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Development of New Materials by Combinatorial Techniques

Authors:
José M. Serra, Instituto de Tecnología Química, UPV-CSIC, Valencia, 46022, Spain jsalfaro@iqn.upv.es Avelino Corma, Instituto de Tecnología Química, UPV-CSIC, Valencia, 46022, Spain acorma@itq.upv.es Estefania Argente, Departamento de Sistemas y Computación, UPV, Valencia, 46022, Spain, eargente@dsic.upv.es Soledad Valero, Departamento de Sistemas y Computación, UPV, Valencia, 46022, Spain, svalero@dsic.upv.es Vicente Botti, Departamento de Sistemas y Computación, UPV, Valencia, 46022, Spain, vbotti@dsic.upv.es

Abstract  This paper shows an example of integration of the different techniques involved in the combinatorial
development of new catalytic materials, showing the joint effort of different scientist and engineers in combined projects between academia and industry. The application of different engineering fields in the discovery an development of new materials, specially of new catalyst, is changing the conventional research methodology in materials science. Indeed, the integration of robotics, computer science, electronics, mechanical and chemical engineering in a research laboratory is increasing significantly the processing throughput and the degree of automation, generating new automated high speed techniques for the experimental work. It is described the development of new experimental tools (robotics systems for material syntehsis and testing equiment) and new software tools for design of experiments and data analysis/minig.

Index Terms  Combinatorial Catalysis, Hight-Throughput Experimentation, Materials Science, Catalysts, Automation, Robotics, Chemistry Laboratory INTRODUCTION
The application of different engineering fields in the discovery an development of new materials, specially of new catalyst, is changing the conventional research methodology. Indeed, the integration of robotics, computer science, electronics, mechanical and chemical engineering in the research laboratory is increasing significantly the processing throughput and the degree of automation, generating new automated high speed techniques for the experimental tasks. Combinatorial catalysis [1-6] is a methodology where a large number of new materials are prepared and tested in a parallel fashion. The global search/optimisation strategy is the main difference with the traditional catalyst research and should allow to reduce the number of experiments needed to find an optimal catalyst composition. Combinatorial catalysis involves the co-ordination of (see Figure 1): high-throughput systems [8-10] for preparation, characterisation and catalytic test; large information data management; and rapid optimisation techniques. This promising approach requires therefore the development and optimisation of the following items: (i) high-throughput equipment, which allows the reliable preparation and characterisation/testing preferentially under realistic conditions of larger quantities of materials (ii) optimisation techniques, adapting their structure and parameters by implementing the chemical knowledge/experience of the experts. With this, it would be possible to increase the number of variables to study and this would result in a potentially rather more powerful final catalyst and shorter search times. Indeed, if this methodology is properly followed it can be very helpful in the scientific understanding of catalysis. The drugs development has known a drastic and successful change in the ’90 by means of fast synthesis and screening of large libraries of diverse formulations on fully automated working stations and analytics. The so-called combinatorial approach, rapidly extended to other research domains (see Figure 2) such as materials science and catalysis, relies on the systemactic screening of the population surface by combining all relevant parameters. Thereby, the investigation strategy shifts from essentially qualitative to highly quantitative studies with data throughput increased by orders of magnitude. The automated screening of large libraries of catalysts is today entirely possible thanks to fast-growing technologies for automation, miniaturization and computation. The figure 3 shows the new advanced technologies and the tool available for the application in the combinatorial approach. Fully automated robots specially designed for fast synthesis and testing of catalyst are now available. However, the high complexity of catalytic systems makes data management (instrument and software integration, data base construction, statistical studies and data mining functions) a challenge.

International Conference on Engineering Education 1

July 21–25, 2003, Valencia, Spain.

