Peter J. Holliman

Optimisation of the anaerobic digestion of agricultural resources

It is in the interest of operators of anaerobic digestion plants to maximise methane production whilst concomitantly reducing the chemical oxygen demand of the digested material. Although the production of biogas through anaerobic digestion is not a new idea, commercial anaerobic digestion processes are often operated at well below their optimal performance due to a variety of factors. This paper reviews current optimisation techniques associated with anaerobic digestion and suggests possible areas where improvements could be made, including the basic design considerations of a single or multi-stage reactor configuration, the type, power and duration of the mixing regime and the retention of active microbial biomass within the reactor. Optimisation of environmental conditions within the digester such as temperature, pH, buffering capacity and fatty acid concentrations is also discussed. The methane-producing potential of various agriculturally sourced feedstocks has been examined, as has the advantages of co-digestion to improve carbon-to-nitrogen ratios and the use of pre-treatments and additives to improve hydrolysis rates or supplement essential nutrients which may be limiting. However, perhaps the greatest shortfall in biogas production is the lack of reliable sensory equipment to monitor key parameters and suitable, parallelised control systems to ensure that the process continually operates at optimal performance. Modern techniques such as software sensors and powerful, flexible controllers are capable of solving these problems. A direct comparison can be made here with, for instance, oil refineries where a more mature technology uses continuous in situ monitoring and associated feedback procedures to routinely deliver continuous, optimal performance.

Perovskite processing for photovoltaics: a spectro-thermal evaluation

Thermal analysis (TGA and DSC), coupled with evolved gas FTIR spectroscopy, has been used to study the changes occurring during, and differences between materials after, the annealing step of mixed-halide methylammonium lead halide perovskites. This is important because, to date, the material is the most efficient light harvester in highly efficient, 3rd generation perovskite photovoltaic devices, and processing plays a significant role in device performance. TGA-FTIR data show only solvent evolution during the annealing step, whilst post-annealing analysis shows that the resulting material still contains a significant amount of residual solvent; however, efficient DMF removal was possible using a silica gel desiccant for a period of 3 days. The data also show that methylammonium halide decomposition does not occur until temperatures well above those used for perovskite processing, suggesting that this is not a significant issue for device manufacture. The absence of a well-defined, reversible tetragonal – cubic phase change around 55 °C in the DSC data of the annealed material, and the presence of HCl in evolved gas analysed following thermal decomposition, demonstrates that CH3NH3I3−xClx does retain some Cl after annealing and does not simply form stoichiometric CH3NH3PbI3 as has been suggested by some workers.

Cobalt-zinc oxide absorbents for low temperature gas desulfurisation

The hydrogen sulfide absorption capacity of a series of cobalt-zinc oxides with nominal Co/Zn atomic ratios of 0/100, 10/90, 20/80, 30/70, 40/60, 50/50, 70/30, 90/10 and 100/0 was determined using a continuous flow absorption apparatus. The reaction of the mixed oxides with H 2 S amounted to ca. 3 monolayers, and is therefore largely confined to the surface of the oxides. The sulfur uptake was found to be proportional to the surface area of the oxides with a Co/Zn ratio ≤40/60, indicating that lattice diffusion played a major role in the rate determining step, and that the main function of the cobalt was to increase the surface area. At high cobalt concentrations, the sulfur uptake increased more than proportionately with surface area and the reaction was virtually stoichiometric for the oxide with a Co/Zn ratio of 100/0. This was associated with a change in the oxide structure from a bulk biphasic ZnO and Co 3 O 4 absorbent with a ZnCo 2 O 4 surface spinel at Co/Zn ratios ≤30 to a monophasic zincian or pure Co 3 O 4 structure at higher cobalt loadings. Analysis of the sulfided mixed oxides showed that microcrystalline membraneous sheets containing cobalt, zinc and sulfur developed on sulfiding. XPS studies of the sulfided oxides indicated that H 2 S reduced the surface spinel found at Co/Zn ratios ≤30/70 and the zincian/pure Co 3 O 4 found at higher cobalt concentrations to CoO and ZnO prior to the formation of their sulfides. The results are interpreted in terms of a surface reconstruction occurring during sulfiding.

