The active sites in different TS-1 zeolites for propylene epoxidation studied by ultraviolet resonance Raman and ultraviolet visible absorption spectroscopies

The titanium species in four kinds of titanium-containing MFI zeolites have been studied by ultraviolet (UV)-Raman and ultraviolet visible (UV-Vis) absorption spectroscopies and by the epoxidation of propylene with diluted H2O2 solution (30%). UV-Raman spectroscopy is proved to be a suitable means to estimate qualitatively the framework titanium in TS-l zeolites. Based on the comparison of the relative intensity ratio I-1125/I-380 of UV-Raman spectra, the TS-1(conv.) sample synthesized hydrothermally by the conventional procedure shows the highest amount of framework titanium. UV-Vis spectroscopy reveals that besides minor anatase. titanium species are mainly tetrahydrally coordinated into the framework for TS-l(conv.) or the Ti-ZSM-5 sample prepared by gas-solid reaction between deboronated B-ZSM-5 and TiCl4 vapor at elevated temperatures. For the TS-1(org.) and TS-1(inorg.) samples synthesized hydrothermally using tetrapropylammonium bromide (TPABr) as template and tetrabutylorthotitanite (TBOT) and TiCl3 as titanium source, respectively, the presence of mononuclear and isolated TiOx species which are proposed to bond to the zeolite extraframework is observed. In addition to the framework titanium species, these isolated TiOx species are assumed to be also active for propylene epoxidation.

Coherent Behavior from Incoherent Knowledge Sources in the Automatic Synthesis of Numerical Computer Programs

A fundamental problem in artificial intelligence is obtaining coherent behavior in rule-based problem solving systems. A good quantitative measure of coherence is time behavior; a system that never, in retrospect, applied a rule needlessly is certainly coherent; a system suffering from combinatorial blowup is certainly behaving incoherently. This report describes a rule-based problem solving system for automatically writing and improving numerical computer programs from specifications. The specifications are in terms of "constraints" among inputs and outputs. The system has solved program synthesis problems involving systems of equations, determining that methods of successive approximation converge, transforming recursion to iteration, and manipulating power series (using differing organizations, control structures, and argument-passing techniques).

Understanding Simple Picture Programs

What are the characteristics of the process by which an intent is transformed into a plan and then a program? How is a program debugged? This paper analyzes these questions in the context of understanding simple turtle programs. To understand and debug a program, a description of its intent is required. For turtle programs, this is a model of the desired geometric picture. a picture language is provided for this purpose. Annotation is necessary for documenting the performance of a program in such a way that the system can examine the procedures behavior as well as consider hypothetical lines of development due to tentative debugging edits. A descriptive framework representing both causality and teleology is developed. To understand the relation between program and model, the plan must be known. The plan is a description of the methodology for accomplishing the model. Concepts are explicated for translating the global intent of a declarative model into the local imperative code of a program. Given the plan, model and program, the system can interpret the picture and recognize inconsistencies. The description of the discrepancies between the picture actually produced by the program and the intended scene is the input to a debugging system. Repair of the program is based on a combination of general debugging techniques and specific fixing knowledge associated with the geometric model primitives. In both the plan and repairing the bugs, the system exhibits an interesting style of analysis. It is capable of debugging itself and reformulating its analysis of a plan or bug in response to self-criticism. In this fashion, it can qualitatively reformulate its theory of the program or error to account for surprises or anomalies.

Automatic Analysis of the Logical Structure of Programs

This report presents a method for viewing complex programs as built up out of simpler ones. The central idea is that typical programs are built up in a small number of stereotyped ways. The method is designed to make it easier for an automatic system to work with programs. It focuses on how the primitive operations performed by a program are combined together in order to produce the actions of the program as a whole. It does not address the issue of how complex data structures are built up from simpler ones, nor the relationships between data structures and the operations performed on them.

Structure and Interpretation of Computer Programs

"The Structure and Interpretation of Computer Programs" is the entry-level subject in Computer Science at the Massachusetts Institute of Technology. It is required of all students at MIT who major in Electrical Engineering or in Computer Science, as one fourth of the "common core curriculum," which also includes two subjects on circuits and linear systems and a subject on the design of digital systems. We have been involved in the development of this subject since 1978, and we have taught this material in its present form since the fall of 1980 to approximately 600 students each year. Most of these students have had little or no prior formal training in computation, although most have played with computers a bit and a few have had extensive programming or hardware design experience. Our design of this introductory Computer Science subject reflects two major concerns. First we want to establish the idea that a computer language is not just a way of getting a computer to perform operations, but rather that it is a novel formal medium for expressing ideas about methodology. Thus, programs must be written for people to read, and only incidentally for machines to execute. Secondly, we believe that the essential material to be addressed by a subject at this level, is not the syntax of particular programming language constructs, nor clever algorithms for computing particular functions of efficiently, not even the mathematical analysis of algorithms and the foundations of computing, but rather the techniques used to control the intellectual complexity of large software systems.

