Promoting active site renewal in heterogeneous olefin metathesis catalysts.

As an atom-efficient strategy for the large-scale interconversion of olefins, heterogeneously catalysed olefin metathesis sees commercial applications in the petrochemical, polymer and speciality chemical industries1. Notably, the thermoneutral and highly selective cross-metathesis of ethylene and 2-butenes1 offers an appealing route for the on-purpose production of propylene to address the C3 shortfall caused by using shale gas as a feedstock in steam crackers2,3. However, key mechanistic details have remained ambiguous for decades, hindering process development and adversely affecting economic viability4 relative to other propylene production technologies2,5. Here, from rigorous kinetic measurements and spectroscopic studies of propylene metathesis over model and industrial WOx/SiO2 catalysts, we identify a hitherto unknown dynamic site renewal and decay cycle, mediated by proton transfers involving proximal Brønsted acidic OH groups, which operates concurrently with the classical Chauvin cycle. We show how this cycle can be manipulated using small quantities of promoter olefins to drastically increase steady-state propylene metathesis rates by up to 30-fold at 250 °C with negligible promoter consumption. The increase in activity and considerable reduction of operating temperature requirements were also observed on MoOx/SiO2 catalysts, showing that this strategy is possibly applicable to other reactions and can address major roadblocks associated with industrial metathesis processes.

Acute Physiological and Perceptual Responses to Whole-Body High-Intensity Interval Training Compared with Equipment-Based Interval and Continuous Training.

Low-volume, time-efficient high-intensity interval training (HIIT), which involves whole-body (WB) callisthenics exercises, has gained worldwide popularity in recent years. However, the physiological and perceptual impact of WB-HIIT in comparison to specialised, equipment-based training is relatively less studied. This study compared the acute physiological and perceptual responses to a single session of WB-HIIT, ergometer-based HIIT (ERG-HIIT) and conventional moderate-intensity continuous training (MICT). Fourteen physically inactive adults (age: 28.4 ± 6.5 years, VO2peak: 31.0 ± 6.2 mL· kg-1· min-1) underwent three main trials (WB-HIIT: 12 x 30-s high-intensity callisthenics workout; ERG: HIIT: 12 x 30-s high-intensity cycling bouts; MICT: 30-min cycling at 50% peak power output) in a randomized cross-over order 3-7 days apart. The mean session heart rate (HR) and perceived exertion were comparable across all three protocols (p > 0.05). WB-HIIT attained a similar peak HR (87.4 ± 9.4 %HRmax) as that of ERG-HIIT (83.0 ± 8.6 %HRmax), and significantly greater than that of MICT (78.7 ± 5.5 %HRmax, p = 0.001). However, WB-HIIT induced significantly higher blood lactate levels (7.2 ± 1.8 mmol/L) compared to both ERG-HIIT (5.1 ± 1.3 mmol/L, p < 0.05) and MICT (3.1 ± 1.5 mmol/L, p < 0.001). The participants reported higher self-efficacy and greater enjoyment with WB-HIIT compared to MICT (p < 0.05). The mean HR and perceived exertion responses to WB-HIIT are comparable to those of equipment-based HIIT and MICT; however, WB-HIIT results in greater metabolic strain than both other modalities. Despite this, the overall perceptual responses to WB-HIIT are positive, suggesting that it could be a viable exercise alternative, especially for individuals with limited exercise time and restricted access to facilities and equipment.

Multiple Surface Site Three-Dimensional Structure Determination of a Supported Molecular Catalyst.

