Krijn P. de Jong

Carbon nanofibers: catalytic synthesis and applications

Carbon nanofibers (diameter range, 3–100 nm; length range, 0.1–1000 µm) have been known for a long time as a nuisance that often emerges during catalytic conversion of carbon-containing gases. The recent outburst of interest in these graphitic materials originates from their potential for unique applications as well as their chemical similarity to fullerenes and carbon nanotubes. In this review, we focus on the growth of nanofibers using metallic particles as a catalyst to precipitate the graphitic carbon. First, we summarize some of the earlier literature that has contributed greatly to understand the nucleation and growth of carbon nanofibers and nanotubes. Thereafter, we describe in detail recent progress to control the fiber surface structure, texture, and growth into mechanically strong agglomerates. It is argued that carbon nanofibers are unique high-surface-area materials (˜200 m2/g) that can expose exclusively either basal graphite planes or edge planes. Subsequently, we will present the recently explored applications of carbon nanofibers: polymer additives, gas storage materials, and catalyst supports. The latter application is described in detail. It is shown that the graphite surface structure and the lyophilicity play a crucial role during metal emplacement and catalytic use in liquid-phase catalysis. A case in point is fiber-supported Pd catalysts for nitrobenzene hydrogenation. Finally, we summarize issues with respect to the large-scale production of carbon nanofibers, including production cost estimates and research items to be dealt with in future work.

Generation, Characterization, and Impact of Mesopores in Zeolite Catalysts

Amongst the current developments in the field of hierarchical pore structures, the creation of mesopores in zeolite crystals is the most frequently employed way to combine micropores with mesopores in one material. In this review an overview is presented of the different approaches to generate and characterize mesopores in zeolite crystals and establish their impact on the catalytic action. Mesopores can be created via several routes from which steaming and acid leaching are the most frequently applied. Novel approaches using secondary carbon templates that are removed after synthesis have recently been launched. For the characterization of mesopores, nitrogen physisorption and electron microscopy are commonly used. More recently, it was shown that electron tomography, a form of three-dimensional transmission electron microscopy, is able to reveal the three-dimensional shape, size, and connectivity of the mesopores. The effect of the presence of mesopores for catalysis is demonstrated for several industrially applied processes that make use of zeolite catalysts: the cracking of heavy oil fractions over zeolite Y, the production of cumene and hydroisomerization of alkanes over mordenite, and synthesis of fine chemicals over Y, ZSM-5, and Beta. For these processes, the mesopores ensure an optimal accessibility and transport of reactants and products, while the zeolite micropores induce the preferred shape-selective properties.

Supported Iron Nanoparticles as Catalysts for Sustainable Production of Lower Olefins

From Plant to Plastic Petroleum is primarily used as fuel, but it is also used in the production of plastics. Thus, if biomass were to replace petroleum as societys carbon feedstock, a means of deriving ethylene and propylene—the principal building blocks of todays commodity plastics— would be helpful. Well-known Fischer-Tropsch (FT) catalysts can transform gasified biomass into a range of hydrocarbon derivatives, but ethylene and propylene tend to constitute a small fraction of the overall product distribution. Torres Galvis et al. (p. 835) now demonstrate a class of iron catalysts on relatively passive supports (carbon nanofibers or α-alumina) that robustly directed the FT process toward light olefins. A class of iron catalysts selectively transforms gasified biomass into the building blocks of common plastics. Lower olefins are key building blocks for the manufacture of plastics, cosmetics, and drugs. Traditionally, olefins with two to four carbons are produced by steam cracking of crude oil–derived naphtha, but there is a pressing need for alternative feedstocks and processes in view of supply limitations and of environmental issues. Although the Fischer-Tropsch synthesis has long offered a means to convert coal, biomass, and natural gas into hydrocarbon derivatives through the intermediacy of synthesis gas (a mixture of molecular hydrogen and carbon monoxide), selectivity toward lower olefins tends to be low. We report on the conversion of synthesis gas to C2 through C4 olefins with selectivity up to 60 weight percent, using catalysts that constitute iron nanoparticles (promoted by sulfur plus sodium) homogeneously dispersed on weakly interactive α-alumina or carbon nanofiber supports.

Towards stable catalysts by controlling collective properties of supported metal nanoparticles

Supported metal nanoparticles play a pivotal role in areas such as nanoelectronics, energy storage/conversion and as catalysts for the sustainable production of fuels and chemicals. However, the tendency of nanoparticles to grow into larger crystallites is an impediment for stable performance. Exemplarily, loss of active surface area by metal particle growth is a major cause of deactivation for supported catalysts. In specific cases particle growth might be mitigated by tuning the properties of individual nanoparticles, such as size, composition and interaction with the support. Here we present an alternative strategy based on control over collective properties, revealing the pronounced impact of the three-dimensional nanospatial distribution of metal particles on catalyst stability. We employ silica-supported copper nanoparticles as catalysts for methanol synthesis as a showcase. Achieving near-maximum interparticle spacings, as accessed quantitatively by electron tomography, slows down deactivation up to an order of magnitude compared with a catalyst with a non-uniform nanoparticle distribution, or a reference Cu/ZnO/Al(2)O(3) catalyst. Our approach paves the way towards the rational design of practically relevant catalysts and other nanomaterials with enhanced stability and functionality, for applications such as sensors, gas storage, batteries and solar fuel production.

