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Boron-containing materials such as hexagonal boron nitride, recently shown to be active and selective catalysts for the oxidative dehydrogenation of propane (ODHP), have been shown to undergo significant surface oxyfunctionalization and restructuring. Although experimental ex situ studies have probed the change in chemical environment on the surface, the structural evolution of it under varying reaction conditions has not been established. Herein we perform global optimization structural search with grand canonical genetic algorithm to explore the chemical space of off-stoichiometric restructuring of hexagonal boron nitride (hBN) surface under ambient as well as ODHP relevant reaction conditions. A grand canonical ensemble representation of the surface is established, and the predicted 11B solid-state NMR spectra are consistent with previous experimental reports. In addition, we investigated the relative sliding of hBN sheets and how it affects the surface chemistry with ab initio molecular dynamics simulations. The B-O linkages on the edges are found to be significantly strained during the sliding, causing the metastable sliding configurations to have higher reactivity towards activation of propane and water.

ispartof: ACS Catalysis vol:12 issue:15 pages:9559-9569 status: published

Titanium silicates of MWW structures with different Si/Ti ratios were prepared via hydrothermal synthesis using piperidine as the structure directing agent and boric acid as the crystallization agent. All the syntheses resulted in highly crystalline materials independent of the Si/Ti ratio. The observed morphology showed MWW-like well-defined thin hexagonal platelets. The synthesized Ti-MWW materials exhibited higher surface areas and partial meso-porosity compared to the commercial TS-1 catalyst. The coordination of the Ti-species was investigated by UV–vis- and IR-spectroscopy. The MWW titanium silicates were tested for the catalytic performance in the epoxidation of propylene in a laboratory-scale trickle bed reactor to compare their clear different physico-chemical properties with the commercial TS-1. The synthesized Ti-MWW materials showed significantly higher catalytic activities, up to 3.5 times, using acetonitrile as the solvent and enhanced epoxide selectivities partially up to 100% in methanol unlike TS-1. The effect of the Ti content in the MWW and the calcination conditions were investigated in propylene epoxidation, revealing the beneficial effect of a lower calcination temperature and an increased Ti content on the activity. The catalytic results were correlated with the physico-chemical properties of the synthesized materials. Graphical Abstract

Less than 10% of the plastics generated globally are recycled, while the rest are incinerated, accumulated in landfills, or leach into the environment. New technologies are emerging to chemically recycle waste plastics that are receiving tremendous interest from academia and industry. Chemists and chemical engineers need to understand the fundamentals of these technologies to design improved systems for chemical recycling and upcycling of waste plastics. In this paper, we review the entire life cycle of plastics and options for the management of plastic waste to address barriers to industrial chemical recycling and further provide perceptions on possible opportunities with such materials. Knowledge and insights to enhance plastic recycling beyond its current scale are provided. Outstanding research problems and where researchers in the field should focus their efforts in the future are also discussed.

We have investigated the synthesis of hexane-1,2,5,6-tetrol (hereafter “tetrol”) from aqueous solutions of biomass-derived levoglucosanol (hereafter “Lgol”) using a (10 wt %)Pt-(10 wt %)WOx/TiO2 ca...

Boron oxide/hydroxide supported on oxidized activated carbon (B/OAC) was shown to be an inexpensive catalyst for the oxidative dehydrogenation (ODH) of propane that offers activity and selectivity comparable to boron nitride. Here, we obtain an atomistic picture of the boron oxide/hydroxide layer in B/OAC by using 35.2 T

Boron oxide/hydroxide supported on oxidized activated carbon (B/OAC) was shown to be an inexpensive catalyst for the oxidative dehydrogenation (ODH) of propane that offers activity and selectivity comparable to boron nitride. Here, we obtain an atomistic picture of the boron oxide/hydroxide layer in B/OAC by using 35.2 T 11B and 17O solid-state NMR experiments. NMR spectra measured at 35.2 T resolve the boron and oxygen sites due to narrowing of the central-transition powder patterns. A 35.2 T 2D 11B{17O} dipolar heteronuclear correlation NMR spectrum revealed the structural connectivity between boron and oxygen atoms. The approach outlined here should be generally applicable to determine atomistic structures of heterogeneous catalysts containing quadrupolar nuclei. ispartof: Journal Of The American Chemical Society vol:144 issue:41 pages:18766-18771 ispartof: location:United States status: published

