Mo/ZSM-5 is one of the most studied and efficient catalysts for the dehydroaromatization of methane (MDA), but the mechanism of its operation remains controversial. Here, we combine an ab initio thermodynamic analysis with a comprehensive mechanistic density functional theory study to address Mo-speciation in the zeolite and identify the active sites under the reaction conditions. We show that the exposure of Mo/ZSM-5 to the MDA conditions yields a range of reduced sites including mono- and binuclear Mo-oxo and Mo-carbide complexes. These sites can catalyze the MDA reaction via two alternative reaction channels, namely, the C-C coupling (ethylene) and the hydrocarbon-pool propagation mechanisms. Our calculations point toward the binuclear Mo-carbide species operating through the hydrocarbon-pool mechanism to be the most catalytically potent species. Although all other Mo sites in the activated catalyst can promote C-H activation in methane, they fail to provide a successful path to the desirable low-molecular-weight products.@en

α-Ga2O3, β-Ga2O3, and I -Ga2O3 as well as the silica-supported catalysts I -Ga2O3/SiO2, β-Ga2O3/SiO2, and Ga(NO3)3-derived Ga/SiO2 were prepared, characterized, and evaluated for propane dehydrogenation (PDH) at 550 °C. The coordination environment and acidity of surface sites in stand-alone and SiO2-supported Ga2O3 catalysts were studied using FTIR, 15N dynamic nuclear polarization surface-enhanced NMR spectroscopy (15N DNP SENS), and DFT modeling of the adsorbed pyridine probe molecule. The spectroscopic data suggest that the Lewis acidic surface Ga sites in I -Ga2O3 and β-Ga2O3 (the latter obtained from colloidal nanocrystals of I -Ga2O3 via thermal treatment at 750 °C) are similar, except that β-Ga2O3 contains a larger relative fraction of weak Ga3+ Lewis acid sites. In contrast, α-Ga2O3 features mostly strong Lewis acid sites. This difference in surface sites parallels their difference in catalytic activities: I.e., weak Lewis acid surface sites are more abundant in β-Ga2O3 relative to α-Ga2O3 and I -Ga2O3 and the increased relative abundance of weak Lewis acidity correlates with a higher initial catalytic activity in PDH, 0.41 > 0.28 > 0.14 mmol C3H6 m-2 (Ga2O3) h-1 at 550 °C, for respectively β-, α-, and I -Ga2O3 with initial propene selectivities of 86, 83, and 88%. Dispersion of I -Ga2O3 or β-Ga2O3 on a silica support introduces strong as well as abundant weak Brønsted acidity to the catalysts, lowering the PDH selectivity. The I -Ga2O3/SiO2 catalyst was slightly more active than β-Ga2O3/SiO2 in PDH (Ga normalized activity) with initial propene formation rates of 11 and 9 mol C3H6 mol Ga-1 h-1 (sel = 76 and 73%, respectively). However, these catalysts deactivated by ca. 55% within 100 min time on stream (TOS) due to coking. In contrast, Ga/SiO2, with mostly tetracoordinated surface Ga sites and abundant, strong Brønsted acid sites, gave a lower activity and selectivity in PDH (3.5 mol C3H6 mol Ga-1 h-1 and 49%, respectively) but showed no deactivation with TOS. DFT calculations using a fully dehydroxylated oxygen-deficient model β-Ga2O3 surface show that tetra- A nd pentacoordinated Ga Lewis acid sites bind pyridine more strongly than tricoordinated Ga sites and a higher relative fraction of strong Lewis acid sites correlates with increased coking. Overall, our results indicate that weakly Lewis acidic, tricoordinated Ga3+ sites are likely driving the superior PDH activity of β-Ga2O3.@en

