Infrared study of the adsorption of methanol on oxidised and reduced Cu/SiO2 catalysts

Infrared spectra are reported of methanol adsorbed at 295 K on reduced Cu/SiO2 and on Cu/SiO2 which had been preoxidised by exposure to excess nitrous oxide. Methanol was chemisorbed on reduced Cu/SiO2 to give methoxy species on both silica and copper, gave a trace of formate on copper via reaction with residual surface oxygen, and was weakly adsorbed at SiOH sites on the silica support. Heating the adsorbed species at 393 K led to the loss of methoxy groups on copper and the concomitant formation of a bidentate surface formate. Heating reduced Cu/SiO2 in methanol at 538 K initially gave both gaseous and adsorbed (on Cu) methyl formate which subsequently decomposed to CO and hydrogen. The reactions of methanol with oxidised Cu/SiO2 were similar to those for the reduced catalyst although surface oxygen promoted the formation of surface methoxy groups on copper. Subsequent heating at 393 K led first to unidentate formate before the appearance of bidentate formate.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 2. -- A fourier-transform infrared spectroscopy study of methanol adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methanol adsorbed at 295 K on ZnO/SiO 2, on reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methanol on ZnO/SiO2 gave methoxy species on ZnO and SiO, in addition to both strongly and weakly physisorbed methanol on SiO2. The corresponding adsorption of methanol on reduced Cu/ZnO/SiO2 also gave methoxy species on Cu and a small amount of bridging formate. Reaction of methanol with a reoxidised Cu/ZnO/SiO2 catalyst resulted in an enhanced quantity of methoxy species on Cu. Heating adsorbed species on Cu/ZnO/SiO2 at 393 K led to the loss of methoxy groups on Cu and the concomitant formation of formate species on both ZnO and Cu. The comparable reaction on a reoxidised Cu/ZnO/SiO2 catalyst gave an increased amount of formate species on ZnO and this correlated with an increased quantity of methoxy groups lost from Cu. An explanation is given in terms of adsorption of formate and formaldehyde species at special sites located at the copper/zinc oxide interface.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces: Part 1. -- A Fourier-transform infrared study of formic acid and formaldehyde adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

Fourier-transform infrared (FTIR) spectra are reported of formic acid and formaldehyde on ZnO/SiO2, reduced Cu/ZnO/SiO2 and reoxidised Cu/ZnO/SiO2 catalyst. Formic acid adsorption on ZnO/SiO2 produced mainly bidentate zinc formate species with a lesser quantity of unidentate zinc formate. Formic acid on reduced Cu/ZnO/SiO2 catalyst resulted not only in the formation of bridging copper formate structures but also in an enhanced amount of formate relative to that for ZnO/SiO2 catalyst. Formic acid on reoxidised Cu/ZnO/SiO2 gave unidentate formate species on copper in addition to zinc formate moieties. The interaction of formaldehyde with ZnO/SiO2 catalyst resulted in the formation of zinc formate species. The same reaction on reduced Cu/ZnO/SiO2 catalyst gave bridging formate on copper and a remarkable increase in the quantity of formate species associated with the zinc oxide. Adsorption of formaldehyde on a reoxidised Cu/ZnO/SiO2 catalyst produced bridging copper formate and again an apparent increase in the concentration of zinc formate species. An explanation in terms of the adsorption of molecules at special sites located at the interface between copper and zinc oxide is given.

Infrared study of CO, CO2, H2 and H2O interactions on potassium-promoted reduced and oxidised silica-supported copper catalysts

FTIR spectra are reported of CO, CO2, H2 and H2O on silica-supported potassium, copper and potassium-copper catalysts. Adsorption of CO on a potassium/silica catalyst resulted in the formation of complexed CO moieties. Whereas exposure of CO2 to the same catalyst produced bands ascribed to CO2 -, bidentate carbonate and complexed CO species. Fully oxidised copper/silica surfaces gave bands due to CO on CuO and isolated Cu2+ cations on silica. Addition of potassium to this catalyst removed a peak attributed to CO adsorption on isolated Cu2+ cations and red-shifted the maximum ascribed to CO adsorbed on CuO. For a reduced copper/silica catalyst bands due to adsorbed CO on both high and low index planes were red-shifted by 10 cm-1 in the presence of potassium, although the strength of the Cu - CO bond did not appear to be increased concomitantly. An explanation in terms of an electrostatic effect between potassium and adsorbed CO is forwarded. A small maximum at ca. 1510 cm-1 for the reduced catalyst increased substantially upon exposing CO to a reoxidised promoted catalyst. Correspondingly, CO2 adsorption allowed the identification of two distinct carboxylate species, one of which was located at an interfacial site between copper and potassium oxide. Carboxylate species reacted with hydrogen at 295 K, on a reduced copper surface, to produce predominantly unidentate formate on potassium. In contrast no interaction was detected on a reoxidised copper catalyst at 295 K until a fraction of the copper surface was in a reduced state. Furthermore the interaction of polar water molecules with carboxylate species resulted in a perturbation of this structure which gave lower C----O stretching frequencies.