Boron-based heterogenous catalysts, such as hexagonal boron nitride (h-BN) as well as supported boron oxides, are highly selective catalysts for the oxidative dehydrogenation (ODH) of light alkanes to olefins. Previous catalytic measurements and molecular characterization of boron-based catalysts by 11B solid-state NMR spectroscopy and other techniques suggests that oxidized/hydrolyzed boron clusters are the catalytically active sites for ODH. However, 11B solid-state NMR spectroscopy often suffers from limited resolution because boron-11 is an I = 3/2 half-integer quadrupolar nucleus. Here, ultra-high magnetic field (B0 = 35.2 T) is used to enhance the resolution of 11B solid-state NMR spectra and unambiguously determine the local structure and connectivity of boron species in h-BN nanotubes used as a ODH catalyst (spent h-BNNT), boron substituted MCM-22 zeolite [B-MWW] and silica supported boron oxide [B/SiO2] before and after use as an ODH catalyst. One-dimensional direct excitation 11B NMR spectra recorded at B0 = 35.2 T are near isotropic in nature, allowing for the easy identification of all boron species. Two-dimensional 1H-11B heteronuclear correlation NMR spectra aid in the identification of boron species with B-OH functionality. Most importantly, 2D 11B dipolar double-quantum single-quantum homonuclear correlation NMR experiments were used to unambiguously probe boron-boron connectivity within all heterogeneous catalysts. These experiments are practically infeasible at lower, more conventional magnetic fields due to a lack of resolution and reduced NMR sensitivity. The detailed molecular structures determined for the amorphous oxidized/hydrolyzed boron layers on these heterogenous catalysts will aid in the future development of next generation ODH catalysts.

The production of ethylene and propylene through aerobic alkane oxidation without significant coproduction of CO and CO2 (COx) presents a challenge to academic and industrial researchers alike. Recently, boron-containing materials such as hexagonal boron nitride (hBN) have been identified as active and selective catalysts for the oxidative dehydrogenation (ODH) of propane to propylene with minimal COx selectivity. Additionally, high olefin selectivity is also obtained in the oxidation of other alkanes and other materials such as metal borides and supported B/SiO2 have been successfully applied to this transformation. Recent advances in the understanding of these catalysts in the oxidation of light alkanes are presented here providing a framework for further study of this exciting field.

Nanoscale coatings of AlOx were deposited onto SiO2 using atomic layer deposition (ALD) to synthesize amorphous silica-alumina (SiAl) catalysts, and these catalysts were investigated for levoglucosanol (Lgol) hydrogenolysis. With decreasing Al2O3 loading, the ratio of Bronsted to Lewis acid sites, measured by NH3-TPD and pyridine-FTIR, systematically increases, while the Al coordination, measured by solid state 27Al NMR, decreases. These structural changes correspond to an increasing mass-normalized rate of Lgol hydrogenolysis. We model the mass-normalized reaction rate as the sum of independent contributions from Bronsted and Lewis sites, showing that Bronsted acid sites on ALD-AlOx/SiO2 catalysts have a 6-times higher turnover frequency (TOF) than Lewis acid sites on these catalysts. Additionally, Lewis acid sites on ALD-AlOx/SiO2 catalysts (potentially related to Al(V) species) have a 4-times higher TOF than Lewis acid sites on bulk γ-Al2O3. The overall mass-normalized reactivity of ALD-AlOx/SiO2 catalysts is due to Lewis acid sites at the highest Al2O3 loading, while it is predominantly due to Bronsted acid sites at the lowest Al2O3 loadings. This work provides a new approach to synthesize amorphous SiAls with tunable Bronsted/Lewis acid site ratio and reveals differences in the reactivity of Bronsted and Lewis acid sites on these materials.

