketone Claisen Rearrangement: Troubleshooting the Transetherification Step by Identifying a Stable Acid Catalyst.

After optimization for retention of catalytic activity, 4-chlorobenzoic acid emerged as the optimal catalyst for the aliphatic ketone Claisen rearrangement. The optimal catalyst enables a one-pot, metal-free, catalytic protocol from allylic alcohols to γ,δ-unsaturated ketones. The optimized process tolerates a range of substrates, including substituents with acid-labile protecting groups. Reaction monitoring and DFT studies of the aliphatic ketone Claisen process agree that the ultimate rearrangement step typically has the highest activation barrier.

Modelling the growth reaction pathways of zincone ALD/MLD hybrid thin films: a DFT study.

ALD/MLD hybrid thin films can be fabricated by combining atomic layer deposition (ALD) and molecular layer deposition (MLD). Even though this deposition method has been extensively used experimentally, the computational work required to acquire the reaction paths during the thin film deposition process is still in dire demand. We investigated hybrid thin films consisting of diethyl zinc and either 4-aminophenol or hydroquinone using both gas-phase and surface reactions to gain extensive knowledge of the complex phenomena occurring during the process of hybrid thin film deposition. We used density functional theory (DFT) to obtain the activation energies of these kinetic-dependent deposition processes. Different processes of ethyl ligand removal as ethane were discovered, and we found that the hydroxyl group of 4-aminophenol was more reactive than the amino group in the migration of hydrogen to an ethyl ligand within a complicated branching reaction chain.

Ab initio molecular dynamics investigation of the Pt(111)-water interface structure in an alkaline environment with high surface OH-coverages.

In this study, we investigate the structure of the Pt(111)-water interface in an alkaline environment with large OH coverages of 1/3, 2/3 and 1 monolayer using a large well-equilibrated system. We observe that the OH coverage influences both the orientational distribution of the water molecules and their density, with more structure associated with higher coverage. At the same time, there is evidence of a highly dynamic hydrogen bond network on the lower coverage systems with substantial exchange of water between the surface and the solvent. In addition to OH and H2O species, which are preferentially located at the top sites, the 1/3 and 2/3 monolayer surfaces also contain O atoms, which are relatively stable and prefer the hollow sites. In contrast, the 1 monolayer surface shows none of these dynamics, and is unlikely to be active. The dynamic coexistence of O, OH and H2O on Pt(111) electrodes in alkaline conditions necessitates the investigation of several possible reaction paths for processess like ORR and water splitting. Finally, the exchange processes observed between the solvent and the interface underscore the need to explicitly include liquid water in simulations of systems similar to Pt(111).

Ion-Specific Effects on Ion and Polyelectrolyte Solvation.

Ion-specific effects on aqueous solvation of monovalent counter ions, Na + ${^+ }$ , K + ${^+ }$ , Cl - ${^- }$ , and Br - ${^- }$ , and two model polyelectrolytes (PEs), poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium) (PDADMA) were here studied with ab initio molecular dynamics (AIMD) and classical molecular dynamics (MD) simulations based on the OPLS-aa force-field which is an empirical fixed point-charge force-field. Ion-specific binding to the PE charge groups was also characterized. Both computational methods predict similar response for the solvation of the PEs but differ notably in description of ion solvation. Notably, AIMD captures the experimentally observed differences in Cl - ${^- }$ and Br - ${^- }$ anion solvation and binding with the PEs, while the classical MD simulations fail to differentiate the ion species response. Furthermore, the findings show that combining AIMD with the computationally less costly classical MD simulations allows benefiting from both the increased accuracy and statistics reach.

Exploration of Vitamin B6-Based Redox-Active Pyridinium Salts Towards the Application in Aqueous Organic Flow Batteries.

Pyridoxal hydrochloride, a vitamin B6 vitamer, was synthetically converted to a series of diverse redox-active benzoyl pyridinium salts. Cyclic voltammetry studies demonstrated redox reversibility under basic conditions, and two of the most promising salts were subjected to laboratory-scale flow battery tests involving galvanostatic cycling at 10 mM in 0.1 M NaOH. In these tests, the battery was charged completely, corresponding to the transfer of two electrons to the electrolyte, but no discharge was observed. Both CV analysis and electrochemical simulations confirmed that the redox wave observed in the experimental voltammograms corresponds to a two-electron process. To explain the irreversibility in the battery tests, we conducted bulk electrolysis with the benzoyl pyridinium salts, affording the corresponding benzylic secondary alcohols. Computational studies suggest that the reduction proceeds in three consecutive steps: first electron transfer (ET), then proton-coupled electron transfer (PCET) and finally proton transfer (PT) to give the secondary alcohol. 1H NMR deuterium exchange studies indicated that the last PT step is not reversible in 0.1 M NaOH, rendering the entire redox process irreversible. The apparent reversibility observed in CV at the basic media likely arises from the slow rate of the PT step at the timescale of the measurement.

