Stable Isolated Metal Atoms as Active Sites for Photocatalytic Hydrogen Evolution

The process of using solar energy to split water to produce hydrogen assisted by an inorganic semiconductor is crucial for solving our energy crisis and environmental problems in the future. However, most semiconductor photocatalysts would not exhibit excellent photocatalytic activity without loading suitable co-catalysts. Generally, the noble metals have been widely applied as co-catalysts, but always agglomerate during the loading process or photocatalytic reaction. Therefore, the utilization efficiency of the noble co-catalysts is still very low on a per metal atom basis if no obvious size effect exists, because heterogeneous catalytic reactions occur on the surface active atoms. Here, for the first time, we have synthesized isolated metal atoms (Pt, Pd, Rh, or Ru) stably by anchoring on TiO2, a model photocatalystic system, by a facile one-step method. The isolated metal atom based photocatalysts show excellent stability for H-2 evolution and can lead to a 6-13-fold increase in photocatalytic activity over the metal clusters loaded on TiO2 by the traditional method. Furthermore, the configurations of isolated atoms as well as the originality of their unusual stability were analyzed by a collaborative work from both experiments and theoretical calculations.

Direct oxidation of amines to nitriles in the presence of ruthenium-terpyridyl complex immobilized on ILs/SILP

The immobilization of a ruthenium complex (Ru2Cl4(az-tpy)2) within a range of supported ionic liquids ([C4C1im]Cl, [C4C1im][NTf2], [C6C1im]Cl, [C4C1pyrr]Br, [C4C1im]Br, [C4C1pyrr]Cl) dispersed silica (SILP) operates as an efficient heterogeneous catalyst in oxidation of long chain linear primary amines to corresponding nitriles. This reaction follows a “green” route using a cheap and easy to handles oxidant (oxygen or air). The conversion was found to be strongly influenced by the alkyl chain length of the amine substrate and the choice of oxidant. No condensation reaction was observed between the starting amines and the selectivity to nitrile is 100%. Moving from a composition of 20 atm N2/5 atm O2 to 5 atm N2/20 atm O2 led to enhancements in the conversion (n-alkylamines) and selectivity (benzonitrile) which have been correlated with an increase of the solubilized oxygen. This was further supported by using different inert gas (nitrogen, helium, argon)/oxygen mixtures indicating that the O2 solubility in the SILP system, has an important effect on conversions and TON in this reaction using SILP catalysts. Experiments performed in the presence of CO2 led to a different behaviour due to the formation of amine-CO2 adducts. The application of the Weisz–Prater criterion confirmed the absence of any diffusional constraints.

In situ catalyst activity control in a novel membrane reactor-Reaction driven wireless electrochemical promotion of catalysis

A dual chamber membrane reactor was used in order to study the effect of macroscopically applied oxygen chemical potential differences to a platinum catalyst supported on a mixed oxygen ion and electronic conducting membrane. It is believed that the oxygen chemical potential difference imposed by the use of an oxygen sweep in one of the reactor chambers causes the back-spillover of oxygen species from the support onto the catalyst surface, resulting in the modification of the catalytic activity. The use of different sweep gases, such as ethylene and hydrogen was investigated as the means to reverse the rate modification by removing the spilt over species from the catalyst surface and returning the system to its initial state. Oxygen sweep in general had a positive effect on the reaction rate with rate increases up to 20% measured. Experimental results showed that hydrogen is a more potent sweep gas than ethylene in terms of the ability to reverse rate modification. A 10% rate loss was observed when using an ethylene sweep as compared with an almost 60% rate decrease when hydrogen was used as the sweep gas. © 2009 Elsevier Ltd. All rights reserved.