Boron-containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron-containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B(2)(OH)(2x)O((3 – x)) (x = 0 – 3) layer. Yet, the precise nature of the active site(s) remains elusive. In this communication, we provide a detailed characterization of zeolite MCM-22 isomorphously substituted with boron (B-MWW). Using (11)B solid-state NMR spectroscopy, we show that the majority of boron species in B-MWW exist as isolated BO(3) units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B-MWW for ODH of propane falsifies the hypothesis that site-isolated BO(3) units are the active site in boron-based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium-based catalysts and provides an important piece of the mechanistic puzzle.

Potential active sites for the conversion of methane to methanol in Cu-exchanged SSZ-13 are identified using a combination of experimentally measured UV-vis-NIR spectroscopy and theoretical modeling.

Stable emissive carbon nanodots were generated in zeolite crystals using near infrared photon irradiation gradually converting the occluded organic template, originally used to synthesize the zeolite crystals, into discrete luminescent species consisting of nano-sized carbogenic fluorophores, as ascertained using Raman microscopy, and steady-state and time-resolved spectroscopic techniques. Photoactivation in a confocal laser fluorescence microscope allows 3D resolved writing of luminescent carbon nanodot patterns inside zeolites providing a cost-effective and non-toxic alternative to previously reported metal-based nanoclusters confined in zeolites, and opens up opportunities in bio-labelling and sensing applications. ispartof: Chemical Communications vol:57 issue:90 pages:11952-11955 ispartof: location:England status: published

Boron-based heterogenous catalysts, such as hexagonal boron nitride (h-BN) as well as supported boron oxides, are highly selective catalysts for the oxidative dehydrogenation (ODH) of light alkanes to olefins. Previous catalytic measurements and molecular characterization of boron-based catalysts by (11)B solid-state NMR spectroscopy and other techniques suggests that oxidized/hydrolyzed boron clusters are the catalytically active sites for ODH. However, (11)B solid-state NMR spectroscopy often suffers from limited resolution because boron-11 is an I = 3/2 half-integer quadrupolar nucleus. Here, ultra-high magnetic field (B(0) = 35.2 T) is used to enhance the resolution of (11)B solid-state NMR spectra and unambiguously determine the local structure and connectivity of boron species in h-BN nanotubes used as a ODH catalyst (spent h-BNNT), boron substituted MCM-22 zeolite [B-MWW] and silica supported boron oxide [B/SiO(2)] before and after use as an ODH catalyst. One-dimensional direct excitation (11)B NMR spectra recorded at B(0) = 35.2 T are near isotropic in nature, allowing for the easy identification of all boron species. Two-dimensional (1)H-(11)B heteronuclear correlation NMR spectra aid in the identification of boron species with B-OH functionality. Most importantly, 2D (11)B dipolar double-quantum single-quantum homonuclear correlation NMR experiments were used to unambiguously probe boron-boron connectivity within all heterogeneous catalysts. These experiments are practically infeasible at lower, more conventional magnetic fields due to a lack of resolution and reduced NMR sensitivity. The detailed molecular structures determined for the amorphous oxidized/hydrolyzed boron layers on these heterogenous catalysts will aid in the future development of next generation ODH catalysts.

The recently reported processing strategy called solvent-targeted recovery and precipitation (STRAP) enables deconstruction of multilayer plastic packaging films into their constituent resins by selective dissolution. It uses a series of solvent washes that are guided by thermodynamic calculations of polymer solubility. In this work, the use of antisolvents in the STRAP process was reduced and solvent mixtures were considered to enable the temperature-controlled dissolution and precipitation of the target polymers in multilayer films. This was considered as a means to further improve the STRAP process and its estimated costs. Two STRAP approaches were compared based on different polymer precipitation techniques: precipitation by the addition of an antisolvent (STRAP-A) and precipitation by decreasing the solvent temperature (STRAP-B). Both approaches were able to separate the constituent polymers in a post-industrial film composed primarily of polyethylene (PE), ethylene vinyl alcohol (EVOH), and polyethylene terephthalate (PET) with near 100 % material efficiency. Technoeconomic analysis indicates that the minimum selling price (MSP) of the recycled resins with STRAP-B is 21.0 % lower than that achieved with STRAP-A. This provides evidence that thermally driven polymer precipitation is an option to reduce the use of antisolvents, making the STRAP process more economically and environmentally attractive. A third process, STRAP-C, was demonstrated with another post-industrial multilayer film of a different composition. The results demonstrate that this process can also recover polymers at similar costs to those of virgin resins, indicating that the STRAP technology is flexible and can remain economically competitive as the plastic feed complexity is increased.

