Showing papers on "Dehydrogenation published in 2016"

Single‐Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions

Abstract: As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity.

Formic acid as a hydrogen storage material – development of homogeneous catalysts for selective hydrogen release

Abstract: Formic acid (FA, HCO2H) receives considerable attention as a hydrogen storage material. In this respect, hydrogenation of CO2 to FA and dehydrogenation of FA are crucial reaction steps. In the past decade, for both reactions, several molecularly defined and nanostructured catalysts have been developed and intensively studied. From 2010 onwards, this review covers recent advancements in this area using homogeneous catalysts. In addition to the development of catalysts for H2 generation, reversible H2 storage including continuous H2 production from formic acid is highlighted. Special focus is put on recent progress in non-noble metal catalysts.

Selective oxidative dehydrogenation of propane to propene using boron nitride catalysts

Abstract: The exothermic oxidative dehydrogenation of propane reaction to generate propene has the potential to be a game-changing technology in the chemical industry. However, even after decades of research, selectivity to propene remains too low to be commercially attractive because of overoxidation of propene to thermodynamically favored CO 2 . Here, we report that hexagonal boron nitride and boron nitride nanotubes exhibit unique and hitherto unanticipated catalytic properties, resulting in great selectivity to olefins. As an example, at 14% propane conversion, we obtain selectivity of 79% propene and 12% ethene, another desired alkene. Based on catalytic experiments, spectroscopic insights, and ab initio modeling, we put forward a mechanistic hypothesis in which oxygen-terminated armchair boron nitride edges are proposed to be the catalytic active sites.

Dehydrogenation of Ammonia Borane by Metal Nanoparticle Catalysts

Abstract: Ammonia borane (AB), having a high hydrogen density of 19.6 wt %, has attracted much attention as a promising chemical hydrogen storage material. In the past few years, a number of highly active metal nanoparticle (NP) catalysts, which are easy to handle and separate, have been developed for AB dehydrogenation. In this Perspective, we summarize new progress in the development of metal NP catalysts, which are categorized into monometallic and heterometallic catalysts, with excellent activity and high recyclability for different AB dehydrogenation pathways, including solvolysis (hydrolysis and methanolysis) in protic solvents and dehydrocoupling in nonprotic solvents, and we survey the corresponding methods for the regeneration of AB. Moreover, the merits and drawbacks of solvolysis and dehydrocoupling are discussed.

Ammonia–Borane and Amine–Borane Dehydrogenation Mediated by Complex Metal Hydrides

Abstract: This review is a comprehensive survey of the last 10 years of research on ammonia-borane and amine-borane dehydrogenation mediated by complex metal hydrides (CMHs), within the broader context of chemical hydrogen storage. The review also collects those cases where CMHs are the catalyst spent form or its resting state. Highlights on the reaction mechanism (strictly dependent on the CMH of choice) and the catalysts efficiency (in terms of equivalents of H2 produced and relative reaction rates) are provided throughout the discussion.

Dehydrogenation of Formic Acid at Room Temperature: Boosting Palladium Nanoparticle Efficiency by Coupling with Pyridinic‐Nitrogen‐Doped Carbon

Abstract: The use of formic acid (FA) to produce molecular H2 is a promising means of efficient energy storage in a fuel-cell-based hydrogen economy. To date, there has been a lack of heterogeneous catalyst systems that are sufficiently active, selective, and stable for clean H2 production by FA decomposition at room temperature. For the first time, we report that flexible pyridinic-N-doped carbon hybrids as support materials can significantly boost the efficiency of palladium nanoparticle for H2 generation; this is due to prominent surface electronic modulation. Under mild conditions, the optimized engineered Pd/CN0.25 catalyst exhibited high performance in both FA dehydrogenation (achieving almost full conversion, and a turnover frequency of 5530 h−1 at 25 °C) and the reversible process of CO2 hydrogenation into FA. This system can lead to a full carbon-neutral energy cycle.

Efficient Visible Light-Driven Splitting of Alcohols into Hydrogen and Corresponding Carbonyl Compounds over a Ni-Modified CdS Photocatalyst.

