Photocatalytic degradation of humic acid in saline waters part 2. Effects of various photocatalytic materials

The present study explores for the first time, the effectiveness of photocatalytic oxidation of. humic acid (HA) in the increasingly important highly saline water. TiO2 (Degussa P25), TiO2 (Anatase), TiO2 (Rutile), TiO2 (Mesoporous) and ZnO dispersions were used as catalysts employing a medium pressure mercury lamp. The effect of platinum loading on P25 and zinc oxide was also investigated. The zinc oxide with 0.3% platinum loading was the most efficient catalyst. The preferred medium for the degradation of HA using ZnO is alkaline, whereas for TiO2 it is acidic. In addition, a comparative study of HA decomposition in artificial seawater (ASW) and natural seawater (NSW) is reported, and the surface areas and band gaps of the catalysts employed were also determined. A spectrophotometric method was used to estimate the extent of degradation of HA. (C) 2003 Elsevier Science B.V. All rights reserved.

Synthesis and catalytic epoxidation potentiality of oxodiperoxo molybdenum(VI) complexes with pyridine-2-carboxaldoxime and pyridine-2-carboxylate: the crystal structure of PMePh3[MoO(O-2)(2)(PyCO)]

[MoO(O-2)(2)(PyCOXH)(H2O)] and PMePh3[MoO(O-2)(2)(PyCO)] (PyCOXH = Pyridine-2-carboxaldoxime and PyCOH = Pyridine-2-carboxylic acid) have been synthesized. Both complexes have been characterized by physico-chemical and spectroscopic methods; in addition, the carboxylate complex has been structurally characterized by X-ray crystallography. The carboxylate complex is a more efficient catalyst than the oxime complex for epoxidation of olefins and shows excellent catalytic activity for the substrates: cyclooctene, cinnamyl alcohol, allyl alcohol and 1-hexene.

Syntheses, structures and efficient catalysis for C–C coupling of some benzaldehyde thiosemicarbazone complexes of palladium

Reaction of the 4-R-benzaldehyde thiosemicarbazones (denoted in general as L-R; R = OCH(3), CH(3), H, Cl and NO(2)) with trans-[Pd(PPh(3))(2)Cl(2)] afforded a group of mixed-ligand complexes (denoted in general as 1-R) incorporating a N,S-coordinated thiosemicarbazone. a triphenylphosphine and a chloride. Similar reaction with Na(2)[PdCl(4)] afforded a family of bis-thiosemicarbazone complexes (denoted in general as 2-R), where each ligand is N,S-coordinated. Crystal structures of 1-CH(3), 1-NO(2), 2-OCH(3), 2-NO(2) and L-NO(2) have been determined. In all the complexes the thiosemicarbazones are coordinated to the metal center, via dissociation of the acidic proton, as bidentate N,S-donors forming five-membered chelate rings. With reference to the structure of the uncoordinated thiosemicarbazone, this coordination mode is associated with a conformational change around the C=N bond. All the 1-R and 2-R complexes display intense absorptions in the visible region. Catalytic activity of the 1-R and 2-R complexes towards some C-C coupling reactions (e.g. Suzuki, Heck and Sonogashira) has been examined and while both are found to be efficient catalysts, 1-R is much better catalyst than 2-R.

Efficient evaluation of highly oscillatory acoustic scattering surface integrals

We consider the approximation of some highly oscillatory weakly singular surface integrals, arising from boundary integral methods with smooth global basis functions for solving problems of high frequency acoustic scattering by three-dimensional convex obstacles, described globally in spherical coordinates. As the frequency of the incident wave increases, the performance of standard quadrature schemes deteriorates. Naive application of asymptotic schemes also fails due to the weak singularity. We propose here a new scheme based on a combination of an asymptotic approach and exact treatment of singularities in an appropriate coordinate system. For the case of a spherical scatterer we demonstrate via error analysis and numerical results that, provided the observation point is sufficiently far from the shadow boundary, a high level of accuracy can be achieved with a minimal computational cost.

Tripleclouds: an efficient method for representing horizontal cloud inhomogeneity in 1D radiation schemes by using three regions at each height

Radiation schemes in general circulation models currently make a number of simplifications when accounting for clouds, one of the most important being the removal of horizontal inhomogeneity. A new scheme is presented that attempts to account for the neglected inhomogeneity by using two regions of cloud in each vertical level of the model as opposed to one. One of these regions is used to represent the optically thinner cloud in the level, and the other represents the optically thicker cloud. So, along with the clear-sky region, the scheme has three regions in each model level and is referred to as “Tripleclouds.” In addition, the scheme has the capability to represent arbitrary vertical overlap between the three regions in pairs of adjacent levels. This scheme is implemented in the Edwards–Slingo radiation code and tested on 250 h of data from 12 different days. The data are derived from cloud retrievals using radar, lidar, and a microwave radiometer at Chilbolton, southern United Kingdom. When the data are grouped into periods equivalent in size to general circulation model grid boxes, the shortwave plane-parallel albedo bias is found to be 8%, while the corresponding bias is found to be less than 1% using Tripleclouds. Similar results are found for the longwave biases. Tripleclouds is then compared to a more conventional method of accounting for inhomogeneity that multiplies optical depths by a constant scaling factor, and Tripleclouds is seen to improve on this method both in terms of top-of-atmosphere radiative flux biases and internal heating rates.

