Boron nitride catalysis Propene is one of the highest-volume organic chemicals produced. has mainly been made from naphtha, but changes in global supply chain are creating shortages. Direct conversion propane, a component natural gas, via reaction with oxygen an attractive alternative, existing approaches produce large fraction unwanted CO and 2 . Grant et al. report that boron nitride, normally unreactive material, high selectivity to catalyze production propene (77%) ethene (13%). Science...

Hexagonal boron nitride (h-BN) and nanotubes (BNNT) were recently reported as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins in gas phase. Previous studies revealed a substantial increase surface oxygen content after exposure ODH conditions (heating ca. 500 °C under flow alkane oxygen); however, complexity these materials has thus far precluded an in-depth understanding oxygenated species. In this contribution, we combine advanced NMR spectroscopy...

Abstract Boron nitride was recently identified as a highly selective catalyst for the oxidative dehydrogenation of propane. In this communication, we report that other boron‐containing materials such boron carbide, titanium boride, nickel cobalt hafnium and tungsten well elemental itself, show same exceptional behavior nitride. X‐ray photoelectron infrared spectroscopy suggest oxyfunctionalization surface. This observation disproves previous mechanistic hypotheses edge sites on would be...

Light olefins such as ethylene and propylene form the foundation of modern chemical industry, with yearly production volumes well into hundreds millions metric tons. Currently, these light are mainly produced via energy-intensive steam cracking. Alternatively, oxidative dehydrogenation (ODH) alkanes to produce allows for lower operation temperatures extended catalyst lifetimes, potentially leading valuable process efficiencies. The potential benefits this route have led significant research...

Boron-containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such propane. To date, no mechanism exists that can explain both unprecedented selectivity, observed surface oxyfunctionalization, peculiar kinetic features this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. argue remarkable product distribution be...

Abstract Hexagonal boron nitride (hBN) is presented as an outstanding catalyst for the selective production of C 4 olefins by oxidative dehydrogenation n ‐butane and isobutane. Unlike catalysts reported previously, hBN limits amount undesired CO x instead forms 2 3 main side products. Kinetic experiments suggest a mechanism in which rates isobutane consumption are dependent on O adsorption. spectroscopic insights used to formulate mechanistic hypotheses formation mechanisms –C olefins.

We report on the oxidative dehydrogenation (ODH) activity of silica-supported boron oxide prepared via incipient wetness impregnation. Characterization pristine and spent catalysts with infrared, Raman, solid-state NMR spectroscopy reveals presence both isolated aggregated oxidized sites. The results these investigations, in combination our earlier work bulk boron-containing ODH (e.g., h-BN, metal borides, elemental boron), give direct evidence that species formed situ surface materials are...

Abstract Boron‐containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously demonstrated by several spectroscopic characterization techniques that surface these boron‐containing ODH oxidize and hydrolyze under reaction conditions, forming an amorphous B 2 (OH) x O (3− /2) ( x= 0–6) layer. Yet, precise nature active site(s) remains elusive. In this Communication, we provide a detailed zeolite...

In recent years, the on-purpose production of 1,3-butadiene (BD) from renewable resources such as ethanol has received increased attention. that context, Lewis acid catalysts play an important role, especially in two-step process, i.e. when a mixture acetaldehyde and is used substrate. As reaction mechanism consists many intermediates occurs over different catalytic functionalities, it notoriously difficult to gain molecular-level insights into mechanism. Here, we present study on acidic...

Boron-based heterogeneous catalysts, such as hexagonal boron nitride (h-BN) well supported oxides, are highly selective catalysts for the oxidative dehydrogenation (ODH) of light alkanes to olefins. Previous catalytic measurements and molecular characterization boron-based by 11B solid-state NMR spectroscopy other techniques suggest that oxidized/hydrolyzed clusters catalytically active sites ODH. However, often suffers from limited resolution because boron-11 is an I = 3/2 half-integer...

