Abstract: In recent decades, as crop production has increased in many areas where irrigation projects have been implemented, the global agricultural development community has promoted irrigation investments. However, due to the disappointing performance of irrigation farming in developing countries, irrigation intervention in Africa South of the Sahara including Ethiopia is an issue of debate. Moreover, several gaps exist in the Ethiopian irrigation farming literature. For instance, evidence about the direct and indirect effects of irrigation water on agriculture is not well documented. The irrigation farming literature has not disentangled the indirect effects of having access to irrigation water from the direct effect and the indirect effects have been underrepresented. Furthermore, most previous studies have applied either a quantitative or qualitative approach and have relied only on revealed data as main type of methodology, making studies that combine qualitative and quantitative research and that use both stated and revealed data underrepresented. In this study, different approaches have been applied to investigate how irrigation water impacts Ethiopia agriculture with special attention being given to disentangling the direct and indirect effects of irrigation water on Ethiopian agriculture. Using a structural equation model, a stochastic production frontier approach, and a discrete choice experiment, I drew evidence regarding the direct and indirect effects of irrigation water on crop revenue of smallholder farmers, the technical efficiency of irrigation user farmers, and the farmers’ willingness to pay to improve poor irrigation schemes from field observations, semi-structured interviews and focus group discussions with farmers, and key informant interviews with the local agricultural agents from the Koga and Fogera Districts of Amhara Region Ethiopia. The results indicate that irrigation water in general has both direct and indirect positive effects on agriculture, and the indirect effect is mediated by both improved farm inputs and the type of crops produced. The results also show that – due to poor extension services and backward agronomic practices, the mean technical efficiency of farmers in Ethiopia is very low, and that large-scale irrigation users are less technically efficient than small-scale irrigation users. Moreover, the results show that improving irrigation schemes shifts the frontier up, and smallholder farmers are strongly willing to contribute financially to the maintenance costs of irrigation schemes. The results offer relevant lessons for policymakers that providing irrigation water supply must be embedded in a comprehensive support package including access to extension services, improved input supply, and access to stable markets.