The complexity of variables during incipient wetness impregnation synthesis of supported metal oxides precludes an in-depth understanding of the chemical reactions governing the formation of the dispersed oxide sites. This contribution describes the use of vapor phase deposition chemistry (also known as grafting) as a tool to systematically investigate the influence of isopropanol solvent on VO(Oi Pr)3 anchoring during synthesis of vanadium oxide on silica. The availability of anchoring sites on silica was found to depend not only on the pretreatment of the silica but also on the solvent present. H-bond donors can reduce the reactivity of isolated silanols whereas disruption of silanol nests by H-bond acceptors can turn unreactive H-bonded silanols into reactive anchoring sites. The model suggested here can inform improved syntheses with increased dispersion of metal oxides on silica.

Catalysts consisting of transition metals (Ni, Co, Cu, and Ru) supported on molybdenum oxide synthesized by atomic layer deposition (ALD) on silica were studied for synthesis gas conversion at 523 ...

The Cu-exchanged zeolite SSZ-13 is a highly active material in the selective catalytic reduction of nitrogen oxides and the conversion of methane to methanol. In this material, a distribution of ac...

We report on the oxidative dehydrogenation (ODH) activity of silica-supported boron oxide prepared via incipient wetness impregnation. Characterization of pristine and spent catalysts with infrared...

Raman spectroscopy is a widely employed tool for characterization of heterogeneous catalysts, although it suffers somewhat from poor sensitivity at low concentrations or under in situ conditions. I...

A series of calcined MgAl mixed metal oxide catalysts with low Cu loadings (0.1 – 1.5 wt%) were tested for ethanol oligomerization to distillate-range molecules. The low Cu loading catalysts (0.1 – 0.6 wt%) had high selectivity to linear chain C4+ alcohols (49 – 63% selectivity) and C6+ esters (45 – 66% of total esters). More specifically, the diesel fuel precursor selectivities were over 75% for low Cu loading catalysts (0.1 – 0.6 wt%), with a decrease to 49% for a higher Cu loading catalyst (>1.2 wt% Cu) due to increased ethyl acetate and acetone formation. Alcohol and ester product selectivities follow a Schultz-Flory distribution. Alcohol selectivity was found to vary inversely with BET surface areas of the catalysts, whereas ester selectivity was found to increase with higher base site counts. However, Cu wt% loading was found to have a stronger impact in overall catalyst activity. The catalysts deactivated proportionally to the number of turnovers mainly due to coking, but could be regenerated by calcination.

Boron-containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface-mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure-dependent relative formation of the main product propylene and by-product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium-based catalysts.

Plastic solid waste (PSW) is an ever-growing environmental challenge for our society, as it not only ends up in landfills but also in waterways and oceans and is consequently entering the food chain. A key strategy to overcome this problem while also preserving carbon resources is to use PSW as a feedstock, evolving towards a circular economy. To implement this, mechanical as well as chemical recycling technologies must be developed. Indeed, owing to the high volume of PSW generated each year, mechanical recycling alone is not adequate for addressing this global challenge. Because of this, chemical recycling via thermal and heterogeneous catalytic conversion has received growing attention. This process has the potential to take PSW and convert it into usable monomers, fuels, synthesis gas, and adsorbents under more sustainable conditions than thermal degradation. This Review highlights the recent research advances in catalytic technologies for PSW conversion and valorization.

The coupling of ethanol to produce C4-compounds by Guerbet condensation at 325 °C was studied using porous mixed oxide catalysts of AlMgO and AlCaO prepared by the emulsion mediated method with and without the addition of Cu. The synthesis procedure was effective in preparing materials with higher porosity and BET area. Cu catalysts show improved yields and selectivities at elevated H2 pressures, which is related to ethanol dehydrogenation equilibrium shifts. Without Cu, AlMgO catalysts were more selective to diethyl ether (45–55 C%) than higher alcohols and aldehydes (30–40 C%), while AlCaO catalysts had no activity for ethanol conversion. The addition of Cu inhibited production of diethyl ether while promoting dehydrogenation to acetaldehyde, the initial step in Guerbet coupling of ethanol. Copper addition increased the activity and the selectivity to higher alcohols and aldehydes (up to 55 C% selectivity) for all catalysts. Olefins and paraffins comprised the majority of the side products formed with Cu-doped catalysts. The ethanol conversion levels off near 30% with decreasing space velocity due to inhibition by water and other products.

