H2 Activation Research Articles

Distinct Site Motifs Activate O2 and H2 on Supported Au Nanoparticles in Liquid Water.

Au nanoparticles catalyze the activation and conversion of small molecules with rates and kinetic barriers that depend on the dimensions of the nanoparticle, composition of the support, and presence of catalytically culpable water molecules that solvate these interfaces. Here, molecular interpretations of steady-state rate measurements, kinetic isotope effects, and structural characterizations reveal how the interface of Au nanoparticles, liquid water, and metal oxide supports mediate the kinetically relevant activation of H2 and sequential reduction of O2-derived intermediates during the formation of H2O2 and H2O. Rates of H2 consumption are 10-100 fold greater on Au nanoparticles supported on metal oxides (e.g., titania) compared to more inert and hydrophobic materials (carbon, boron nitride). Similarly, Au nanoparticles on reducible and Lewis acidic supports (e.g., lanthana) bind dioxygen intermediates more strongly and present lower barriers (<22 kJ mol-1) for O-O bond dissociation than inert interfaces formed with silica (>70 kJ mol-1). Selectivities for H2O2 formation increase significantly as the diameters of the Au nanoparticles increase because differences in nanoparticle size change the relative fractions of exposed sites that exist at Au-support interfaces. In contrast, site-normalized rates and barriers for H2 activation depend weakly on the size of Au nanoparticles and the associated differences in active site motifs. These findings suggest that H2O aids the activation of H2 at sites present across all surface Au atoms when nanoparticles are solvated by water. However, molecular O2 preferentially binds and dissociates at Au-support interfaces, leading to greater structure sensitivity for barriers of O-O dissociation across different support identities and sizes of Au nanoparticles. These insights differ from prior knowledge from studies of gas-phase reactions of H2 and O2 upon Au nanoparticle catalysts within dilute vapor pressures of water (10-4 to 0.1 kPa H2O), in which catalysis occurs at the perimeter of the Au-support interface. In contrast, contacting Au catalysts with liquid water (55.5 M H2O) expands catalysis to all surface Au atoms and enables appreciable H2O2 formation.

Selectivity Control by Relay Catalysis in CO and CO2 Hydrogenation to Multicarbon Compounds.

ConspectusThe hydrogenative conversion of both CO and CO2 into high-value multicarbon (C2+) compounds, such as olefins, aromatic hydrocarbons, ethanol, and liquid fuels, has attracted much recent attention. The hydrogenation of CO is related to the chemical utilization of various carbon resources including shale gas, biomass, coal, and carbon-containing wastes via syngas (a mixture of H2 and CO), while the hydrogenation of CO2 by green H2 to chemicals and liquid fuels would contribute to recycling CO2 for carbon neutrality. The state-of-the-art technologies for the hydrogenation of CO/CO2 to C2+ compounds primarily rely on a direct route via Fischer-Tropsch (FT) synthesis and an indirect route via two methanol-mediated processes, i.e., methanol synthesis from CO/CO2 and methanol to C2+ compounds. The direct route would be more energy- and cost-efficient owing to the reduced operation units, but the product selectivity of the direct route via FT synthesis is limited by the Anderson-Schulz-Flory (ASF) distribution. Selectivity control for the direct hydrogenation of CO/CO2 to a high-value C2+ compound is one of the most challenging goals in the field of C1 chemistry, i.e., chemistry for the transformation of one-carbon (C1) molecules.We have developed a relay-catalysis strategy to solve the selectivity challenge arising from the complicated reaction network in the hydrogenation of CO/CO2 to C2+ compounds involving multiple intermediates and reaction channels, which inevitably lead to side reactions and byproducts over a conventional heterogeneous catalyst. The core of relay catalysis is to design a single tandem-reaction channel, which can direct the reaction to the target product controllably, by choosing appropriate intermediates (or intermediate products) and reaction steps connecting these intermediates, and arranging optimized yet matched catalysts to implement these steps like a relay. This Account showcases representative relay-catalysis systems developed by our group in the past decade for the synthesis of liquid fuels, lower (C2-C4) olefins, aromatics, and C2+ oxygenates from CO/CO2 with selectivity breaking the limitation of conventional catalysts. These relay systems are typically composed of a metal or metal oxide for CO/CO2/H2 activation and a zeolite for C-C coupling or reconstruction, as well as a third or even a fourth catalyst component with other functions if necessary. The mechanisms for the activation of H2 and CO/CO2 on metal oxides, which are distinct from that on the conventional transition or noble metal surfaces, are discussed with emphasis on the role of oxygen vacancies. Zeolites catalyze the conversion of intermediates (including hydrocracking/isomerization of heavier hydrocarbons, methanol-to-hydrocarbon reactions, and carbonylation of methanol/dimethyl ether) in the relay system, and the selectivity is mainly controlled by the Brønsted acidity and the shape-selectivity or the confinement effect of zeolites. We demonstrate that the thermodynamic/kinetic matching of the relay steps, the proximity and spatial arrangement of the catalyst components, and the transportation of intermediates/products in sequence are the key issues guiding the selection of each catalyst component and the construction of an efficient relay-catalysis system. Our methodology would also be useful for the transformation of other C1 molecules via controlled C-C coupling, inspiring more efforts toward precision catalysis.

