In-situ FT-IR spectroscopic studies of fuel cell electro-catalysis: From single-crystal to nanoparticle surfaces

The work presented in this article shows the power of the variable temperature, in-situ FT-IR spectroscopy system developed in Newcastle with respect to the investigation of fuel cell electro-catalysis. On the Ru(0001) electrode surface, CO co-adsorbs with the oxygen-containing adlayers to form mixed [CO+(2x2)-O(H)] domains. The electro-oxidation of the Ru(0001) surface leads to the formation of active (1x1)-O(H) domains, and the oxidation of adsorbed CO then takes place at the perimeter of these domains. At 20 degrees C, the adsorbed CO is present as rather compact islands. In contrast, at 60 degrees C, the COads is present as a relatively looser and weaker adlayer. Higher temperature was also found to facilitate the surface diffusion and oxidation of COads. No dissociation or electro-oxidation of methanol was observed at potentials below approximately 950mV; however, the Ru(0001) surface at high anodic potentials was observed to be very active. On both Pt and PtRu nanoparticle surfaces, only one linear bond CO adsorbate was formed from methanol adsorption, and the PtRu surface significantly promoted both methanol dissociative adsorption to CO and its further oxidation to CO2. Increasing temperature from 20 to 60 degrees C significantly facilitates the methanol turnover to CO2.

Genetic programming based formulation for fresh and hardened properties of self-compacting concrete containing pulverised fuel ash

Self-compacting concrete (SCC) flows into place and around obstructions under its own weight to fill the formwork completely and self-compact without any segregation and blocking. Elimination of the need for compaction leads to better quality concrete and substantial improvement of working conditions. This investigation aimed to show possible applicability of genetic programming (GP) to model and formulate the fresh and hardened properties of self-compacting concrete (SCC) containing pulverised fuel ash (PFA) based on experimental data. Twenty-six mixes were made with 0.38 to 0.72 water-to-binder ratio (W/B), 183–317 kg/m³ of cement content, 29–261 kg/m³ of PFA, and 0 to 1% of superplasticizer, by mass of powder. Parameters of SCC mixes modelled by genetic programming were the slump flow, JRing combined to the Orimet, JRing combined to cone, and the compressive strength at 7, 28 and 90 days. GP is constructed of training and testing data using the experimental results obtained in this study. The results of genetic programming models are compared with experimental results and are found to be quite accurate. GP has showed a strong potential as a feasible tool for modelling the fresh properties and the compressive strength of SCC containing PFA and produced analytical prediction of these properties as a function as the mix ingredients. Results showed that the GP model thus developed is not only capable of accurately predicting the slump flow, JRing combined to the Orimet, JRing combined to cone, and the compressive strength used in the training process, but it can also effectively predict the above properties for new mixes designed within the practical range with the variation of mix ingredients.

Simulation of whole building coupled hygrothermal-airflow transfer in different climates

The coupled heat, air and moisture transfer between building envelopes and indoor air is complicated, and has a significant influence on the indoor environment and the energy performance of buildings. In the paper, a model for predicting coupled multi-zone hygrothermal-airflow transfer is presented. Both heat and moisture transfer in the building envelope and multi-zone indoor airflow are simultaneously considered; their interactions are modeled. The coupled system model is implemented into Matlab–Simulink, and is validated by using a series of testing tools and experiments. The new program is applied to investigate the moisture transfer effect on indoor air humidity and building energy consumption in different climates (hot-humid, temperate and hot-dry climates). The results show that not accounting for hygrothermal effects in modeling will result in overestimation of energy costs for hot and humid climate situations and possible over sizing of plant leading to inefficient operation.