Abstract: One of the main objectives of implementing a circular economy system is the reuse and recycling of resources. Closing material cycles and renewable-based electricity and fuel production are essential to such systems. To achieve a high degree of circularity, waste streams have to be rethought and integrated from a cradle-to-grave to a cradle-to-cradle approach. However, today’s circular economy strategies mostly focus on current waste streams, while past waste streams, buried in landfills, could play an important role when recovering resources and energy. Hence, a well-thought-out circular economy strategy should include the re-integration of past waste streams. A grave-to-cradle approach is needed. Landfill mining (LFM), i.e. the excavation and processing of formerly buried waste to energy and materials, aims at utilizing these past waste streams. Doing so could bear potential economic, environmental, and societal burdens and benefits. Originating from landfill remediation projects, landfill mining has been further developed towards resource recovery. Today, using up-to-date technologies and following the most stringent environmental and social criteria, the concept is also known as enhanced landfill mining (ELFM). Throughout the relevant scientific literature, most attention is given to advances in technological development for (E)LFM, as well as its techno-economic and environmental assessment. Societal assessments of LFM projects are rare and treat societal impacts only selectively or from unilateral societal perspectives. If stakeholders are included in societal (E)LFM assessments, only industrial actors, like landfill operators, and governmental actors are asked to participate. A holistic stakeholder assessment for (E)LFM is missing. Moreover, the diverse societal impacts – ranging from socio-environmental benefits through the mitigation of health risks, over socio-economic benefits through land reclamation, and social benefits through community engagement, for example – are either only studied selectively or evaluated as one, entangling various societal effects. A holistic and specific assessment of societal factors affecting (E)LFM implementation is also missing. This thesis uses an anticipatory approach to tackle these challenges. This approach aims to integrate stakeholder values and include uncertainty through the use of multiple social perspectives and prospective modeling tools. In-depth interviews were conducted to develop a typology of (E)LFM stakeholders and to elicit the most important stakeholder needs. Stakeholders were selected along an extended quadruple helix framework, including industrial, institutional, scientific, and community actors. Furthermore, using system dynamics tools, namely causal loop diagrams, societal systems of (E)LFM could be visualized and analyzed. Finally, a discrete choice experiment was conducted to evaluate a set of societal factors representing the conversion of a landfill into a public park for recreational use. The in-depth interviews included landfill operators, technology providers and incubators, local governments and governmental institutions, as well as researchers and community members. To structure the diverse perspectives of stakeholders on (E)LFM, five stakeholder archetypes were developed: The Entrepreneur, the Engaged Citizen, the Visionary, the Technology Enthusiast, and the Skeptic. The archetypes capture important characteristics and opinions approaching (E)LFM implementation. They differ in risk perceptions, knowledge base, influence on (E)LFM’s systemic and project implementation, and their main concerns and motivations. Furthermore, 18 stakeholder needs were derived from the interviews. This includes societal, environmental, regulatory, and techno-economic needs. The needs are put in relation to the affected stakeholders and sustainability dimensions. Uncertainties that could potentially be reduced through the fulfillment of each need are qualitatively assessed. Quantitatively, stakeholders were focusing on societal, regulatory, and techno-economic needs, whereas qualitative emphasis was given to environmental needs, especially the avoidance of impacts from primary resource production. When meeting stakeholder needs fairly, intra- and inter-dimensional trade-offs have to be considered as different perspectives can lead to different and sometimes contradicting implications for (E)LFM implementation. To conceptualize societal systems of (E)LFM, causal loop diagrams were developed following system dynamics methodology. The visualizations show how (E)LFM is embedded in its societal context. Variables comprising the societal impact were analyzed, and mechanisms affecting the public project acceptance and the market acceptance of (E)LFM products worked out. Leverage points were identified, helping (E)LFM practitioners and policymakers to minimize potential risks and maximize potential benefits. To these count technological choices, stakeholder involvement, the after-use, quality standards, and LFM regulation in general, amongst others. To disentangle and evaluate societal impacts of (E)LFM, a discrete choice experiment was conducted deriving the utility of five distinct attributes: the size of a landfill, the project duration, job creation, disamenities, and climate impacts. To determine the willingness to pay, perform scenario analysis, and model policy simulations, a sixth attribute was added representing a cost factor for project implementation. Environmental considerations are most important to the sample, while project duration and disamenities also play a significant role. The scenario analysis and policy simulations show that taxing households for (E)LFM implementation is a viable option, especially for environmentally beneficial projects. Nonetheless, a favorable combination of the remaining attributes can compensate utility losses for environmentally questionable projects. As risks of classical landfill management practices are likely to grow with an updated evaluation of after-care periods lasting up to 100 years and more, positive effects of (E)LFM become even more noteworthy. Nonetheless, (E)LFM projects also pose potential risks like groundwater contamination or the reintroduction of hazardous materials. If executed poorly, (E)LFM projects could potentially do more harm than good. A mix of policy measures is recommended to push a major part of potential (E)LFM projects from being environmentally beneficial and economically inefficient to being societally, environmentally, and economically favorable. Overall, more research is necessary to integrate (E)LFM into circular economy strategies and build a sensible grave-to-cradle approach.