Unveiling the Structure-Property Relationship of MgO-Supported Ni Ammonia Decomposition Catalysts from Bulk to Atomic Structure by In Situ/Operando Studies.

Ammonia is currently being studied intensively as a hydrogen carrier in the context of the energy transition. The endothermic decomposition reaction requires the use of suitable catalysts. In this study, transition metal Ni on MgO as a support is investigated with respect to its catalytic properties. The synthesis method and the type of activation process contribute significantly to the catalytic properties. Both methods, coprecipitation (CP) and wet impregnation (WI), lead to the formation of Mg1-xNixO solid solutions as catalyst precursors. X-ray absorption studies reveal that CP leads to a more homogeneous distribution of Ni2+ cations in the solid solution, which is advantageous for a homogeneous distribution of active Ni catalysts on the MgO support. Activation in hydrogen at 900 °C reduces nickel, which migrates to the support surface and forms metal nanoparticles between 6 nm (CP) and 9 nm (WI), as shown by ex situ STEM. Due to the homogeneously distributed Ni2+ cations in the solid solution structure, CP samples are more difficult to activate and require harsher conditions to reduce the Ni. The combination of in situ X-ray diffraction (XRD) and operando total scattering experiments allows a structure-property investigation of the bulk down to the atomic level during the catalytic reaction. Activation in H2 at 900 °C for 2 h leads to the formation of large Ni particles (20-30 nm) for the samples synthesized by the WI method, whereas Ni stays significantly smaller for the CP samples (10-20 nm). Sintering has a negative influence on the catalytic conversion of the WI samples, which is significantly lower compared to the conversion observed for the CP samples. Interestingly, metallic Ni redisperses during cooling and becomes invisible for conventional XRD but can still be detected by total scattering methods. The conditions of activation in NH3 at 650 °C are not suitable to form enough reduced Ni nanoparticles from the solid solution and are, therefore, not a suitable activation procedure. The activity steadily increases in the samples activated at 650 °C in NH3 (Group 1) compared to the samples activated at 650 °C in H2 and then reaches the best activity in the samples activated at 900 °C in H2. Only the combination of complementary in situ and ex situ characterization methods provides enough information to identify important structure-property relationships among these promising ammonia decomposition catalysts.

