In this study, we investigated the wettability and agglomeration characteristics of polymer microspheres coated with low-temperature deposited SiO2 in a fluidized bed atomic layer deposition (ALD) setup. Surface characterization revealed the presence of a significant amount of deposited Si-OH groups within the first cycles. A drastic decrease in agglomerate size, water contact angle (WCA), and droplet absorption time of the powder was observed when coating was applied. Furthermore, we observed an increase in the amount of Si-OH present on the particle surface with increasing coating cycles, while no significant improvement in water affinity was found after the first coating cycles. Our findings suggest that surface coverage is the primary factor in improving the colloid stability of particles, coated at low temperatures. The low temperature operation of our system introduced a chemical vapor deposition (CVD) component to our coating process, which allowed full surface coverage to be achieved within the first two coating cycles.@en

Safe-and-sustainable-by-design (SSbD) is a concept that takes a systems approach by integrating safety, sustainability, and functionality throughout a product’s the life cycle. This paper proposes a framework based on a prospective life cycle assessment for early safety and sustainability assessment. The framework’s purpose is to identify environmental sustainability and toxicity hotspots early in the innovation process for future SSbD applicability. If this is impossible, key performance indicators are assessed. Environmental sustainability aspects, such as global warming potential (GWP) and cumulative energy demand (CED), and toxicity aspects, such as human toxicity potential and freshwater ecotoxicity potential, were assessed upon applying the framework on a case study. The case study regarded using nano-titanium dioxide (P25-TiO2) or a modified nano-coated version (Cu2O-coated/P25-TiO2) as photocatalysts to produce hydrogen from water using sunlight. Although there was a decrease in environmental impact (GWP and CED), the modified nano-coated version had a relatively higher level of human toxicity and freshwater eco-toxicity. For the presented case study, SSbD alternatives need to be considered that improve the photocatalytic activity but are not toxic to the environment. This case study illustrates the importance of performing an early safety and environmental sustainability assessment to avoid the development of toxic alternatives.@en

A detailed study on the synthesis of Pt3Co intermetallic nanoparticles supported on ceria via preferential chemical vapor deposition was conducted, leading to a fundamental understanding of the deposition process and the Co-Pt alloying. This understanding helps us to develop a facile and scalable method for preferential adding of a metal on the surface of another metal already supported on an oxide which facilitates the design of novel structured nanoparticles. The fluidized flow reactor eliminated the deposition profile and resulted in Pt3Co nanoparticles uniformly and homogeneously distributed on ceria. The kinetic study of cobalt deposition on the platinum surface, in accordance with DFT calculations, demonstrates that the platinum surface catalyzes the deposition reaction; while the ceria surface is inert in the preferential deposition temperature window between 150 °C and 180 °C. The obtained sample was characterized by in situ XRD, HAADF-STEM, FT-IR, and XAS methods. The results indicate the formation of uniform Pt3Co nanoparticles with an average size of 1.1 nm. This sample showed superior catalytic activity in preferential oxidation of CO with an almost twice higher CO conversion rate and CO2 selectivity compared to a classically synthesized sample with successive impregnation.@en

Preparing supported nanoparticles with a well-defined structure, uniform particle size, and composition using conventional catalyst synthesis methods, such as impregnation, precipitation, and deposition-precipitation is challenging. Furthermore, these liquid phase methods require significant solvent consumption, which has sustainable issues and requires complex purification processes, usually leaving impurities on the catalyst, affecting its selectivity and activity. In this work, we employed atomic layer deposition (ALD, a vapor phase synthesis method) to synthesize electrocatalysts with well-controlled core-shell and alloy structures for CO2 reduction to formic acid. With this approach, the structural control of the catalysts is down to the atomic scale, and the effect of core-shell and alloy structure on Pt−Pd bimetallic catalysts has been investigated. It is shown that the Pt−Pd alloy catalyst displays a 46 % faradaic efficiency toward formic acid, outperforming Pt@Pd and Pd@Pt core-shell structures that show faradaic efficiencies of 22 % and 11 %, respectively. Moreover, both core-shell bimetallic catalysts (Pd@Pt and Pt@Pd) are not stable under electroreduction conditions. These catalysts restructure to more thermodynamically stable structures, such as segregated clusters or alloy particles, during the electrochemical reduction reaction, altering the catalytic selectivity.@en

Extending the lifetime of electrocatalytic materials is a major challenge in electrocatalysis. Here, we employ atomic layer deposition (ALD) to coat the surface of carbon black supported platinum nanoparticles (Pt/CB) with an ultra-thin layer of silicon dioxide (SiO2) to prevent deactivation of the catalyst during H2 evolution. Our results show that after an accelerated durability test (ADT) the current density at −0.2 V vs. reversible hydrogen electrode (RHE) of the unprotected Pt/CB catalyst was reduced by 34%. By contrast, after coating the Pt/CB catalyst with 2 SiO2 ALD cycles, the current density at the same potential was reduced by 7% after the ADT procedure, whereas when the Pt/CB sample was coated with 5 SiO2 ALD cycles, the current density was reduced by only 2% after the ADT. Characterization of the Pt particles after electrochemical testing shows that the average particle size of the uncoated Pt/CB catalyst increases by roughly 16% after the ADT, whereas it only increases by 3% for the Pt/CB catalyst coated with 5 cycles of SiO2 ALD. In addition, the coating also strongly reduces the detachment of Pt nanoparticles, as shown by a strong decrease in the Pt concentration in the electrolyte after the ADT. However, 20 cycles of SiO2 ALD coating results in an over-thick coating that has an inhibitory effect on the catalytic activity. In summary, we demonstrate that only a few cycles of SiO2 ALD can strongly improve the stability of Pt catalyst for the hydrogen evolution reaction.@en