A combined temperature-programmed reaction spectroscopy and Fourier-transform infrared spectroscopy study of CO2/H2 and CO/CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol-synthesis catalysts

The reaction of CO2 and H2 with ZnO/SiO2 catalyst at 295 K gave predominantly hydrogencarbonate on zinc oxide and a small quantity of formate was evolved after heating at 393 K. Elevation of the reaction temperature to 503 K enhanced the rate of formation of zinc formate species. Significantly these formate species decomposed at 573 K almost entirely to CO2 and H2. Even after exposure of CO2-H2 or CO-CO2-H2 mixtures to highly defected ZnO/SiO2 catalyst, the formate species produced still decomposed to give CO2 and H2. It was concluded that carboxylate species which were formed at oxygen anion vacancies on polar Zn planes were not significantly hydrogenated to formate. Consequently it was proposed that the non-polar planes on zinc oxide contained sites which were specific for the synthesis of methanol. The interaction of CO2 and H2 with reduced Cu/ZnO/SiO2 catalyst at 393 K gave copper formate species in addition to substantial quantities of formate created at interfacial sites between copper and zinc oxide. It was deduced that interfacial formate species were produced from the hydrogenation of interfacial bidentate carbonate structures. The relevance of interfacial formate species in the methanol synthesis reaction is discussed. Experiments concerning the reaction of CO2-H2 with physical mixtures of Cu/SiO2 and ZnO/SiO2 gave results which were simply characteristic of the individual components. By careful consideration of previous data a detailed proposal regarding the role of spillover hydrogen is outlined. Admission of CO to a gaseous CO2-H2 feedstock resulted in a considerably diminished amount of formate species on copper. This was ascribed to a combination of over-reduction of the surface and site-blockage.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 3. -- Fourier-transform infrared study of methyl formate adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methyl formate adsorbed at 295 K on ZnO/SiO2, reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methyl formate on ZnO/SiO2 gave adsorbed zinc formate species and strongly physisorbed molecular methanol on silica. The comparable reaction of methyl formate with reduced Cu/ZnO/SiO2 catalyst produced bridging formate species on copper and a diminished quantity of zinc formate relative to that formed on ZnO/SiO2 catalyst. This effect is explained in terms of site blockage on the ZnO surface by small copper clusters. Addition of methyl formate to a reoxidised Cu/ZnO/SiO2 catalyst produced a considerably greater amount of formate species on zinc oxide and methoxy groups on copper were detected. The increase in concentration of zinc formate species was rationalised in terms of rearrangement of unidentate copper formate species to become bonded to copper and zinc oxide sites located at the interface between these two components.

In situ observation of structural changes in polycrystalline silver catalysts by environmental scanning electron microscopy

Morphology changes induced in polycrystalline silver catalysts as a result of heating in either oxygen, water or oxygen-methanol atmospheres have been investigated by environmental scanning electron microscopy (ESEM), FT-Raman spectroscopy and temperature programmed desorption (TPD). The silver catalyst of interest consisted of two distinct particle types, one of which contained a significant concentration of sub-surface hydroxy species (in addition to surface adsorbed atomic oxygen). Heating the sample to 663 K resulted in the production of 'pin-holes' in the silver structure as a consequence of near-surface explosions caused by sub-surface hydroxy recombination. Furthermore, 'pin-holes' were predominantly found in the vicinity of surface defects, such as platelets and edge structures. Reaction between methanol and oxygen also resulted in the formation of 'pin-holes' in the silver surface, which were inherently associated with the catalytic process. A reaction mechanism is suggested that involves the interaction of methanol with sub-surface oxygen species to form sub-surface hydroxy groups. The sub-surface hydroxy species subsequently erupt through the silver surface to again produce 'pin-holes'.