Abstract: Achieving global sustainability goals will require cleaner and cheaper technologies. Public policy is central to achieving these goals and, in turn, ensuring a quicker pace of change. A major obstacle lies in the fact that technologies cannot be considered isolated entities: they are embedded in a powerful social context of cultural, organisational and institutional systems. This intertwining of different elements is referred to as a socio-technical system. This thesis discusses how socio-technical systems have, over time, allowed locked-in configurations to emerge, referring to a combination of systematic forces that perpetuate unsustainable infrastructures embedded in society. Such lock-ins can inhibit innovation and competitiveness of low-carbon and sustainable technologies, and this thesis looks to concrete solutions for unlocking them. Vital to this objective lies better understanding preferences, intentions, and behaviour of actors involved at each stage of technological development to improve public policy design. A discrete choice experiment – a quantitative non-market valuation method – was, therefore, a core method used to model preferences of key target groups. Target groups considered in the four components of the thesis include i) industry players, ii) policymakers, iii) farmers, and iv) the general public in Belgium, France, Germany, Italy and Spain. The thesis seeks to establish how both economic and regulatory instruments can be leveraged to overcome lock-in. One conclusion sees that implementing an efficient environmental tax regime – an economic instrument – requires balancing political feasibility and public acceptance considerations in line with tax and environmental policy. Results indicate that public acceptance for environmental taxation increases with earmarking. Another conclusion highlights the importance of taking behavioural and habitual considerations into account – both when considering policymakers’ investment decisions, and farmers’ decisions to adopting agro-ecological practices when responding to regulatory instruments. Overall, policy design should emphasise a more continuous and systemic approach to innovation and technology policy on the road to accelerating socio-technical transitions to sustainability.

Abstract: High-energy lithium-rich layered transition metal oxides are capable of delivering record electrochemical capacity and energy density as positive electrodes for Li-ion batteries. Their electrochemical behavior is extremely complex due to sophisticated interplay between crystal structure, electronic structure, and defect structure. Here we unravel an extra level of this complexity by revealing that the most typical representative Li1.2Ni0.13Mn0.54Co0.13O2 material, prepared by a conventional coprecipitation technique with Na2CO3 as a precipitating agent, contains abundant coherent (001) grain boundaries with a Na-enriched P2-structured block due to segregation of the residual sodium traces. The trigonal prismatic oxygen coordination of Na triggers multiple nanoscale twinning, giving rise to incoherent (104) boundaries. The cationic layers at the (001) grain boundaries are filled with transition metal cations being Mn-depleted and Co-enriched; this makes them virtually not permeable for the Li+ cations, and therefore they negatively influence the Li diffusion in and out of the spherical agglomerates. These results demonstrate that besides the mechanisms intrinsic to the crystal and electronic structure of Li-rich cathodes, their rate capability might also be depreciated by peculiar microstructural aspects. Dedicated engineering of grain boundaries opens a way for improving inherently sluggish kinetics of these materials.

Abstract: In typical seed-mediated syntheses of metal nanocrystals, the shape of the nanocrystal is determined largely by the seed nucleation environment and subsequent growth environment (where “environment” refers to the chemical environment, including the surfactant and additives). In this approach, crystallinity is typically determined by the seeds, and surfaces are controlled by the environment(s). However, surface energies, and crystallinity, are both influenced by the choice of environment(s). This limits the permutations of crystallinity and surface facets that can be mixed and matched to generate new nanocrystal morphologies. Here, we control post-seed growth to deliberately incorporate twin planes during the growth stage to deliver new final morphologies, including twinned cubes and bipyramids from single-crystal seeds. The nature and number of twin planes, together with surfactant control of facet growth, define the final nanoparticle morphology. Moreover, by breaking symmetry, the twin planes introduce new facet orientations. This additional mechanism opens new routes for the synthesis of different morphologies and facet orientations.

Abstract: Single-atom catalysts (SACs) have recently attracted broad scientific interests due to their unique structural feature, the single-atom dispersion. Optimized electronic structure as well as high stability are required for single-atom catalysts to enable efficient electrochemical production of H2O2. Herein, we report a facile synthesis method that stabilizes atomic Pd species on the reduced graphene oxide/Ndoped carbon hollow carbon nanospheres (Pd1/N-C). Pd1/N-C exhibited remarkable electrochemical H2O2 production rate with high faradaic efficiency, reaching 80%. The single-atom structure and its high H2O2 production rate were maintained even after 10,000 cycle stability test. The existence of single-atom Pd as well as its coordination with N species is responsible for its high activity, selectivity, and stability. The N coordination number and substrate doping around Pd atoms are found to be critical for an optimized adsorption energy of intermediate *OOH, resulting in efficient electrochemical H2O2 production. (C) 2020 Elsevier Inc. All rights reserved.

