Unifying views on catalyst deactivation

Fernández, Antonio José Martín; Mitchell, Sharon; Mondelli, Cecilia; Jaydev, Shibashish D.; Pérez‐Ramírez, Javier

doi:10.1038/s41929-022-00842-y

Cited by 172 publications

(132 citation statements)

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“…The performance of any (electro)catalytic reaction is described by three main parameters: activity, selectivity, and stability. , The goal is to form as much (activity) of a single product (selectivity) as possible for a long period of time (stability). To reach the sustainability goals in 2050, a lot of research is currently devoted to the optimization of activity and selectivity through material development and systems approaches ( e.g., membranes, gas diffusion electrodes, electrolyte composition), − whereas the other key descriptor of electrocatalysis is often overlooked: stability. , Record selectivities approaching unity have already been reported for the different classes of C 1 –C 2 products from CO 2 reduction (e.g., CO, formate, methane, ethylene) at current densities that are almost on par with industrial needs (100–300 mA/cm 2 ) . It was recently brought forward that in this endeavor for superior activity and selectivity, the target electrode material should be as simple and cost-effective as possible; otherwise “electrocatalysis goes nuts” .…”

Section: Introductionmentioning

confidence: 99%

“…In situ characterization techniques offer the possibility to probe the electrocatalyst–reactant interactions over multiple length scales depending on the method of choice (Figure ). ,− For example, electrocatalyst morphology, composition, and surface but also adsorbed intermediates and electrode–electrolyte interfaces have been studied with various vibrational spectroscopies (e.g., infrared, IR, and Raman), − microscopies (e.g., atomic force microscopy, AFM, and transmission electron microscopy, TEM), − and X-ray characterization techniques (e.g., X-ray absorption spectroscopy, XAS, X-ray photoelectron spectroscopy, XPS, and X-ray diffraction, XRD). ,,, Despite the unmatched time and space resolution of certain techniques, some of them cannot straightforwardly be applied to electrocatalysis research. Due to the need for aqueous electrolytes in electrocatalytic reactions, some techniques of interest are in fact limited for in situ characterization of electrocatalysts at work.…”

Section: Introductionmentioning

confidence: 99%

“…Very often, the in situ characterization cells can only operate at moderate current density, which also limits the direct application of the in situ findings for practical implementation of the electrocatalysts under study. In general, the three descriptors of catalysis (activity, selectivity, and stability) are influenced by a wide variety of parameters over multiple length scales. ,,,, For example, the electrolyte composition has been found to drastically influence eCO2RR, and the presence of small amounts of subsurface oxygen have been shown to have major consequences for the reaction output . This calls for a multiscale approach, where multiple techniques are combined simultaneously to elucidate the factors that determine catalyst activity and selectivity, but most of all stability.…”

Section: Introductionmentioning

confidence: 99%

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The Necessity for Multiscale In Situ Characterization of Tailored Electrocatalyst Nanoparticle Stability

Stam

2023

Chem. Mater.

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Tailored nanoparticles have opened up several exciting avenues to boost the activity and selectivity of structure-sensitive electrocatalytic reactions, such as the electrochemical carbon dioxide (CO2) reduction (eCO2RR). Colloidal chemistry provides the perfect toolbox to synthesize electrocatalyst nanoparticles on demand with atomic precision, in order to control and steer the electrocatalytic reactions of interest to the desired products. Not only does colloidal chemistry offer a means to prepare nanoparticles with well-defined sizes and shapes, it also allows easy deposition on any desired substrate (e.g., porous substrates) due to the solution processability. But what you see after synthesis with ex situ characterization techniques is not always what you get during the electrocatalytic reaction. Like any other electrocatalyst material, colloidal nanoparticles are prone to restructuring, and hence, the reaction output is altered due to destabilization of the electrocatalyst. This destabilization of the electrocatalyst nanoparticles is currently one of the major bottlenecks for the widespread implementation of electrocatalysts in the chemical industry. This calls for the necessary development and application of in situ characterization techniques to probe the morphology and composition of the tailored electrocatalyst nanoparticles over multiple length scales, in order to rationally design the next generation of stable electrocatalyst nanoparticles. Through detailed spatiotemporal in situ characterization, we can take full advantage of the possibilities that colloidal chemistry offers for electrocatalyst preparation with superior activity, selectivity, and stability. In this perspective, the necessity for in situ characterization of electrocatalyst nanoparticle stability is highlighted. For this purpose, first the progress of colloidal nanoparticles for electrocatalytic conversion reactions is briefly discussed, after which the focus shifts toward in situ characterization of the (in)stability of the tailored nanoparticles during the reaction of interest, ideally under industrially relevant conditions. This perspective shows that in situ characterization of electrocatalyst deactivation requires a multiscale approach, and that without combined in situ characterization we will remain blind to several aspects that are known to influence electrocatalyst performance.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Necessity for Multiscale In Situ Characterization of Tailored Electrocatalyst Nanoparticle Stability

Stam

2023

Chem. Mater.

