The First Decade of Colloidal Lead Halide Perovskite Quantum Dots (in our Laboratory)
Ten years after the discovery of colloidal lead halide perovskite nanocrystals (LHP NCs), the field has witnessed substantial progress in synthetic methods, understanding of their surface chemistry and unique optical properties, precise control over NC size, shape, and composition. Ligand engineering, particularly with cationic and zwitterionic head groups, massively enhanced NC stability, compatibility with organic solvents, and photoluminescence efficiency. These breakthroughs allowed for the self-assembly of monodisperse NCs into complex long-range ordered superlattices and enabled the exploration of collective optical phenomena, such as superfluorescence. The development of low-cost scalable approaches like microfluidic systems and mechanochemical synthesis paved the way for the commercialization of LHP NCs, particularly for the down-conversion films in blue-backlit LCDs and as thermally-efficient color converters in pixelated displays. This review aims to trace the journey of these advancements, focusing on contributions from Switzerland, and outline future directions in this rapidly evolving field, such as quantum light sources, photocatalysis, etc.
Overview of Tacticity Control in Radical Polymerization
The stereoregularity of a polymer plays a key role in determining its properties. While stereocontrol can easily be achieved in coordination and ionic polymerization, it remains a challenge with radical polymerization. Considering the ubiquity and versatility of radical polymerization, significant efforts have been made over the past 50 years to address this issue. In this mini review, we highlight some of the strategies that have been developed to enable stereospecific radical polymerization, from the use of Lewis acid additives to the application of high electric fields. We hope that this review will provide the reader with a comprehensive overview of the current state of the art and equip them with the foundational knowledge needed to explore new avenues in this domain.
Waste-to-Taste: Transforming Wet Byproducts of the Food Industry into New Nutritious Foods
Food and beverage production generates enormous amounts of spent residues in the form of pomaces, pulps, grains, skins, seeds, etc. Although these sidestreams remain nutritious, their conversion to foods can be complicated by issues of digestibility and processing, particularly when the residues are wet and therefore highly susceptible to microbial degradation. Ideally, these sidestreams could be stabilized and then re-circulated into food, instead of being diverted to waste, animal feed, or biofuels. Indeed, the end-of-life of our food crops is increasingly important to consider in the context of circularity, ensuring that land, water, and chemical inputs to agriculture are sustainable. In the context of wet byproducts from the food industry, we discuss two separate case studies that look at how to valorize and extend the longevity of nutritionally-rich but underutilized sidestreams. The first study examines the fermentation of okara into an edible tempeh-like cake, while the second investigates ProSeed's approach to drying and valorizing brewer's spent grain. We conclude with some words on the nuance and challenges involved in saving from waste the highly perishable but nutritious side products of current food and beverage production.
Intermolecular Interactions and their Implications in Solid-State Photon Interconversion
Photon interconversion promises to alleviate thermalization losses for high energy photons and facilitates utilization of sub-bandgap photons - effectively enabling the optimal use of the entire solar spectrum. However, for solid-state device applications, the impact of intermolecular interactions on the energetic landscape underlying singlet fission and triplet-triplet annihilation upconversion cannot be neglected. In the following, the implications of molecular arrangement, intermolecular coupling strength and molecular orientation on the respective processes of solid-state singlet fission and triplet-triplet annihilation are discussed.
Electrified Enhanced Recovery of Lithium from Unconventional Sources
Demand for lithium is expected to quadruple by the end of the decade. Without new sources of production, the supply-demand curve is expected to invert. Traditional geological reserves will not be able to meet the anticipated gap, thus unconventional sources of lithium will need to be utilized, setting the stage for fierce competition for perhaps the most critical of mineral resources required for the energy transition. Direct Lithium Extraction refers to the umbrella of technologies being developed to access lithium from unconventional sources. Electrochemical extraction offers significant promise for its selectivity and low operating cost when coupled with renewable energy. This review aims to describe materials and process design considerations for electrochemical extraction of lithium from aqueous sources with a specific emphasis on ζ-V2O5 designed in our research group as an insertion host. We point to specific strategies for improving capacity and selectivity for electrochemical lithium extraction based on materials design across length scales. Strategies range from site-selective modification of insertion hosts to controlled tortuosity of ion diffusion pathways in porous electrode architectures. Electrochemical lithium extraction from unconventional sources stands poised to be a linchpin of a sustainable economy when coupled with cleaning of wastewater, hydrogen generation, and recovery of ancillary critical metals.