DFT Mechanistic Investigation into Ni(II)-Catalyzed Hydroxylation of Benzene to Phenol by H2O2.

Introduction of oxygen into aromatic C-H bonds is intriguing from both fundamental and practical perspectives. Although the 3d metal-catalyzed hydroxylation of arenes by H2O2 has been developed by several prominent researchers, a definitive mechanism for these crucial transformations remains elusive. Herein, density functional theory calculations were used to shed light on the mechanism of the established hydroxylation reaction of benzene with H2O2, catalyzed by [NiII(tepa)]2+ (tepa = tris[2-(pyridin-2-yl)ethyl]amine). Dinickel(III) bis(µ-oxo) species have been proposed as the key intermediate responsible for the benzene hydroxylation reaction. Our findings indicate that while the dinickel dioxygen species can be generated as a stable structure, it cannot serve as an active catalyst in this transformation. The calculations allowed us to unveil an unprecedented mechanism composed of six main steps as follows: (i) deprotonation of coordinated H2O2, (ii) oxidative addition, (iii) water elimination, (iv) benzene addition, (v) ketone generation, and (vi) tautomerization and regeneration of the active catalyst. Addition of benzene to oxygen, which occurs via a radical mechanism, turns out to be the rate-determining step in the overall reaction. This study demonstrates the critical role of Ni-oxyl species in such transformations, highlighting how the unpaired spin density value on oxygen and positive charges on the Ni-O• complex affect the activation barrier for benzene addition.

Kinetics of N2 Release from Diazo Compounds: A Combined Machine Learning-Density Functional Theory Study.

Diazo compounds are commonly employed as carbene precursors in carbene transfer reactions during a variety of functionalization procedures. Release of N2 gas from diazo compounds may lead to carbene formation, and the ease of this process is highly dependent on the characteristics of the substituents located in the vicinity of the diazo moiety. A quantum mechanical density functional theory assisted by machine learning was used to investigate the relationship between the chemical features of diazo compounds and the activation energy required for N2 elimination. Our results suggest that diazo molecules, possessing a higher positive partial charge on the carbene carbon and more negative charge on the terminal nitrogen, encounter a lower energy barrier. A more positive C charge decreases the π-donor ability of the carbene lone pair to the π* orbital of N2, while the more negative N charge is a result of a weak interaction between N2 lone pair and vacant p orbital of the carbene. The findings of this study can pave the way for molecular engineering for the purpose of carbene generation, which serves as a crucial intermediate for many chemical transformations in synthetic chemistry.

Density functional theory and machine learning for electrochemical square-scheme prediction: an application to quinone-type molecules relevant to redox flow batteries.

Proton-electron transfer (PET) reactions are rather common in chemistry and crucial in energy storage applications. How electrons and protons are involved or which mechanism dominates is strongly molecule and pH dependent. Quantum chemical methods can be used to assess redox potential (Ered.) and acidity constant (pKa) values but the computations are rather time consuming. In this work, supervised machine learning (ML) models are used to predict PET reactions and analyze molecular space. The data for ML have been created by density functional theory (DFT) calculations. Random forest regression models are trained and tested on a dataset that we created. The dataset contains more than 8200 quinone-type organic molecules that each underwent two proton and two electron transfer reactions. Both structural and chemical descriptors are used. The HOMO of the reactant and LUMO of the product participating in the oxidation reaction appeared to be strongly associated with Ered.. Trained models using a SMILES-based structural descriptor can efficiently predict the pKa and Ered. with a mean absolute error of less than 1 and 66 mV, respectively. Good prediction accuracy of R2 > 0.76 and >0.90 was also obtained on the external test set for Ered. and pKa, respectively. This hybrid DFT-ML study can be applied to speed up the screening of quinone-type molecules for energy storage and other applications.

Understanding Electron Transfer Reactions Using Constrained Density Functional Theory: Complications Due to Surface Interactions.