The promotional effects on photocatalytic hydrogen production of CuxO clusters deposited using atomic layer deposition (ALD) on P25 TiO2 are presented. The structural and surface chemistry study of CuxO/TiO2 samples, along with first principles density functional theory simulations, reveal the strong interaction of ALD deposited CuxO with TiO2, leading to the stabilization of CuxO clusters on the surface; it also demonstrated substantial reduction of Ti4+ to Ti3+ on the surface of CuxO/TiO2 samples after CuxO ALD. The CuxO/TiO2 photocatalysts showed remarkable improvement in hydrogen productivity, with 11 times greater hydrogen production for the optimum sample compared to unmodified P25. With the combination of the hydrogen production data and characterization of CuxO/TiO2 photocatalysts, we inferred that ALD deposited CuxO clusters have a dual promotional effect: increased charge carrier separation and improved light absorption, consistent with known copper promoted TiO2 photocatalysts and generation of a substantial amount of surface Ti3+ which results in self-doping of TiO2 and improves its photo-activity for hydrogen production. The obtained data were also employed to modify the previously proposed expanding photocatalytic area and overlap model to describe the effect of cocatalyst size and weight loading on photocatalyst activity. Comparing the trend of surface Ti3+ content increase and the photocatalytically promoted area, calculated with our model, suggests that the depletion zone formed around the heterojunction of CuxO-TiO2 is the main active area for hydrogen production, and the hydrogen productivity of the photocatalyst depends on the surface coverage by this active area. However, the overlap of these areas suppresses the activity of the photocatalyst.@en

Polymer nanocomposites (NCs) offer outstanding potential for dielectric applications including insulation materials. The large interfacial area introduced by the nanoscale fillers plays a major role in improving the dielectric properties of NCs. Therefore, an effort to tailor the properties of these interfaces can lead to substantial improvement of the material’s macroscopic dielectric response. Grafting electrically active functional groups to the surface of nanoparticles (NPs) in a controlled manner can yield reproducible alterations in charge trapping and transport as well as space charge phenomena in nanodielectrics. In the present study, fumed silica NPs are surface modified with polyurea from phenyl diisocyanate (PDIC) and ethylenediamine (ED) via molecular layer deposition (MLD) in a fluidized bed. The modified NPs are then incorporated into a polymer blend based on polypropylene (PP)/ethylene-octene-copolymer (EOC), and their morphological and dielectric properties are investigated. We demonstrate the alterations in the electronic structure of silica upon depositing urea units using density functional theory (DFT) calculations. Subsequently, the effect of urea functionalization on the dielectric properties of NCs is studied using thermally stimulated depolarization current (TSDC) and broadband dielectric spectroscopy (BDS) methods. The DFT calculations reveal the contribution of both shallow and deep traps upon deposition of urea units onto the NPs. It could be concluded that the deposition of polyurea on NPs results in a bi-modal distribution of trap depths that are related to each monomer in the urea units and can lead to a reduction of space charge formation at filler-polymer interfaces. MLD offers a promising tool for tailoring the interfacial interactions in dielectric NCs.@en

The ever-growing level of carbon dioxide (CO2) in our atmosphere, is at once a threat and an opportunity. The development of sustainable and cost-effective pathways to convert CO2 to value-added chemicals is central to reducing its atmospheric presence. Electrochemical CO2 reduction reactions (CO2RRs) driven by renewable electricity are among the most promising techniques to utilize this abundant resource; however, in order to reach a system viable for industrial implementation, continued improvements to the design of electrocatalysts is essential to improve the economic prospects of the technology. This review summarizes recent developments in heterogeneous porphyrin-based electrocatalysts for CO2 capture and conversion. We specifically discuss the various chemical modifications necessary for different immobilization strategies, and how these choices influence catalytic properties. Although a variety of molecular catalysts have been proposed for CO2RRs, the stability and tunability of porphyrin-based catalysts make their use particularly promising in this field. We discuss the current challenges facing CO2RRs using these catalysts and our own solutions that have been pursued to address these hurdles.@en

Electrochemical CO2 reduction is a promising way of closing the carbon cycle while synthesizing useful commodity chemicals and fuels. One of the possible routes to scale up the process is CO2 reduction at elevated pressure, as this is a way to increase the concentration of poorly soluble CO2 in aqueous systems. Yet, not many studies focus on this route, owing to the inherent challenges with high-pressure systems, such as leaks, product quantification, and ease of operation. In this study, we use a high-pressure flow cell setup to investigate the impact of CO2 pressure on the electrochemical performance of a copper foam electrode for CO2 reduction within a pressure range of 1 to 25 bar. Our initial findings using a 0.5 M potassium bicarbonate (KHCO3) electrolyte show a consistent improvement in selectivity towards CO2 reduction products, with HCOOH being the dominant product. By conducting a systematic exploration of operating parameters including applied current density, applied CO2 pressure, cation effect, and electrolyte concentration, the selectivity towards formate (HCOOH) is optimized, achieving a remarkable 70 % faradaic efficiency (FE) under moderate conditions of 25 bar in a 0.5 M cesium bicarbonate (CsHCO3) electrolyte. Additionally, we report the synthesis of isopropanol with a FE of 11 % at the 25 bar in 0.5 M KHCO3 which is the highest reported selectivity towards isopropanol on copper using a bicarbonate system.@en