Impact of the structure and reactivity of nickel particles on the catalytic growth of carbon nanofibers

Catalytically grown fishbone carbon nanofibers (CNF), are prepared by the decomposition of carbon-containing gases (CH4, CO/H2 or C2H4/H2) over a silica-supported nickel catalyst and an unsupported nickel catalyst at 550 ◦ C. It turns out that both the nickel particle size and the nature of the carbon-containing gas significantly affects the CNF growth process. We demonstrate that at the chosen temperature small supported nickel particles need a carbon-containing gas with a relatively low reactivity, like CH4 or CO/H2, to produce CNF. The resulting fishbone CNF have a uniform and small diameter (25 nm). The CNF thus synthesized hold great potential, e.g. as catalyst support material. However, the large unsupported nickel particles only produce CNF using a reactive carbon-containing gas, like C2H4/H2. The CNF thus obtained show a variety of morphologies with a large range of diameters (50–500 nm). The CNF yield is a subtle interplay between the nickel particle size and consequently the exposed crystal planes on the one hand and the reactivity of the carbon-containing gas on the other.

Synthesis of supported catalysts by impregnation and drying using aqueous chelated metal complexes

Abstract Work is reviewed on the synthesis of supported metal and metal oxide catalysts using impregnation of an aqueous solution of chelated metal ions followed by drying. The nature of the aqueous solutions of chelated complexes is discussed first. Upon solvent evaporation a steep increase in viscosity is apparent, which inhibits redistribution of impregnated solution upon drying of the support bodies. Furthermore, a gel-like phase is formed that favors high dispersions of the active phase after full drying. Second, several examples are dealt with in some detail, in particular supported iron, nickel, and cobalt–molybdenum catalysts. Finally an overview is presented for metal and metal oxide precursors that can be suitably deposited upon support materials using chelated aqueous metal complex solutions.

Three‐Dimensional Transmission Electron Microscopic Observations of Mesopores in Dealuminated Zeolite Y

Supported by NWO under grant 98037. The research of AJK has been made possible by a fellowship of the Royal Netherlands Academy of Arts and Sciences (KNAW). The authors thank J.E.M.J. Raaymakers for the nitrogen physisorption measurements, A.J.M. Mens for the XPS measurements, J.A.R. van Veen and E.J. Creyghton for physical data and useful discussions and Shell International Chemicals and Zeolyst for the samples.

Zeolite Y Crystals with Trimodal Porosity as Ideal Hydrocracking Catalysts

Effektive Poren: Zeolith-Y-Kristalle mit Mikroporen (ca. 1 nm), kleinen (ca. 3 nm) und grosen Mesoporen (ca. 30 nm) wurden aus zuvor mit Dampf und Saure behandeltem Material durch Auslaugen mit Base erhalten. Die Zeolith-Y-Kristalle mit trimodaler Porositat (siehe elektronentomographische Aufnahme) zeigen beim Hydrocracking eine nahezu ideale Selektivitat fur und erhohte Ausbeuten an Kerosin und Diesel.

Electron Tomography for Heterogeneous Catalysts and Related Nanostructured Materials

The full potential in catalyst development will only be realized if characterization techniques are available that can probe materials with subnanometer resolution. One of the most employed techniques to image heterogeneous catalysts at the nanometer and subnanometer scale is transmission electron microscopy (TEM). As suggested by the name, TEM uses electrons transmitted through the object for imaging. Since the interaction between electrons and matter is very strong, only thin parts, commonly much less than a micron in thickness, are imaged. Since heterogeneous catalysts are, in most cases, structured on a much smaller length scale, the sample thickness can be reduced to TEM requirements by appropriate preparation techniques and is, therefore, no limitation.

Iron Particle Size Effects for Direct Production of Lower Olefins from Synthesis Gas

The Fischer-Tropsch synthesis of lower olefins (FTO) is an alternative process for the production of key chemical building blocks from non-petroleum-based sources such as natural gas, coal, or biomass. The influence of the iron carbide particle size of promoted and unpromoted carbon nanofiber supported catalysts on the conversion of synthesis gas has been investigated at 340-350 °C, H(2)/CO = 1, and pressures of 1 and 20 bar. The surface-specific activity (apparent TOF) based on the initial activity of unpromoted catalysts at 1 bar increased 6-8-fold when the average iron carbide size decreased from 7 to 2 nm, while methane and lower olefins selectivity were not affected. The same decrease in particle size for catalysts promoted by Na plus S resulted at 20 bar in a 2-fold increase of the apparent TOF based on initial activity which was mainly caused by a higher yield of methane for the smallest particles. Presumably, methane formation takes place at highly active low coordination sites residing at corners and edges, which are more abundant on small iron carbide particles. Lower olefins are produced at promoted (stepped) terrace sites that are available and active, quite independent of size. These results demonstrate that the iron carbide particle size plays a crucial role in the design of active and selective FTO catalysts.