The kinetic rates of electrochemical reactions depend on electrodes and molecules in question. In a flow battery, where the electrolyte molecules are charged and discharged on the electrodes, the efficiency of the electron transfer is of crucial importance for the performance of the device. The purpose of this work is to present a systematic atomic-level computational protocol for studying electron transfer between electrolyte and electrode. The computations are done by using constrained density functional theory (CDFT) to ensure that the electron is either on the electrode or in the electrolyte. The ab initio molecular dynamics (AIMD) is used to simulate the movement of the atoms. We use the Marcus theory to predict electron transfer rates and the combined CDFT-AIMD approach to compute the parameters for the Marcus theory where it is needed. We model the electrode with a single layer of graphene and methylviologen, 4,4'-dimethyldiquat, desalted basic red 5, 2-hydroxy-1,4-naphthaquinone, and 1,1-di(2-ethanol)-4,4-bipyridinium were selected for the electrolyte molecules. All of these molecules undergo consecutive electrochemical reactions with one electron being transferred at each stage. Because of significant electrode-molecule interactions, it is not possible to evaluate outer-sphere ET. This theoretical study contributes toward the development of a realistic-level prediction of electron transfer kinetics suitable for energy storage applications.

Temperature-Controlled Syngas Production via Electrochemical CO2 Reduction on a CoTPP/MWCNT Composite in a Flow Cell.

The mixture of CO and H2, known as syngas, is a building block for many substantial chemicals and fuels. Electrochemical reduction of CO2 and H2O to syngas would be a promising alternative approach for its synthesis due to negative carbon emission footprint when using renewable energy to power the reaction. Herein, we present temperature-controlled syngas production by electrochemical CO2 and H2O reduction on a cobalt tetraphenylporphyrin/multiwalled carbon nanotube (CoTPP/MWCNT) composite in a flow cell in the temperature range of 20-50 °C. The experimental results show that for all the applied potentials the ratio of H2/CO increases with increasing temperature. Interestingly, at -0.6 V RHE and 40 °C, the H2/CO ratio reaches a value of 1.2 which is essential for the synthesis of oxo-alcohols. In addition, at -1.0 V RHE and 20 °C, the composite shows very high selectivity toward CO formation, reaching a Faradaic efficiency of ca. 98%. This high selectivity of CO formation is investigated by density functional theory modeling which underlines that the potential-induced oxidation states of the CoTPP catalyst play a vital role in the high selectivity of CO production. Furthermore, the stability of the formed intermediate species is evaluated in terms of the pKa value for further reactions. These experimental and theoretical findings would provide an alternative way for syngas production and help us to understand the mechanism of molecular catalysts in dynamic conditions.

Universal Trends between Acid Dissociation Constants in Protic and Aprotic Solvents.

pKa values in non-aqueous solvents are of critical importance in many areas of chemistry. Our knowledge is, despite their relevance, still limited to the most fundamental properties and few pKa values in the most common solvents. Taking advantage of a recently introduced computationally efficient procedure we computed the pKa values of 182 compounds in 21 solvents. This data set is used to establish for the first time universal trends between all solvents. Our computations indicate, that the total charge of the molecule and the charge of the acidic group combined with the Kamlet-Taft solvatochromic parameters are sufficient to predict pKa values with at least semi- quantitative accuracy. We find, that neutral acids such as alcohols are strongly affected by the solvent properties. This is contrasted by cationic acids like ammonium ions whose pKa is often almost completely independent from the choice of solvent.

How to Predict the pK a of Any Compound in Any Solvent.

Acid-base properties of molecules in nonaqueous solvents are of critical importance for almost all areas of chemistry. Despite this very high relevance, our knowledge is still mostly limited to the pK a of rather few compounds in the most common solvents, and a simple yet truly general computational procedure to predict pK a's of any compound in any solvent is still missing. In this contribution, we describe such a procedure. Our method requires only the experimental pK a of a reference compound in water and a few standard quantum-chemical calculations. This method is tested through computing the proton solvation energy in 39 solvents and by comparing the pK a of 142 simple compounds in 12 solvents. Our computations indicate that the method to compute the proton solvation energy is robust with respect to the detailed computational setup and the construction of the solvation model. The unscaled pK a's computed using an implicit solvation model on the other hand differ significantly from the experimental data. These differences are partly associated with the poor quality of the experimental data and the well-known shortcomings of implicit solvation models. General linear scaling relationships to correct this error are suggested for protic and aprotic media. Using these relationships, the deviations between experiment and computations drop to a level comparable to that observed in water, which highlights the efficiency of our method.