Abstract: The maximum a posteriori (MAP) probability rule for atom column detection can also be used as a tool to evaluate the relation between scanning transmission electron microscopy (STEM) image quality and atom detectability. In this chapter, a new image-quality measure is proposed that correlates well with atom detectability, namely the integrated contrast-to-noise ratio (ICNR). Furthermore, the working principle of the MAP probability rule is described in detail showing a close relation to the principles of model-selection methods.

Abstract: In this chapter, the principles of detection theory are used to quantify the probability of error for atom counting from high-resolution scanning transmission electron microscopy (HRSTEM) images. Binary and multiple hypothesis testing have been investigated in order to determine the limits to the precision with which the number of atoms in a projected atomic column can be estimated. The probability of error has been calculated when using STEM images, scattering cross-sections or peak intensities as a criterion to count atoms. Based on this analysis, we conclude that scattering cross-sections perform almost equally well as images and perform better than peak intensities. Furthermore, the optimal STEM detector design can be derived for atom counting using the expression of the probability of error. We show that for very thin objects the low-angle annular dark-field (LAADF) regime is optimal and that for thicker objects the optimal inner detector angle increases.

Abstract: An efficient model-based estimation algorithm is introduced to quantify the atomic column positions and intensities from atomic-resolution (scanning) transmission electron microscopy ((S)TEM) images. This algorithm uses the least squares estimator on image segments containing individual columns fully accounting for overlap between neighboring columns, enabling the analysis of a large field of view. To provide end-users with this well-established quantification method, a user friendly program, StatSTEM, is developed which is freely available under a GNU public license. In this chapter, this efficient algorithm is applied to three different nanostructures for which the analysis of a large field of view is required.

Abstract: Understanding light–matter interactions in nanomaterials is crucial for
optoelectronic, photonic, and plasmonic applications. Specifically, metal
nanoparticles (NPs) strongly interact with light and can undergo shape
transformations, fragmentation and ablation upon (pulsed) laser excitation.
Despite being vital for technological applications, experimental insight into
the underlying atomistic processes is still lacking due to the complexity of
such measurements. Herein, atomic resolution electron tomography is performed
on the same mesoporous-silica-coated gold nanorod, before and after
femtosecond laser irradiation, to assess the missing information. Combined
with molecular dynamics (MD) simulations based on the experimentally
determined 3D atomic-scale morphology, the complex atomistic rearrangements,
causing shape deformations and defect generation, are unraveled.
These rearrangements are simultaneously driven by surface diffusion, facet
restructuring, and strain formation, and are influenced by subtleties in the
atomic distribution at the surface.

Abstract: In this work, the effects of Si-doping in Cu2ZnSnS4 are examined computationally and experimentally. The density functional theory calculations show that an increasing concentration of Si (from x = 0 to x = 1) yields a band gap rise due to shifting of the conduction band minimum towards higher energy states in the Cu2Zn(Sn1-xSix)S-4. CZTSiS thin film prepared by co-sputtering process shows Cu2Zn(Sn1-xSix)S-4 (Si-rich) and Cu2ZnSnS4 (S-rich) kesterite phases on the surface and in the bulk of the sample, respectively. A significant change in surface electronic properties is observed in CZTSiS thin film. Si-doping in CZTS inverts the band bending at grain-boundaries from downward to upward and the Fermi level of CZTSiS shifts upward. Further, the coating of the CdS and ZnO layer improves the photocurrent to approximate to 5.57 mA cm(-2) at -0.41 V-RHE in the CZTSiS/CdS/ZnO sample, which is 2.39 times higher than that of pure CZTS. The flat band potential increases from CZTS approximate to 0.43 V-RHE to CZTSiS/CdS/ZnO approximate to 1.31 V-RHE indicating the faster carrier separation process at the electrode-electrolyte interface in the latter sample. CdS/ZnO layers over CZTSiS significantly reduce the charge transfer resistance at the semiconductor-electrolyte interface.