The structural characterization of supported molecular catalysts is challenging due to the low density of active sites and the presence of several organic/organometallic surface groups resulting from the often complex surface chemistry associated with support functionalization. Here, we provide a complete atomic-scale description of all surface sites in an N-heterocyclic carbene based on iridium and supported on silica, at all stages of its synthesis. By combining a suitable isotope labeling strategy with the implementation of multinuclear dipolar recoupling DNP-enhanced NMR experiments, the 3D structure of the Ir-NHC sites, as well as that of the synthesis intermediates were determined. As a significant fraction of parent surface fragments does not react during the multistep synthesis, site-selective experiments were implemented to specifically probe proximities between the organometallic groups and the solid support. The NMR-derived structure of the iridium sites points to a well-defined conformation. By interpreting EXAFS spectroscopy and chemical analysis data augmented by computational studies, the presence of two coordination geometries is demonstrated: Ir-NHC fragments coordinated by a 1,5-cyclooctadiene and one Cl ligand, as well as, more surprisingly, a fragment coordinated by two NHC and two Cl ligands. This study demonstrates a unique methodology to disclose individual surface structures in complex, multisite environments, a long-standing challenge in the field of heterogeneous/supported catalysts, while revealing new, unexpected structural features of metallo-NHC-supported substrates. It also highlights the potentially large diversity of surface sites present in functional materials prepared by surface chemistry, an essential knowledge to design materials with improved performances.

Well-Defined Silica-Supported Tungsten(IV)-Oxo Complex: Olefin Metathesis Activity, Initiation, and Role of Brønsted Acid Sites.

Despite the importance of the heterogeneous tungsten-oxo-based olefin metathesis catalyst (WO3/SiO2) in industry, understanding of its initiation mechanism is still very limited. It has been proposed that reduced W(IV)-oxo surface species act as precatalysts. In order to understand the reactivity and initiation mechanism of surface W(IV)-oxo species, we synthesized a well-defined silica-supported W(IV)-oxo species, (≡SiO)WO(OtBuF6)(py)3 (F6@SiO2-700; OtBuF6 = OC(CH3)(CF3)2; py = pyridine), via surface organometallic chemistry (SOMC). F6@SiO2-700 was shown to be highly active in olefin metathesis upon removal of pyridine ligands through the addition of tris(pentafluorophenyl)borane (B(C6F5)3) or thermal treatment under high vacuum. The metathesis activity toward olefins with and without allylic C-H groups, namely ß-methylstyrene and styrene, respectively, was investigated. In the case of styrene, we demonstrated the role of surface OH groups in initiating metathesis activity. We proposed that the presence of strong Brønsted acidic OH sites, which likely arises from the presence of adjacent W sites in the catalyst as revealed by 15N-labeled pyridine adsorption, can assist styrene metathesis. In contrast, initiation of olefins with allylic C-H groups (e.g., ß-methylstyrene) is independent of the surface OH density and likely involves an allylic C-H activation mechanism, like the molecular W(IV)-oxo species. This study indicates that initiation mechanisms depend on the olefinic substrates and reveals the synergistic effect of Brønsted acidic surface sites and reduced W(IV) sites in the initiation of olefin metathesis.

Silica-Supported MnII Sites as Efficient Catalysts for Carbonyl Hydroboration, Hydrosilylation, and Transesterification.

Manganese, the third most abundant transition-metal element after iron and titanium, has recently been demonstrated to be an effective homogeneous catalyst in numerous reactions. Herein, the preparation of silica-supported MnII sites is reported using Surface Organometallic Chemistry (SOMC), combined with tailored thermolytic molecular precursors approach based on Mn2 [OSi(OtBu)3 ]4 and Mn{N(SiMe3 )2 }2 ⋅THF. These supported MnII sites, free of organic ligands, efficiently catalyze numerous reactions: hydroboration and hydrosilylation of ketones and aldehydes as well as the transesterification of industrially relevant substrates.

Highly Productive Propane Dehydrogenation Catalyst Using Silica-Supported Ga-Pt Nanoparticles Generated from Single-Sites.

The development of more effective alkane dehydrogenation catalysts is a key technological challenge for the production of olefins from shale gas, an abundant source of light hydrocarbons. Surface organometallic chemistry provides an original approach to generate nanometric Ga-Pt bimetallic particles supported on partially dehydroxylated silica containing gallium single-sites, which displays high activity, selectivity, and stability in propane dehydrogenation. This catalyst was prepared via sequential grafting of a platinum precursor onto silica possessing site-isolated gallium sites followed by H2 reduction. Monitoring generation of the reduced species, Gaδ+Pt0/SiO2, via in situ X-ray absorption spectroscopy reveals formation of a Ga xPt (0.5 < x < 0.9) alloy with a fraction of gallium remaining as isolated sites. This bimetallic material exhibits catalytic performance that far surpasses each of the individual components and other reported Ga-Pt based catalysts; this is attributed to the highly dispersed Ga xPt alloyed structure on a support with low Brønsted acidity containing gallium single-sites.