Reassignment of magic numbers for icosahedral Au clusters: 310, 564, 928 and 1426.

Icosahedral Au clusters with three and four shells of atoms are found to deviate significantly from the commonly assumed Mackay structures. By introducing additional atoms in the surface shell and creating a vacancy in the center of the cluster, the calculated energy per atom can be lowered significantly, according to several different descriptions of the interatomic interaction. Analogous icosahedral structures with five and six shells of atoms are generated using the same structural motifs and are similarly found to be more stable than Mackay icosahedra. The lowest energy per atom obtained here is for clusters containing 310, 564, 928 and 1426 atoms, as compared with the commonly assumed magic numbers of 309, 561, 923 and 1415. Some of the vertices in the optimized clusters have a hexagonal ring of atoms, rather than a pentagon, with the vertex atom missing. An inner shell atom in some cases moves outwards by more than an Ångström into the surface shell at such a vertex site. This feature, as well as the wide distribution of nearest-neighbor distances in the surface layer, can strongly influence the properties of icosahedral clusters, for example catalytic activity. The structural optimization is initially carried out using the GOUST method with atomic forces estimated with the EMT empirical potential function, but the atomic coordinates are then refined by minimization using electron density functional theory (DFT) or Gaussian approximation potential (GAP). A single energy barrier is found to separate the Mackay icosahedron from a lower energy structure where a string of atoms moves outwards in a concerted manner from the center so as to create a central vacancy while placing an additional atom in the surface shell.

High-Quality Graphene Using Boudouard Reaction.

Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.

Dynamics and Surface Propensity of H+ and OH- within Rigid Interfacial Water: Implications for Electrocatalysis.

Facile solvent reorganization promoting ion transfer across the solid-liquid interface is considered a prerequisite for efficient electrocatalysis. We provide first-principles insight into this notion by examining water self-ion dynamics at a highly rigid NaCl(100)-water interface. Through extensive density functional theory molecular dynamics simulations, we demonstrate for both acidic and alkaline solutions that Grotthuss dynamics is not impeded by a rigid water structure. Conversely, decreased proton transfer barriers and a striking propensity of H3O+ and OH- for stationary interfacial water are found. Differences in the ideal hydration structure of the ions, however, distinguish their behavior at the water contact layer. While hydronium can maintain its optimal solvation, the preferentially hypercoordinated hydroxide is repelled from the immediate vicinity of the surface due to interfacial coordination reduction. This has implications for alkaline hydrogen electrosorption in which the formation of undercoordinated OH- at the surface is proposed to contribute to the observed sluggish kinetics.

Hydrogen adsorption trends on two metal-doped Ni2P surfaces for optimal catalyst design.

In this study, we looked at the hydrogen evolution reaction on the doubly doped Ni3P2 terminated Ni2P surface. Two Ni atoms in the first three layers of the Ni2P surface model were exchanged with two transition metal atoms. We limited our investigation to combinations of Al, Co, and Fe based on their individual effectiveness as Ni2P dopants in our previous computational studies. The DFT calculated hydrogen adsorption free energy was employed as a predictor of the materials' catalytic HER activity. Our results indicate that the combination of Co and Fe dopants most improves the catalytic activity of the surface through the creation of multiple novel and active catalytic sites.

From absolute potentials to a generalized computational standard hydrogen electrode for aqueous and non-aqueous solvents.

We describe a simple and efficient procedure to compute a conversion factor for the absolute potential of the standard hydrogen electrode in water to any other solvent. In contrast to earlier methods our procedure only requires the pKa of an arbitrary acid in water and few simple quantum chemical calculations as input. Thus, it is not affected adversely by experimental shortcomings related to measurements in non-aqueous solvents. By combining this conversion factor with the absolute potential in water, the absolute potential in the solvent of interest is obtained. Based on this procedure a new generalized computational standard hydrogen electrode for the computation of electron transfer and proton-coupled electron transfer potentials in non-aqueous solvents and ionic liquids is developed. This enables for the first time the reliable prediction of redox potentials in any solvent. The method is tested through calculation of absolute potentials in 36 solvents. Using the Kamlet-Taft linear solvation energy model we find that the relative absolute potentials consistently increase with decreasing polarisability and decreasing hydrogen bonding ability. For protic solvents good agreement with literature is observed while significant deviations are found for aprotic solvents. The obtained conversion factors are independent of the quantum chemical method, while minor differences are observed between solvation models. This does, however, not affect the global trends.