Abstract Bulk boron materials, such as hexagonal nitride (h‐BN), are highly selective catalysts for the oxidative dehydrogenation of propane (ODHP). Previous attempts to improve productivity these systems involved immobilization on silica and resulted in less catalysts. Here, we report that acid‐treated, activated carbon‐supported prepared via incipient wetness impregnation with boric acid (B/OAC) exhibits equal propylene selectivity improved (kg kg cat −1 hr ) compared h‐BN....

Supported vanadium materials are promising catalysts for the oxidative dehydrogenation of propane to propylene (ODHP), but a lack mechanistic understanding limits rational design with improved selectivity. Adding Ta V/SiO2 increases selectivity, as well activity, leading superior performance compared state-of-the-art boron-based systems. In this contribution, we utilize surprising promotional effect elucidate key elements cycle. Through combination characterization techniques, computational...

Abstract The front cover artwork for Issue 19/2017 is provided by the Hermans Laboratory at UW‐Madison (USA). image shows Swedish Chef who, being offered scientific freedom to explore new recipes, discovered that boron most efficient catalyst oxidative upgrading of natural gas‐derived alkanes highly‐desired olefins. It a good reminder community despite decades systematic research on ODH, serendipitous breakthroughs are still possible and can lead insights applications. See Communication...

In recent years, hexagonal boron nitride (hBN) has emerged as an unexpected catalyst for the oxidative dehydrogenation of alkanes. Here, versatility hBN was extended to alkane cracking chemistry by investigating production ethylene and propylene from n-butane. Cracking selectivity primarily controlled ratio n-butane O2 within reactant feed. Under -lean conditions, increasing temperature led increased decreased COx . addition surface-mediated chemistry, homogeneous gas-phase reactions likely...

We present the controlled grafting synthesis of pinacolborane on amorphous silica. 11B solid-state NMR and IR spectroscopies reveal that precursor molecule anchors monopodally to surface can form hydrogen-bonding interactions with neighboring unreacted silanol groups. The extent hydrogen bonding be by silica pretreatment dehydration temperature. Thermal treatment grafted boron materials under vacuum generates clusters oxidized/hydrolyzed regardless weight loading, illustrating is highly...

In the oxidative dehydrogenation of propane over boron nitride, propylene selectivity is lost due to unselective gas-phase chemistry.

In this work, we investigate the influence of Sn-loading and pore size MCM-41 materials on catalytic nopol production. Sn(IV) was anchored onto by incipient wetness impregnation with metal coverages within 0.01 0.5 Sn nm–2 (i.e., below monolayer content). We provide evidence that at 0.06 nm–2, is predominantly present as isolated centers, whereas higher octahedral and/or oligomeric species are formed, which exhibit lower activity. The rate production over Sn/MCM-41 ten times than analogous...

Abstract Boron‐containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously demonstrated by several spectroscopic characterization techniques that surface these boron‐containing ODH oxidize and hydrolyze under reaction conditions, forming an amorphous B 2 (OH) x O (3− /2) ( x= 0–6) layer. Yet, precise nature active site(s) remains elusive. In this Communication, we provide a detailed zeolite...

Abstract The reactions of acetone and hydroxyacetone over heteroatom doped BEA zeolites (Sn, Mo, W) in the presence absence H 2 O vapor are investigated using infrared spectroscopy. Acetone is converted to mesityl oxide Sn‐BEA exclusively. At higher temperatures, larger oxygenates such as phorones, aromatics, coke form. co‐adsorbed water suppresses tautomerization. also beneficial for minimizing formation at high temperatures. Hydroxyacetone into 2‐hydroxypropanal Sn‐BEA, exhibiting affinity...

Abstract Boron‐containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such propane. To date, no mechanism exists that can explain both unprecedented selectivity, observed surface oxyfunctionalization, peculiar kinetic features this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. argue remarkable product...