Many catalytic reactions suffer from product inhibition, which especially hard to control in homogeneous hydrogenation due to the scaling relation between the inhibited and active states of the catalyst. We recently reported one such pathway in Mn(I) hydrogenation and demonstrated that addition of alkoxide bases could affect the thermodynamic favorability of this reaction and selectively suppress the product inhibition. Since external reaction promotors are formally not involved in reaction thermodynamics, we set to investigate the explicit molecular interactions behind these apparently environmental effects. Herein, we reveal that the thermodynamic landscape of the inhibitory process exhibits a non-monotonic dependence on the base concentration. This study related this phenomenon to the presence of two dominant mechanisms operating at different base concentrations. Specifically, the base additives can enhance the ionic strength and lower the free energy of the inhibited state at low promotor concentration. At high base concentrations this study suggested the formation of highly labile alcohol-alkoxide clusters which stabilize the free alcohol and make its addition to the catalyst unfavourable, thereby suppressing the inhibition. While relatively weak, such noncovalent interactions between reactants and reaction environment can cause substantial perturbations to the free energy of catalytic process, ultimately deciding its fate.@en

Sulfated zirconium oxide (SZO) catalyzes the hydrogenolysis of isotactic polypropylene (iPP, Mw=13.3 kDa, Đ=2.4, <mmmm>=94 %) or high-density polyethylene (HDPE, Mn=2.5 kDa, Đ=3.6) to branched alkane products. We propose that this reactivity is driven by the pyrosulfate sites SZO, which open under mild conditions to transiently form adsorbed SO3 and sulfate groups. This adsorbed SO3 is a very strong Lewis acid that binds 15N-pyridine or triethylphosphineoxide (TEPO) (ΔEads>−39 kcal mol−1), reacts with Ph3CH to form Ph3C+, and mediates H/D exchange in dihydroanthracene-d4. DFT studies show that pyrosulfate sites open with a modest 26.1 kcal mol−1 barrier to form the adsorbed SO3 and sulfate in the presence of a tetramer of propylene. Hydride abstraction from the tertiary C−H in this model is exothermic and subsequent β-scission forms cleaved products. Analysis of the energetics provided here brackets the hydride ion affinity (HIA) of the adsorbed SO3 between 226.2 to 237.9 kcal mol−1, among largest values reported for a formally neutral Lewis acid. This study explains how SZO, a classic heterogeneous catalyst, can form carbocations by a redox neutral hydride abstraction reaction by very strong Lewis sites.@en

Plastic waste is a major environmental issue; converting it directly into valuable chemicals by using catalysts is a promising alternative to plastic recycling. Here, we report the selective catalytic cracking of polypropylene (PP), a typical commodity plastic, to high-value light olefins (C2–C5), below pyrolytic temperature (290 °C) and without external hydrogen supply, by using zeolite catalysts. Among the H+-form zeolites with different structures, HMFI showed the highest yields of light hydrocarbons (C2–C5), of which light olefins (C2–C5) were the major products. The HMFI-catalyzed PP conversion was applicable to the upcycling of a model PP waste, resulting in a 61.9% light hydrocarbon yield. The results of catalytic and in situ IR experiments using model HMFI catalysts with a small amount of external Brønsted acid sites suggested that the Brønsted acid sites on the external surface of HMFI are indispensable for the PP conversion and are posited to be the active sites for the cracking of PP into short-chain (oligomeric) hydrocarbon species as intermediate products. Density functional theory analyses were conducted to determine plausible reaction pathways by adopting 2,4-dimethylheptene as the shortest unit of the oligomeric species. The obtained results show that the β-scission of 2,4-dimethylheptene by Brønsted acid sites yields isobutene and propylene (or a propyl alkoxide group) via carbocation intermediates with an activation energy below 118 kJ mol–1. Operando UV–vis and IR experiments under the reaction conditions, combined with ex situ 1H NMR and 13C NMR analyses of the spent catalyst, show that some of the olefins are further converted to light or heavy aromatics (coke deposit), probably via carbenium ion species.@en