Characterisation of SiO2-supported nickel catalysts for carbon dioxide reforming of methane

The CO2-methane reformation reaction over Ni/SiO2 catalysts has been extensively studied using a range of temperature-programmed techniques and characterisation of the catalysts by thermogravimetry (TG), X-ray diffraction (XRD) and electron microscopy (TEM). The results indicate a strong correlation between the microstructure of the catalyst and its performance. The role of both CO2 and CH4 in the reaction has been investigated and the role of methyl radicals in the reaction mechanism highlighted. A reaction mechanism involving dissociatively adsorbed CO2 and methyl radicals has been proposed.

Characterization of precursors to methanol synthesis catalysts Cu/ZnO system

The composition of a series of hydroxycarbonate precursors to copper/zinc oxide methanol synthesis catalysts prepared under conditions reported as optimum for catalytic activity has been studied. Techniques employed included thermogravimetry (TG), temperature-programmed decomposition (TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman and FTIR spectroscopies. Evidence was obtained for various structural phases including hydrozincite, copper hydrozincite, aurichalcite, zincian malachite and malachite (the concentrations of which depended upon the exact Cu/Zn ratio used). Significantly, previously reported phases such as gerhardite and rosasite were not identified when catalysts were synthesized at optimum solution pH and temperature values, and after appropriate aging periods. Calcination of the hydroxycarbonate precursors resulted in the formation of catalysts containing an intimate mixture of copper and zinc oxides. Temperature-programmed reduction (TPR) revealed that a number of discrete copper oxide species were present in the catalyst, the precise concentrations of which were determined to be related to the structure of the catalyst precursor. Copper hydrozincite decomposed to give zinc oxide particles decorated by highly dispersed, small copper oxide species. Aurichalcite appeared to result ultimately in the most intimately mixed catalyst structure whereas zincian malachite decomposed to produce larger copper oxide and zinc oxide grains. The reason for the stabilization of small copper oxide and zinc oxide clusters by aurichalcite was investigated by using carefully selected calcination temperatures. It was concluded that the unique formation of an 'anion-modified' oxide resulting from the initial decomposition stage of aurichalcite was responsible for the 'binding' of copper species to zinc moieties.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

Formation of polypyrrole and polythiophene within Cu2+- and H+-mordenite hosts studied by EPR and UV-VIS spectroscopy

The reactions of pyrrole and thiophene monomers in copper-exchanged mordenite have been investigated using EPR and UV–VIS absorption spectroscopy. The EPR spectra show a decrease in the intensity of the Cu2+ signal and the appearance of a radical signal due to the formation of oxidatively coupled oligomeric and/or polymeric species in the zeolite host. The reaction ceases when ca. 50% of the copper has reacted and differences in the form of the residual Cu2+ signal between the thiophene and pyrrole reactions suggest a greater degree of penetration of the reaction into the zeolite host for pyrrole, in agreement with previous XPS measurements. The EPR signal intensities show that the average length of the polymer chain that is associated with each radical centre is 15–20 and 5–7 monomer units for polypyrrole and polythiophene, respectively. The widths of the EPR signals suggest that these are at least partly due to small oligomers. The UV–VIS absorption spectra of the thiophene system show bands in three main regions: 2.8–3.0 eV (A), 2.3 eV (B) and 1.6–1.9 eV (D, E, F). Bands A and D–F occur in regions which have previously been observed for small oligomers, 4–6 monomer units in length. Band B is assigned to longer chain polythiophene molecules. We therefore conclude that the reaction between thiophene and copper-loaded mordenite produces a mixture of short oligomers together with some long chain polythiophene. The UV–VIS spectra of the pyrrole system show bands in the regions 3.6 eV (A), 2.7–3.0 eV (B, C) and 1.5–1.9 eV (D, F). Assignments of these bands are less certain than for the thiophene case because of the lack of literature data on the spectra of pyrrole oligomers.

Spectroscopic investigation of the polymerisation of pyrrole and thiophene within zeolite channels

The reaction of pyrrole and thiophene monomers with copper- or nickel-exchanged mordenite has been investigated using X-ray photoelectron (XPS) and photoacoustic infrared (PAIRS) spectroscopies. Because of the differing oxidising powers of the cations studied, polymerisation occurred only with copper-exchanged mordenite. PAIRS and XPS data indicated that both polypyrrole and polythiophene were partially oxidised when synthesised within the zeolite structure. IR spectra of polythiophene and polythiophene and polypyrrole showed intense bands typical of ring vibrations which could couple to the large dipole change induced by charges moving along the polythiophene chain. In addition it was noted that only vibrations typical of oxidised polymer structures were recorded, suggesting that the charge carrier was located within these segments. Furthermore, N 1s spectra contained a high binding energy peak at 402.5 eV which was attributed to a positively charged nitrogen species, in agreement with IR data. Significantly, C 1s spectra confirmed that molecular wires were formed within the confines of the zeolite lattice. Depth-profiling experiments suggested that polypyrrole was distributed throughout the entire zeolite host. By contrast, polythiophene may have been restricted to the uppermost zeolite channels owing to the ability of sulfur species to bond to CuI sites [produced by reduction of copper(II) ions during the polymerisation process], thus obstructing movement along the channels.