The surface sites of sulfated zirconia studied in situ by laser-induced fluorescence spectroscopy

The surface sites of sulfated zirconia were investigated in situ by laser-induced fluorescence spectroscopy using aniline as the probe molecule. Different from the cases for many other oxides, the aniline adsorbed on the unique active sites of sulfated zirconia at r.t. is changed into another species, which emits a characteristic fluorescence band at 422 nm. The results illustrate that the sulfate groups in sulfated zirconia are favorable for the generation of these unique active sites, which also rarely exist on pure zirconia composed of tetragonal and monoclinic phases but do not exist on pure zirconia composed of monoclinic phase. (C) 2004 Elsevier B.V. All rights reserved.

The synergic effect between Mo species and acid sites in Mo/HMCM-22 catalysts for methane aromatization

The acid properties of Mo/HMCM-22 catalyst, which is the precursor form of the working catalyst for methane aromatization reaction, and the synergic effect between Mo species and acid sites were studied and characterized by various characterization techniques. It is concluded that Bronsted and Lewis acidities of HMCM-22 are modified due to the introduction of molybdenum. We suggest a monomer of Mo species is formed by the exchange of Mo species with the Bronsted acid sites. On the other hand, coordinate unsaturated sites (CUS) are suggested to be responsible for the formation of newly detected Lewis acid sites. Computer modelling is established and coupling with experimental results, it is then speculated that the effective activation of methane is properly accomplished on Mo species accommodated in the 12 MR supercages of MCM-22 zeolite whereas the Bronsted acid sites in the same channel system play a key role for the formation of benzene. A much more pronounced volcano-typed reactivity curve of the Mo/HMCM-22 catalysts, as compared with that of the Mo/HZSM-5, with respect to Mo loading is found and this can be well understood due to the unique channel structure of MCM-22 zeolite and synergic effect between Mo species and acid sites.

Methane dehydroaromatization over Mo/HZSM-5 catalysts: The reactivity of MoCx species formed from MoOx associated and non-associated with Bronsted acid sites

The catalytic performances of methane dehydroaromatization (MDA) under non-oxidative conditions over 6 wt.% Mo/HZSM-5 catalysts calcined for different durations of time at 773 K have been investigated in combination with ex situ H-1 MAS NMR characterization. Prolongation of the calcination time at 773 K is in favor of the diffusion of the Mo species on the external surface and the migration of Mo species into the channels, resulting in a further decrease in the number of Bronsted acid sites, while causing only a slight change in the Mo contents of the bulk and in the framework structure of the HZSM-5 zeolite. The MoQ(x) species associated and non-associated with the Bronsted acid sites can be estimated quantitatively based on the 1H MAS NMR measurements as well as on the assumption of a stoichiometry ratio of 1: 1 between the Mo species and the Bronsted acid sites. Calcining the 6 wt.% Mo/HZSM-5 catalyst at 773 K for 18 h can cause the MoOx species to associate with the Bronsted acid sites, while a 6 Wt-% MO/SiO2 sample can be taken as a catalyst in which all MoOx species are non-associated with the Bronsted acid sites. The TOF data at different times on stream on the 6 wt.% Mo/HZSM-5 catalyst calcined at 773 K for 18 h and on the 6 Wt-% MO/SiO2 catalyst reveal that the MoCx species formed from MoOx associated with the Bronsted acid sites are more active and stable than those formed from MoOx non-associated with the Bronsted acid sites. An analysis of the TPO profiles recorded on the used 6 wt.% Mo/HZSM-5 catalysts calcined for different durations of time combined with the TGA measurements also reveals that the more of the MoCx species formed from MoOx species associated with the Br6nsted acid sites, the lower the amount of coke that will be deposited on it. The decrease of the coke amount is mainly due to a decrease in the coke burnt-off at high temperature. (c) 2005 Elsevier B.V. All rights reserved.

Invertebrates of ancient heavy metal spoil and smelting tip sites in southern Jordan: Thier distribution and use as bioindicators of metalliferous pollution derived from ancient sources

Pyatt, B. Amos, D. Grattan, J. Pyatt, A. Terrell-Nield, C. Invertebrates of ancient heavy metal spoil and smelting tip sites in southern Jordan: Thier distribution and use as bioindicators of metalliferous pollution derived from ancient sources. Journal of Arid Environments. 2002. 52 pp 53-62