Mark J. Biggs

Carbon Nanotubes for Dye‐Sensitized Solar Cells

As one type of emerging photovoltaic cell, dye-sensitized solar cells (DSSCs) are an attractive potential source of renewable energy due to their eco-friendliness, ease of fabrication, and cost effectiveness. However, in DSSCs, the rarity and high cost of some electrode materials (transparent conducting oxide and platinum) and the inefficient performance caused by slow electron transport, poor light-harvesting efficiency, and significant charge recombination are critical issues. Recent research has shown that carbon nanotubes (CNTs) are promising candidates to overcome these issues due to their unique electrical, optical, chemical, physical, as well as catalytic properties. This article provides a comprehensive review of the research that has focused on the application of CNTs and their hybrids in transparent conducting electrodes (TCEs), in semiconducting layers, and in counter electrodes of DSSCs. At the end of this review, some important research directions for the future use of CNTs in DSSCs are also provided.

The COCO2 product ratio for a porous char particle within an incipiently fluidized bed: a numerical study

By comparing results generated from an advanced single-particle model with those obtained from experiment, we find reaction does occur within the boundary layer of a stationary char resident within the emulsion phase of a fluidized bed, with the extent of reaction diminishing as superficial gas velocity increases. Comparison also shows that the CO-O2, CO2and CCO2 reactions all affect the particle related COCO2 product ratio, with the influence of each varying with temperature. These observations help explain the peculiar product ratio/temperature profile recently reported by Linjewile and Agarwal (1995, Fuel74, 5) and suggest, for the first time, a relationship between the product ratio and char particle size. The model results show that boundary layer reaction influences the heat transfer coefficient associated with a char that is burning within a fluidized bed, and that any correlations which do not explicitly account for this may only serve as an approximation.

Virtual porous carbons: what they are and what they can be used for

We use the term “virtual porous carbon” (VPC) to describe computer-based molecular models of nanoporous carbons that go beyond the ubiquitous slit pore model and seek to engage with the geometric, topological and chemical heterogeneity that characterises almost every form of nanoporous carbon. A small number of these models have been developed and used since the early 1990s. These models and their use are reviewed. Included are three more detailed examples of the use of our VPC model. The first is concerned with the study of solid-like adsorbate in nanoporous carbons, the second with the absolute assessment of multi-isotherm based methods for determining the fractal dimension, and the final one is concerned with the fundamental study of diffusion in nanoporous carbons.

Free energy of adsorption for a peptide at a liquid/solid interface via nonequilibrium molecular dynamics

Protein adsorption is of wide interest including in many technological applications such as tissue engineering, nanotechnology, biosensors, drug delivery, and vaccine production among others. Understanding the fundamentals of such technologies and their design would be greatly aided by an ability to efficiently predict the conformation of an adsorbed protein and its free energy of adsorption. In the study reported here, we show that this is possible when data obtained from nonequilibrium thermodynamic integration (NETI) combined with steered molecular dynamics (SMD) is subject to bootstrapping. For the met-enkephalin pentapeptide at a water-graphite interface, we were able to obtain accurate predictions for the location of the adsorbed peptide and its free energy of adsorption from around 50 and 80 SMD simulations, respectively. It was also shown that adsorption in this system is both energetically and entropically driven. The free energy of adsorption was also decomposed into that associated with formation of the cavity in the water near the graphite surface sufficient to accommodate the adsorbed peptide and that associated with insertion of the peptide into this cavity. This decomposition reveals that the former is modestly energetically and entropically unfavorable, whereas the latter is the opposite in both regards to a much greater extent.

Solution processed graphene structures for perovskite solar cells

Organometallic trihalide perovskite light absorber based solar cells have drawn increasing attention because of their recent rapid increase in power conversion efficiency (PCE). These photovoltaic cells have relied significantly on transparent conducting oxide (TCO) electrodes which are costly and brittle. Herein, solution processed transparent conductive graphene films (TCGFs) are utilized, for the first time, as an alternative to traditional TCO electrodes at the electron collecting layer in perovskite solar cells (PSCs). By investigating and optimizing the trade-off between transparency and sheet resistance (Rs) of the graphene films, a PCE of 0.62% is achieved. This PCE is further improved to 0.81% by incorporating graphene structures into both compact and mesoporous TiO2 layers of the solar cell. We anticipate that the present study will lead to further work to develop graphene-based transparent conductive electrodes for future solar cell devices.