Structure–activity relationships over Ru/NiAl2O4 catalysts in anisole demethoxylation: spectroscopic and kinetic studies

Demethoxylation was kinetically and spectroscopically studied over three catalysts with different Ru0/Ruδ+ ratios. In-situ spectroscopic tests demonstrated that the synergy between Ru0 and Ruδ+ was crucial, and Ru0 was in charge of H2 activation and adsorption of aromatic ring while Ruδ+ adsorbed with O in methoxyl. A Langmuir–Hinshelwood kinetic model was proposed, and ratio of Ru0/Ruδ+ was the key in deciding the rate-determining step (RDS): i) desorption of toluene was RDS over catalyst with high Ru0 ratio; ii) dissociation of H2 was RDS over Ruδ+ enriched catalyst; iii) demethoxylation was rate-determined by CO water–gas shift (WGS) when Ru0/Ruδ+ approached ~ 1. The best performance was obtained over Ru/NiAl2O4-200, which effectively enabled both C-O bond activation and rapid recovery of adsorption sites for aromatic rings. Finally, in-situ DRIFT studies on methoxy decomposition and CO-WGS unraveled that the electronic composition of Ru was more stable in Ru/NiAl2O4-200 which contributes to its excellence.

Regulation of Ni valence state and synergistic effects of supports in the hydrodeoxygenation of lignin-derived vanillin using pseudoboehmite-supported Ni catalysts

ABSTRACT Preparing 2-methoxy-4-methylphenol (MMP) through the vanillin (VAN) route is a crucial step in the high-value utilization of lignin (VTM). In this study, a series of Ni/PB catalysts were synthesized using pseudoboehmite (PB) as a carrier. Changes in the valence states of Ni were induced through H2 activation, while the impacts of reaction temperature, initial pressure, and catalyst addition were investigated based on the VTM process. The results revealed that PB exhibited a distinct mesoporous structure (average pore size of 5.8 nm), with Ni loaded in small particles size (3.88 nm). Ni species on the catalyst existed in a + 2-valence state, undergoing a change after H2 activation, with an increase in Ni0 promoting enhanced activity. The Ni/PB-450 catalyst exhibited excellent activity at 250°C for 3 hours (VAN conversion and MMP selectivity > 99%), and the catalyst demonstrated good durability, maintaining 99.1% VAN conversion and 80% MMP selectivity after two cycles. Combining the characterization and experimental results, the etherification and hydrogenation of VAN were identified as the primary reaction pathways. This study aimed to provide a new avenue for the high-value utilization of lignin and its derivatives through controlled catalyst preparation.

CO2 hydrogenation to methanol over the copper promoted In2O3 catalyst

The metal promoted In2O3 catalysts for CO2 hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity. However, there was still no experimental confirmation if copper could be a good promoter for In2O3. Herein, the Cu promoted In2O3 catalyst was prepared using a deposition-precipitation method. Such prepared Cu/In2O3 catalyst shows significantly higher CO2 conversion and space time yield (STY) of methanol, compared to the un-promoted In2O3 catalyst. The loading of Cu facilitates the activation of both H2 and CO2 with the interface between the Cu cluster and defective In2O3 as the active site. The Cu/In2O3 catalyst takes the CO hydrogenation pathway for methanol synthesis from CO2 hydrogenation. It exhibits a unique size effect on the CO adsorption. At temperatures below 250 °C, CO adsorption on Cu/In2O3 is stronger than that on In2O3, causing higher methanol selectivity. With increasing temperatures, the Cu catalyst aggregates, which leads to the formation of weak CO adsorption site and causes a decrease in the methanol selectivity. Compared with other metal promoted In2O3 catalysts, it can be concluded that the catalyst with stronger CO adsorption possesses higher methanol selectivity.

Heterolytic H2 Activation in Heterogeneous Hydrogenation/Hydroprocessing Catalysis

AbstractIn heterogeneous catalysis, heterolytic H2 activation for (selective) hydrogenation and hydroprocessing reactions involves the dissociation of adsorbed H2 molecules into proton (Hδ+) and hydride (Hδ−) on the catalyst surface. This approach offers several advantages, including high selectivity for polar bond (s), a low energy barrier for H2 dissociation, a high capacity for reaction‐favorable H2 adsorption, and reduced catalyst poisoning. This requires the construction of frustrated Lewis pairs on the catalyst surface, satisfying specific criteria, such as having an abundant quantity of Lewis pairs with steric hindrance and maintaining a certain distance of 3–5 Å between the pairs. This review highlights intrinsic catalyst properties for heterolytic H2 activation based on state‐of‐the‐art reports. The main components necessary for this activation include supports with strong basic sites and/or oxygen vacancies, and/or metals of single atom. For this purpose, designed catalytic materials aim to strengthen the Lewis acidity and basicity, improve the polarization of Lewis pairs, enrich oxygen vacancies, maximize the interfacial area between metal species and Lewis base, and enhance metal–support interaction. Therefore, heterogeneous catalysts retaining such heterolytic H2 activation characteristics will be significantly effective in various hydrogenation and hydroprocessing reactions.