Method for the accurate prediction of electron transfer potentials using an effective absolute potential.

A protocol for the accurate computation of electron transfer (ET) potentials from ab initio and density functional theory (DFT) calculations is described. The method relies on experimental pKa values, which can be measured accurately, to compute a computational setup dependent effective absolute potential. The effective absolute potentials calculated using this protocol display strong variations between the different computational setups and deviate in several cases significantly from the "generally accepted" value of 4.28 V. The most accurate estimate, obtained from CCSD(T)/aug-ccpvqz, indicates an absolute potential of 4.14 V for the normal hydrogen electrode (nhe) in water. Using the effective absolute potential in combination with CCSD(T) and a moderately sized basis, we are able to predict ET potentials accurately for a test set of small organic molecules (σ = 0.13 V). Similarly we find the effective absolute potential method to perform equally good or better for all considered DFT functionals compared to using one of the literature values for the absolute potential. For, M06-2X, which comprises the most accurate DFT method, standard deviation of 0.18 V is obtained. This improved performance is a result of using the most appropriate effective absolute potential for a given method.

Water Oxidation at Neutral pH using a Highly Active Copper-Based Electrocatalyst.

The sluggish kinetics of the oxygen evolution reaction (OER) at the anode severely limit hydrogen production at the cathode in water splitting systems. Although electrocatalytic systems based on cheap and earth-abundant copper catalysts have shown promise for water oxidation under basic conditions, only very few examples with high overpotential can be operated under acidic or neutral conditions, even though hydrogen evolution in the latter case is much easier. This work presents an efficient and robust Cu-based molecular catalyst, which self-assembles as a periodic film from its precursors under aqueous conditions on the surface of a glassy carbon electrode. This film catalyzes the OER under neutral conditions with impressively low overpotential. In controlled potential electrolysis, a stable catalytic current of 1.0 mA cm-2 can be achieved at only 2.0 V (vs. RHE) and no significant decrease in the catalytic current is observed even after prolonged bulk electrolysis. The catalyst displays first-order kinetics and a single site mechanism for water oxidation with a TOF (kcat ) of 0.6 s-1 . DFT calculations on of the periodic Cu(TCA)2 (HTCA=1-mesityl-1H-1,2,3-triazole-4-carboxylic acid) film reveal that TCA defects within the film create CuI active sites that provide a low overpotential route for OER, which involves CuI , CuII -OH, CuIII =O and CuII -OOH intermediates and is enabled at a potential of 1.54 V (vs. RHE), requiring an overpotential of 0.31 V. This corresponds well with an overpotential of approximately 0.29 V obtained experimentally for the grown catalytic film after 100 CV cycles at pH 6. However, to reach a higher current density of 1 mA cm-2 , an overpotential of 0.72 V is required.

Active site manipulation in MoS2 cluster electrocatalysts by transition metal doping.

The development of non-platinum group metal catalysts for the hydrogen evolution reaction (HER) in water electrolyser devices is essential for their widespread and sustainable deployment. In recent years, molybdenum disulfide (MoS2) catalysts have received significant attention as they not only exhibit good electrocatalytic HER activity but also, crucially, acid-stability. However, further performance enhancement is required for these materials to be competitive with Pt and to that end transition metal doping of MoS2 has been explored as a route to further increasing its catalytic activity. In this work, cluster beam deposition was employed to produce controlled cobalt-doped MoS2 clusters (MoS2-Co). We demonstrate that, in contrast to previous observations of performance enhancement in MoS2 resulting from nickel doping (MoS2-Ni), the introduction of Co has a detrimental effect on HER activity. The contrasting behaviours of Ni and Co doping are rationalized by density functional theory (DFT) calculations, which suggest that HER-active surface vacancies are deactivated by combination with Co dopant atoms, whilst their activity is retained, or even partially enhanced, by combination with Ni dopant atoms. Furthermore, the adatom dopant-vacancy combination kinetics appear to be more than three orders of magnitude faster in MoS2-Co than for MoS2-Ni. These findings highlight a fundamental difference in the influence of transition metal dopants on the HER performance of MoS2 electrocatalysts and stress the importance of considering surface atomic defects when predicting their behaviour.