Early Years of High-Throughput Experimentation and Combinatorial Approaches in Catalysis and Materials Science.

This is a report on the early years of combinatorial materials science and technology. High-throughput technologies (HTTs) are found in life- and materials-science laboratories. Although HTTs have long been the standard in life sciences in academia as well as in industry, HTTs in materials science have become the standard in industry but not in academia. In life science, successful drugs developed with HTTs have been reported, but there is no information on successful materials developed with HTTs that have made it to the market. Some initial development of HTTs in materials science is summarized, especially early applications of artificial intelligence. This outlook attempts to summarize the development of combinatorial materials sciences from the early years to today.

Application of a simultaneous TGA-DSC thermal analysis system for high-throughput screening of catalytic activity.

We present here the use of a simultaneous TGA/DSC thermal analyzer as a high-throughput reactor system to measure after calibration the heat of reaction and therefore the catalytic activity of heterogeneous catalysts in a fast, reliable and reproducible manner. By coupling the gas outlet of the analyzer with a mass spectrometer via a heated capillary additional data can be acquired. As a test reaction the oxidation of carbon monoxide with synthetic air, using Hopcalite and several transition and noble metals as catalysts, was chosen. The setup presented allows the rapid sequential screening of about 70 catalysts per day.

Synthesis and mechanical properties of organic-inorganic hybrid materials from lignin and polysiloxanes.

The preparation of silica-containing organic-inorganic hybrid materials composed of kraft lignin, alkoxysilanes, and organic linkers was investigated. 3-Glycidyloxypropyltrimethoxysilane, 3-(triethoxysilyl)propylisocyanate (IPTES), and bis(trimethoxysilyl)hexane were selected as the most promising linkers. The best materials obtained showed improved mechanical and thermal properties compared with lignin itself. The reaction of the hydroxyl groups with IPTES and the sol-gel reaction between the organic linker molecules were studied by attenuated total reflectance FTIR and solid-state ²9Si magic-angle spinning NMR spectroscopy. The homogeneous composition was demonstrated by electron microscopy and energy-dispersive X-ray spectroscopy mapping. The mechanical properties were investigated by microindentation and dynamic mechanical thermal analysis.

Infrared thermography as a high-throughput tool in catalysis research.

The so-called "emissivity corrected infrared thermography" (ecIRT) has been successfully developed and used to great effect in the field of combinatorial high-throughput studies in catalysis. A short introduction to the basics of ecIRT and the description of a typical setup is given. Research efforts from 1998 until present are summarized and selected publications with IRT applications in catalysis are highlighted. The last section of the article covers potential problems, which the observant may misinterpret as activity of the materials. The effects are classified and it is explained why they occur and what can be done to bypass them.

High-throughput technology for novel SO2 oxidation catalysts.

We review the state of the art and explain the need for better SO2 oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO2 to SO3. High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO2 oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO2 conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO3 from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations.

Optimized droplet-based microfluidics scheme for sol-gel reactions.

A droplet-based microfluidic reaction scheme is developed where the chemical reactants are dispensed with precise volume control into pairs of droplets. The reaction is activated by coalescing droplet pairs and fast mixing inside the coalesced droplets. Furthermore, the pre-processing of the chemical products is included in the microfluidic device. This reaction scheme allows the performing of precisely volume controlled reactions and long operation times without any clogging even if precipitates or sticky gels are formed during the reaction. Using this approach and optimizing the reaction parameters, we generate mesoporous silica microspheres from a rapid gelation optimized sol-gel synthesis route. The produced silica particles have a superior surface area of 820 m(2) g(-1) and a narrow pore radius distribution of around 2.4 nm.

Visualization of high-dimensional combinatorial catalysis data.

The role of various techniques for visualization of high-dimensional data is demonstrated in the context of combinatorial high-throughput experimentation (HTE). Applying visualization tools, we identify which constituents of catalysts are associated with final products in a huge combinatorially generated data set of heterogeneous catalysts, and catalytic activity regions are identified with respect to pentanary composition spreads of catalysts. A radial visualization scheme directly visualizes pentanary composition spreads in two-dimensional (2D) space and catalytic activity of a final product by combining high-throughput results from five slate libraries. A glyph plot provides many possibilities for visualizing high-dimensional data with interactive tools. For catalyst discovery and lead optimization, this work demonstrates how large multidimensional catalysis data sets are visualized in terms of quantitative composition activity relationships (QCAR) to effectively identify the relevant key role of compositions (i.e., lead compositions) of catalysts.

Combinatorial and high-throughput materials science.

There is increasing acceptance of high-throughput technologies for the discovery, development, and optimization of materials and catalysts in industry. Over the years, the relative synchronous development of technologies for parallel synthesis and characterization has been accompanied by developments in associated software and information technologies. This Review aims to provide a comprehensive overview on the state of the art of the field by selected examples. Technologies developed to aid research on complex materials are covered as well as databases, design of experiment, data-mining technologies, modeling approaches, and evolutionary strategies for development. Different methods for parallel synthesis provide single sample libraries, gradient libraries for electronic or optical materials, similar to polymers and catalysts, and products produced through formulation strategies. Many examples illustrate the variety of isolated solutions and document the barely recognized variety of new methods for the synthesis and analysis of almost any material. The Review ends with a summary of success stories and statements on still-present problems and future tasks.