Scalability of efficient parallel K-Means

Clustering is defined as the grouping of similar items in a set, and is an important process within the field of data mining. As the amount of data for various applications continues to increase, in terms of its size and dimensionality, it is necessary to have efficient clustering methods. A popular clustering algorithm is K-Means, which adopts a greedy approach to produce a set of K-clusters with associated centres of mass, and uses a squared error distortion measure to determine convergence. Methods for improving the efficiency of K-Means have been largely explored in two main directions. The amount of computation can be significantly reduced by adopting a more efficient data structure, notably a multi-dimensional binary search tree (KD-Tree) to store either centroids or data points. A second direction is parallel processing, where data and computation loads are distributed over many processing nodes. However, little work has been done to provide a parallel formulation of the efficient sequential techniques based on KD-Trees. Such approaches are expected to have an irregular distribution of computation load and can suffer from load imbalance. This issue has so far limited the adoption of these efficient K-Means techniques in parallel computational environments. In this work, we provide a parallel formulation for the KD-Tree based K-Means algorithm and address its load balancing issues.

Space-efficient Indexing of Chess Endgame Tables

Chess endgame tables should provide efficiently the value and depth of any required position during play. The indexing of an endgame’s positions is crucial to meeting this objective. This paper updates Heinz’ previous review of approaches to indexing and describes the latest approach by the first and third authors. Heinz’ and Nalimov’s endgame tables (EGTs) encompass the en passant rule and have the most compact index schemes to date. Nalimov’s EGTs, to the Distance-to-Mate (DTM) metric, require only 30.6 × 10^9 elements in total for all the 3-to-5-man endgames and are individually more compact than previous tables. His new index scheme has proved itself while generating the tables and in the 1999 World Computer Chess Championship where many of the top programs used the new suite of EGTs.

Space-efficient indexing of endgame tables for chess

Chess endgame tables should provide efficiently the value and depth of any required position during play. The indexing of an endgame’s positions is crucial to meeting this objective. This paper updates Heinz’ previous review of approaches to indexing and describes the latest approach by the first and third authors. Heinz’ and Nalimov’s endgame tables (EGTs) encompass the en passant rule and have the most compact index schemes to date. Nalimov’s EGTs, to the Distance-to-Mate (DTM) metric, require only 30.6 × 109 elements in total for all the 3-to-5-man endgames and are individually more compact than previous tables. His new index scheme has proved itself while generating the tables and in the 1999 World Computer Chess Championship where many of the top programs used the new suite of EGTs.

Efficient operator pipelining in a bit serial genetic algorithm engine

The authors propose a bit serial pipeline used to perform the genetic operators in a hardware genetic algorithm. The bit-serial nature of the dataflow allows the operators to be pipelined, resulting in an architecture which is area efficient, easily scaled and is independent of the lengths of the chromosomes. An FPGA implementation of the device achieves a throughput of >25 million genes per second

Computationally efficient expressions for the collision efficiency between electrically charged aerosol particles and cloud droplets

A multiple factor parametrization is described to permit the efficient calculation of collision efficiency (E) between electrically charged aerosol particles and neutral cloud droplets in numerical models of cloud and climate. The four-parameter representation summarizes the results obtained from a detailed microphysical model of E, which accounts for the different forces acting on the aerosol in the path of falling cloud droplets. The parametrization's range of validity is for aerosol particle radii of 0.4 to 10 mu m, aerosol particle densities of I to 2.0 g cm(-3), aerosol particle charges from neutral to 100 elementary charges and drop radii from 18.55 to 142 mu m. The parametrization yields values of E well within an order of magnitude of the detailed model's values, from a dataset of 3978 E values. Of these values 95% have modelled to parametrized ratios between 0.5 and 1.5 for aerosol particle sizes ranging between 0.4 and 2.0 mu m, and about 96% in the second size range. This parametrization speeds up the calculation of E by a factor of similar to 10(3) compared with the original microphysical model, permitting the inclusion of electric charge effects in numerical cloud and climate models.

Model catalyst studies of the strong metal-support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110)

Model catalysts of Pd nanoparticles and films on TiO2 (I 10) were fabricated by metal vapour deposition (MVD). Molecular beam measurements show that the particles are active for CO adsorption, with a global sticking probability of 0.25, but that they are deactivated by annealing above 600 K, an effect indicative of SMSI. The Pd nanoparticles are single crystals oriented with their (I 11) plane parallel to the surface plane of the titania. Analysis of the surface by atomic resolution STM shows that new structures have formed at the surface of the Pd nanoparticles and films after annealing above 800 K. There are only two structures, a zigzag arrangement and a much more complex "pinwheel" structure. The former has a unit cell containing 7 atoms, and the latter is a bigger unit cell containing 25 atoms. These new structures are due to an overlayer of titania that has appeared on the surface of the Pd nanoparticles after annealing, and it is proposed that the surface layer that causes the SMSI effect is a mixed alloy of Pd and Ti, with only two discrete ratios of atoms: Pd/Ti of 1: 1 (pinwheel) and 1:2 (zigzag). We propose that it is these structures that cause the SMSI effect. (c) 2005 Elsevier Inc. All rights reserved.