α-Ga2O3, β-Ga2O3, and I -Ga2O3 as well as the silica-supported catalysts I -Ga2O3/SiO2, β-Ga2O3/SiO2, and Ga(NO3)3-derived Ga/SiO2 were prepared, characterized, and evaluated for propane dehydrogenation (PDH) at 550 °C. The coordination environment and acidity of surface sites in stand-alone and SiO2-supported Ga2O3 catalysts were studied using FTIR, 15N dynamic nuclear polarization surface-enhanced NMR spectroscopy (15N DNP SENS), and DFT modeling of the adsorbed pyridine probe molecule. The spectroscopic data suggest that the Lewis acidic surface Ga sites in I -Ga2O3 and β-Ga2O3 (the latter obtained from colloidal nanocrystals of I -Ga2O3 via thermal treatment at 750 °C) are similar, except that β-Ga2O3 contains a larger relative fraction of weak Ga3+ Lewis acid sites. In contrast, α-Ga2O3 features mostly strong Lewis acid sites. This difference in surface sites parallels their difference in catalytic activities: I.e., weak Lewis acid surface sites are more abundant in β-Ga2O3 relative to α-Ga2O3 and I -Ga2O3 and the increased relative abundance of weak Lewis acidity correlates with a higher initial catalytic activity in PDH, 0.41 > 0.28 > 0.14 mmol C3H6 m-2 (Ga2O3) h-1 at 550 °C, for respectively β-, α-, and I -Ga2O3 with initial propene selectivities of 86, 83, and 88%. Dispersion of I -Ga2O3 or β-Ga2O3 on a silica support introduces strong as well as abundant weak Brønsted acidity to the catalysts, lowering the PDH selectivity. The I -Ga2O3/SiO2 catalyst was slightly more active than β-Ga2O3/SiO2 in PDH (Ga normalized activity) with initial propene formation rates of 11 and 9 mol C3H6 mol Ga-1 h-1 (sel = 76 and 73%, respectively). However, these catalysts deactivated by ca. 55% within 100 min time on stream (TOS) due to coking. In contrast, Ga/SiO2, with mostly tetracoordinated surface Ga sites and abundant, strong Brønsted acid sites, gave a lower activity and selectivity in PDH (3.5 mol C3H6 mol Ga-1 h-1 and 49%, respectively) but showed no deactivation with TOS. DFT calculations using a fully dehydroxylated oxygen-deficient model β-Ga2O3 surface show that tetra- A nd pentacoordinated Ga Lewis acid sites bind pyridine more strongly than tricoordinated Ga sites and a higher relative fraction of strong Lewis acid sites correlates with increased coking. Overall, our results indicate that weakly Lewis acidic, tricoordinated Ga3+ sites are likely driving the superior PDH activity of β-Ga2O3.@en