Distributed low-power image processing in wireless sensor networks for intelligent video surveillance applications

Distributed Wireless Smart Camera (DWSC) network is a special type of Wireless Sensor Network (WSN) that processes captured images in a distributed manner. While image processing on DWSCs sees a great potential for growth, with its applications possessing a vast practical application domain such as security surveillance and health care, it suffers from tremendous constraints. In addition to the limitations of conventional WSNs, image processing on DWSCs requires more computational power, bandwidth and energy that presents significant challenges for large scale deployments. This dissertation has developed a number of algorithms that are highly scalable, portable, energy efficient and performance efficient, with considerations of practical constraints imposed by the hardware and the nature of WSN. More specifically, these algorithms tackle the problems of multi-object tracking and localisation in distributed wireless smart camera net- works and optimal camera configuration determination. Addressing the first problem of multi-object tracking and localisation requires solving a large array of sub-problems. The sub-problems that are discussed in this dissertation are calibration of internal parameters, multi-camera calibration for localisation and object handover for tracking. These topics have been covered extensively in computer vision literatures, however new algorithms must be invented to accommodate the various constraints introduced and required by the DWSC platform. A technique has been developed for the automatic calibration of low-cost cameras which are assumed to be restricted in their freedom of movement to either pan or tilt movements. Camera internal parameters, including focal length, principal point, lens distortion parameter and the angle and axis of rotation, can be recovered from a minimum set of two images of the camera, provided that the axis of rotation between the two images goes through the camera's optical centre and is parallel to either the vertical (panning) or horizontal (tilting) axis of the image. For object localisation, a novel approach has been developed for the calibration of a network of non-overlapping DWSCs in terms of their ground plane homographies, which can then be used for localising objects. In the proposed approach, a robot travels through the camera network while updating its position in a global coordinate frame, which it broadcasts to the cameras. The cameras use this, along with the image plane location of the robot, to compute a mapping from their image planes to the global coordinate frame. This is combined with an occupancy map generated by the robot during the mapping process to localised objects moving within the network. In addition, to deal with the problem of object handover between DWSCs of non-overlapping fields of view, a highly-scalable, distributed protocol has been designed. Cameras that follow the proposed protocol transmit object descriptions to a selected set of neighbours that are determined using a predictive forwarding strategy. The received descriptions are then matched at the subsequent camera on the object's path using a probability maximisation process with locally generated descriptions. The second problem of camera placement emerges naturally when these pervasive devices are put into real use. The locations, orientations, lens types etc. of the cameras must be chosen in a way that the utility of the network is maximised (e.g. maximum coverage) while user requirements are met. To deal with this, a statistical formulation of the problem of determining optimal camera configurations has been introduced and a Trans-Dimensional Simulated Annealing (TDSA) algorithm has been proposed to effectively solve the problem.