Electrochemical promotion of catalysis controlled by chemical potential difference across a mixed ionic-electronic conducting ceramic membrane - An example of wireless NEMCA

A La_0.6Sr_0.4Co_0.2F_0.8O₃ mixed ionic electronic conducting (MIEC) membrane was used in a dual chamber reactor for the promotion of the catalytic activity of a platinum catalyst for ethylene oxidation. By controlling the oxygen chemical potential difference across the membrane, a driving force for oxygen ions to migrate across the membrane and backspillover onto the catalyst surface is established. The reaction is then promoted by the formation of a double layer of oxide anions on the catalyst surface. Thelectronic conductivity of the membrane material eliminates the need for an external circuit to pump the promoting oxide ion species through the membrane and onto the catalyst surface. This renders this "wireless" system simpler and more amenable for large-scale practical application. Preliminary experiments show that the reaction rate of ethylene oxidation can indeed be promoted by almost one order of magnitude upon exposure to an oxygen atmosphere on the sweep side of the membrane reactor, and thus inducing an oxygen chemical potential difference across the membrane, as compared to the rate under an inert sweep gas. Moreover, the rate does not return to its initial unpromoted value upon cessation of the oxygen flow on the sweep side, but remains permanently promoted. A number of comparisons are drawn between the classical electrochemical promotion that utilises an external circuit and the "wireless" system that utilises chemical potential differences. In addition a 'surface oxygen capture' model is proposed to explain the permanent promotion of the catalyst activity. © 2007 Springer Science+Business Media, LLC.

Electrochemical promotion of catalysis using solid-state proton-conducting membranes

A solid-state electrochemical reactor with ceramic proton-conducting membrane has been used to study the effect of electrochemically induced hydrogen spillover on the catalytic activity of platinum during ethylene oxidation. Suitable proton-conducting electrolyte membranes (Gd-doped BaPrO ₃ (BPG) and Y-doped BaZrO₃ (BZY)) were fabricated. These materials were chosen because of their protonic conductivity in the operational temperature region of the reaction (400-700 °C). The BZY-based electrochemical cell was used to investigate the open-circuit voltage (OCV) dependence on H₂ partial pressure with comparison being made to the theoretical OCV as predicted by the Nernst equation. Furthermore, the BZY pellets were used to study the effect of proton transfer of the catalytic activity of platinum during ethylene oxidation. The reaction was found to exhibit electrochemical promotion at 400 °C and to be electrophilic in nature, i.e. proton addition to the platinum surface resulted in an increase in reaction rate. At higher temperatures, the rate was not affected, within experimental error, by proton addition or removal. Under similar conditions, AC impedance showed that there was a large overall cell resistance at 400 °C with significantly decreased resistance at higher temperatures. It is possible that there could be a relationship between large cell resistances and the onset of electrochemical promotion in this system but there is, as yet, no conclusive evidence for this. © 2003 Elsevier B.V. All rights reserved.

Combining Bio- and Chemo-Catalysis for the Conversion of Bio-Renewable Alcohols: Homogeneous Iridium Catalysed Hydrogen Transfer Initiated Dehydration of 1,3-Propanediol to Aldehydes

Combining whole cell biocatalysis and chemocatalysis in a single reaction sequence avoids unnecessary separations, and the associated waste and energy consumption. Bacterial fermentation has been employed to convert waste glycerol from biodiesel production into 1,3-propanediol. This 1,3-propanediol can be extracted selectively from the aqueous fermentation broth using ionic liquids. 1,3-propanediol in ionic liquid solution was converted to propanal by hydrogen transfer initiated dehydration (HTID) catalysed by a Cp*IrCl2(NHC) (Cp* = pentamethylcyclopentadienyl; NHC = carbene ligand) complex. The use of an ionic liquid solvent enabled the reaction to be performed under reduced pressure, facilitating the isolation of the product, and improving the reaction selectivity. The Ir(III) catalyst in ionic liquid was found to be highly recyclable.