Miniaturization of heterogeneous catalytic reactors: Prospects for new developments in catalysis and process engineering

This paper gives an overview of the research done since 1999 at Eindhoven University of Technology in the Netherlands in the field of miniaturization of heterogeneous catalytic reactors. It is described that different incentives exist for the development of these microstructured reaction systems. These include the need for efficient research instruments in catalyst development and screening, the need for small-scale reactor devices for hydrogen production for low-power electricity generation with fuel cells, and the recent quest for intensified processing equipment and novel process architectures (as in the fine chemicals sector). It is demonstrated that also in microreaction engineering, catalytic engineering and reactor design go hand-in-hand. This is illustrated by the design of an integrated microreactor and heat-exchanger for optimum performance of a highly exothermic catalytic reaction, viz. ammonia oxidation. It is argued that future developments in catalytic microreaction technology will depend on the availability of very active catalysts (and catalyst coating techniques) for which microreactors may become the natural housing.

A quantitative research on S- and SO2-poisoning Pt/Vulcan carbon fuel cell catalyst

A quantitative research on S and SO2 poisoning Pt/Vulcan carbon (Pt/VC) catalysts for fuel cells was conducted by the three-electrode method. Pt/VC electrodes were contaminated by submersion in a SO2- containing solution made up of 0.2 mM Na2SO3 and 0.5 M H2SO4 for different periods of time, and held at 0.05 V (vs. RHE) in 0.5 M H2SO4 solutions in order to gain zero-valence sulfur (S0) poisoned electrodes. The sulfur coverage of Pt was determined from the total charge consumed as the sulfur was oxidized from S0 at 0.05 V (vs. RHE) to sulfate at >1.1 V (vs. RHE). The summation of initial coverage of S0 (S) and coverage of H (H) are approximately equal to 1 (H + S = 1) when 0.5

Variable selection via RIVAL and its application in nuclear material detection

In many situations, the number of data points is fixed, and the asymptotic convergence results of popular model selection tools may not be useful. A new algorithm for model selection, RIVAL (removing irrelevant variables amidst Lasso iterations), is presented and shown to be particularly effective for a large but fixed number of data points. The algorithm is motivated by an application of nuclear material detection where all unknown parameters are to be non-negative. Thus, positive Lasso and its variants are analyzed. Then, RIVAL is proposed and is shown to have some desirable properties, namely the number of data points needed to have convergence is smaller than existing methods.

Process simulation of co-firing torrefied biomass in a 220 MWe coal-fired power plant

Torrefaction based co-firing in a pulverized coal boiler has been proposed for large percentage of biomass co-firing. A 220 MWe pulverized coal-power plant is simulated using Aspen Plus for full understanding the impacts of an additional torrefaction unit on the efficiency of the whole power plant, the studied process includes biomass drying, biomass torrefaction, mill systems, biomass/coal devolatilization and combustion, heat exchanges and power generation. Palm kernel shells (PKS) were torrefied at same residence time but 4 different temperatures, to prepare 4 torrefied biomasses with different degrees of torrefaction. During biomass torrefaction processes, the mass loss properties and released gaseous components have been studied. In addition, process simulations at varying torrefaction degrees and biomass co-firing ratios have been carried out to understand the properties of CO₂ emission and electricity efficiency in the studied torrefaction based co-firing power plant. According to the experimental results, the mole fractions of CO ₂ and CO account for 69-91% and 4-27% in torrefied gases. The predicted results also showed that the electrical efficiency reduced when increasing either torrefaction temperature or substitution ratio of biomass. A deep torrefaction may not be recommended, because the power saved from biomass grinding is less than the heat consumed by the extra torrefaction process, depending on the heat sources. 