Discovery of new heterogeneous catalysts for the selective oxidation of propane to acrolein.

Combinatorial synthesis and screening technique have been applied to investigate the catalytic activity and selectivity of ternary and quaternary mixed-metal oxide catalysts for the selective oxidation of propane. The catalyst libraries were prepared via a modified sol-gel method using a synthesis robot and library design software, and examined for the catalytic activities in a simple high-throughput reactor system connected to a mass spectrometer for product analysis. Ternary Mo-Cr-Te, V-Cr-Sb, and Mo-V-Cr catalysts have been selected for potential candidate by composition spread approach. In a next generation composition spread library, the composition space of these three ternary compositions was sampled. Screening of this 198-member library provided substantial evidence that each ternary system has its own optimum composition where acrolein formation is highest. In addition, the composition space of the quaternary reference system Mo-V-Te-Nb mixed-oxides has also been prepared and sampled.

A QCAR-approach to materials modeling.

Little is known about the relationship between the function and structure of materials. Materials (solids with a function) are complex entities and a better knowledge of the parameters that contribute to function is desirable. Here, we present modeling approaches that correlate chemical composition with function of heterogeneous catalysts. The complete composition space of the mixed oxides of Ni-Cr-Mn and of Ni-Co-Mo-Mn (10% spacing) have been measured for the oxidation of propene to acroleine. The data have been collected, visualized and modeled. Different mathematical approaches such as Support Vector Machines, multilevel B-splines approximation and Kriging have been applied to model this relationship. High-throughput screening data of ternary and quaternary composition spreads are approximated to locate catalysts of high activity within the search space. For quaternary systems, slice plots offer a good tool for visualization of the results. Using these approximation techniques, the composition of the most active catalysts can be predicted. The study documents that distinct relationships between chemical composition and catalytic function exist and can be described by mathematical models.

MS-Express: data-extracting and -processing software for high-throughput experimentation with mass spectrometry.

High-throughput experiments (HTE) result in large amounts of raw data that have to be evaluated for sample classification. Especially mass spectrometry, a widely used detection method in catalytic HTE applications, produces enormous amounts of data. In the past few years, in catalysts research, several test rigs based on mass spectrometric detection have been independently reported by different groups. In a typical HTE, the catalysts are tested sequentially; the recording of the scans, however, occurs continuously. For this reason, the scans of interest have to be extracted from the raw data, and scans belonging to the same sample have to be averaged in a tedious procedure before further processing. In this publication, we present our custom-designed software MS-Express (mass spectrometry data-extracting and -processing software), an efficient tool for HTE MS data evaluation. MS-Express not only sorts the data, it also establishes statistical significance with the help of reference and blank data and provides concise information about abundance and intensity distributions of expected peaks. A special feature is that the program also reports unexpected MS signals, which potentially lead to unexpected discoveries.

Combinatorial Chemistry-Challenge and Chance for the Development of New Catalysts and Materials.

One should not underestimate the capability of the combinatorial method in solid-state chemistry; this is the opinion of the author. Combinatorial chemistry can provide a large number of new compounds, but once the components that are interesting for a certain application have been successfully selected, the techniques of conventional catalysis and materials research are required. The strengths of conventional chemistry lie in the optimization, systematic modification, and improvement of new lead structures. In contrast, discovery is the potential strength of combinatorial chemistry. Careful design is most important for the synthesis of useful libraries, since the diversity of the periodic table is much too large to be accessed comprehensively or systematically by such large libraries.

Detection of Catalytic Activity in Combinatorial Libraries of Heterogeneous Catalysts by IR Thermography.

Only about 200 µg of catalyst are required to identify the catalytically active materials on a combinatorial library of heterogeneous catalysts by IR thermography. The procedure is highly sensitive, and temperature differences arising from catalytic activity of hydrogenations and oxidations have been reliably detected down to 0.1 K.

Modified, Amorphous Titania-A Hybrid Semiconductor for Detoxification and Current Generation by Visible Light.

Amorphous, microporous TiO2 hybrid semiconductors modified with transition metals induce generation of a photocurrent and photocatalytic degradation of the water contaminant 4-chlorophenol through photoinduced charge separation (the postulated mechanism is shown in the picture, Ar=4-ClC6 H4 ). In contrast to the previously known crystalline titania photocatalysts, which are active only when excited with UV light, the amorphous semiconductors modified with platinum, rhodium, and gold chloride enable both processes also with visible light.

Combinatorial Material Libraries on the Microgram Scale with an Example of Hydrothermal Synthesis.

In a 8-µL multichambered microreactor (the photo shows the components) material libraries can be produced in a simple manner through combinatorial hydrothermal synthesis. In a model experiment the synthesis of the zeolite TS-1 has been varied combinatorially. The resulting library is characterized directly by automated microdiffraction.