Selective Alkane Oxidation by Manganese Oxide: Site Isolation of MnOx Chains at the Surface of MnWO4 Nanorods

The electronic and structural properties of vanadium‐containing phases govern the formation of isolated active sites at the surface of these catalysts for selective alkane oxidation. This concept is not restricted to vanadium oxide. The deliberate use of hydrothermal techniques can turn the typical combustion catalyst manganese oxide into a selective catalyst for oxidative propane dehydrogenation. Nanostructured, crystalline MnWO₄ serves as the support that stabilizes a defect‐rich MnO_x surface phase. Oxygen defects can be reversibly replenished and depleted at the reaction temperature. Terminating MnO_x zigzag chains on the (010) crystal planes are suspected to bear structurally site‐isolated oxygen defects that account for the unexpectedly good performance of the catalyst in propane activation.     

Towards a Practical Development of Light‐Driven Acceptorless Alkane Dehydrogenation

The efficient catalytic dehydrogenation of alkanes to olefins is one of the most investigated reactions in organic synthesis. In the coming years, an increased supply of shorter‐chain alkanes from natural and shale gas will offer new opportunities for inexpensive carbon feedstock through such dehydrogenation processes. Existing methods for alkane dehydrogenation using heterogeneous catalysts require harsh reaction conditions and have a lack of selectivity, whereas homogeneous catalysis methods result in significant waste generation. A strong need exists for atom‐efficient alkane dehydrogenations on a useful scale. Herein, we have developed improved acceptorless catalytic systems under optimal light transmittance conditions using trans‐[Rh(PMe₃)₂(CO)Cl] as the catalyst with different additives. Unprecedented catalyst turnover numbers are obtained for the dehydrogenation of cyclic and linear (from C₄) alkanes and liquid organic hydrogen carriers. These reactions proceed with unique conversion, thereby providing a basis for practical alkane dehydrogenations.     

Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

Although hexagonal boron nitride (h‐BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas‐phase methyl radicals (CH₃^.) in the ODHP reaction over boron‐based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV‐PIMS), which uncovers the existence of gas‐phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C?H activation of propane, while C₂ and C₁ products can be formed via both surface‐mediated and gas‐phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron‐based catalysts.     

Thermally Stable and Regenerable Platinum–Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

Ceria (CeO₂) supports are unique in their ability to trap ionic platinum (Pt), providing exceptional stability for isolated single atoms of Pt. The reactivity and stability of single‐atom Pt species was explored for the industrially important light alkane dehydrogenation reaction. The single‐atom Pt/CeO₂ catalysts are stable during propane dehydrogenation, but are not selective for propylene. DFT calculations show strong adsorption of the olefin produced, leading to further unwanted reactions. In contrast, when tin (Sn) is added to CeO₂, the single‐atom Pt catalyst undergoes an activation phase where it transforms into Pt–Sn clusters under reaction conditions. Formation of small Pt–Sn clusters allows the catalyst to achieve high selectivity towards propylene because of facile desorption of the product. The CeO₂‐supported Pt–Sn clusters are very stable, even during extended reaction at 680 °C. Coke formation is almost completely suppressed by adding water vapor to the feed. Furthermore, upon oxidation the Pt–Sn clusters readily revert to the atomically dispersed species on CeO₂, making Pt–Sn/CeO₂ a fully regenerable catalyst.     

Three‐Phase Photocatalysis for the Enhanced Selectivity and Activity of CO2 Reduction on a Hydrophobic Surface

The photocatalytic CO₂ reduction reaction (CRR) represents a promising route for the clean utilization of stranded renewable resources, but poor selectivity resulting from the competing hydrogen evolution reaction (HER) in aqueous solution limits its practical applicability. In the present contribution a photocatalyst with hydrophobic surfaces was fabricated. It facilitates an efficient three‐phase contact of CO₂ (gas), H₂O (liquid), and catalyst (solid). Thus, concentrated CO₂ molecules in the gas phase contact the catalyst surface directly, and can overcome the mass‐transfer limitations of CO₂, inhibit the HER because of lowering proton contacts, and overall enhance the CRR. Even when loaded with platinum nanoparticles, one of the most efficient HER promotion cocatalysts, the three‐phase photocatalyst maintains a selectivity of 87.9 %. Overall, three‐phase photocatalysis provides a general and reliable method to enhance the competitiveness of the CRR.     