Flexible fault ride through strategy for wind farm clusters in power systems with high wind power penetration

This paper investigates a flexible fault ride through strategy for power systems in China with high wind power penetration. The strategy comprises of adaptive fault ride through requirements and maximum power restrictions of the wind farms with weak fault ride through capabilities. The slight faults and moderate faults with high probability are the main defending objective of the strategy. The adaptive fault ride through requirement in the strategy consists of two sub fault ride through requirements, a temporary slight voltage ride through requirement corresponding to a slight fault incident, with a moderate voltage ride through requirement corresponding to a moderate fault. The temporary overloading capability of the wind farm is reflected in both requirements to enhance the capability to defend slight faults and to avoid tripping when the crowbar is disconnected after moderate faults are cleared. For those wind farms that cannot meet the adaptive fault ride through requirement, restrictions are put on the maximum power output. Simulation results show that the flexible fault ride through strategy increases the fault ride through capability of the wind farm clusters and reduces the wind power curtailment during faults.

Photosensitized destruction of Chlorella vulgaris by methylene blue or nuclear fast red combined with hydrogen peroxide under visible light irradiation

A considerable number of investigations have started to elucidate the essential roles biological agents play in the biodeterioration of stone. Chemical biocides are becoming increasingly banned because of the environmental and health hazards associated with these toxic substances. The present study reports the photodynamic effect of Methylene Blue (MB) and Nuclear Fast Red (NFR) in the presence of hydrogen peroxide (H₂O₂) on the destruction of the algae Chlorella vulgaris (C. vulgaris) under irradiation with visible light. Illumination of C. vulgaris in the presence of MB or NFR combined with H₂O₂ results in the decomposition of both the algal species and the photosensitizer. The photodynamic effect was investigated under aerobic and anaerobic conditions. Differences in mechanism type are reported and are dependent on both the presence and the absence of oxygen. The behavior of each photosensitizer leads to a Type II mechanism and a Type I/Type II combination for MB and NFR, respectively, being concluded. This novel combination could be effective for the remediation of biofilm-colonized stone surfaces.

Design of an automated solar concentrator for the pyrolysis of scrap rubber

An automated solar reactor system was designed and built to carry out catalytic pyrolysis of scrap rubber tires at 550°C. To maximize solar energy concentration, a two degrees-of-freedom automated sun tracking system was developed and implemented. Both the azimuth and zenith angles were controlled via feedback from six photo-resistors positioned on a Fresnel lens. The pyrolysis of rubber tires was tested with the presence of two types of acidic catalysts, H-beta and H-USY. Additionally, a photoactive TiO<inf>2</inf> catalyst was used and the products were compared in terms of gas yields and composition. The catalysts were characterized by BET analysis and the pyrolysis gases and liquids were analyzed using GC-MS. The oil and gas yields were relatively high with the highest gas yield reaching 32.8% with H-beta catalyst while TiO<inf>2</inf> gave the same results as thermal pyrolysis without any catalyst. In the presence of zeolites, the dominant gasoline-like components in the gas were propene and cyclobutene. The TiO<inf>2</inf> and non-catalytic experiments produced a gas containing gasoline-like products of mainly isoprene (76.4% and 88.4% respectively). As for the liquids they were composed of numerous components spread over a wide distribution of C<inf>10</inf> to C<inf>29</inf> hydrocarbons of naphthalene and cyclohexane/ene derivatives.

Co-tape casting fabrication, field assistant sintering and evaluation of a coke resistant La0.2Sr0.7TiO3-Ni/YSZ functional gradient anode supported solid oxide fuel cell

The ability to directly utilize hydrocarbons and other renewable liquid fuels is one of the most important issues affecting the large scale deployment of solid oxide fuel cells (SOFCs). Herein we designed La_0.2Sr_0.7TiO₃-Ni/YSZ functional gradient anode (FGA) supported SOFCs, prepared with a co-tape casting method and sintered using the field assisted sintering technique (FAST). Through SEM observations, it was confirmed that the FGA structure was achieved and well maintained after the FAST process. Distortion and delamination which usually results after conventional sintering was successfully avoided. The La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs showed a maximum power density of 600mWcm^-2 at 750°C, and was stable for 70h in CH₄. No carbon deposition was detected using Raman spectroscopy. These results confirm the potential coke resistance of La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs.