Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

Approximation algorithms for dynamic resource allocation

We consider a problem of allocating limited quantities of M types of resources among N independent activities that evolve over T epochs. In each epoch, we assign to each activity a task which consumes resources, generates utility, and determines the subsequent state of the activity. We study the complexity of, and approximation algorithms for, maximizing average utility.     

Heuristic Solution Methods for the Multilevel Generalized Assignment Problem

The multilevel generalized assignment problem is a problem of assigning agents to tasks where the agents can perform tasks at more than one efficiency level. A profit is associated with each assignment and the objective of the problem is profit maximization. Two heuristic solution methods are presented for the problem. The heuristics are developed from solution methods for the generalized assignment problem. One method uses a regret minimization approach whilst the other method uses a repair approach on a relaxation of the problem. The heuristics are able to solve moderately large instances of the problem rapidly and effectively. Procedures for deriving an upper bound on the solution of the problem are also described. On larger and harder instances of the problem one heuristic is particularly effective.     

Regular population monotonic allocation schemes

The paper introduces a refinement of the notion of population monotonic allocation scheme, called regular population monotonic allocation scheme (regularpmas). This refinement is based on economic situations in which players may have to select new partners from a set of potential players and in which there exist certain capacity constraints. A sufficient condition for the existence of a regularpmas is given. For the class of games with regularpmas, we prove that the core coincides with the Davis and Maschler and the Mas-Colell bargaining sets.     

An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

Ceramic Films via Organometallic Complex as Single Source Precursor

Fe2(CO)6(μ-S2) was used as a single source precursor in attempt to produce FeS film via MOCVD. Pyrolysis of Fe2(CO)6(μ-S2) at temperature below 500℃ produced Fe1-xS or Fe7S8 powder as indicated by its powder X-ray spectra. At 750 ℃, polycrystalline FeS powder was obtained. In film deposition, polycrystalline Fe1-xS or Fe7Ss films were obtained on Si(100) and Ag/Si(100) substrates below 500 ℃. SEM micrographs showed the film on Si(100) substrate containing whisker like grains. However, pillar like grains were obtained on Ag/Si(100) substrate.Deposition rates are also different for different substrates as evaluated by the thickness of the films, which were obtained by SEM micrographs of the cross section of the films. At 750℃, similar polycrystalline Fe1-xS or Fe7S8 film was obtained.     

Allocating electricity transmission costs through tracing: a game-theoretic rationale

Tracing is a method of assigning flows in an electricity network to particular generators and loads, assuming perfect mixing at each node. It can be used to assign costs to transmission users. We show that the resulting allocation is equal to the Shapley value of an equivalent co-operative game.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Some new classes of stochastic order relations among arithmetic random variables, with applications in actuarial sciences

Recently, Fishbum and Lavalle (1995) and Lefèvre and Utev (1996) have considered some stochastic order relations specific for arithmetic random variables. The present work is concerned with these orderings, together with two other classes of stochastic order relations closely related. First, attention is paid to characterizations and various properties of all these orderings. Then, sufficient conditions of crossing-type for the two new classes of orderings are derived and extrema among discrete random variables are deduced. This is applied in actuarial sciences to obtain new bounds for the classical single life premiums as well as for the probability of ruin in the compound binomial risk model.     

Compensatory transfers in two-player decision problems

This paper presents an axiomatic characterization of a family of solutions to two-player quasi-linear social choice problems. In these problems the players select a single action from a set available to them. They may also transfer money between themselves.The solutions form a one-parameter family, where the parameter is a non-negative number, t.The solutions can be interpreted as follows: Any efficient action can be selected. Based on this action, compute for each player a “best claim for compensation”. A claim for compensation is the difference between the value of an alternative action and the selected efficient action, minus a penalty proportional to the extent to which the alternative action is inefficient. The coefficient of proportionality of this penalty is t. The best claim for compensation for a player is the maximum of this computed claim over all possible alternative actions. The solution, at the parameter value t, is to implement the chosen efficient action and make a monetary transfer equal to the average of these two best claims. The characterization relies on three main axioms. The paper presents and justifies these axioms and compares them to related conditions used in other bargaining contexts. In Nash Bargaining Theory, the axioms analogous to these three are in conflict with each other. In contrast, in the quasi-linear social choice setting of this paper, all three conditions can be satisfied simultaneously.This work was supported by the Division of Research at the Harvard Business School. Thanks are due to the Cowles Foundation for Research in Economics at Yale University for its kind hospitality during the Spring of 2002. I have received helpful advice and comments from Youngsub Chun, Ehud Kalai, Herve Moulin, Al Roth, Ilya Segal, Adam Szeidl, Richard Zeckhauser, and other members of the Theory Seminars at Harvard, MIT, Princeton, Rice and Northwestern.