especially suited for the synthesis of zeolites and mesoporuous materials. in prediction problems. acidity promoters and metallic promoters) is selected and incorporated to the catalyst formulation in view of its expected catalytic effect. One application of such algorithms developed by our group for the development of enhanced catalyst for oil refining process[5]. i. in character recognition. Traditionally.. The first reactor has been employed in the search of new catalyst for different processes in oil refining and petrochemistry. Valencia. The figure 4 shows two different HTE reactors designed. chemistry). . artificial intelligence (AI) techniques have an important potential for modelling and prediction of complex high-dimensional data. The figure 5 shows a picture of different synthesis robots developed in our laboratory. in which each component (metal oxide. Artificial neural networks have been mainly used in classification problems. 2003. Catalytic evaluation was carried out by means of a 16 parallel fixed bed reactor system (equipment shown if figure 4a). The equipment shown in figure 5a can synthetize new materials under hydrothermal conditions. International Conference on Engineering Education 2 July 21–25. An adapted genetic algorithm was applied to the search of new solid bifunctional catalysts. engineers and researchers. robotics. These ANN kinetic models could be promptly obtained for a series of catalysts and rapidly determine which are the reaction conditions for optimal catalytic performance of each material. and the integration of ANNs techniques with evolutionary strategies in material discovery. Artificial neural networks have successfully been applied to conventional catalytic modelling and design of solid catalysts. since the essence of this methodology is the combination of all different techniques (software. for the development of new chemical reactors for the simultaneous test of different catalyst. It is as well necessary the same interdisciplinary effort for the development and setting up of new synthesis robotic systems. analysis and prediction of results of the composition of NOx over zeolites [16]. In addition. Among these techniques. chemical and electronics engineers during a prolonged time (even years). who applied previous experiences or fundamental knowledge in order to carry out the experimental design and to establish relationships between the different experimental results. Those applications [13] include: design of ammoxidation of propylene catalyst [14]. those models can be applied for further catalyst scale up and. Three evolving cycles have been run and an important improvement in the catalyst activity has been found. The first issue is the development and setting up of the accelerated tools. the large number of variables in play and the application of complex optimisation algorithms for the experimental design makes difficult the direct human interpretation of data derived from high throughput experimentation. (ii) the comprehension and modelling of the organised data and (iii) the global search strategy to optimise the catalytic performance. constructed and set up in our laboratory. Spain. allowing the analysis and prediction of catalytic results within a population of catalysts produced by combinatorial techniques[17]. automation.e. process control and optimisation. two application of NNs to the prediction of catalytic performance: (i) ANN catalyst compositional models. data management is referred to software techniques for (i) the efficient administration and schedule of large amounts of experimental data. The calytic performance of the best ranked catalyst of each generation are displayed in figure 6. in negotiation problems. In the case of combinatorial catalysis. The problem was initially focused by means of a knowledge-based catalyst formulation. This prediction capability suggested us that this NN model can serve as theorical (in silico) pre-screening of different catalyst enabling to save experimental work. In our research group we have worked on the development of artificial intelligence (AI) techniques for design of experiments and for data mining and prediction. process eng. artificial neural networks (NN) could be useful in the chemical field. correlating composition and synthesis variables with catalytic performance and (ii) ANN kinetic models. data mining techniques have been applied [11-12] in order to find relationships and patterns between the input and output data derived from accelerated experimentation. under 30 bar and 200-240ºC. in control and automation. For example.. In the frame of combinatorial catalysis. In figure 7 the prediction performance of a NN model for the reaction of oxidative dehydrogenation of ethane is displayed. One example of the first time of techniques is the application of genetic algorithms to the design of series of catalysts and optimisation of their catalytic performance. correlating reaction conditions with catalytic performance. Recently.RESEARCH LINES The everyday running of a combinatorial laboratory requires the interdisciplinary work of different technicians. it is necessary the common work of mechanical. The robotic system of figure 5b is employed for catalyst preparation by impregnation or ion exchange with a series of active components. design of methane oxidative decoupling catalyst [15]. the processing and understanding of the experimental outputs (characterisation and catalytic performances) was accomplished by the researchers. The last application [18] is referred to modelling experimental kinetic data in order to obtain rapidly black box models of the behaviour of a catalytic reactor. The automation engineers have to work in close cooperation with the chemists in order to reproduce as close as possible the convetional synthesis procedure and jointly evaluate the influence of the operative modification of such procedure. The other AI techniques developed in our group are neural networks. The first reported applications include the design of solid catalyst for different reactions of interest. Hence. in information processing.

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FIGURES AND TABLES FIGURE 1 CONCEPTUAL SCHEME OF THE COMBINATORIAL APPROACH IN THE DEVELOPMENT OF NEW CATALYSTS. . Preparation Characterisation & Reaction Data-base & Conclusions Fast Libray synthesis High Throughput Testing Data Management Search Strategy FIGURE 2 APPLICATION OF HIGHTROUGHPUT TECHNIQUES TO DIFFERENT CHEMISTRY FIELDS Pharmacy Fine Chemistry 1990s Polymers Base Chemistry 2000 2001 Oil Refining 2005 1970s 1980s 1999 FIGURE 3 DRIVING TECHNOLOGIES OF HIGHTHROUGHPUT EXPERIMENTATION / COMBINATORIAL APPROACH Microelectronics Micromechanics Robotics Automation Computing Powerful computers New sensor and detector Miniaturised devices (MEMS) New methods for automated synthesis New methods for materials testing Experimental data analysis (IA) Design of experiments (IA) Simulation and Prediction of exp. Valencia. 2003. Spain. data Optics International Conference on Engineering Education 4 July 21–25.

( A) (B) FIGURE 5 HIGHTHROUGHPUT S YSTEMS FOR S OLID M ATERIAL SYNTHESIS: (A ) ROBOT FOR H YDROTHERMAL S YNTHESIS AND (B ) ROBOT FOR CATALYSTS PREPARATION BY IMPREGNATION/ION EXCHANGE . . Spain.FIGURE 4 HIGHTHROUGHPUT SYSTEMS FOR CATALYTIC CESTING: (A) 16-REACTOR RIG FOR TESTING UNDER INDUSTRIAL IEACTION CONDITIONS AND (B) 36-REACTOR SYSTEM ABLE TO WORK SEQUENTIALLY OR BY PULSES. Valencia. ( A) (B) International Conference on Engineering Education 5 July 21–25. 2003.

.FIGURE 6 GENETIC ALGORITHM APPLIED TO ISOMERISATION OF LIGHT PARAFING FOR GASOLINE PRODUCTION: BEST CATALYSTS FOR THE SUCCEEDED GENERATION. Spain. Valencia. 2003. 100 O2 Conversion % 75 50 25 0 1 2 3 4 5 6 Samples 7 8 9 10 Experimental results Predictions Confidence Interval International Conference on Engineering Education 6 July 21–25. 100 Relative Activity % 75 50 25 0 1 2 3 4 3rd 6 7 8 1st Generation 9 10 5 FIGURE 7 EXPERIMENTAL AND PREDICTED RESULTS OF O2 CONVERSION OF A NN (TRAINING DATA 40 SAMPLES AND TESTING DATA 10 SAMPLES) MODEL FOR THE MEACTION OF OXIDATIVE DEHYDROGENATION OF ETHANE.