Combining Bio- and Chemo-catalysis for the Sustainable Production of Chemicals

The combination of bio- and chemo-catalysis to form a single synthetic route is a powerful methodology for the improvement of chemical synthesis. The extreme methods of biocatalysis (whole cell and isolated enzyme) fulfill very different roles. Biocatalysis by isolated enzymes enables highly efficient chemical transformations of extremely high selectivity and low contamination; however, conditions and substrates are limited to a narrow range. Whole cell biocatalysis enables the conversion of crude substrates, such as those derived from biomass; however, the products tend to be impure and delivered in dilute aqueous solution. Chemocatalysis is a well-established technique, and the addition of chemical catalysis and chemocatalytic methods to biocatalysis enables synthetic chemists to avoid the shortcomings of a biocatalytic step. For example, in enzymatic catalysis the addition of a chemical catalyst can allow the conversion of a racemic alcohol to an enantiopure, instead of racemic, product. In whole cell biocatalysis chemical reagents can assist the separation, transformation, and further isolation of the functionality of interest. The cooperation of bio- and chemocatalysts enables sustainable production of chemicals that would be impossible using biocatalysis alone, while achieving selectivities and using substrates not currently possible with chemocatalysis alone.

Heterogeneous error-resilient scheme for spectral analysis in ultra-low power wearable electrocardiogram devices

Wearable devices performing advanced bio-signal analysis algorithms are aimed to foster a revolution in healthcare provision of chronic cardiac diseases. In this context, energy efficiency is of paramount importance, as long-term monitoring must be ensured while relying on a tiny power source. Operating at a scaled supply voltage, just above the threshold voltage, effectively helps in saving substantial energy, but it makes circuits, and especially memories, more prone to errors, threatening the correct execution of algorithms. The use of error detection and correction codes may help to protect the entire memory content, however it incurs in large area and energy overheads which may not be compatible with the tight energy budgets of wearable systems. To cope with this challenge, in this paper we propose to limit the overhead of traditional schemes by selectively detecting and correcting errors only in data highly impacting the end-to-end quality of service of ultra-low power wearable electrocardiogram (ECG) devices. This partition adopts the protection of either significant words or significant bits of each data element, according to the application characteristics (statistical properties of the data in the application buffers), and its impact in determining the output. The proposed heterogeneous error protection scheme in real ECG signals allows substantial energy savings (11% in wearable devices) compared to state-of-the-art approaches, like ECC, in which the whole memory is protected against errors. At the same time, it also results in negligible output quality degradation in the evaluated power spectrum analysis application of ECG signals.

The VINEYARD Approach: Versatile, Integrated, Accelerator-Based, Heterogeneous Data Centres.

Emerging web applications like cloud computing, Big Data and social networks have created the need for powerful centres hosting hundreds of thousands of servers. Currently, the data centres are based on general purpose processors that provide high flexibility buts lack the energy efficiency of customized accelerators. VINEYARD aims to develop an integrated platform for energy-efficient data centres based on new servers with novel, coarse-grain and fine-grain, programmable hardware accelerators. It will, also, build a high-level programming framework for allowing end-users to seamlessly utilize these accelerators in heterogeneous computing systems by employing typical data-centre programming frameworks (e.g. MapReduce, Storm, Spark, etc.). This programming framework will, further, allow the hardware accelerators to be swapped in and out of the heterogeneous infrastructure so as to offer high flexibility and energy efficiency. VINEYARD will foster the expansion of the soft-IP core industry, currently limited in the embedded systems, to the data-centre market. VINEYARD plans to demonstrate the advantages of its approach in three real use-cases (a) a bio-informatics application for high-accuracy brain modeling, (b) two critical financial applications, and (c) a big-data analysis application.

A Scalable Runtime for the ECOSCALE Heterogeneous Exascale Hardware Platform

Exascale computation is the next target of high performance computing. In the push to create exascale computing platforms, simply increasing the number of hardware devices is not an acceptable option given the limitations of power consumption, heat dissipation, and programming models which are designed for current hardware platforms. Instead, new hardware technologies, coupled with improved programming abstractions and more autonomous runtime systems, are required to achieve this goal. This position paper presents the design of a new runtime for a new heterogeneous hardware platform being developed to explore energy efficient, high performance computing. By combining a number of different technologies, this framework will both simplify the programming of current and future HPC applications, as well as automating the scheduling of data and computation across this new hardware platform. In particular, this work explores the use of FPGAs to achieve both the power and performance goals of exascale, as well as utilising the runtime to automatically effect dynamic configuration and reconfiguration of these platforms.