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“…The interactions between these components and their interconversions form large and highly interconnected reaction networks that determine the overall behavior and the performance of the catalytic system. The experimental and computational mechanistic studies aim at identifying the state of the catalytic species and key reaction intermediates, their role in the main catalytic mechanism, and the competing reaction channels toward unselective conversion routes or catalyst deactivation. − Such mechanistic insights are critically important for guiding the design and optimization of new and improved catalytic systems in a rational manner. − …”

Section: Introductionmentioning

confidence: 99%

ReNeGate: A Reaction Network Graph-Theoretical Tool for Automated Mechanistic Studies in Computational Homogeneous Catalysis

Hashemi

Bougueroua

Gaigeot

et al. 2022

J. Chem. Theory Comput.

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Exploration of the chemical reaction space of chemical transformations in multicomponent mixtures is one of the main challenges in contemporary computational chemistry. To remove expert bias from mechanistic studies and to discover new chemistries, an automated graph-theoretical methodology is proposed, which puts forward a network formalism of homogeneous catalysis reactions and utilizes a network analysis tool for mechanistic studies. The method can be used for analyzing trajectories with single and multiple catalytic species and can provide unique conformers of catalysts including multinuclear catalyst clusters along with other catalytic mixture components. The presented three-step approach has the integrated ability to handle multicomponent catalytic systems of arbitrary complexity (mixtures of reactants, catalyst precursors, ligands, additives, and solvents). It is not limited to predefined chemical rules, does not require prealignment of reaction mixture components consistent with a reaction coordinate, and is not agnostic to the chemical nature of transformations. Conformer exploration, reactive event identification, and reaction network analysis are the main steps taken for identifying the pathways in catalytic systems given the starting precatalytic reaction mixture as the input. Such a methodology allows us to efficiently explore catalytic systems in realistic conditions for either previously observed or completely unknown reactive events in the context of a network representing different intermediates. Our workflow for the catalytic reaction space exploration exclusively focuses on the identification of thermodynamically feasible conversion channels, representative of the (secondary) catalyst deactivation or inhibition paths, which are usually most difficult to anticipate based solely on expert chemical knowledge. Thus, the expert bias is sought to be removed at all steps, and the chemical intuition is limited to the choice of the thermodynamic constraint imposed by the applicable experimental conditions in terms of threshold energy values for allowed transformations. The capabilities of the proposed methodology have been tested by exploring the reactivity of Mn complexes relevant for catalytic hydrogenation chemistry to verify previously postulated activation mechanisms and unravel unexpected reaction channels relevant to rare deactivation events.

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“…The experimental and computational mechanistic studies aim at identifying the state of the catalytic species and key reaction intermediates, their role in the main catalytic mechanism and the competing reaction channels towards unselective conversion routes or catalyst deactivation. [6][7][8][9][10][11][12][13] Such mechanistic insights are critically important for guiding the design and optimization of new and improved catalytic systems in a rational manner. [14][15][16][17][18] Catalytic reactivity is determined by complex networks of chemical transformations that take place simultaneously or consequently between the different (transient) components of the catalytic mixture.…”

Section: Introductionmentioning

confidence: 99%

ReNeGate: Reaction Network Graph Theoretical tool for automated mechanistic studies in computational homogeneous catalysis

Hashemi

Bougueroua

Gaigeot

et al. 2022

Preprint

View full text Add to dashboard Cite

Exploration of the chemical reaction space of chemical transformations in multicomponent mixtures is a challenge for modern computational protocols. In order to remove expert bias from mechanistic studies and to discover new chemistries, an automated graph-theoretical methodology is proposed to provide mechanistic analysis in catalytic systems. The primary advantage of the presented three-step approach over the existing automated pathways generation methods is the integrated ability to handle multicomponent catalytic systems of arbitrary complexity (mixtures of reactants, catalyst precursors, ligands, additives, and solvent). It is not limited to pre-defined chemical rules, does not require pre-alignment of reaction mixture components consistent with a reaction coordinate and is not agnostic to the chemical nature of transformations. Conformer exploration, Reactive event identification and Reaction network analysis are the main steps taken for understanding the underlying mechanistic pathways in catalytic mixtures given the reaction mixture as the input. Such a methodology allows to comprehensively explore the catalytic systems in realistic conditions for either previously observed or completely unknown reactive events. The expert bias is sought to be removed in either of the steps and chemical intuition is limited to the choice of the thermodynamic constraint imposed by the applicable experimental conditions in terms of threshold energy values for allowed transformations. The capabilities of the proposed methodology have been tested by exploring reactivity of Mn complexes relevant for catalytic hydrogenation chemistry to verify previously postulated activation mechanisms and unravel unexpected reaction channels relevant to rare deactivation events.

show abstract

Unifying views on catalyst deactivation

Cited by 172 publications

References 100 publications

The Necessity for Multiscale In Situ Characterization of Tailored Electrocatalyst Nanoparticle Stability

The Necessity for Multiscale In Situ Characterization of Tailored Electrocatalyst Nanoparticle Stability

ReNeGate: A Reaction Network Graph-Theoretical Tool for Automated Mechanistic Studies in Computational Homogeneous Catalysis

ReNeGate: Reaction Network Graph Theoretical tool for automated mechanistic studies in computational homogeneous catalysis

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