Zonal activation of molecular carbon dioxide and hydrogen over dual sites Ni-Co-MgO catalyst for CO2 methanation: Synergistic catalysis of Ni and Co species

An in-depth mechanism in zonal activation of CO2 and H2 molecular over dual-active sites has not been revealed yet. Here, Ni-Co-MgO was rationally constructed to elucidate the CO2 methanation mechanism. The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt. Notably, electron-enriched Coδ− species participated in efficient chemisorption and activation of CO2 to generate monodentate carbonate. Simultaneously, plentiful available Ni0 sites facilitated H2 dissociation, thus CO2 and H2 were smoothly activated at zones of Coδ− species and Ni0, respectively. Detailed in situ DRIFTS, quasi situ XPS, TPSR, and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ− species and Ni0. The zonal activation of CO2 and H2 by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.

MoOx regulating Ni-based catalyst anchored on N-doped carbon microspheres for catalytic hydrogenation of nitroarenes

Reasonable modification of Ni-based catalysts is crucial for improving their catalytic activity in the nitroarenes hydrogenation but remaining a major challenge. Herein, a MoOx-promoted Ni-based bimetallic catalyst with fine Ni nanoparticles (only about 5.7 nm) anchored on N-doped carbon microspheres (NiMo1@NC-500) was prepared for the first time by a simple one-pot hydrothermal strategy and exhibits excellent catalytic activity for the probe reaction of nitrobenzene hydrogenation. The characterization and DFT calculations results elucidated that Ni and MoO2 sites promoted the activation and adsorption of H2; while the NiNx sites significantly enhanced the adsorption of the reaction substrate nitrobenzene. This synergistic adsorption mode endowed the catalyst with excellent nitrobenzene hydrogenation performance under mild conditions (80 °C, 1 MPa H2, 3 h). Moreover, the as-prepared catalyst exhibited robust stability for no less than 6 cycles and outstanding generality for the hydrogenation of other substituted nitroarenes, which provide a profound insight for the preparation of efficient and economical catalysts for the reduction of nitroarenes.

Hexacoordinated tin complexes catalyse imine hydrogenation with H2.

Frustrated Lewis pair (FLP) hydrogenation catalysts predominantly use alkyl- and aryl-substituted Lewis acids (LA) that offer a limited number of combinations of substituents, limiting our ability to tune their properties and, ultimately, their reactivity. Nevertheless, main-group complexes have numerous ligands available for such purposes, which could enable us to broaden the range of FLP catalysis. Supporting this hypothesis, we demonstrate here that hexacoordinated tin complexes with Schiff base ligands catalyse imine hydrogenation via activation of H2(g). As shown by hydrogen-deuterium scrambling, [Sn(tBu2Salen)(OTf)2] activated H2(g) at 25 °C and 10 bar of H2. After tuning the ligands, we found that [Sn(Salen)Cl2] was the most efficient imine hydrogenation catalyst despite having the lowest activity in H2(g) activation. Moreover, various imines were hydrogenated in yields up to 98% thereby opening up opportunities for developing novel FLP hydrogenation catalysts based on hexacoordinated LA of main-group elements.

Activation of H2 using ansa-aminoboranes: solvent effects, dynamics, and spin hyperpolarization.