Significant efforts have been dedicated to the direct syngas conversion into ethanol, however, achieving a high ethanol yield remains a formidable task. In this study, we present the direct syngas-to-ethanol conversion over Li-promoted RhOx/MgO catalyst (RhOx/Li2O/MgO). The ethanol space-time yield (EtOH STY) and selectivity reached 12.2 mmol gcat–1 h–1 and 20%, respectively, at a 35% CO conversion over the RhOx/Li2O/MgO catalyst. The RhOx/Li2O/MgO catalyst demonstrated superior performance in terms of both ethanol selectivity and STY compared to Rh/Li2O catalysts on other support materials and Rh/MgO catalysts promoted with other alkali metals. In situ/operando spectroscopic techniques, combined with other characterisations and theoretical calculations, have elucidated the interactions between Li2O and Rh on the MgO surface. These interactions promote the formation of new active sites and weaken CO adsorption on the Rh surface, thereby enhancing ethanol production. This work provides a promising strategy for improving ethanol yield in syngas conversion processes.@en

Herein, we present a practical strategy to enhance the performance of a multiphase system for bicarbonate hydrogenation based on a molecular Ru-PNP pincer catalyst. This study demonstrates that the use of organic antioxidants not only mitigates catalyst degradation but also significantly boosts its intrinsic activity. This enables efficient catalyst recycling at ultra-low concentrations. Systematic screening and optimization of a range of organic antioxidants has identified TDTBP (tris(2,4-di-tert-butylphenyl) phosphite) as being exceptionally efficient in stabilizing and enhancing the performance of the Ru-PNP catalyst. With the optimized system an unprecedented integral turnover frequency (TOF) of 115,000 h⁻¹ and a total turnover number (TTON) of 9.43×10⁶ across four recycling tests were demonstrated, conducted at a reaction temperature of 90 ºC and H₂ pressure of 50 bar. These findings represent a substantial advancement in sustainable formate/formic acid production, offering a scalable and highly efficient method suitable for industrial-scale application.

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In the past decade, computational tools have become integral to catalyst design. They continue to offer significant support to experimental organic synthesis and catalysis researchers aiming for optimal reaction outcomes. More recently, data-driven approaches utilizing machine learning have garnered considerable attention for their expansive capabilities. This Perspective provides an overview of diverse initiatives in the realm of computational catalyst design and introduces our automated tools tailored for high-throughput in silico exploration of the chemical space. While valuable insights are gained through methods for high-throughput in silico exploration and analysis of chemical space, their degree of automation and modularity are key. We argue that the integration of data-driven, automated and modular workflows is key to enhancing homogeneous catalyst design on an unprecedented scale, contributing to the advancement of catalysis research.

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The current state-of-the-art electron-transfer modeling primarily focuses on the kinetics of charge transfer between an electroactive species and an inert electrode. Experimental studies have revealed that the existing Butler–Volmer model fails to satisfactorily replicate experimental voltammetry results for both solution-based and surface-bound redox couples. Consequently, experimentalists lack an accurate tool for predicting electron-transfer kinetics. In response to this challenge, we developed a density functional theory-based approach for accurately predicting current peak potentials by using the Marcus–Hush model. Through extensive cyclic voltammetry simulations, we conducted a thorough exploration that offers valuable insights for conducting well-informed studies in the field of electrochemistry.@en

Some of our recent developments and applications of algorithmic graph theory for extracting the physical and chemical properties of materials from molecular dynamics simulations are presented. From the chemical viewpoint, the power of graph theory is illustrated in the search for a catalyst's active sites at a silica solid surface. From the physical viewpoint, we present graph algorithms that recognize the structural motifs that exist at the silica/liquid water interface. Statistical analyses of the instances of these surface–water motifs provide a detailed understanding of the structures and dynamics at the aqueous interface.@en

Electrocatalytic reduction of organic halides and subsequent carboxylation are promising methods for the valorization of CO2 as a C1 source in synthetic organic chemistry. The reaction mechanism underlying the selectivity and reduction mechanism of benzyl halides is highly dependent on the nature of the electrode material as well as the processes, composition, and structure of the liquid phase at the electrode–solution interface. Herein, we present a computational study on the influence of the electric double layer (EDL) on the activation of benzyl halides at different applied potentials over the Au (111) cathode. Using a multiscale modeling approach, we demonstrate that, under realistic electrocatalytic conditions, the formation of a dense EDL over the cathode hampers the diffusion of benzyl halides toward the electrode surface. A combination of classical molecular dynamics simulations and density functional theory calculations reveals the most favorable benzyl halide electro-carboxylation pathway over the EDL that does not require direct substrate adsorption to the cathode surface. The dense EDL promotes the dissociative reduction of the benzyl halides via the outer-sphere electron transfer from the cathode surface to the electrolyte. Such a reduction mechanism results in a benzyl radical intermediate, which is then converted to benzyl anions in the EDL via an additional electron transfer step.@en