The catalytic properties of zeolites are intimately linked to the distribution and relative positions of Al atoms and defects in the pore network. However, characterizing this distribution is challenging, in particular when different local Al arrangements are considered. In this contribution we use a combination of first principles calculations and experimental measurements to develop a model for the Al-distribution in protonated SSZ-13. We furthermore apply this model to understand trends in OH-IR, 27Al-NMR and 29Si-NMR spectra. We use a Boltzmann distribution to predict the proton position for a given local Al configuration and show that for each configuration several H positions are occupied. Therefore a multi-peak spectrum in OH-IR vibrational spectroscopy is observed for all Al configurations, which is in line with experimentally measured spectra for zeolites at different Si/Al ratios. From NMR spectroscopy we find that the proton position leads to significant shifts in 27Al-NMR and 29Si-NMR spectra due to the modification of the local strain, which is lost when a uniform background charge is introduced. These findings are supported by experimental measurements. Finally we discuss the shortcomings of the presented model in terms of unit cell size and the impact of adjacent unit cells.

Boron-containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface-mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure-dependent relative formation of the main product propylene and by-product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium-based catalysts.

Hexagonal boron nitride (h-BN) and boron nitride nanotubes (BNNT) were recently reported as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins in the gas phase. Previous studies revealed a substantial increase in surface oxygen content after exposure to ODH conditions (heating to ca. 500 °C under a flow of alkane and oxygen); however, the complexity of these materials has thus far precluded an in-depth understanding of the oxygenated surface species. In this contribution, we combine advanced NMR spectroscopy experiments with scanning electron microscopy and soft X-ray absorption spectroscopy to characterize the molecular structure of the oxygen functionalized phase that arises on h-BN and BNNT following catalytic testing for ODH of propane. The pristine BN materials are readily oxidized and hydrolyzed under ODH reaction conditions to yield a phase consisting of three-coordinate boron sites with variable numbers of hydroxyl and bridging oxide groups which is denoted B(OH)

In this contribution, we investigate the effect of various reactor parameters on the oxidative dehydrogenation (ODH) of propane using a hexagonal boron nitride (hBN) heterogeneous catalyst. The analysis begins with an assessment of the influence of mass and heat transport on the observed ODH activity. Unexpected experimental results during this analysis prompted us to investigate the use of SiC as an inert catalyst diluent, and we found an increase in propane conversion with increasing diluent content in the reactor. Control experiments suggested that SiC itself is catalytically inactive and that there may be a significant influence of gas-phase chemistry on the observed reactivity.

Covalent organic framework (COF) represents an emerging class of porous materials that have exhibited great potential in various applications, particularly in catalysis. In this work, we report a newly designed 2D COF with incorporated Re complex, which exhibits intrinsic light absorption and charge separation (CS) properties. We show that this hybrid catalyst can efficiently reduce CO2 to form CO under visible light illumination with high electivity (98%) and better activity than its homogeneous Re counterpart. More importantly, using advanced transient optical and X-ray absorption spectroscopy and in situ diffuse reflectance spectroscopy, we unraveled three key intermediates that are responsible for CS, the induction period, and rate limiting step in catalysis. This work not only demonstrates the potential of COFs as next generation photocatalysts for solar fuel conversion but also provide unprecedented insight into the mechanistic origins for light-driven CO2 reduction.