Abstract: Splitting of alcohols into hydrogen and corresponding carbonyl compounds has potential applications in hydrogen production and chemical industry. Herein, we report that a heterogeneous photocatalyst (Ni-modified CdS nanoparticles) could efficiently split alcohols into hydrogen and corresponding aldehydes or ketones in a stoichiometric manner under visible light irradiation. Optimized apparent quantum yields of 38%, 46%, and 48% were obtained at 447 nm for dehydrogenation of methanol, ethanol, and 2-propanol, respectively. In the case of dehydrogenation of 2-propanol, a turnover number of greater than 44 000 was achieved. To our knowledge, these are unprecedented values for photocatalytic splitting of liquid alcohols under visible light to date. Besides, the current catalyst system functions well with other aliphatic and aromatic alcohols, affording the corresponding carbonyl compounds with good to excellent conversion and outstanding selectivity. Moreover, mechanistic investigations suggest that an interf...

Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride MnI and FeII PNP Pincer Complexes

Abstract: Herein, we describe an efficient coupling of alcohols and amines catalyzed by well-defined isoelectronic hydride Mn(I) and Fe(II) complexes, which are stabilized by a PNP ligand based on the 2,6-diaminopyridine scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant non-precious metal catalysts, and is based on the acceptorless alcohol dehydrogenation concept. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted in good to excellent isolated yields. Although in the case of Mn selectively imines were obtained, with Fe-exclusively monoalkylated amines were formed. These reactions proceed under base-free conditions and required the addition of molecular sieves.

Role of Sn in the Regeneration of Pt/γ-Al2O3 Light Alkane Dehydrogenation Catalysts

Abstract: Alumina-supported Pt is one of the major industrial catalysts for light alkane dehydrogenation. This catalyst loses activity during reaction, with coke formation often considered as the reason for deactivation. As we show in this study, the amount and nature of carbon deposits do not directly correlate with the loss of activity. Rather, it is the transformation of subnanometer Pt species into larger Pt nanoparticles that appears to be responsible for the loss of catalytic activity. Surprisingly, a portion of the Sn remains atomically dispersed on the alumina surface in the spent catalyst and helps in the redispersion of the Pt. In the absence of Sn on the alumina support, the larger Pt nanoparticles formed during reaction are not redispersed during oxidative regeneration. It is known that Sn is added as a promoter in the industrial catalyst to help in achieving high propene selectivity and to minimize coke formation. This work shows that an important role of Sn is to help in the regeneration of Pt, by providing nucleation sites on the alumina surface. Aberration-corrected scanning transmission electron microscopy helps to provide unique insights into the operating characteristics of an industrially important catalyst by demonstrating the role of promoter elements, such as Sn, in the oxidative regeneration of Pt on γ-Al2O3.

Visible-Light Photocatalysis of Aerobic Oxidation Reactions Using Carbazolic Conjugated Microporous Polymers

Abstract: Carbazolic conjugated microporous polymer (C-CMP) is obtained via straightforward carbazole-based oxidative coupling polymerization. C-CMP exhibits high porosity and a specific surface area of 1137 m2 g–1, and it is thermally stable to 600 °C in nitrogen. C-CMP is shown to be a highly effective heterogeneous photocatalyst for a wide range of reactions, including the oxidative coupling of primary amines, aerobic dehydrogenation of nonactive secondary amine substrates such as pharmaceutically relevant nitrogen heterocycles, and selective oxidation of sulfide using molecular oxygen and visible light. This work highlights the potential of developing photoactive N-containing CMPs as a highly stable, molecularly tunable, reusable, and metal-free visible light photocatalysts for a wide variety of organic transformations.

Nature of the Active Sites of VOx/Al2O3 Catalysts for Propane Dehydrogenation

Abstract: Supported VOx catalysts are promising for use in propane dehydrogenation (PDH) because of the relatively superior activity and stable performance upon regeneration. However, the nature of the active sites and reaction mechanism during PDH over VOx-based catalysts remains elusive. We examined active species by attaining various fractions of V5+, V4+, and V3+ ions by adjusting the surface vanadium density on an alumina support. The results reveal a close relationship between TOF and the fraction of V3+ ion, indicating that V3+ was more active for PDH. In situ diffuse reflectance infrared Fourier transform spectroscopy showed the same strong adsorbed species during both propane dehydrogenation and propylene hydrogenation. The results indicated that such an intermediate may correspond to V species containing a C═C bond, i.e., V–C3H5, and a reaction mechanism was proposed accordingly.