C-H Activation and Proton Transfer Initiate Alkene Metathesis Activity of the Tungsten(IV)-Oxo Complex.

In alkene metathesis, while group 6 (Mo or W) high-oxidation state alkylidenes are accepted to be key reaction intermediates for both homogeneous and heterogeneous catalysts, it has been proposed that low valent species in their +4 oxidation state can serve as precatalysts. However, the activation mechanism for these latter species-generating alkylidenes-is still an open question. Here, we report the syntheses of tungsten(IV)-oxo bisalkoxide molecular complexes stabilized by pyridine ligands, WO(OR)2py3 (R = CMe(CF3)2 (2a), R = Si(O tBu)3 (2b), and R = C(CF3)3 (2c); py = pyridine), and show that upon activation with B(C6F5)3 they display alkene metathesis activities comparable to W(VI)-oxo alkylidenes. The initiation mechanism is examined by kinetic, isotope labeling and computational studies. Experimental evidence reveals that the presence of an allylic CH group in the alkene reactant is crucial for initiating alkene metathesis. Deuterium labeling of the allylic C-H group shows a primary kinetic isotope effect on the rate of initiation. DFT calculations support the formation of an allyl hydride intermediate via activation of the allylic C-H bond and show that formation of the metallacyclobutane from the allyl "hydride" involves a proton transfer facilitated by the coordination of a Lewis acid (B(C6F5)3) and assisted by a Lewis base (pyridine). This proton transfer step is rate determining and yields the metathesis active species.

Silica-Supported Pentamethylcyclopentadienyl Ytterbium(II) and Samarium(II) Sites: Ultrahigh Molecular Weight Polyethylene without Co-Catalyst.

Designing highly active supported ethylene polymerization catalysts that do not require a co-catalyst to generate electrophilic metal alkyl species is still a challenge despite its industrial relevance. Described herein is the synthesis and characterization of well-defined silica-supported cyclopentadienyl LnII sites (Ln=Yb and Sm) of general formula [(≡SiO)LnCp*]. These well-defined surface species are highly activite towards ethylene polymerization in the absence of added co-catalyst. Initiation is proposed to occur by single electron transfer.

Bridging the Gap between Industrial and Well-Defined Supported Catalysts.

Many industrial catalysts contain isolated metal sites on the surface of oxide supports. Although such catalysts have been used in a broad range of processes for more than 40 years, there is often a very limited understanding about the structure of the catalytically active sites. This Review discusses how surface organometallic chemistry (SOMC) engineers surface sites with well-defined structures and provides insight into the nature of the active sites of industrial catalysts; the Review focuses in particular on olefin production and conversion processes.

Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH3)3-x(CF3)x}3] (MoF0, x = 0; MoF3, x = 1; MoF6, x = 2; MoF9, x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF0 < MoF3 < MoF6 before sharply decreasing for MoF9, with a similar effect for the supported systems (MoF0 ≈ MoF9 < MoF6 < MoF3). This is consistent with the different kinetic behavior (zeroth order in alkyne for MoF9 derivatives instead of first order for the others) and the isolation of stable metallacyclobutadiene intermediates of MoF9 for both molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF6, prior to a sharp decrease in reactivity for MoF9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13C NMR chemical shift tensors.

Deep-Learning-Based Probabilistic Forecasting of Electric Vehicle Charging Load With a Novel Queuing Model.

With the emerging electric vehicle (EV) and fast charging technologies, EV load forecasting has become a concern for planners and operators of EV charging stations (CSs). Due to the nonstationary feature of the traffic flow (TF) and the erratic nature of the charging procedures, EV charging load is difficult to accurately forecast. In this article, TF is first predicted using a deep-learning-based convolutional neural network (CNN), and different forecast uncertainties are evaluated to formulate the TF prediction intervals (PIs). Then, the EV arrival rates are calculated according to the historical data and the proposed mixture model. Based on TF forecasting and arrival rate results, the EV charging process is studied to convert the TF to the charging load using a novel probabilistic queuing model that takes into consideration charging service limitations and driver behaviors. The proposed models are assessed using the actual TF data, and the results show that the uncertainties of the EV charging load can be learned comprehensively, indicating significant potential for practical applications.