Spin hyperpolarization generated upon activation of parahydrogen, the spin-0 isomer of H2, by ansa-aminoboranes (AABs) constitutes a rare but interesting example of applied metal-free catalysis in parahydrogen-induced polarization (PHIP). AAB molecular moieties made of light elements would be useful in important areas of NMR, such as chemosensing and the production of hyperpolarized substances, or generally in NMR sensitivity enhancement. At the same time, little is known about the detailed mechanistic aspects of underlying chemical processes. Herein, we present a joint experimental-computational study of the kinetic and thermodynamic aspects of H2 activation by AABs, for the first time providing molecular-level details and results of PHIP experiments with AABs in various solvents. Specifically, a large number of kinetic and thermodynamic parameters are measured experimentally for H2 activation by 2-aminophenylboranes of variable steric bulkiness of the boryl site. A clear correlation between the experimental and DFT-predicted thermochemical parameters is observed. PHIP effects in toluene, dichloromethane, and acetonitrile are characterized and rationalized based on the use of the kinetic and nuclear spin relaxation parameters. Altogether, the obtained results provide valuable information for the further rational design of efficient AAB catalysts for metal-free PHIP based on frustrated Lewis pair (FLP) chemistry.

New insight into the catalytic mechanism of ester hydrogenation over the Cu/ZnO catalyst: the contribution of hydrogen spillover.

The dimethyl maleate hydrogenation activity of Cu, ZnO-X and physically mixed Cu+ZnO-X samples was systematically investigated to probe the essential role of ZnO in ester hydrogenation processes. Cu samples exhibited high CC bond hydrogenation ability with dimethyl succinate as the main product. Comparatively, ZnO was inactive in hydrogenation due to its weak ability to dissociate hydrogen while the CO group could be activated and adsorbed on the ZnO surface. Interestingly, physical mixing with ZnO significantly improved the CO hydrogenation activity of Cu samples. The H2-TPD results reveal the origin of "Cu-ZnO synergy": hydrogen atoms formed on the copper surface can spill over to the ZnO surface and react with the adsorbed CO group.

Steric control of Mg-Mg bond formation vs. N2 activation in the reduction of bulky magnesium diamide complexes.

Reduction of the magnesium(II) diamide [Mg(TripNON)] (TripNON = 4,5-bis(2,4,6-triisopropylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) with 5% w/w K/KI leads to a good yield of a dianionic dimagnesium(I) species, as its potassium salt, [{K(TripNON)Mg}2]. An X-ray crystallographic analysis shows the molecule to contain a very long Mg-Mg bond (3.137(2) Å). The formation of [{K(TripNON)Mg}2] contrasts with a previously reported reduction of a magnesium(II) complex incorporating a bulkier diamide ligand, which instead afforded a magnesium-dinitrogen complex. In the current study, [{K(TripNON)Mg}2] has been shown to be a viable reagent for the reductive activation of CO, H2 and N2O.

Hollow cubic CuSe@CdS with tunable size for plasmon-induced Vis-NIR driven photocatalytic properties.

The rational design of the dimension and geometry of a plasmonic semiconductor cocatalyst is vitally important for efficient utilization of near-infrared (NIR) light and superior photocatalytic hydrogen generation. Herein, hollow cubic CuSe@CdS composites with different sizes and strong localized surface plasmon resonance (LSPR) were prepared by selenizing size-tunable Cu2O templates and loading CdS nanoparticles. The size of hollow cubic CuSe can affect the surface area and the conduction band potential through the size effect, regulating the carrier behavior of the CuSe@CdS heterojunction. The CuSe@CdS composites show enhanced and wide absorption in the full spectrum due to the LSPR effect of CuSe. Meanwhile, the composites show excellent photocatalytic hydrogen capacity in the full spectrum in a 0.35 M Na2S/0.25 M Na2SO3 sacrificial reagent solution. The best hydrogen production rate of CSCE2 is 1.518 mmol g-1 h-1 (5.54 times higher than that of CdS) under Vis light (780 > λ > 420 nm) irradiation and 0.28 mmol g-1 h-1 under NIR light (λ > 780 nm) illumination. Interestingly, the photocatalytic activity for H2 under Vis-NIR light (λ > 420 nm) is about 3 times (up to 4.45 mmol g-1 h-1) higher than that without NIR light assistance, due to the photothermal effect. Various analyses and DFT calculations demonstrate that the p-n heterojunction formed in the composites consists of p-type CuSe and n-type CdS, which achieves efficient carrier transfer and separation under the synergistic effect of the size effect and the photothermal effect. In addition, the expansion of the photocatalytic performance to the NIR range is mainly due to the "hot-electron" injection mechanism induced by the LSPR effect of CuSe. The reasonable design coupled with the plasmonic materials offers a new path to achieving the highly efficient conversion of solar energy to hydrogen energy.