Carbon Dynamics on the Molybdenum Carbide Surface during Catalytic Propane Dehydrogenation

The effect of the gas‐phase chemical potential on surface chemistry and reactivity of molybdenum carbide has been investigated in catalytic reactions of propane in oxidizing and reducing reactant mixtures by adding H₂, O₂, H₂O, and CO₂ to a C₃H₈/N₂ feed. The balance between surface oxidation state, phase stability, carbon deposition, and the complex reaction network involving dehydrogenation reactions, hydrogenolysis, metathesis, water‐gas shift reaction, hydrogenation, and steam reforming is discussed. Raman spectroscopy and a surface‐sensitive study by means of in situ X‐ray photoelectron spectroscopy evidence that the dynamic formation of surface carbon species under a reducing atmosphere strongly shifts the product spectrum to the C₃‐alkene at the expense of hydrogenolysis products. A similar response of selectivity, which is accompanied by a boost of activity, is observed by tuning the oxidation state of Mo in the presence of mild oxidants, such as H₂O and CO₂, in the feed as well as by V doping. The results obtained allow us to draw a picture of the active catalyst surface and to propose a structure–activity correlation as a map for catalyst optimization.     

BiMo基复合氧化物催化剂丙烷直接氧化至丙烯醛研究

The effects of the available zoon above the catalyst bed on the performance of the catalyst were investigated. It has been suggested that propylene is an intermediate species in the reaction of propane to acrolein， and a two-step reaction scheme is proposed， the first step is oxidative dehydrogenation of propane to propylene in the gas phase then followed by the second step， the selective oxidation of propylene to acrolein on the surface of the catalyst. The performance of the catalyst depends on both the oxidative dehydrogenation of propane to propylene in the gas phase and the selective oxidation of propylene to acrolein on the catalyst surface. The thermal cracking， homogeneous oxidative dehydrogenation and heterogeneous catalytic dehydrogenation of propane as well as the selective catalytic oxidation of propane to acrolein over BiMoO based mixed oxides catalysts were studied. Under the optimum reaction conditions of propane dehydrogenation and selective oxidation of propylene， the selectivity and the yield of acrolein approached to 45mol% and 14mol%， respectively under about 30mol% propane conversion.     

Encapsulation of Crabtree's Catalyst in Sulfonated MIL‐101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment

Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL‐101(Cr) metal–organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non‐functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well‐defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways.     

Monitoring in situ catalytically active states of Ru catalysts for different methanol oxidation pathways

One of the prerequisites for the detailed understanding of heterogeneous catalysis is the identification of the dynamic response of the catalyst surface under variable reaction conditions. The present study of methanol oxidation on different model Ru pre-catalysts, performed approaching the realistic catalytic reaction conditions, provides direct evidence of the significant effect of reactants' chemical potentials and temperature on the catalyst surface composition and the corresponding catalytic activity and selectivity. The experiments were carried out for three regimes of oxygen potentials in the 10(-1) mbar pressure range, combining in situ analysis of the catalyst surface by synchrotron-based photoelectron core level spectroscopy with simultaneous monitoring of the products released in the gas phase by mass spectroscopy. Metallic Ru with adsorbed oxygen and transient 'surface oxide', RuO(x), with varying x have been identified as the catalytically active states under specific reaction conditions, favouring partial or full oxidation pathways. It has been shown that the composition of catalytically active steady states, exhibiting different activity and selectivity, evolves under the reaction conditions, independent of the crystallographic orientation and the initial pre-catalyst chemical state, metallic Ru or RuO(2).     

超临界相CO加氢合成甲醇,异丁醇的研究

以正十一～十三烷的混合物为超临界介质,在反应温度３６０～４１０℃、合成气压力７５ＭＰａ、进气空速１７００ｈ－１、介质压力１７８ＭＰａ、总压９３ＭＰａ的实验条件下,研究了固定床反应器中Ｚｎ－Ｃｒ、Ｃｕ－Ｚｎ－Ｃｒ催化剂在超临界相和气相条件下合成甲醇、异丁醇的性能。结果表明,超临界相反应的ＣＯ转化率高于气相反应。在超临界条件下反应,醇类选择性随着温度升高下降较慢,而气相反应醇类选择性随着温度升高下降较快。气相反应产物以甲醇、异丁醇为主,含少量乙醇和正丙醇,超临界相反应的产物分布与气相反应的明显不同,甲醇含量减少,乙醇、正丙醇和异丁醇都有不同程度增加。超临界流体的存在对合成醇链增长有影响,在不同催化剂上的产物分布有较大差异     