Adding Zn to the ZSM-5 zeolite effectively increases the aromatic selectivity in the methanol-to-aromatics (MTA) process. The formation of metal-derived Lewis acid sites promotes the dehydrogenation but at the cost of a rapid deactivation of the catalyst by coke, due to the increased aromatic formation. In this work, we impregnated a Zn-modified catalyst (2 wt%) with variable contents of Ca (0.02 and 0.5 wt%) and evaluated their kinetic behavior in the MTA and ethane dehydrogenation reactions. The results proved the superior performance of the Zn(2)Ca(0.02) catalyst due to a synergistic effect between the two metals. The Ca ions limit coke formation from excessive aromatization, increasing catalyst stability and removing Zn clusters, resulting in a recovery of Brønsted acid sites (BAS) active for the formation of light aromatics. Combining these effects results in a more efficient and viable catalyst for aromatic production from methanol.@en

Data-driven catalyst design is a promising approach for addressing the challenges in identifying suitable catalysts for synthetic transformations. Models with descriptor calculations relying solely on the precatalyst structure are potentially generalizable but may overlook catalyst-substrate interactions. This study explores substrate-specific interactions in the context of Rh-catalyzed asymmetric hydrogenation to elucidate the impact of substrate inclusion on the catalyst structure and on the descriptors derived from it. We compare a catalyst-substrate complex with methyl 2-acetamidoacrylate as a model substrate with the generic precatalyst structure involving a placeholder substrate, norbornadiene, across 11 Rh-based catalysts with bidentate bisphosphine ligands. For these systems, a full conformer ensemble analysis reveals an intriguing finding: the rigid substrate induces conformational freedom in the ligand. This flexibility gives rise to a more diverse conformer landscape, showing a previously overlooked aspect of catalyst-substrate dynamics. Electronic descriptor variations particularly highlight differences between substrate-specific and precatalyst structures. This study suggests that generic precatalyst-like models may lack crucial insights into the conformational freedom of the catalyst. We speculate that such conformational freedom may be a more general phenomenon that can influence the development of generalizable predictive models of computational TM-based catalysis.

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Enantioselective hydrogenation of olefins by Rh-based chiral catalysts has been extensively studied for more than 50 years. Naively, one would expect that everything about this transformation is known and that selecting a catalyst that induces the desired reactivity or selectivity is a trivial task. Nonetheless, ligand engineering or selection for any new prochiral olefin remains an empirical trial-error exercise. In this study, we investigated whether machine learning techniques could be used to accelerate the identification of the most efficient chiral ligand. For this purpose, we used high throughput experimentation to build a large dataset consisting of results for Rh-catalyzed asymmetric olefin hydrogenation, specially designed for applications in machine learning. We showcased its alignment with existing literature while addressing observed discrepancies. Additionally, a computational framework for the automated and reproducible quantum-chemistry based featurization of catalyst structures was created. Together with less computationally demanding representations, these descriptors were fed into our machine learning pipeline for both out-of-domain and in-domain prediction tasks of selectivity and reactivity. For out-of-domain purposes, our models provided limited efficacy. It was found that even the most expensive descriptors do not impart significant meaning to the model predictions. The in-domain application, while partly successful for predictions of conversion, emphasizes the need for evaluating the cost-benefit ratio of computationally intensive descriptors and for tailored descriptor design. Challenges persist in predicting enantioselectivity, calling for caution in interpreting results from small datasets. Our insights underscore the importance of dataset diversity with broad substrate inclusion and suggest that mechanistic considerations could improve the accuracy of statistical models.

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The premise of most studies on the homogeneous electrocatalytic CO₂ reduction reaction (CO₂RR) is a good understanding of the reaction mechanisms. Yet, analyzing the reaction intermediates formed at the working electrode is challenging and not always attainable. Here, we present a new, general approach to studying the reaction intermediates applied for CO₂RR catalyzed by a series of cobalt complexes. The cobalt complexes were based on the TPA-ligands (TPA = tris(2-pyridylmethyl)amine) modified by amino groups in the secondary coordination sphere. By combining the electrochemical experiments, electrochemistry-coupled electrospray ionization mass spectrometry, with density functional theory (DFT) calculations, we identify and spectroscopically characterize the key reaction intermediates in the CO₂RR and the competing hydrogen-evolution reaction (HER). Additionally, the experiments revealed the rarely reported in situ changes in the secondary coordination sphere of the cobalt complexes by the CO₂-initiated transformation of the amino substituents to carbamates. This launched an even faster alternative HER pathway. The interplay of three catalytic cycles, as derived from the experiments and supported by the DFT calculations, explains the trends that cobalt complexes exhibit during the CO₂RR and HER. Additionally, this study demonstrates the need for a molecular perspective in the electrocatalytic activation of small molecules efficiently obtained by the EC-ESI-MS technique.