α-Ga2O3, β-Ga2O3, and I -Ga2O3 as well as the silica-supported catalysts I -Ga2O3/SiO2, β-Ga2O3/SiO2, and Ga(NO3)3-derived Ga/SiO2 were prepared, characterized, and evaluated for propane dehydrogenation (PDH) at 550 °C. The coordination environment and acidity of surface sites in stand-alone and SiO2-supported Ga2O3 catalysts were studied using FTIR, 15N dynamic nuclear polarization surface-enhanced NMR spectroscopy (15N DNP SENS), and DFT modeling of the adsorbed pyridine probe molecule. The spectroscopic data suggest that the Lewis acidic surface Ga sites in I -Ga2O3 and β-Ga2O3 (the latter obtained from colloidal nanocrystals of I -Ga2O3 via thermal treatment at 750 °C) are similar, except that β-Ga2O3 contains a larger relative fraction of weak Ga3+ Lewis acid sites. In contrast, α-Ga2O3 features mostly strong Lewis acid sites. This difference in surface sites parallels their difference in catalytic activities: I.e., weak Lewis acid surface sites are more abundant in β-Ga2O3 relative to α-Ga2O3 and I -Ga2O3 and the increased relative abundance of weak Lewis acidity correlates with a higher initial catalytic activity in PDH, 0.41 > 0.28 > 0.14 mmol C3H6 m-2 (Ga2O3) h-1 at 550 °C, for respectively β-, α-, and I -Ga2O3 with initial propene selectivities of 86, 83, and 88%. Dispersion of I -Ga2O3 or β-Ga2O3 on a silica support introduces strong as well as abundant weak Brønsted acidity to the catalysts, lowering the PDH selectivity. The I -Ga2O3/SiO2 catalyst was slightly more active than β-Ga2O3/SiO2 in PDH (Ga normalized activity) with initial propene formation rates of 11 and 9 mol C3H6 mol Ga-1 h-1 (sel = 76 and 73%, respectively). However, these catalysts deactivated by ca. 55% within 100 min time on stream (TOS) due to coking. In contrast, Ga/SiO2, with mostly tetracoordinated surface Ga sites and abundant, strong Brønsted acid sites, gave a lower activity and selectivity in PDH (3.5 mol C3H6 mol Ga-1 h-1 and 49%, respectively) but showed no deactivation with TOS. DFT calculations using a fully dehydroxylated oxygen-deficient model β-Ga2O3 surface show that tetra- A nd pentacoordinated Ga Lewis acid sites bind pyridine more strongly than tricoordinated Ga sites and a higher relative fraction of strong Lewis acid sites correlates with increased coking. Overall, our results indicate that weakly Lewis acidic, tricoordinated Ga3+ sites are likely driving the superior PDH activity of β-Ga2O3.@en

α-Ga2O3, β-Ga2O3, and I -Ga2O3 as well as the silica-supported catalysts I -Ga2O3/SiO2, β-Ga2O3/SiO2, and Ga(NO3)3-derived Ga/SiO2 were prepared, characterized, and evaluated for propane dehydrogenation (PDH) at 550 °C. The coordination environment and acidity of surface sites in stand-alone and SiO2-supported Ga2O3 catalysts were studied using FTIR, 15N dynamic nuclear polarization surface-enhanced NMR spectroscopy (15N DNP SENS), and DFT modeling of the adsorbed pyridine probe molecule. The spectroscopic data suggest that the Lewis acidic surface Ga sites in I -Ga2O3 and β-Ga2O3 (the latter obtained from colloidal nanocrystals of I -Ga2O3 via thermal treatment at 750 °C) are similar, except that β-Ga2O3 contains a larger relative fraction of weak Ga3+ Lewis acid sites. In contrast, α-Ga2O3 features mostly strong Lewis acid sites. This difference in surface sites parallels their difference in catalytic activities: I.e., weak Lewis acid surface sites are more abundant in β-Ga2O3 relative to α-Ga2O3 and I -Ga2O3 and the increased relative abundance of weak Lewis acidity correlates with a higher initial catalytic activity in PDH, 0.41 > 0.28 > 0.14 mmol C3H6 m-2 (Ga2O3) h-1 at 550 °C, for respectively β-, α-, and I -Ga2O3 with initial propene selectivities of 86, 83, and 88%. Dispersion of I -Ga2O3 or β-Ga2O3 on a silica support introduces strong as well as abundant weak Brønsted acidity to the catalysts, lowering the PDH selectivity. The I -Ga2O3/SiO2 catalyst was slightly more active than β-Ga2O3/SiO2 in PDH (Ga normalized activity) with initial propene formation rates of 11 and 9 mol C3H6 mol Ga-1 h-1 (sel = 76 and 73%, respectively). However, these catalysts deactivated by ca. 55% within 100 min time on stream (TOS) due to coking. In contrast, Ga/SiO2, with mostly tetracoordinated surface Ga sites and abundant, strong Brønsted acid sites, gave a lower activity and selectivity in PDH (3.5 mol C3H6 mol Ga-1 h-1 and 49%, respectively) but showed no deactivation with TOS. DFT calculations using a fully dehydroxylated oxygen-deficient model β-Ga2O3 surface show that tetra- A nd pentacoordinated Ga Lewis acid sites bind pyridine more strongly than tricoordinated Ga sites and a higher relative fraction of strong Lewis acid sites correlates with increased coking. Overall, our results indicate that weakly Lewis acidic, tricoordinated Ga3+ sites are likely driving the superior PDH activity of β-Ga2O3.@en