Zeolite collapse and polyamorphism

The phenomenology of zeolite collapse is outlined, drawing on recent synchrotron x-ray diffraction experiments and computer simulations of low density cage structures like zeolite A and zeolite Y. Attention is drawn to the importance of polyamorphism in destabilizing this type of microporous crystal and its role in order-disorder as well as amorphous-amorphous transitions, together with associated differences in entropy and density between polyamorphic phases and the precursor zeolite. Magic angle spinning NMR and inelastic x-ray scattering are used to highlight changes in structural order and mechanical rigidity between the starting zeolite and the final high density polyamorph. In conclusion, two-level systems detected with inelastic neutron scattering are described and their involvement in dictating the dynamics of the collapse of zeolitic cage structures.

Characterisation of cobalt–zinc hydroxycarbonates and their products of decomposition

A series of cobalt–zinc hydroxycarbonate precursors with nominal Co/Zn atomic ratios of 0/100, 10/90, 20/80, 30/70, 40/60, 50/50, 70/30, 90/10 and 100/0 have been synthesized from their mixed metal nitrates and ammonium carbonate by a coprecipitation route. X-Ray and electron diffraction studies of the precursors revealed that hydrozincite, Zn 5 (CO 3 ) 2 (OH) 6 , was the major phase at Co/Zn ratios≤30/70 and spherocobaltite, CoCO 3 , predominated at Co/Zn ratios of 50/50 to 90/10. The Co/Zn 100/0 precursor formed only the metastable basic carbonate Co(CO 3 ) 0.5 (OH) 1.0 0.1H 2 O. UV–VIS–NIR diffuse reflectance spectroscopy revealed that the cobalt was present in the 2+ oxidation state in an octahedral environment in all the precursors. Decomposition of the Co/Zn precursors at 350 °C resulted in the formation of ZnO as the major phase at low Co loadings and Co 3 O 4 as the major phase at high loadings. The highest surface areas were attained from the decomposition of basic cobalt carbonate or spherocobaltite containing little or no zinc in solid solution. XPS studies of the oxides revealed that only Co 3+ and Zn 2+ ions were present at the surface at Co/Zn ratios≤30/70 indicating the presence of the ‘surface spinel’, ZnCo 2 O 4 . Co 2+ was detected at higher Co loadings.

Dissolved organic carbon and trihalomethane precursor removal at a UK upland water treatment works

The removal of dissolved organic carbon (DOC) during potable water treatment is important for maintaining aesthetic water quality standards, minimising concentrations of micro-pollutants, controlling bacterial regrowth within distribution systems and, crucially, because it contains a sub-component that can act as trihalomethane (THM) precursors. In this study, the concentration and characteristics of raw water DOC and THM formation potential (THMFP) entering an upland potable water treatment works were analysed over twelve months. Correlations between raw water DOC characteristics, standardised THMFP (STHMFP) and % DOC removal were also investigated. DOC and THM precursor removal during a series of treatment stages was examined over this period, as well as potential selectivity in the removal of DOC fractions, to assess the importance of different treatment stages for DOC removal and THM amelioration. Though THMFP removal remained high and fairly stable throughout the study period (83-89%), the data suggest that this was mostly the result of high DOC removal rates rather than the selective removal of THM precursors. Whilst this chemical agnosticism makes DOC removal more robust, it may make the overall process more vulnerable to exceeding permissible THM concentrations under changing climatic conditions. The kinetics of the reaction between DOC and chlorine appeared to vary seasonally, indicating temporal changes in the proportions of fast- and slow-reacting precursors with implications for THM concentrations at the point of delivery to the consumer. The initial treatment stages, comprising coagulation-flocculation and dissolved air floatation (DAF) were by far the most important in terms of bulk DOC removal and the preferential removal of THM precursors, though, surprisingly, DOC quality was also modified following chlorination and secondary rapid gravity filtration (RGF). Though net THM concentration decreased following initial treatment stages, a doubling in the proportion of brominated THMs (BrTHMs), which are reported to be more carcinogenic, was also observed.