Molecular Factors of Catalytic Selectivity

Selectivity—the production of one molecule out of many other thermodynamically feasible product molecules—is the key concept in developing clean processes that do not produce by‐products (green chemistry). Small differences in the potential‐energy barriers of single reaction steps control which reaction channel is more likely to yield the desired product molecule (selectivity), while the overall activation energy of the reaction controls the turnover rates (activity). Recent studies have demonstrated that tailoring parameters at the atomic or molecular level—such as the surface structures of active sites—gives turnover rates and reaction selectivities that depend on the nanoparticle size and shape. Here, we highlight seven molecular components that influence the selectivity of heterogeneous catalyst reactions on single‐crystal model surfaces and colloid nanoparticles: surface structure, adsorbate‐induced restructuring, adsorbate mobility, reaction intermediates, surface composition, charge transport, and oxidation states. We show the importance of the single factors by means of examples and describe in situ analyses that permit their roles in surface reactions to be investigated.     

Ag-MoO3催化丙烯直接气相环氧化反应的原位红外研究

制备了对丙烯直接气相环氧化具有较好催化性能的Ag-MoO3催化剂, 采用原位FT-IR技术研究了丙烯、环氧丙烷及丙烯+氧气的混合气在Ag和Ag-MoO3催化剂表面上的吸附及反应行为. 研究表明, 丙烯在Ag和Ag-MoO3催化剂表面上吸附后, 均不发生化学反应, 而环氧丙烷吸附后在较高温度下则发生开环和聚合反应直至产生积炭. 与Ag催化剂相比, 在Ag-MoO3催化剂上, MoO3的加入在降低催化剂活性的同时, 在一定程度上抑制了产物环氧丙烷的开环及深度反应, 使环氧丙烷的选择性提高. 另外, 在较低的反应温度和较短的滞留时间下, 环氧丙烷发生深度反应的程度明显降低.     

Pyrolysis of liquefied petroleum gas assisted by radicals desorbed from mesh catalyst surface

The purpose of this study is to understand the reactions on the catalyst surface and in the gas phase during the catalytic pyrolysis of light hydrocarbons. To avoid the complexity of internal pore diffusion and heat transfer limitation, nickel mesh without pore structure was used as a catalyst for the catalytic pyrolysis of a commercial liquefied petroleum gas (LPG) sample in a quartz tube reactor and in a wire‐mesh reactor over a temperature range of 600–850°C. With a Ni mesh catalyst, no catalyst deactivation associated with coke formation was observed at high gas flow rate. Our experimental results indicate that the desorption of radicals from the catalyst surface is an important process in the catalytic pyrolysis of LPG using the Ni mesh catalyst. The desorption of radicals across the gas–catalyst interface is greatly facilitated by increasing gas flow rate passing through the mesh. The desorbed radicals would initiate and/or enhance the gas‐phase radical chain reactions and lead to improved reaction rates for the pyrolysis of LPG although the product selectivities remained unchanged. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 637–646, 2003     

Towards the design of novel boron‐ and nitrogen‐substituted ammonia‐borane and bifunctional arene ruthenium catalysts for hydrogen storage

