Supramolecular polymers are defined as polymeric arrays of monomeric units that are brought together by reversible and highly directional non-covalent interactions, resulting in polymeric properties in dilute and concentrated solution as well as in the bulk. In the recent past, we have shown that a large variety of supramolecular polymers can be created using a variety of directional interactions. Two main systems are studied. The first class makes use of multiple-hydrogen bonding and the dynamics of the interactions are crucial for the understanding of the molecular and macroscopic properties of these flexible polymers. In less than ten years after their discovery, ureidopyrimidinone-based polymers are close to being commercialized and this is primarily due to the fundamental insights obtained from these flexible and disordered systems. The second class is based on more ordered one-dimensional stacks, making use of pi-pi interactions and/or hydrogen bonding and this class represents the rigid rod supramolecular polymers and therefore a possible candidate for high-end applications, like electronic devices. More recently, the understanding of supramolecular polymers is extended by focusing on the mechanisms of the supramolecular polymerization processes. Next to an open-association model for flexible chains, we have disclosed experimental evidence for the nucleation-growth mechanism for structured one-dimensional polymer arrays. In the research proposed in this TOP-grant proposal, we are aiming at a full understanding at the molecular level of all mechanistic features of supramolecular polymerization processes on the one hand. On the other hand, we will use this knowledge in the design, synthesis, characterization and application of novel functional materials with unprecedented properties. As is well accepted for covalent polymers, the mechanism of formation (step versus chain versus ring-opening polymerization) is leading to the understanding of the polymer properties. We are convinced that the same basic understanding of the mechanism of non-covalent or supramolecular polymerization processes will be as crucial as for covalent polymers or macromolecules. With a firm understanding of the pathways of formation and the dynamics involved (kinetic stability versus thermodynamic equilibrium) these novel materials will open the way to arrive at complex molecular systems based on multiple components. Supramolecular polymerization processes will be investigated by four related but different research topics, in which the two fist ones focus on the mechanism of the polymerization process and the last two are using this knowledge for creating novel materials.

Nowadays, individuals interact with companies/institutions in different ways: over the telephone, on mobile devices, tablets, or through self-service machines. Depending on the system used, they make decisions orally (by speaking) or manually (e.g., by touch on a tablet). Surprisingly, scant attention has been paid to the possibility that merely changing the way individuals express decisions - here termed as expression modalities - might impact how and what kind of decisions they make. Yet, companies and government institutions frequently offer individuals innovative ways to express their decisions (e.g., voice control mode in a mobile banking app) possibly unaware that a change in modality might impact individuals decisions. The aim of my three projects is to understand differences between oral and manual expression modalities with the goal of deriving managerial implications and public policy recommendations. Predominantly (but not exclusively) utilizing experimental research, individuals will be asked to make decisions either orally or manually. Project 1 explores whether these different expression modalities will trigger fundamentally different decision-making processes. I propose that speaking prompts automatic, impulsive decisions while manual responding prompts cognitive, reasoned decisions. This difference has important - positive and negative - consequences for decisions that we make daily. In project 2, I explore the influence of utilizing oral or manual expression modality on financial decision making; in particular individuals? likelihood to save money. If speech triggers more automatic, impulsive decisions, this suggests that individuals are less likely to save money (= cognitive/reasoned decision) when using voice-controlled than touch-activated systems. Finally, project 3 fulfills the purpose to explore a positive consequence of orally expressed decisions: if speaking triggers automatic, intuitive decisions, I argue that it increases decision satisfaction with decisions that require intuition. The results of the projects will be insightful to guide various stakeholders (e.g., policy makers) in designing strategies to increase savings and decision satisfaction.

In view of the emerging climate crisis reducing the carbon footprint has become pivotal. The direct catalytic valorization of CO2 from its diluted mixtures (atmosphere, flue gas, biogas, etc.) to valuable C1 molecules is the most straightforward solution, although it poses several unsolved scientific challenges. In this project a library of potentially game-changing catalysts for the direct hydrogenation of diluted CO2 to CO and CH4 will be designed in order to explore the direct utilization of lean CO2 streams. The research will focus on nanostructured transition metals particles supported on reducible oxides, possessing both high CO2 affinity and hydrogenation activity.

A central challenge for the society in the coming decades is to secure an adequate and more sustainable supply of energy and chemicals. Concerns about the greenhouse effect and the depletion of fossil fuels reserves necessitate the replacement of crude oil by alternative feedstocks on the short term. Biomass is a desirable renewable feedstock as it can in principle close the carbon cycle associated with the utilization of the biomass-derived liquid fuels. From biomass a large variety of chemicals and fuels can be produced to serve virtually every purpose that the oil-derived compounds currently serve. To efficiently utilize biomass, novel and improved catalytic processes must be developed that selectively alter or remove excessive functionalities from this renewable feedstock. In the transition period to a sustainable energy production from biomass, wind and solar as primary energy sources, more efficient utilization of natural gas is desirable as it is the cleanest of the available fossil fuels. There is a number of experimental research projects carried out in our group aimed at the rational design of novel catalytic processes for the selective valorization of biomass and natural gas as well as for the more sustainable production of bulk chemicals. Undoubtedly, rational design of novel catalytic materials and processes necessitate a deep molecular-level understanding of the reaction mechanisms underlying activity and selectivity patterns of the respective catalytic transformations. This project aims at the quantum chemical study of the reaction mechanisms and the fundamental factors that determine selectivity and reactivity of various catalytic processes such as selective oxidation of methane, alcohol oxidation, sugar transformations, as well as chemical transformations of carbon dioxide. The theoretical outcomes will form a solid basis for the improved understanding of these catalytic systems and provide input into the tailored design of novel catalytic systems. In our experience, such studies are extremely useful in synergy with experimental research. All the projects described in this proposal involve complementary experimental investigations.

The purpose of this computational project is to calculate the chemical bond order energy density using implementations of COHP and COOP in combination with PDOS?s calculations, for different species adsorbed to transition metal surfaces. A useful example of this approach we have recently published for oxide catalysis. We will compare this with the insights brought by the Natural Bond Orbitals (NBO) analysis, and by the Energy Decomposition Analysis (EDA) approaches. All these chemical tools have been implemented very recently for periodic plane-wave codes. The topics of interest of the present application are : (i) to investigate the crystal structure prediction power of COHP for bulk alloys, (ii) to investigate using the build up methodology (COHP+NBO+EDA) chemical bonding characteristics and trends for atoms and molecules on all 3d/4d/5d transition metals and to establish new, useful scalling relationships, and (iii) improve the predictability of Bronsted?Evans?Polanyi relations for transition states through a more precise definition of the proportionality constant for the model system.