α-Ga2O3, β-Ga2O3, and I -Ga2O3 as well as the silica-supported catalysts I -Ga2O3/SiO2, β-Ga2O3/SiO2, and Ga(NO3)3-derived Ga/SiO2 were prepared, characterized, and evaluated for propane dehydrogenation (PDH) at 550 °C. The coordination environment and acidity of surface sites in stand-alone and SiO2-supported Ga2O3 catalysts were studied using FTIR, 15N dynamic nuclear polarization surface-enhanced NMR spectroscopy (15N DNP SENS), and DFT modeling of the adsorbed pyridine probe molecule. The spectroscopic data suggest that the Lewis acidic surface Ga sites in I -Ga2O3 and β-Ga2O3 (the latter obtained from colloidal nanocrystals of I -Ga2O3 via thermal treatment at 750 °C) are similar, except that β-Ga2O3 contains a larger relative fraction of weak Ga3+ Lewis acid sites. In contrast, α-Ga2O3 features mostly strong Lewis acid sites. This difference in surface sites parallels their difference in catalytic activities: I.e., weak Lewis acid surface sites are more abundant in β-Ga2O3 relative to α-Ga2O3 and I -Ga2O3 and the increased relative abundance of weak Lewis acidity correlates with a higher initial catalytic activity in PDH, 0.41 > 0.28 > 0.14 mmol C3H6 m-2 (Ga2O3) h-1 at 550 °C, for respectively β-, α-, and I -Ga2O3 with initial propene selectivities of 86, 83, and 88%. Dispersion of I -Ga2O3 or β-Ga2O3 on a silica support introduces strong as well as abundant weak Brønsted acidity to the catalysts, lowering the PDH selectivity. The I -Ga2O3/SiO2 catalyst was slightly more active than β-Ga2O3/SiO2 in PDH (Ga normalized activity) with initial propene formation rates of 11 and 9 mol C3H6 mol Ga-1 h-1 (sel = 76 and 73%, respectively). However, these catalysts deactivated by ca. 55% within 100 min time on stream (TOS) due to coking. In contrast, Ga/SiO2, with mostly tetracoordinated surface Ga sites and abundant, strong Brønsted acid sites, gave a lower activity and selectivity in PDH (3.5 mol C3H6 mol Ga-1 h-1 and 49%, respectively) but showed no deactivation with TOS. DFT calculations using a fully dehydroxylated oxygen-deficient model β-Ga2O3 surface show that tetra- A nd pentacoordinated Ga Lewis acid sites bind pyridine more strongly than tricoordinated Ga sites and a higher relative fraction of strong Lewis acid sites correlates with increased coking. Overall, our results indicate that weakly Lewis acidic, tricoordinated Ga3+ sites are likely driving the superior PDH activity of β-Ga2O3.@en

Computational chemistry provides a versatile toolbox for studying mechanistic details of catalytic reactions and holds promise to deliver practical strategies to enable the rational in silico catalyst design. The versatile reactivity and nontrivial electronic structure effects, common for systems based on 3d transition metals, introduce additional complexity that may represent a particular challenge to the standard computational strategies. In this review, we discuss the challenges and capabilities of modern electronic structure methods for studying the reaction mechanisms promoted by 3d transition metal molecular catalysts. Particular focus will be placed on the ways of addressing the multiconfigurational problem in electronic structure calculations and the role of expert bias in the practical utilization of the available methods. The development of density functionals designed to address transition metals is also discussed. Special emphasis is placed on the methods that account for solvation effects and the multicomponent nature of practical catalytic systems. This is followed by an overview of recent computational studies addressing the mechanistic complexity of catalytic processes by molecular catalysts based on 3d metals. Cases that involve noninnocent ligands, multicomponent reaction systems, metal-ligand and metal-metal cooperativity, as well as modeling complex catalytic systems such as metal-organic frameworks are presented. Conventionally, computational studies on catalytic mechanisms are heavily dependent on the chemical intuition and expert input of the researcher. Recent developments in advanced automated methods for reaction path analysis hold promise for eliminating such human-bias from computational catalysis studies. A brief overview of these approaches is presented in the final section of the review. The paper is closed with general concluding remarks.@en