Frustrated Lewis pairs on pentacoordinated Al3+-enriched Al2O3 promote heterolytic hydrogen activation and hydrogenation.

As an emerging class of metal-free catalysts, frustrated Lewis pairs (FLPs) catalysts have been greatly constructed and applied in many fields. Homogeneous FLPs have witnessed significant development, while limited heterogeneous FLPs catalysts are available. Herein, we report that heterogeneous FLPs on pentacoordinated Al3+-enriched Al2O3 readily promote the heterolytic activation of H2 and thus hydrogenation catalysis. The defect-rich Al2O3 was prepared by simple calcination of a carboxylate-containing Al precursor. Combinatorial studies confirmed the presence of rich FLPs on the surface of the defective Al2O3. In contrast to conventional alumina (γ-Al2O3), the FLP-containing Al2O3 can activate H2 in the absence of any transition metal species. More importantly, H2 was activated by surface FLPs in a heterolytic pathway, leading to the hydrogenation of styrene in a stepwise process. This work paves the way for the exploration of more underlying heterogeneous FLPs catalysts and further understanding of accurate active sites and catalytic mechanisms of heterogeneous FLPs at the molecular level.

Green synthesis of 3D core-shell SnS2/SnS-Cd0.5Zn0.5S multi-heterojunction for efficient photocatalytic H2 evolution.

Low charge carrier separation efficiency is one of the key factors restricting photocatalytic hydrogen evolution performance. It is an effective strategy to build heterojunctions to steer charge migration. Herein, a series of x-SnS2/SnS-Cd0.5Zn0.5S (x-SS-CZS) nanosphere composites with varying mass ratios of SnS2/SnS (SS) were prepared through in situ hydrothermal synthesis. Moreover, XRD, TEM, and XPS were used to characterize the 3D core-shell SS-CZS multi-heterojunction composite. The 5-SS-CZS heterojunction composite with 5 wt% content of SS exhibits a remarkable hydrogen evolution rate of 168.85 mmol g-1 h-1, which is 5.4 times higher than that of pristine twin CZS (31.08 mmol g-1 h-1) and 1.9 times higher than that of 5-SnS2-CZS (88.21 mmol g-1 h-1). Furthermore, the composite catalyst showed excellent photostability after four cycles of reactions under visible light illumination. The apparent quantum yield at λ = 420 nm could reach up to 24.78%. The excellent hydrogen evolution performance of 5-SS-CZS nanospheres is ascribed to the following factors: (1) a core-shell catalyst with broad spectral absorption improves light utilization efficiency, (2) hybrid material with large surface area provides more active sites and shows the highest H2 activity, (3) a multi-heterojunction composite extends the lifetime of photoinduced carriers and accelerates charge separation and migration, and (4) SS as a hole trapping agent enhances the photocatalytic stability performance. This work proposes a possible photocatalytic mechanism, while also providing a novel approach for the synthesis of highly active and stable photocatalysts.

Theoretical study on hydroformylation catalyzed by cationic cobalt(II) complexes.

