Solvent Selection in Homogeneous Catalysis—Optimization of Kinetics and Reaction Performance

Huxoll, Fabian; Jameel, Froze; Bianga, Jonas; Seidensticker, Thomas; Stein, Matthias; Sadowski, Gabriele; Vogt, Dieter

doi:10.1021/acscatal.0c04431

Cited by 24 publications

(25 citation statements)

References 36 publications

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“…Although for years it had been considered just as a passive medium where reaction events take place, its critical role on catalyzed reactions is nowadays well recognized [1]. Indeed, selection of the best solvent to carry out one reaction is crucial for the reaction performance and is a mandatory step in the optimization of reaction conditions [2]. At the macroscopic level, the solvent influences the solubility of the species present along the reaction pathway.…”

Section: Introductionmentioning

confidence: 99%

Beyond Continuum Solvent Models in Computational Homogeneous Catalysis

2021

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In homogeneous catalysis solvent is an inherent part of the catalytic system. As such, it must be considered in the computational modeling. The most common approach to include solvent effects in quantum mechanical calculations is by means of continuum solvent models. When they are properly used, average solvent effects are efficiently captured, mainly those related with solvent polarity. However, neglecting atomistic description of solvent molecules has its limitations, and continuum solvent models all alone cannot be applied to whatever situation. In many cases, inclusion of explicit solvent molecules in the quantum mechanical description of the system is mandatory. The purpose of this article is to highlight through selected examples what are the reasons that urge to go beyond the continuum models to the employment of micro-solvated (cluster-continuum) of fully explicit solvent models, in this way setting the limits of continuum solvent models in computational homogeneous catalysis. These examples showcase that inclusion of solvent molecules in the calculation not only can improve the description of already known mechanisms but can yield new mechanistic views of a reaction. With the aim of systematizing the use of explicit solvent models, after discussing the success and limitations of continuum solvent models, issues related with solvent coordination and solvent dynamics, solvent effects in reactions involving small, charged species, as well as reactions in protic solvents and the role of solvent as reagent itself are successively considered.

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Section: Introductionmentioning

confidence: 99%

Beyond Continuum Solvent Models in Computational Homogeneous Catalysis

2021

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“…This was successfully demonstrated in earlier works applying an activity coefficientbased solvent-selection approach using modified UNIFAC (Dortmund). 18,22 Based on eq 3, doubling the thermodynamic activity of reactant results in a doubled reaction rate. Accordingly, the highest reaction rates and turnover frequencies are achieved in reaction mixtures that lead to the highest thermodynamic activities of the reactants.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…). 18 Consequently, the thermodynamic activity of CO and/or H 2 in the liquid is constant and thus does not affect the reaction rate as long as the composition of the gas phase does not change and the gas phase is in equilibrium with the liquid phase. It is worth mentioning that while the thermodynamic activity of the gases does not depend on the solvent, their solubility in the liquid, of course, does.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

Predicting Solvent Effects on Homogeneity and Kinetics of the Hydroaminomethylation: A Thermodynamic Approach Using PC-SAFT

Huxoll

Kampwerth

Seidensticker

et al. 2022

Ind. Eng. Chem. Res.

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Solvents may significantly affect the phase behavior and kinetics of chemical reactions. Especially for complex reactions performed in mixtures of different solvents, it requires a high experimental effort to quantify these effects. This work focuses on a novel thermodynamic approach to predict solvent effects on both reaction rates and phase behavior. We applied this method to the homogeneously catalyzed hydroaminomethylation of 1-decene in a thermomorphic multiphase system of methanol and n-dodecane. For that purpose, the thermodynamic activities of the reactants and the liquid–liquid equilibrium of the multicomponent reaction system were successfully modeled using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT). An increasing concentration of n-dodecane in the solvent mixture was predicted not only to limit the working space for the reaction due to unwanted phase separation but also to massively reduce the reaction rate. These results were in good agreement with batch experiments and homogeneity tests performed in this work. The approach is applicable to a wide variety of liquid-phase reactions and thus is a valuable tool for reducing the experimental effort to a minimum.

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“…Different reaction solvents will make the reaction proceed at different rates, the productivity is different, so will the activity and selectivity of the catalyst be different. In the selection of reaction solvent, solvent parameters such as HSE (health, safety and environment) should be taken into account [15]. Screening appropriate solvent system can promote the process of reaction with minimal experimental work [16].…”

Section: Electrochemical Oxidation Reaction Solventmentioning

confidence: 99%

Recent Development and Perspectives of Solvents and Electrode Materials for Electrochemical Oxidative Degradation of Lignin

Zhou

Tao

et al. 2022

Electroanalysis

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Lignin is the most abundant potential renewable resource of aromatic structural units. Turning lignin into high-value compounds, such as fuels, adhesives or refined chemicals, is the cornerstone and focus of biorefinery in the future. Depolymerization of lignin can convert its macromolecules towards smaller molecules (monomers or oligomers) allowing it to be used for further applications. Electrochemical depolymerization is an excellent method of green and sustainable transformation, which can effectively avoid reagent waste and mild reaction. This review pretents the research progress of lignin electrochemical oxidation in recent years, summarizes the effects of solvent system (alkaline solvent, ionic liquid and deep eutectic solvents, as well as different lignin concentration and medium), electrode materials (platinum, gold, copper, nickel, cobalt, lead dioxide, tin dioxide and titaniumbased metal electrodes) and electrolytic parameters (current density, temperature, reaction time and photocatalysis) on the oxidative degradation efficiency and product distribution of lignin, and prospects its development. The development of low-cost electrode materials and efficient solvent systems will still be an important direction for the high-value and high-quality application of lignin.

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Solvent Selection in Homogeneous Catalysis—Optimization of Kinetics and Reaction Performance

Cited by 24 publications

References 36 publications

Beyond Continuum Solvent Models in Computational Homogeneous Catalysis

Beyond Continuum Solvent Models in Computational Homogeneous Catalysis

Predicting Solvent Effects on Homogeneity and Kinetics of the Hydroaminomethylation: A Thermodynamic Approach Using PC-SAFT

Recent Development and Perspectives of Solvents and Electrode Materials for Electrochemical Oxidative Degradation of Lignin

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