Three γ/β-Ga2O3 nanoparticle catalysts that differ in the relative ratio of γ-Ga2O3 to β-Ga2O3 were prepared to evaluate the effect of H2 treatment (500 °C, 2 h) on the coordination environment of bulk and surface Ga sites, Lewis acidity and catalytic activity in propane dehydrogenation (PDH). Independent of the H2 treatment, the initial PDH activity of the γ/β-Ga2O3 catalysts increases with the fraction of the β-Ga2O3 phase. This is explained by the presence of weak Lewis acid sites (LAS) in β-Ga2O3 while such sites are absent in γ-Ga2O3. Treatment with H2 increases the catalytic activity of all three γ/β-Ga2O3 catalysts but for different reasons. For catalysts with higher fractions of β-Ga2O3, H2 treatment increases further the relative abundance of weak LAS, likely by generating coordinatively unsaturated Ga sites (such as tricoordinated Ga sites nearby oxygen vacancies). In contrast, H2 treatment of a catalyst containing a predominant fraction of γ-Ga2O3 phase induces disorder in the sub-surface structure of the nanoparticle, that is, it forms gallium and oxygen vacancies in the bulk and favors migration of gallium, and likely also of oxygen, to the surface. This induces a surface reconstruction that notably increases the fraction of strong LAS (and proportionally decreases the fraction of medium LAS), while creating no weak LAS in γ-Ga2O3-H2. Therefore, the increase in the catalytic activity of H2-treated γ-Ga2O3 is explained by the higher density of surface Ga sites in γ-Ga2O3-H2 relative to calcined γ-Ga2O3. H2-treated catalysts that contain a higher relative amount of weak LAS also feature a higher relative abundance of gallium hydride species associated with a low frequency FTIR band at ca. 1931–1939 cm−1, that is, weak LAS likely give weakly-bound hydrides in β-Ga2O3. Our results highlight that weak LAS in unsupported Ga2O3 catalysts are more active in PDH than mild or strong LAS.@en

The reaction mechanism of ester hydrogenation catalyzed by a bidentate aminophosphine ligated manganese catalyst was studied by DFT calculations. Particular emphasize was placed on the role of the alkoxide base additives. The presence of such basic promoters as KOtBu can improve the catalyst activity by lowering the activation barriers of H2 dissociation as well as the hydrogenation step. The promoting effect of KOtBu on H2 activation is much stronger than that of tert-butoxides with other alkali metals, which is crucial for the catalyst regeneration from the deactivated Mn-alkoxide species in the resting state.@en

Structural heterogeneity defines the properties of many functional polymers and it is often crucial for their performance and ability to withstand mechanical impact. Such heterogeneity, however, poses a tremendous challenge for characterization of these materials and limits our ability to design them rationally. Herein we present a practical methodology capable of resolving the complex mechanical behavior and tracking mechanical impact in discrete phases of segmented polyurethane—a typical example of a structurally complex polymer. Using direct optical imaging of photoluminescence produced by a small-molecule organometallic mechano-responsive sensor we observe in real time how polymer phases dissipate energy, restructure, and breakdown upon mechanical impact. Owing to its simplicity and robustness, this method has potential in describing the evolution of complex soft-matter systems for which global characterization techniques fall short of providing molecular-level insight.@en