Hydroformylation is one of the most important homogeneous reactions in industrial production. Herein, a density functional theory (DFT) method was employed to investigate two proposed reaction mechanisms of hydroformylation catalyzed by cationic cobalt(II) complexes, the carbonyl dissociative mechanism and the associative mechanism. The calculated results showed that the heterolytic H2 activation is the rate-determining step for both the dissociative mechanism and the associative mechanism, with energy barriers of 26.8 kcal mol-1 and 40.5 kcal mol-1, respectively. Meanwhile, the regioselectivity, the spin multiplicity of the catalyst and the substituent effects on the reaction were also investigated. The most stable cobalt(II) catalyst has a doublet state and the linear aldehyde is the dominant product. In addition, it was found that the energy barrier of the reaction decreased when the electron density of the Co center of the catalyst was increased by changing the ligand. The catalytic activity of the catalyst was proposed to be the best when the PEt2 group of the ligand is replaced by the P(tBu)2 group. This study might not only provide new insights for hydroformylation catalyzed by cobalt but also facilitate theory-guided design of novel transition metal catalysts for hydroformylation.

Internal Coulombic assistance in intermolecular frustrated Lewis pair activation of dihydrogen

Phosphonium zwitterions promote FLP-type H2 activation with amines or phosphanes with Coulombic assistance by the one-atom bridged silicate side-arm.

Exploring the electronic and steric effects on the dimerization of intramolecular frustrated Lewis pairs: a comparison between aminoboranes and aminoalanes.

The dimerization of intramolecular aminoborane and aminoalane frustrated Lewis pairs was investigated using density functional theory. We systematically varied the substituents to gradually increase their bulkiness, including H, CH3, t-Bu, Ph, and Mes groups. Starting from the most stable conformer of the monomers, a frustrated Lewis pair or classic Lewis adduct, we studied the dimerization process for all systems, revealing significant variations in the Gibbs free energy. Dimerization was favored in four aminoboranes and six aminoalanes, depending on the specific combinations of substituents. Applying an energy decomposition analysis, we found that the preparation energy of the monomers and the non-orbital interactions between them are the primary contributors to the observed energetic differences, showing a clear linear relationship. Additionally, we analyzed the electronic effects by increasing the acidity of the Lewis acid, observing a shift toward endergonic and exergonic directions in aminoboranes and aminoalanes, respectively. This shift was attributed to the stabilization of a classic Lewis adduct. This study underscores three crucial factors influencing dimer formation: (i) substituent size, (ii) stabilization of the classic Lewis adduct conformation, and (iii) covalent radii of the Lewis centers. Understanding these factors is essential for designing FLPs and preventing unwanted dimerization that could affect their catalytic performance in H2 activation processes.

Enhancing CO2 Hydrogenation Using a Heterogeneous Bimetal NiAl-Deposited Metal-Organic Framework NU-1000: Insights from First-Principles Calculations.

The hydrogenation of CO2 to high-value-added liquid fuels is crucial for greenhouse gas emission reduction and optimal utilization of carbon resources. Developing supported heterogeneous catalysts is a key strategy in this context, as they offer well-defined active sites for in-depth mechanistic studies and improved catalyst design. Here, we conducted extensive first-principles calculations to systematically explore the reaction mechanisms for CO2 hydrogenation on a heterogeneous bimetal NiAl-deposited metal-organic framework (MOF) NU-1000 and its catalytic performance as atomically dispersed catalysts for CO2 hydrogenation to formic acid (HCOOH), formaldehyde (H2CO), and methanol (CH3OH). The present results reveal that the presence of the NiAl-oxo cluster deposited on NU-1000 efficiently activates H2, and the facile heterolysis of H2 on Ni and adjacent O sites serves as a precursor to the hydrogenation of CO2 into various C1 products HCOOH, H2CO, and CH3OH. Generally, H2 activation is the rate-determining step in the entire CO2 hydrogenation process, the corresponding relatively low free energy barriers range from 14.5 to 15.9 kcal/mol, and the desorption of products on NiAl-deposited NU-1000 is relatively facile. Although the Al atom does not directly participate in the reaction, its presence provides exposed oxygen sites that facilitate the heterolytic cleavage of H2 and the hydrogenation of C1 intermediates, which plays an important role in enhancing the catalytic activity of the Ni site. The present study demonstrates that the catalytic performance of NU-1000 can be finely tuned by depositing heterometal-oxo clusters, and the porous MOF should be an attractive platform for the construction of atomically dispersed catalysts.