Explicit numerical simulation of suspension flow with deposition in porous media: influence of local flow field variation on deposition processes predicted by trajectory methods

Abstract A new explicit numerical simulation (ENS) method based on lattice-gas automata (LGA) is introduced here for the flow of solid/fluid suspensions with deposition in porous media. The ENS method explicitly resolves the dynamics of the individual solid particles and the suspending fluid in the domain defined by the pore walls and solid particle surfaces. After describing the new method, it is applied to the study of solid/fluid suspension flow with deposition in a constriction and in a model random porous solid. This study clearly demonstrates that the deposits strongly influence the local flow fields, which in turn affect the deposition process indicating that this interplay should be modelled if accurate results are desired from trajectory methods.

Microfluidic hydrodynamic focusing based synthesis of POPC liposomes for model biological systems

Lipid vesicles have received significant attention in areas ranging from pharmaceutical and biomedical engineering to novel materials and nanotechnology. Microfluidic-based synthesis of liposomes offers a number of advantages over the more traditional synthesis methods such as extrusion and sonication. One such microfluidic approach is microfluidic hydrodynamic focusing (MHF), which has been used to synthesize nanoparticles and vesicles of various lipids. We show here that this method can be utilized in synthesis of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) vesicles with controllable size. Since POPC is among the primary constituents of cellular membranes, this work is of direct applicability to modelling of biological systems and development of nano-containers with higher biologic compatibility for pharmaceutical and medical applications.

Combustion of a porous char particle in an incipiently fluidized bed

Abstract A simple single particle model has been developed for the combustion of carbon. The heterogeneous reactions of carbon oxidation and gasification are assumed to take place inside the porous char, while the homogeneous oxidation of carbon monoxide is assumed to occur in the film surrounding the burning particle. Depending on the extent of consumption of oxygen by the primary product CO, oxygen may or may not reach the char surface. Hence, the formulation leads to a single film porous particle model in the case where oxygen reaches the particle surface, and a double film porous particle model when oxygen does not reach the char particle surface. Analytical expressions are derived for the concentration profiles for the different gaseous species. The application of the model is illustrated through calculations relevant for combustion of carbon in an incipiently fluidized bed. These simulations, then, reflect the combustion behavior in the dense phase of a bubbling fluidized bed. The model successfully predicts the experimental observation of two extrema in CO/CO2 product ratio at the surface of a burning particle. Parametric studies were conducted to assess the effect of char and inert particle sizes, moisture content and the bulk species concentration on the CO/CO2 product ratio, as well as the average rates of species consumption (or generation). The results show that char gasification reaction influences the carbon consumption behavior significantly at high temperatures. The CO/CO2 product ratio at the surface increases—as a consequence of a decrease in the net film oxidation rate—with an increase in the size of bed particles. The CO/CO2 product ratio is also enhanced by a decrease in char size and gas phase moisture content. The temperature corresponding to a minimum in CO/CO2 ratio increases in a similar fashion. An increase in particle porosity and specific internal surface area led to a decrease in this temperature. The model results also permit identification of the three regimes of combustion.

Carbonaceous Dye-Sensitized Solar Cell Photoelectrodes

High photovoltaic efficiency is one of the most important keys to the commercialization of dye sensitized solar cells (DSSCs) in the quickly growing renewable electricity generation market. The heart of the DSSC system is a wide bandgap semiconductor based photoelectrode film that helps to adsorb dye molecules and transport the injected electrons away into the electrical circuit. However, charge recombination, poor light harvesting efficiency and slow electron transport of the nanocrystalline oxide photoelectrode film are major issues in the DSSCs performance. Recently, semiconducting composites based on carbonaceous materials (carbon nanoparticles, carbon nanotubes (CNTs), and graphene) have been shown to be promising materials for the photoelectrode of DSSCs due to their fascinating properties and low cost. After a brief introduction to development of nanocrystalline oxide based films, this Review outlines advancements that have been achieved in the application of carbonaceous‐based materials in the photoelectrode of DSSCs and how these advancements have improved performance. In addition, several of the unsolved issues in this research area are discussed and some important future directions are also highlighted.

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores

Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of the widely used ionic liquid (EMI-TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can only accommodate a single layer of ions. Instead, equally-charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. This finding opens the door for the design of better materials for electrochemical applications.