Conversion of alkanes to linear alkylsilanes using an iridium–iron-catalysed tandem dehydrogenation–isomerization–hydrosilylation

Abstract: The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical-they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C-H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization-hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters.

Self-supported CoP nanosheet arrays: a non-precious metal catalyst for efficient hydrogen generation from alkaline NaBH4 solution

Abstract: Hydrogen can be catalytically generated on a large scale by hydrolysis of NaBH4. In this communication, we describe the development of cobalt phosphide nanosheet arrays on Ti mesh (CoP/Ti mesh) as a robust and highly active monolithic catalyst for the hydrolytic dehydrogenation of NaBH4 in alkaline solutions. A hydrogen generation rate of 6100 mL(H2) min−1 g(CoP)−1 and an activation energy of 42.01 kJ mol−1 were achieved under air-saturated atmospheric conditions, which are superior to those of most reported catalysts, with good durability and reusability.

Platinum-Modified ZnO/Al2O3 for Propane Dehydrogenation: Minimized Platinum Usage and Improved Catalytic Stability

Abstract: Compared to metallic platinum and chromium oxide, zinc oxide (ZnO) is an inexpensive and low-toxic alternative for the direct dehydrogenation of propane (PDH). However, besides the limited activity, conventional zinc-based catalysts suffer from serious deactivation, because of ZnO reduction and/or carbon deposition. Considering the high cost of platinum, reducing the amount of platinum in the catalyst is always desirable. This paper describes a catalyst comprising ZnO modified by trace platinum supported on Al2O3, where the Zn2+ species serve as active sites and platinum acts as a promoter. This catalyst contains less platinum than traditional platinum-based catalysts and is much more stable than conventional ZnO catalyst or commercial chromium-based systems during PDH. It is proposed that ZnO was promoted to a stronger Lewis acid by platinum; thus, easier C–H activation and accelerated H2 desorption were achieved.

Cu-Catalyzed Sequential Dehydrogenation–Conjugate Addition for β-Functionalization of Saturated Ketones: Scope and Mechanism

Abstract: The first copper-catalyzed direct β-functionalization of saturated ketones is reported. This protocol enables diverse ketones to couple with a wide range of nitrogen, oxygen and carbon nucleophiles in generally good yields under operationally simple conditions. The detailed mechanistic studies including kinetic studies, KIE measurements, identification of reaction intermediates, EPR and UV–visible experiments were conducted, which reveal that this reaction proceeds via a novel radical-based dehydrogenation to enone and subsequent conjugate addition sequence.

Unravelling the Mechanism of Basic Aqueous Methanol Dehydrogenation Catalyzed by Ru-PNP Pincer Complexes.

Abstract: Ruthenium PNP complex 1a (RuH(CO)Cl(HN(C2H4Pi-Pr2)2)) represents a state-of-the-art catalyst for low-temperature (<100 °C) aqueous methanol dehydrogenation to H2 and CO2. Herein, we describe an investigation that combines experiment, spectroscopy, and theory to provide a mechanistic rationale for this process. During catalysis, the presence of two anionic resting states was revealed, Ru–dihydride (3–) and Ru–monohydride (4–) that are deprotonated at nitrogen in the pincer ligand backbone. DFT calculations showed that O- and CH- coordination modes of methoxide to ruthenium compete, and form complexes 4– and 3–, respectively. Not only does the reaction rate increase with increasing KOH, but the ratio of 3–/4– increases, demonstrating that the “inner-sphere” C—H cleavage, via C—H coordination of methoxide to Ru, is promoted by base. Protonation of 3– liberates H2 gas and formaldehyde, the latter of which is rapidly consumed by KOH to give the corresponding gem-diolate and provides the overall driving force f...

Unraveling the formation mechanism of graphitic nitrogen-doping in thermally treated graphene with ammonia

Abstract: Nitrogen-doped graphene (N-graphene) has attractive properties that has been widely studied over the years. However, its possible formation process still remains unclear. Here, we propose a highly feasible formation mechanism of the graphitic-N doing in thermally treated graphene with ammonia by performing ab initio molecular dynamic simulations at experimental conditions. Results show that among the commonly native point defects in graphene, only the single vacancy 5-9 and divacancy 555-777 have the desirable electronic structures to trap N-containing groups and to mediate the subsequent dehydrogenation processes. The local structure of the defective graphene in combining with the thermodynamic and kinetic effect plays a crucial role in dominating the complex atomic rearrangement to form graphitic-N which heals the corresponding defect perfectly. The importance of the symmetry, the localized force field, the interaction of multiple trapped N-containing groups, as well as the catalytic effect of the temporarily formed bridge-N are emphasized, and the predicted doping configuration agrees well with the experimental observation. Hence, the revealed mechanism will be helpful for realizing the targeted synthesis of N-graphene with reduced defects and desired properties.

A prolific catalyst for dehydrogenation of neat formic acid

Abstract: Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments.

Carbon dispersed copper-cobalt alloy nanoparticles: A cost-effective heterogeneous catalyst with exceptional performance in the hydrolytic dehydrogenation of ammonia-borane

Abstract: Herein, we report the development of a new and cost-effective nanocatalyst for the hydrolytic dehydrogenation of ammonia-borane (NH3BH3), which is considered to be one of the most promising solid hydrogen carriers due to its high gravimetric hydrogen storage capacity (19.6 wt%) and low molecular weight. The new catalyst system consisting of bimetallic copper-cobalt alloy nanoparticles supported on activated carbon was simply and reproducibly prepared by surfactant-free deposition-reduction technique at room temperature. The characterization of this new catalytic material was done by the combination of multi-pronged techniques including ICP-MS, XRD, XPS, BFTEM, HR-TEM, STEM and HAADF-STEM-line analysis. The sum of their results revealed that the formation of copper-cobalt alloy nanoparticles (dmean = 1.8 nm) on the surface of activated carbon (CuCo/C). These new carbon supported copper-cobalt alloy nanoparticles act as highly active catalyst in the hydrolytic dehydrogenation of ammonia-borane, providing an initial turnover frequency of TOF = 2700 h−1 at 298 K, which is not only higher than all the non-noble metal catalysts but also higher than the majority of the noble metal based homogeneous and heterogeneous catalysts employed in the same reaction. More importantly, easy recovery and high durability of these supported CuCo nanoparticles make CuCo/C recyclable heterogeneous catalyst for the hydrolytic dehydrogenation of ammonia-borane. They retain almost their inherent activity even at 10th catalytic reuse in the hydrolytic dehydrogenation of ammonia-borane at 298 K.

PdAu-MnOx nanoparticles supported on amine-functionalized SiO2 for the room temperature dehydrogenation of formic acid in the absence of additives

Abstract: Formic acid (HCOOH) has recently been suggested as a promising hydrogen carrier for fuel cell applications. However efficient hydrogen production through the decomposition of formic acid in the absence of additives under mild thermodynamic conditions constitutes a major challenge because of the ease poisoning of active metals with CO formed as intermediate during formic acid decomposition. Recently, we have reported (App. Catal. B: Env. 164 (2015) 324) our discovery that the separately nucleated MnO x nanoparticles act as CO-sponge around catalytically active Pd nanoparticles exist on the same support and enhances both the activity and CO-resistivity of Pd nanoparticles. Using this important finding, herein, we present a new catalyst system consists of the physical mixture of PdAu alloy and MnO x nanoparticles supported on amine-grafted silica (PdAu-MnO x /N-SiO 2 ) for the room temperature dehydrogenation of formic acid in the absence of any additives. PdAu-MnO x /N-SiO 2 catalyst was simply prepared by deposition–reduction technique in water at room temperature with high reproducibility and characterized by the combination of various spectroscopic tools including ICP-OES, P-XRD, DR/UV–vis, XPS, BFTEM, STEM-EDX, STEM-line analysis and CO-stripping voltammetry techniques. The sum of their results shows that the formation of physical mixture of PdAu alloy and MnO x ( d mean = 2.2 nm) nanoparticles on the surface of support material. This new catalytic material facilitates the hydrogen liberation through the additive-free formic acid dehydrogenation at room temperature with previously unprecedented activity (TOF = 785 mol H 2 mol catalyst −1 h −1 ), converging to that of the existing state of the art homogenous catalysts. This new superior catalytic system enables facile catalyst recovery and very high stability against agglomeration, leaching and CO poisoning, which make it highly reusable catalyst (retains >92% activity and 85% conversion at the 5th catalytic reuse) in the additive-free formic acid dehydrogenation at room temperature.

Physicochemical Stabilization of Pt against Sintering for a Dehydrogenation Catalyst with High Activity, Selectivity, and Durability

Abstract: Suppressing irreversible catalyst deactivation is critical in heterogeneous catalysis. In particular, deactivation via sintering of active sites is a significant issue for reactions involving harsh reaction/regeneration conditions. In this work, we developed a PtGa/γ-Al2O3 alkane dehydrogenation catalyst with exceptionally high activity, selectivity, and long-term stability by markedly suppressing Pt sintering under harsh conditions (reaction/regeneration at >823 K). To stabilize Pt, physical and chemical stabilization strategies were synergistically combined. For the former, Pt was introduced during the synthesis of γ-Al2O3 via sol–gel chemistry, which can increase the interfacial contact between Pt and γ-Al2O3 due to the partial entrapment of Pt in γ-Al2O3. For the latter, atomically dispersed Ce was doped on γ-Al2O3, which can stabilize Pt via strong Pt–O–Ce interactions. Because of effective Pt stabilization, the catalyst showed remarkably steady activity and selectivity behaviors over the repeated re...

Enantioselective Alcohol C–H Functionalization for Polyketide Construction: Unlocking Redox-Economy and Site-Selectivity for Ideal Chemical Synthesis

Abstract: The development and application of stereoselective and site-selective catalytic methods that directly convert lower alcohols to higher alcohols are described. These processes merge the characteristics of transfer hydrogenation and carbonyl addition, exploiting alcohols and π-unsaturated reactants as redox pairs, which upon hydrogen transfer generate transient carbonyl–organometal pairs en route to products of C–C coupling. Unlike classical carbonyl additions, stoichiometric organometallic reagents and discrete alcohol-to-carbonyl redox reactions are not required. Additionally, due to a kinetic preference for primary alcohol dehydrogenation, the site-selective modification of glycols and higher polyols is possible, streamlining or eliminating use of protecting groups. The total syntheses of several iconic type I polyketide natural products were undertaken using these methods. In each case, the target compounds were prepared in significantly fewer steps than previously achieved.

Ni–M–O (M = Sn, Ti, W) Catalysts Prepared by a Dry Mixing Method for Oxidative Dehydrogenation of Ethane

Abstract: A new generation of Ni–Sn–O, Ni–Ti–O, and Ni–W–O catalysts has been prepared by a solid-state grinding method. In each case the doping metal varied from 2.5% to 20%. These catalysts exhibited higher activity and selectivity for ethane oxidative dehydrogenation (ODH) than conventionally prepared mixed oxides. Detailed characterization was achieved using XRD, N2 adsorption, H2-TPR, SEM, TEM, and HAADF-STEM in order to study the detailed atomic structure and textural properties of the synthesized catalysts. Two kinds of typical structures are found in these mixed oxides, which are (major) “NixMyO” (M = Sn, Ti, W) solid solution phases (NiO crystalline structure with doping atom incorporated in the lattice) and (minor) secondary phases (SnO2, TiO2, or WO3). The secondary phase exists as a thin layer around small “NixMyO” particles, lowering the aggregation of nanoparticles during the synthesis. DFT calculations on the formation energies of M-doped NiO structures (M = Sn, Ti, W) clearly confirm the thermodynam...