An examination of learning design in elite springboard diving

The overarching aim of this programme of work was to evaluate the effectiveness of the existing learning environment within the Australian Institute of Sport (AIS) elite springboard diving programme. Unique to the current research programme, is the application of ideas from an established theory of motor learning, specifically ecological dynamics, to an applied high performance training environment. In this research programme springboard diving is examined as a complex system, where individual, task, and environmental constraints are continually interacting to shape performance. As a consequence, this thesis presents some necessary and unique insights into representative learning design and movement adaptations in a sample of elite athletes. The questions examined in this programme of work relate to how best to structure practice, which is central to developing an effective learning environment in a high performance setting. Specifically, the series of studies reported in the chapters of this doctoral thesis: (i) provide evidence for the importance of designing representative practice tasks in training; (ii) establish that completed and baulked (prematurely terminated) take-offs are not different enough to justify the abortion of a planned dive; and (iii), confirm that elite athletes performing complex skills are able to adapt their movement patterns to achieve consistent performance outcomes from variable dive take-off conditions. Chapters One and Two of the thesis provide an overview of the theoretical ideas framing the programme of work, and include a review of literature pertinent to the research aims and subsequent empirical chapters. Chapter Three examined the representativeness of take-off tasks completed in the two AIS diving training facilities routinely used in springboard diving. Results highlighted differences in the preparatory phase of reverse dive take-offs completed by elite divers during normal training tasks in the dry-land and aquatic training environments. The most noticeable differences in dive take-off between environments began during the hurdle (step, jump, height and flight) where the diver generates the necessary momentum to complete the dive. Consequently, greater step lengths, jump heights and flight times, resulted in greater board depression prior to take-off in the aquatic environment where the dives required greater amounts of rotation. The differences observed between the preparatory phases of reverse dive take-offs completed in the dry-land and aquatic training environments are arguably a consequence of the constraints of the training environment. Specifically, differences in the environmental information available to the athletes, and the need to alter the landing (feet first vs. wrist first landing) from the take-off, resulted in a decoupling of important perception and action information and a decomposition of the dive take-off task. In attempting to only practise high quality dives, many athletes have followed a traditional motor learning approach (Schmidt, 1975) and tried to eliminate take-off variations during training. Chapter Four examined whether observable differences existed between the movement kinematics of elite divers in the preparation phases of baulked (prematurely terminated) and completed take-offs that might justify this approach to training. Qualitative and quantitative analyses of variability within conditions revealed greater consistency and less variability when dives were completed, and greater variability amongst baulked take-offs for all participants. Based on these findings, it is probable that athletes choose to abort a planned take-off when they detect small variations from the movement patterns (e.g., step lengths, jump height, springboard depression) of highly practiced comfortable dives. However, with no major differences in coordination patterns (topology of the angle-angle plots), and the potential for negative performance outcomes in competition, there appears to be no training advantage in baulking on unsatisfactory take-offs during training, except when a threat of injury is perceived by the athlete. Instead, it was considered that enhancing the athletes' movement adaptability would be a more functional motor learning strategy. In Chapter Five, a twelve-week training programme was conducted to determine whether a sample of elite divers were able to adapt their movement patterns and complete dives successfully, regardless of the perceived quality of their preparatory movements on the springboard. The data indeed suggested that elite divers were able to adapt their movements during the preparatory phase of the take-off and complete good quality dives under more varied take-off conditions; displaying greater consistency and stability in the key performance outcome (dive entry). These findings are in line with previous research findings from other sports (e.g., shooting, triple jump and basketball) and demonstrate how functional or compensatory movement variability can afford greater flexibility in task execution. By previously only practising dives with good quality take-offs, it can be argued that divers only developed strong couplings between information and movement under very specific performance circumstances. As a result, this sample was sometimes characterised by poor performance in competition when the athletes experienced a suboptimal take-off. Throughout this training programme, where divers were encouraged to minimise baulking and attempt to complete every dive, they demonstrated that it was possible to strengthen the information and movement coupling in a variety of performance circumstances, widening of the basin of performance solutions and providing alternative couplings to solve a performance problem even when the take-off was not ideal. The results of this programme of research provide theoretical and experimental implications for understanding representative learning design and movement pattern variability in applied sports science research. Theoretically, this PhD programme contributes empirical evidence to demonstrate the importance of representative design in the training environments of high performance sports programmes. Specifically, this thesis advocates for the design of learning environments that effectively capture and enhance functional and flexible movement responses representative of performance contexts. Further, data from this thesis showed that elite athletes performing complex tasks were able to adapt their movements in the preparatory phase and complete good quality dives under more varied take-off conditions. This finding signals some significant practical implications for athletes, coaches and sports scientists. As such, it is recommended that care should be taken by coaches when designing practice tasks since the clear implication is that athletes need to practice adapting movement patterns during ongoing regulation of multi-articular coordination tasks. For example, volleyball servers can adapt to small variations in the ball toss phase, long jumpers can visually regulate gait as they prepare for the take-off, and springboard divers need to continue to practice adapting their take-off from the hurdle step. In summary, the studies of this programme of work have confirmed that the task constraints of training environments in elite sport performance programmes need to provide a faithful simulation of a competitive performance environment in order that performance outcomes may be stabilised with practice. Further, it is apparent that training environments can be enhanced by ensuring the representative design of task constraints, which have high action fidelity with the performance context. Ultimately, this study recommends that the traditional coaching adage 'perfect practice makes perfect", be reconsidered; instead advocating that practice should be, as Bernstein (1967) suggested, "repetition without repetition".