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Supported rhenium (Re) catalysts are emerging as promising candidates for hydrogenation reactions, which are crucial in industrial processes such as biomass valorization, CO2 reduction, and petroleum refining. However, despite their broad application, the structural and mechanistic understanding of these systems remains limited. The strong oxophilic nature of Re, combined with its ability to adopt multiple oxidation states, complicates the characterization of the active species even with advanced experimental techniques. In this study, we employ density functional theory calculations, alongside ab initio thermodynamic analysis, to systematically explore the structural and electronic properties of single-atom Re catalysts on a TiO2 surface, providing insights that could inform the rational catalyst design. Our calculations reveal the formation of stable Re polyhydrides on the surface under hydrogen-rich conditions. Notably, even in highly reducing environments, Re species with low formal oxidation states are thermodynamically unfavorable. The stable Re species identified on TiO2 surfaces demonstrate high reactivity toward CO2 hydrogenation. The electronic properties and computed X-ray photoelectron spectroscopy (XPS) signatures of the feasible surface species are highly influenced by the ligand environment. This work highlights the limitation of routine interpretation of experimental XPS characterization data in terms of the formal oxidation state.@en

Computational chemistry pipelines typically commence with geometry generation, well-established for organic compounds but presenting a considerable challenge for transition metal complexes. This paper introduces MACE, an automated computational workflow for converting chemist SMILES/MOL representations of the ligands and the metal center to 3D coordinates for all feasible stereochemical configurations for mononuclear octahedral and square planar complexes directly suitable for quantum chemical computations and implementation in high-throughput computational chemistry workflows. The workflow is validated through a structural screening of a data set of transition metal complexes extracted from the Cambridge Structural Database. To further illustrate the power and capabilities of MACE, we present the results of a model DFT study on the hemilability of pincer ligands in Ru, Fe, and Mn complexes, which highlights the utility of the workflow for both focused mechanistic studies and larger-scale high-throughput pipelines.

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Organic electrochemistry is currently experiencing an era of renaissance, which is closely related to the possibility of carrying out organic transformations under mild conditions, with high selectivity, high yields, and without the use of toxic solvents. Combination of organic electrochemistry with alternative approaches, such as photo-chemistry was found to have great potential due to induced synergy effects. In this work, we propose for the first time utilization of plasmon triggering of enhanced and regio-controlled organic chemical transformation performed in photoelectrochemical regime. The advantages of the proposed route is demonstrated in the model amination reaction with formation of C−N bond between pyrazole and substituted benzene derivatives. Amination was performed in photo-electrochemical mode on the surface of plasmon active Au@Pt electrode with attention focused on the impact of plasmon triggering on the reaction efficiency and regio-selectivity. The ability to enhance the reaction rate significantly and to tune products regio-selectivity is demonstrated. We also performed density functional theory calculations to inquire about the reaction mechanism and potentially explain the plasmon contribution to electrochemical reaction rate and regioselectivity.

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Effective assessment of catalytic performance is the foundation for the rational design and development of new catalysts with superior performance. The ubiquitous screening/optimization studies use reaction yields as the sole performance metric in an approach that often neglects the complexity of the catalytic system and intrinsic reactivities of the catalysts. Using an example of hydrogenation catalysis, we examine the transient behavior of catalysts that are often encountered in activation, deactivation and catalytic turnover processes. Each of these processes and the reaction environment in which they take place are gradually shown to determine the real-time catalyst speciation and the resulting kinetics of the overall catalytic reaction. As a result, the catalyst performance becomes a complex and time-dependent metric defined by multiple descriptors apart from the reaction yield. This behaviour is not limited to hydrogenation catalysis and affects various catalytic transformations. In this feature article, we discuss these catalytically relevant descriptors in an attempt to arrive at a comprehensive depiction of catalytic performance.