The catalytic conversion of synthesis gas to value-added oxygenates and light hydrocarbons was studied on Rh and Rh–Mn clusters on tungsten carbide-overcoated silica (WxC/SiO2) at 523 K, 580 psi, and CO/H2 = 1/1. The WxC-modified SiO2 support was prepared by the overcoating of WOx on SiO2 using atomic layer deposition (ALD) followed by carburization. The reactivities of Rh/WxC/SiO2 catalysts with varying number of ALD cycles (number of cycles = 2, 5, 10, 20, and 30) were measured and showed that 5 ALD cycles of WxC suppressed the formation of methane. All WxC-modified catalysts showed enhancement in selectivity toward methanol and ethanol through CO hydrogenation and acetaldehyde hydrogenation, respectively. These catalysts also improved the overall turnover frequency (TOF). The addition of Mn species further promoted the activity and the selectivity toward ethanol and C2+ hydrocarbons, especially light alkenes. The best performing Rh-2Mn/5cycle-WxC/SiO2 catalyst (Rh:Mn molar ratio = 1:2) achieved 84.7% s...

Industrial dimerization of ethylene to 1-butene is achieved with catalysts bearing ligand structures and activated by a co-catalyst. Here, we report that a Cr-promoted cobalt oxide on carbon catalyst was able to produce 1-butene with 53.5–82.4% total selectivity at ethylene conversions between 8.9 and 31.5% without the use of a co-catalyst. The Cr-promoted catalyst showed enhanced activity and stability compared to the nonpromoted catalyst. The characterization results revealed that the incorporation of Cr into the cobalt oxide on carbon catalyst was able to decrease the cobalt oxide particle size. Charge transfer from Cr to Co was also observed in the Cr-promoted catalyst compared to monometallic Co and Cr on carbon. The kinetic model built to rationalize the experimental observations predicted a 50% increase in active site dispersion in the Cr-promoted catalyst, which explained the 1.6× apparent reaction rate increase compared to the nonpromoted catalyst.

Correction for ‘Expanding plastics recycling technologies: chemical aspects, technology status and challenges’ by Houqian Li et al., Green Chem., 2022, 24, 8899–9002, https://doi.org/10.1039/D2GC02588D.

Cellulose-derived tetrahydrofuran-dimethanol (THFDM) can be converted over Pt-WOx/TiO2 catalysts to 1,6-hexanediol (1,6-HDO) with up to 70% yield. This reaction involves ring-opening of THFDM to 1,2,6-hexanetriol (HTO) and then hydrogenolysis of HTO to 1,6-HDO. Hydrogen atoms spill over from Pt sites onto WOx/TiO2 to reduce the W═O functional group and create Bronsted acid sites. Similar catalytic activity for THFDM conversion can be been obtained with a physical mixture of Pt/TiO2 and WOx/TiO2 due to hydrogen spillover over spatially separate Pt and WOx when a reducible support (TiO2) is used.

Cobalt oxide supported on N-doped carbon catalysts were investigated for 1-butene oligomerization. The materials were synthesized by treating activated carbon with nitric acid and subsequently with NH3 at 200, 400, 600, and 800 °C, followed by impregnation with cobalt. The 1-butene oligomerization selectivity increased with ammonia treatment temperature of the carbon support. The oligomerization selectivity of cobalt oxide on N-doped carbon synthesized at 800 °C (800A-CoOx/N-C) is 2.6 times higher than previously reported cobalt oxide on N-doped carbon synthesized with NH4OH (2A-CoOx/N-C). Over 70% of the butene dimers were linear C8 olefins for all catalysts. The oligomerization selectivity increased with 1-butene conversion. The catalysts were characterized by elemental analysis, N2 adsorption, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). The nitrogen content of the catalysts increases with ammonia treatment temperature as confirmed by element...

A nitrogen-doped carbon-supported cobalt oxide catalyst is able to oligomerize ethylene, propylene, 1-butene and 1-hexene into mixtures of oligomers with above 94.1% dimers. Higher than 72.5% of the dimers produced from 1-butene and 1-hexene are internal linear olefins, while the dimer products from propylene oligomerization are 47.0% linear including 5.9% 1-hexene. Ethylene had the highest oligomerization activity with 56.1–87.0% 1-butene selectivity. The selectivity to linear alpha olefins decreases with an increasing oligomer chain length during ethylene oligomerization. The oligomers formed from ethylene conversion follow a Schulz-Flory distribution. Cossee type mechanism rationalizes the product selectivity from the four olefin feeds, suggesting that a 1,2-2,1 insertion sequence is critical to obtaining linear olefin products. The catalyst was inactive in oligomerizing internal olefins.