Embryonic X-ray amorphous semi-formed MFI-type zeolite units mixed with the Cu–Zn–Al catalyst have been used for the direct synthesis of dimethyl ether (DME) from syngas. The hybrid catalyst with embryonic zeolite (EZ) with the particle size of 5 nm has demonstrated superior performance in terms of activity, selectivity, and stability compared to the crystalline ZSM-5 zeolite counterpart and the amorphous aluminosilicate material. The FTIR pyridine adsorption uncovered several types of active sites in EZ, including Brønsted acid sites of medium strength. The DFT modeling pointed out the key role of defect sites leading to lower strength of the acid sites in the embryonic MFI zeolite in comparison with the fully crystalline material. The effect of embryonic zeolite on the DME synthesis has been assigned to enhanced transport of methanol from Cu to ultra-small zeolite precursor units with moderate acidity, hence promoting the efficient dehydration to DME with high selectivity and stability.@en

The catalytic asymmetric transfer hydrogenation (ATH) of ketones is a powerful methodology for the practical and efficient installation of chiral centers. Herein, we describe the synthesis, characterization, and catalytic application of a series of manganese complexes bearing simple chiral diamine ligands. We performed an extensive experimental and computational mechanistic study and present the first detailed experimental kinetic study of Mn-catalyzed ATH. We demonstrate that conventional mechanistic approaches toward catalyst optimization fail and how apparently different precatalysts lead to identical intermediates and thus catalytic performance. Ultimately, the Mn-N,N complexes under study enable quantitative ATH of acetophenones to the corresponding chiral alcohols with 75-87% ee.@en

The Brønsted acidity of synthetic mica-montmorillonite (SMM) clay was studied by periodic DFT calculations. Different structural models were compared to determine the Brønsted acidity of protons of the SMM clay based on (i) isomorphous substitution of Si4+ by Al3+ in the tetrahedral silicate layer and additional NiF-doping (ii) in the platelets and (iii) at the edge terminations of the clay platelets. The acid strength was judged from the computed adsorption energies of ammonia and pyridine. The SMM acidity is mainly determined by the composition of the clay platelets. The strongest acidity is found in structures in which octahedral [AlO]+ is replaced by [NiF]+ adjacent to tetrahedral [Si-(OH)-Al] moieties in the tetrahedral layer. For the Brønsted acid sites in the interlayer of SMM, modification with either Ni2+ or F- in the octahedral layers has only a minor influence on the acidity. Our data indicate that Brønsted acid sites, properly modified in the second coordination shell by electron-withdrawing F, in the interlayer and at defect sites at the edges of clay platelets (intralayer sites) can contribute to the enhanced acidity in NiF-modified SMM. Although the predicted acidity of SMM by ammonia adsorption is higher than that of faujasite zeolite, the reactivity judged from propene protonation demonstrates that zeolites are more reactive than clays. This difference seems to be the result of the curved nature of the micropores of zeolites, which stabilizes the transition states for an acid-catalyzed reaction more than flat surfaces of clays do.@en

Transition metal-zeolite composites are versatile catalytic materials for a wide range of industrial and lab-scale processes. Significant advances in fabrication and characterization of well-defined metal centers confined in zeolite matrixes have greatly expanded the library of available materials and, accordingly, their catalytic utility. In this review, we summarize recent developments in the field from the perspective of materials chemistry, focusing on synthesis, postsynthesis modification, (operando) spectroscopy characterization, and computational modeling of transition metal-zeolite catalysts.@en

The original Fig. 6 presented incorrect thermodynamic data for the conversion 4c + KOtBu → 2 + KOMe. A revised Fig. 6 is now provided. These changes do not affect the article text and its conclusions.@en

An "on water" organocatalytic cyanoarylmethylation of aryl acetonitrile to isatins is developed, giving products in high yields and up to excellent diastereoselectivities. A remarkable enhancement of reaction rates and diastereoselectivities by water was observed under mild conditions. Moreover, this approach provides a highly efficient and environmentally benign access to thermodynamic 3-hydroxy-3-cyanomethyl oxindoles.@en