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The stoichiometric conversion of methane to methanol by Cu-exchanged zeolites can be brought to highest yields by the presence of extraframework Al and high CH₄ chemical potentials. Combining theory and experiments, the differences in chemical reactivity of monometallic Cu-oxo and bimetallic Cu-Al-oxo nanoclusters stabilized in zeolite mordenite (MOR) are investigated. Cu-L₃ edge X-ray absorption near-edge structure (XANES), infrared (IR), and ultraviolet-visible (UV-vis) spectroscopies, in combination with CH₄ oxidation activity tests, support the presence of two types of active clusters in MOR and allow quantification of the relative proportions of each type in dependence of the Cu concentration. Ab initio molecular dynamics (MD) calculations and thermodynamic analyses indicate that the superior performance of materials enriched in Cu-Al-oxo clusters is related to the activity of two μ-oxo bridges in the cluster. Replacing H₂O with ethanol in the product extraction step led to the formation of ethyl methyl ether, expanding this way the applicability of these materials for the activation and functionalization of CH₄. We show that competition between different ion-exchanged metal-oxo structures during the synthesis of Cu-exchanged zeolites determines the formation of active species, and this provides guidelines for the synthesis of highly active materials for CH₄ activation and functionalization.

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The nature of hydrocarbon pool (HCP) intermediates in the methanol-to-hydrocarbons (MTH) process has been thoroughly investigated, especially for BEA- and CHA-type zeolite catalysts like H-β and H-SAPO-34. Herein, we further reveal the dynamic mechanistic details of the MTH process over the H-ZSM-5 catalyst at 400 °C, based on the dual-cycle mechanism and HCP in this medium-pore zeolite. Application of switching sequences of ¹³C-labeled and unlabeled methanol pulses over a model H-ZSM-5 catalyst combined with on-line MS analysis and a recently reported technique called “fast scanning-pulse GC analysis” provides a direct and quantitative insight into the MTH reactions under quasi-steady-state conditions. The transient product responses showed the almost instant formation of hydrocarbons upon a small pulse of methanol, followed by secondary formation of light aromatics via HCP decomposition and olefin alkylation-dealkylation, especially in a long catalyst bed when methanol is quickly consumed in the initial reaction zone in the catalyst bed. The isotopic analysis of typical aliphatic C₃₊ product responses after switching ¹³C-methanol pulses to the unlabeled methanol pulses showed a fast isotope scrambling in the formation of C₃₊ species. MS analysis of the light aromatics indicates a complete consecutive but slower isotope incorporation process of ¹²C into ¹³C-aromatics. Results provide direct experimental confirmation of the kinetically preferred olefin-based cycle over the aromatic-based cycle. The sequential isotopic incorporation strongly suggests that the paring reaction pathway through aromatic ring contraction and re-expansion steps is operative. In the appearance of aromatics upon pulsing methanol over larger catalyst beds, four processes are directly discerned, involving the displacement of adsorbed species by formed water, isotope incorporation yielding directly labeled and unlabeled products through the paring mechanism and direct aromatization, and HCP conversion through secondary reactions.

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Rational plastic recycling is critical for addressing the environmental challenges associated with plastic waste. Among the various recycling methods, chemical recycling, particularly via homogeneous catalysis, holds promise for converting plastic waste into valuable products. Post-consumer polymer wastes could present a challenge for catalytic upcycling due to the structural inhomogeneity and functionalization of the polyolefin chains. The impact of substrate aging on the performance of the upcycling catalyst can be viewed as an “inverse problem” of heterogeneous catalysis and has not received sufficient attention in mechanistic studies on this subject. Herein, we present a density functional theory study on the dehydrogenative upcycling of polyethylene (PE) with different in-chain impurities, representing the chemistry of post-consumption PE wastes. We selected the (^tBu4POCOP)-Ir pincer complex catalyzed dehydrogenation of PE as our model reaction. The calculations reveal that common in-chain impurities found in PE, such as carbonyl, hydroxyl, epoxides, and chlorine atoms, inhibit the overall catalyst performance. These impurities form stable molecular complexes with the catalyst, leading to a substantial increase in the energy barriers of the initial reaction step, the C-H bond addition. We also observe that the reaction on the ideal crystalline PE is also impeded. However, highly distorted PE chains exhibit greater susceptibility toward the (^tBu4POCOP)-Ir catalyst. Our mechanistic studies demonstrated that the reaction on the side alkane chains is kinetically favorable compared with the reaction on the PE backbone. The study highlights the critical role of in-chain heterogenieties in the catalytic activation of polymer chains and provides valuable insights into the development of effective technologies for upcycling plastic waste.

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