Electronic‐structure density functional theory calculations have been performed to construct the potential energy surface for H₂ release from ammonia‐borane, with a novel bifunctional cationic ruthenium catalyst based on the sterically bulky β‐diketiminato ligand (Schreiber et al., ACS Catal. 2012, 2, 2505). The focus is on identifying both a suitable substitution pattern for ammonia‐borane optimized for chemical hydrogen storage and allowing for low‐energy dehydrogenation. The interaction of ammonia‐borane, and related substituted ammonia‐boranes, with a bifunctional η⁶‐arene ruthenium catalyst and associated variants is investigated for dehydrogenation. Interestingly, in a number of cases, hydride‐proton transfer from the substituted ammonia‐borane to the catalyst undergoes a barrier‐less process in the gas phase, with rapid formation of hydrogenated catalyst in the gas phase. Amongst the catalysts considered, N,N‐difluoro ammonia‐borane and N‐phenyl ammonia‐borane systems resulted in negative activation energy barriers. However, these types of ammonia‐boranes are inherently thermodynamically unstable and undergo barrierless decay in the gas phase. Apart from N,N‐difluoro ammonia‐borane, the interaction between different types of catalyst and ammonia borane was modeled in the solvent phase, revealing free‐energy barriers slightly higher than those in the gas phase. Amongst the various potential candidate Ru‐complexes screened, few are found to differ in terms of efficiency for the dehydrogenation (rate‐limiting) step. To model dehydrogenation more accurately, a selection of explicit protic solvent molecules was considered, with the goal of lowering energy barriers for H‐H recombination. It was found that primary (1°), 2°, and 3° alcohols are the most suitable to enhance reaction rate. © 2014 Wiley Periodicals, Inc.     

Direct Non‐Oxidative Methane Conversion in a Millisecond Catalytic Wall Reactor

Direct non‐oxidative methane conversion (DNMC) has been recognized as a single‐step technology that directly converts methane into olefins and higher hydrocarbons. High reaction temperature and low catalyst durability, resulting from the endothermic reaction and coke deposition, are two main challenges. We show that a millisecond catalytic wall reactor enables stable methane conversion, C₂₊ selectivity, coke yield, and long‐term durability. These effects originate from initiation of the DNMC on a reactor wall and maintenance of the reaction by gas‐phase chemistry within the reactor compartment. The results obtained under various temperatures and gas flow rates form a basis for optimizing the process towards lighter C₂ or heavier aromatic products. A process simulation was done by Aspen Plus to understand the practical implications of this reactor in DNMC. High carbon and thermal efficiencies and low cost of the reactor materials are realized, indicating the technoeconomic viability of this DNMC technology.     

The Formation of Surface Lithium–Iron Ternary Hydride and its Function on Catalytic Ammonia Synthesis at Low Temperatures

Lithium hydride (LiH) has a strong effect on iron leading to an approximately 3 orders of magnitude increase in catalytic ammonia synthesis. The existence of lithium–iron ternary hydride species at the surface/interface of the catalyst were identified and characterized for the first time by gas‐phase optical spectroscopy coupled with mass spectrometry and quantum chemical calculations. The ternary hydride species may serve as centers that readily activate and hydrogenate dinitrogen, forming Fe‐(NH₂)‐Li and LiNH₂ moieties—possibly through a redox reaction of dinitrogen and hydridic hydrogen (LiH) that is mediated by iron—showing distinct differences from ammonia formation mediated by conventional iron or ruthenium‐based catalysts. Hydrogen‐associated activation and conversion of dinitrogen are discussed.     

Terbium–organic framework as heterogeneous Lewis acid catalyst for β‐aminoalcohol synthesis: Efficient,reusable and green catalytic method

A terbium–organic framework (Tb‐MOF) was prepared using a previously reported procedure. Tb‐MOF was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, powder X‐ray diffraction and surface area analysis. Tb‐MOF was employed as a heterogeneous Lewis acid catalyst for the synthesis of β‐aminoalcohols. Also, the effect of ultrasonic irradiation was examined in the catalytic aminolysis of styrene oxide. The reaction conditions were optimized by variation of reaction time, catalyst concentration and solvent. A variety of β‐aminoalcohols were synthesized and characterized. The Tb‐MOF catalyst showed excellent selectivity and high yield for these transformations.     

甲烷在Ni/TiO2催化剂表面的活化

考察了Ni/TiO2催化剂甲烷部分氧化和二氧化碳重整制合成气的反应活性,实验表明,以TiO2为载体的镍系催化剂对于甲烷部分氧化制合成气反应具有较好的活性,尤其对H2的选择性较高,对二氧化碳重整制合成气反应具有较好的低温反应活性.采用脉冲-质谱在线分析等技术,在无气相氧条件下向Ni/TiO2催化剂脉冲CH4,发现甲烷在催化剂表面的活化（转化）及其氧化产物的选择性与金属催化剂表面氧的浓度密切相关.CH4与Ni/TiO2催化剂作用过程中存在明显的氢溢流和氧溢流现象,可能是这种溢流效应使得Ni/TiO2催化剂具有良好的反应活性和抗积碳性能.