Olefin metathesis: what have we learned about homogeneous and heterogeneous catalysts from surface organometallic chemistry?

Since its early days, olefin metathesis has been in the focus of scientific discussions and technology development. While heterogeneous olefin metathesis catalysts based on supported group 6 metal oxides have been used for decades in the petrochemical industry, detailed mechanistic studies and the development of molecular organometallic chemistry have led to the development of robust and widely used homogeneous catalysts based on well-defined alkylidenes that have found applications for the synthesis of fine and bulk chemicals and are also used in the polymer industry. The development of the chemistry of high-oxidation group 5-7 alkylidenes and the use of surface organometallic chemistry (SOMC) principles unlocked the preparation of so-called well-defined supported olefin metathesis catalysts. The high activity and stability (often superior to their molecular analogues) and molecular-level characterisation of these systems, that were first reported in 2001, opened the possibility for the first direct structure-activity relationships for supported metathesis catalysts. This review describes first the history of SOMC in the field of olefin metathesis, and then focuses on what has happened since 2007, the date of our last comprehensive reviews in this field.

Enhanced CH3OH selectivity in CO2 hydrogenation using Cu-based catalysts generated via SOMC from GaIII single-sites.

Small and narrowly distributed nanoparticles of copper alloyed with gallium supported on silica containing residual GaIII sites can be obtained via surface organometallic chemistry in a two-step process: (i) formation of isolated GaIII surface sites on SiO2 and (ii) subsequent grafting of a CuI precursor, [Cu(O t Bu)]4, followed by a treatment under H2 to generate CuGa x alloys. This material is highly active and selective for CO2 hydrogenation to CH3OH. In situ X-ray absorption spectroscopy shows that gallium is oxidized under reaction conditions while copper remains as Cu0. This CuGa material only stabilizes methoxy surface species while no formate is detected according to ex situ infrared and solid-state nuclear magnetic resonance spectroscopy.

Silica-supported isolated molybdenum di-oxo species: formation and activation with organosilicon agent for olefin metathesis.

A well-defined silica-supported molybdenum dioxo species, ([triple bond, length as m-dash]SiO)2Mo(O)2, is prepared by grafting Mo(O)2[OSi(OtBu)3]2 on partially dehydroxylated silica SiO2-700, followed by thermal treatment under high-vaccum and calcination. Activated by an organosilicon agent the resulting material is active for olefin metathesis at 30 °C.

Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents.

Alkene metathesis is a widely and increasingly used reaction in academia and industry because of its efficiency in terms of atom economy and its wide applicability. This reaction is notably responsible for the production of several million tons of propene annually. Such industrial processes rely on inexpensive silica-supported tungsten oxide catalysts, which operate at high temperatures (>350 °C), in contrast with the mild room temperature reaction conditions typically used with the corresponding molecular alkene metathesis homogeneous catalysts. This large difference in the temperature requirements is generally thought to arise from the difficulty in generating active sites (carbenes or metallacyclobutanes) in the classical metal oxide catalysts and prevents broader applicability, notably with functionalized substrates. We report here a low temperature activation process of well-defined metal oxo surface species using organosilicon reductants, which generate a large amount of active species at only 70 °C (0.6 active sites/W). This high activity at low temperature broadens the scope of these catalysts to functionalized substrates. This activation process can also be applied to classical industrial catalysts. We provide evidence for the formation of a metallacyclopentane intermediate and propose how the active species are formed.

Phosphine-catalyzed cage carbon functionalization of o-carborane: facile synthesis of alkenylcarboranes.

A phosphine-catalyzed alkenylation reaction of o-carborane with electron-deficient alkynes at the C-H vertex of the o-carborane cage has been developed, which led to the preparation of a series of 1-alkenyl-o-carboranes in moderate to very good yields with excellent regio- and stereoselectivity. This highly efficient and simple method represents the first example of organophosphine catalyzed C-H functionalization of o-carborane.