The Changing Landscape of Materials Discovery
In this perspective, we will discuss the impact of some of the most recent advancements in materials discovery, particularly focusing on the role of robotics, artificial intelligence, and self-driving laboratories, as well as their implications for the Swiss research landscape. While it seems timely to aim for broad, revolutionary breakthroughs in this field, we argue that more incremental steps - such as, for example, fully automatic grinding of solid powders or fully automated Rietveld refinements - may have a more significant impact on materials discovery, at least in the short run. In the center of these considerations is how small, interdisciplinary groups can drive significant progress by contributing targeted innovations, such as e.g.robotic sample preparation or computational predictions. Additionally, given the large investments that are necessary for future infrastructures in materials discovery, we discuss the potential case for the establishment - in the long run - of a national infrastructure, a Swiss Materials Discovery Lab, to support automated material synthesis and advanced characterization, ultimately accelerating innovation in both academic and industrial settings.
Intermetallic Materials for High-Capacity Hydrogen Storage Systems
In this article, we provide an overview of hydrogen storage materials, taking our previous results as examples. Towards the end of the paper, we present a case study in order to highlight the effects of substitutional alloying, compositional additives, and nanostructuring on the hydrogen sorption properties of magnesium-based intermetallics. Specifically, partial substitution of Mg by Li and d-elements by p-elements leads to structural changes, inducing disorder and the formation of high-entropy alloys. Our approach showcases the methodology to enhance the H2-capacity and to provide a positive boost to the H2-storage performance, including lower temperatures of H2 desorption, better thermodynamics and kinetics, lower temperatures of hydrogen uptake/ release for Metal-Hydride Hydrogen Storage (MHHS) systems and higher capacity of anodes for Metal-Hydride batteries (MHB) together with lower prices of raw materials.
The Chemistry of Atmospheric Aerosols: At the Nexus Between Climate, Energy, and Air Quality
Atmospheric aerosols can be emitted directly as particles or formed in the atmosphere from phase transitions of gaseous compounds with low enough vapor pressure. During their lifecycle in the atmosphere, aerosols undergo multiphase changes, altering chemical composition, reactivity, physical and optical properties, ultimately influencing how they impact climate, human health and ecosystems. The understanding of the chemical processes in the atmosphere is crucial to assess these effects. Here we provide a brief overview on relevant aerosol chemical processes and measurement techniques with no claim to completeness and describe the Swiss contribution to the European infrastructure ACTRIS for long-term monitoring and its relevance for the research field.
Oxidative Properties of Atmospheric Particles and their Biological Effects
Particulate Matter (PM) is the most toxic component in polluted air causing over 6 million deaths per year worldwide according to World Health Organisation estimates. Due to the highly complex composition of PM in the atmosphere, with thousands of inorganic and especially organic components, it is unknown which particle sources are responsible for their toxicity. In recent years it emerged that overall oxidising particle properties might directly link particle composition with health effects. This review summarises contributions of Swiss research groups to the chemical and biological characterisation of PM oxidising properties and identification of biological responses such as oxidative stress due to PM exposure.
Molecular Mechanisms of Aerosol Nucleation: from CLOUD Chamber Experiments to Field Observations
Atmospheric aerosol particles contribute to over four million premature deaths annually and play a critical role in modulating Earth's climate. Most atmospheric particles and more than 50% of the cloud condensation nuclei are formed through a secondary process named new particle formation involving unique precursor vapors. This article summarizes current knowledge of how new atmospheric particles form, based on experiments at the CERN CLOUD chamber. While the role of sulfuric acid has long been known, other vapors like highly oxygenated organic molecules and iodine oxoacids are also important, along with stabilizers like ammonia, amines, and ions from cosmic rays. We explain how findings from CLOUD experiments help us understand particle formation in various atmospheric conditions and improve air quality and climate models.
Unveiling the Implicit: Arctic Coastal Aerosol Processes
Arctic coasts cover more than 101,000 km and emulsify terrestrial, marine and socio-economic ecosystems. All three components produce specific emissions that contribute to the mix of atmospheric constituents, which are processed and dispersed in the coastal atmosphere to contribute to cloud formation through cloud condensation nuclei and ice nucleating particles. Clouds strongly influence the coastal energy balance. Importantly, Arctic coastal ecosystems are exposed to multiple pressures such as the warming atmosphere and ocean, the thawing cryosphere and the expanding anthropogenic activities. This means that coastal emissions and atmospheric processes are in constant evolution. Given the large area covered by coasts and the mix of emission sources, coastal aerosol processes deserve quantification to better understand their role in accelerated Arctic climate change.
Fine Particle pH and Sensitivity to NH and HNO over South Korea During KORUS-AQ
Using a new approach that constrains thermodynamic modeling of aerosol composition with measured gas-to-particle partitioning of inorganic nitrate, we estimate the acidity levels for aerosol sampled in the South Korean planetary boundary layer during the NASA/NIER KORUS-AQ field campaign. The pH (mean ± 1σ = 2.43±0.68) and aerosol liquid water content determined were then used to determine the 'chemical regime' of the inorganic fraction of particulate matter (PM) sensitivity to ammonia and nitrate availability. We found that the aerosol formation is always sensitive to HNO3 levels, especially in highly polluted regions, while it is only exclusively sensitive to NH3 in some rural/remote regions. Nitrate levels are further promoted because dry deposition velocity is low and allows its accumulation in the boundary layer. Because of this, HNO3 reductions achieved by NOX controls prove to be the most effective approach for all conditions examined, and that NH3 emissions can only partially affect PM reduction for the specific season and region. Despite the benefits of controlling PM formation to reduce ammonium-nitrate aerosol and PM mass, changes in the acidity domain can significantly affect other processes and sources of aerosol toxicity (e.g. solubilization of Fe, Cu and other metals) as well as the deposition patterns of these trace species and reactive nitrogen.