Rapid, continuous in situ monitoring of dye sensitisation in dye-sensitized solar cells

Two alternative techniques to the traditional dye desorption method are presented which enable rapid, continuous in situ measurement of dye uptake in porous TiO2 films used in dye-sensitized solar cells (DSC). Measurement of dye uptake is crucial for the rapid up-scaling of DSC technology since currently this is a rate limiting process step typically taking hours to achieve. Most reported measurements of dye sorption have involved desorbing dye at set intervals using a base (e.g.NaOH) followed by UV-vis spectroscopy. Whilst this method is accurate and quantitative, it is time-consuming, destructive of the devices and in situ measurements are impossible. The latter are important as dyeing speeds increase. Here we present two methods to measure the temporal evolution of colour at the interface of porous TiO2 films with TCO-coated glass. The first method uses digital image capture and subsequent image analysis to extract RGB (red-green-blue) colour data enabling a rapid quantification of dye uptake over periods from seconds to hours. The second method uses UV-visible reflectance spectroscopy providing more highly resolved wavelength data; important as DSC co-sensitisation is becoming increasingly important. There is a clear correlation between the two in situ methods reported here as well as with traditional dye desorption methods for measurements made over a period of hours. These methods represent important new tools for the development of ultra-fast dye sensitisation for DSC.

Mixed Co–Zn–Al oxides as absorbents for low-temperature gas desulfurisation

High-surface-area zinc–cobalt–aluminium oxides have been prepared from coprecipitated hydroxycarbonate precursors. The oxides were tested for their H2S uptake in a microreactor at 303 K. The precursors all adopted a hydrotalcite-type structure, whilst the oxides were also all single-phase materials. Their structures were either based on that of ZnO or Co3O4, which suggested the presence of solid solutions with all the ions dissolved into one phase. A comparison of the H2S uptake of these materials with that of the Co–Zn oxides suggested that the presence of aluminium ions in the oxide gave rise to an increase in their surface areas, but that the modified compounds did not absorb significantly more H2S. Indeed, the more Co-rich cobalt–zinc–aluminium oxides absorbed less H2S than Co–Zn oxides prepared in a similar way.

Development of selective, ultra-fast multiple co-sensitization to control dye loading in dye-sensitized solar cells

Enhancing the spectral response of dye-sensitized solar cells (DSC) is essential to increasing device efficiency and a key approach to achieve this is co-sensitization (i.e. the use of multiple dyes to absorb light from different parts of the solar spectrum). However, precise control of dye loading within DSC mesoporous metal oxide photo-anodes is non-trivial especially for very rapid processing (minutes). This is further complicated by dyes having very different partition (Kd) and molar extinction (e) coefficients which strongly influence dye uptake and spectral response, respectively. Here, we present a highly versatile, ultra-fast (ca. 5 min) desorption and re-dyeing method for dye-sensitized solar cells which can be used to precisely control dye loading in photo-electrode films. This method has been successfully applied to re-dye, partially desorb and re-dye and selectively desorb and re-dye photo-electrodes using examples of a Ru-bipy dye (N719) and also organic dyes (SQ1 and D149) giving η up to 8.1% for a device containing the organic dye D149 and re-dyed with the Ru dye N719. The paper also illustrates how this method can be used to rapidly screen large numbers of dyes (and/or dye combinations) and also illustrates how it can also be used to selectively study dye loading.

A study of dye anchoring points in half-squarylium dyes for dye-sensitized solar cells

This paper reports the synthesis of a series of new half-squaraine dyes (Hf-SQ) based around a common chromophoric unit consisting of linked indoline and squaric acid moieties. Carboxylate groups have been incorporated onto this core structure at four different points to study the influence of the anchoring group position on dye-sensitized solar cell (DSC) device performance. Dyes have been linked to TiO2 directly through the squaric acid moiety, through a modified squaric acid unit where a vinyl dicyano group has replaced one carbonyl, via an alkyl carboxylate attached to the indole N or through a carboxylate attached to the 4 position of a benzyl indole. Contact angle measurements have been studied to investigate the hydrophobic/hydrophilic properties of the dyes and the results have been compared to N719 and Z907. Full characterization data of all the dyes and synthetic intermediates are reported including single-crystal X-ray structural analysis for dye precursors; the indole (2a) and the half-squarylium esters (3a) and (6b), as well as the dyes (4c), (8) and (12). Dye colours range from yellow to red/brown in solution (λmax range from 430 to 476 nm) with e ranging from 38000 to 133100 M−1 cm−1. The performance of the dyes in DSCs shows the highest efficiency yet reported for a Hf-SQ dye (η = 5.0%) for 1 cm2 devices with a spectral response ranging from 400 to 700 nm depending on the dye substituents. Co-sensitization of half-squarylium dye (7b) with squaraine dye (SQ2) resulted in a broader spectral response and an improved device efficiency (η = 6.1%). Density functional theory (DFT) calculations and cyclic voltammetry have been used to study the influence of linker position on dye HOMO–LUMO levels and the data has been correlated with I–V and EQE data.