The Swiss National Air Pollution Monitoring Network (NABEL) - Bridging Science and Environmental Policy
Awareness of atmospheric air quality in Switzerland became a concern in the 1960s, as a result of which the Swiss National Air Pollution Monitoring Network (Nationales Beobachtungsnetz für Luftfremdstoffe - NABEL) was created in the 1970s. This paper describes the establishment and evolution of NABEL, emphasizing its important role in monitoring air quality in Switzerland, and its contribution to international observation networks and research. The network's history, legal framework, and measurement program are described, and exemplary time-series of air quality parameters are given. NABEL is an excellent example for reliable, long-term air quality monitoring and demonstrates the importance of such monitoring for air pollution control at both national and international levels.
History of Atmospheric Chemistry in Switzerland
This paper presents an overview on atmospheric chemistry, beginning with international aspects since the Roman Empire, and then focusing on the developments in Switzerland. Finally, the institutions dealing with atmospheric chemistry along with relevant scientists are briefly described.
Ammonia Emissions from Swiss Agriculture and their Effects on Atmospheric Chemistry and Ecosystems
Ammonia (NH3) is an important atmospheric pollutant due to its contribution to secondary inorganic aerosol formation and its deposition and impacts on (semi-)natural ecosystems. Therefore various efforts have been made to limit emissions to the atmosphere. The predominant emission source in Switzerland is livestock agriculture, wherein NH3 is volatilised from ammonium contained in animal manure. While modelled NH3 emissions based on agricultural activity data indicate a minor decrease since 2000, concentration measurements do not reflect this trend. This can at least partly be attributed to a decline in the transformation of NH3 to particulate ammonium due to significantly decreased emission of oxidised nitrogen and sulfur compounds in the past decade. The partitioning between the gaseous and the particulate phase also determines the deposition pathway (dry or wet deposition) and thus the average lifetime and transport distance in the atmosphere. Gaseous NH3 is subject to fast dry deposition and is deposited preferentially to ecosystems close to the source. Once deposited into an ecosystem, NH3 leads to eutrophication and acidification of water and soils, which change the plant community composition and microbial functioning, especially in N-sensitive ecosystems. Although NH3 can also cause direct toxicity to plants, assessments of ecosystem impacts are generally collated using the critical load approach, which includes the input of all N compounds. These reveal that in 2020, 87% of forests, 94% of raised bogs, 74% of fens, and 42% of dry mountain grasslands likely experienced adverse impacts from N exceedances in Switzerland. To improve this situation, considerable NH3 emission abatement efforts are needed in the future.
Multiphase Chemistry in the Atmosphere
Earth's atmosphere comprises a complex mix of gas and condensed phases, where condensed phases facilitate multiphase chemical reactions that would not occur in the gas phase alone. These reactions drive dynamic physical and chemical processes across various spatial and temporal scales, playing a crucial role in the cycling of atmospheric trace constituents. Multiphase chemistry significantly influences geochemical cycles, human health, and climate. This review focuses on the chemical steps governing the cycling of important species, such as halogens, reactive nitrogen, and organics, within aerosol particles, a key type of atmospheric condensed phases, and at condensed phase-air interfaces. These interfaces include mineral oxides, ice, and aqueous solutions found in particulate matter, clouds, snow, and on oceanic and terrestrial surfaces. This review also discusses the important role of redox chemical cycling, the hydrogen bonding network and water activity in these processes.
Hack Your Chemistry
Chemistry has a habit of surprising us. As we dig deeper, sometimes what we find will change the course of our research.
Chemical Tools for Monitoring and Targeting Collagen Cross-linking
The formation of collagen, the most abundant protein in mammals, is vital for the integrity of skin, tendons, and tissue in essentially any organ. Excessive collagen formation is, however, characteristic of fibrotic and malignant diseases, which include major global health issues. The diagnosis of abnormal collagen production and deposition is, therefore, critical for disease prognosis and helps guide treatment decisions. Here, we summarize our research on the development of tailored tools for monitoring and targeting excessive collagen crosslinking. We anticipate these tools will provide a deep understanding at the molecular level of collagen formation in normal and disease conditions with applications in imaging and disease treatment.
Corrigendum: Design and Application of a Gas Diffusion Electrode (GDE) Cell for Operando and Studies