Action research on electrochemistry learning. Conceptual modelling intervention to promote disciplinary understanding, scientific inquiry, and reasoning

Students in engineering-science programmes often struggle with theoretical concepts, while they tend to adopt a surface approach to learning. We suggest that this can be tackled by promoting a specific higher-order thinking skill (HOTS) that enables drawing connections between physical phenomena and theoretical concepts representing them. We designed an intervention to support students in achieving deep insight into electrochemical phenomena, while developing this HOTS. Such intervention aims to scaffold students' learning and development by introducing conceptual modelling as an essential thinking skill of engineering-scientists, and as a strategy to build scientific understanding of natural phenomena. Therefore, conceptual modelling constitutes a main learning objective of this novel course. This paper reports an empirical investigation into how students deal with concepts and complexity, and to what extent the intervention has any measurable effects on the learning outcomes. This phenomenological investigation integrates considerations from various disciplines, and relies on multiple data sources, i.e., students' documents (lab journals and reports), observations of students in action (in discussions with their tutors and while performing lab experiments), and video stimulated-recall interviews. The results show little effect of the intervention, as implemented, suggesting how challenging it is for students (and instructors) to shift from traditional learning-and-teaching approaches, towards an epistemology of knowledge construction for specific problems. The findings are informative for revision of the intervention and generate specific recommendations. Concurrently, our operationalisation of the conceptual framework proves powerful in detecting qualitative differences in HOTS. Plausible implications for research and educational practice in science-engineering education are discussed.</p

Exploring the mechanical properties of additively manufactured carbon-rich zirconia 3D microarchitectures

Two-photon lithography (TPL) is a promising technique for manufacturing ceramic microstructures with nanoscale resolution. The process relies on tailor-made precursor resins rich in metal-organic and organic constituents, which can lead to carbon-based residues incorporated within the ceramic microstructures. While these are generally considered unwanted impurities, our study reveals that the presence of carbon-rich residues in the form of graphitic and disordered carbon in tetragonal (t-) ZrO2 can benefit the mechanical strength of TPL microstructures. In order to achieve a better understanding of these effects, we deconvolute the structural and materials contributions to the strength of the 3D microarchitectures by comparing them to plain micropillars. We vary the organic content by different thermal treatments, resulting in different crystal structures. The highest compression strength of 3.73 ± 0.21 GPa and ductility are reached for the t-ZrO2 micropillars, which also contain the highest carbon content. This paradoxical finding opens up new perspectives and will foster the development of “brick and mortar”-like ceramic microarchitectures

One-step sculpting of silicon microstructures from pillars to needles for water and oil repelling surfaces

Surfaces that repel both water and oil effectively (contact angles > 150°) are rare. Here we detail the microfabrication method of silicon surfaces with such properties. The method is based on careful tuning of the process conditions in a reactive etching protocol. We investigate the influence of SF6, O2 and CHF3 gases during the etching process using the same pitch of a photolithographic mask. Varying the loading conditions during etching, we optimized the conditions to fabricate homogeneous pedestal-like structures. The roughness of the microstructures could also effectively be controlled by tuning the dry plasma etching conditions. The wetting behavior of the resulting microstructures was evaluated in terms of the water and oil contact angles. Excitingly, the surfaces can be engineered from superhydrophobic to omniphobic by variation of the aforementioned predefined parameter

Additive manufacturing of 3D yttria-stabilized zirconia microarchitectures

The additive manufacturing (AM) of yttria-stabilized zirconia (YSZ) microarchitectures with sub-micrometer precision via two-photon lithography (TPL), utilizing custom photoresin containing zirconium and yttrium monomers is investigated. YSZ 3D microarchitectures can be formed at low temperatures (600 °C). The low-temperature phase stabilization of ZrO2 doped with Y2O3 demonstrates that doping ZrO2 with ≈ 10 mol% Y2O3 stabilizes the c-ZrO2 phase. The approach does not utilize YSZ particles as additives. Instead, the crystallization of the YSZ phase is initiated after printing, i.e., during thermal processing in the air at 600 °C – 1200 °C for one and two hours. The YSZ microarchitectures are characterized in detail. This includes understanding the role of defect chemistry, which has been overlooked in TPL-enabled micro-ceramics. Upon UV excitation, defect-related yellowish-green emission is observed from YSZ microarchitectures associated with intrinsic and extrinsic centers, correlated with the charge compensation due to Y3+ doping. The mechanical properties of the microarchitectures are assessed with manufactured micropillars. Micropillar compression yields the intrinsic mechanical strength of YSZ. The highest strength is observed for micropillars annealed at 600 °C, and this characteristic decreased with an increase in the annealing temperature. The deformation behavior gradually changes from ductile to brittle-like, correlating with the Hall–Petch strengthening mechanism.</p

Bacterial viability on chemically modified silicon nanowire arrays

The global threat of antimicrobial resistance is driving an urgent need for novel antimicrobial strategies. Functional surfaces are essential to prevent spreading of infection and reduce surface contamination. In this study we have fabricated and characterized multiscale-functional nanotopographies with three levels of functionalization: (1) nanostructure topography in the form of silicon nanowires, (2) covalent chemical modification with (3-aminopropyl)triethoxysilane, and (3) incorporation of chlorhexidine digluconate. Cell viability assays were carried out on two model microorganisms E. coli and S. aureus over these nanotopographic surfaces. Using SEM we have identified two growth modes producing distinctive multicellular structures, i.e. in plane growth for E. coli and out of plane growth for S. aureus. We have also shown that these chemically modified SiNWs arrays are effective in reducing the number of planktonic and surface-attached microorganisms

Acetaminophen oxidation under solar light using Fe-BiOBr as a mild Photo-Fenton catalyst

Acetaminophen is an analgesic used as a first-choice treatment for pain and fever. When individuals consume acetaminophen, a portion of the drug is excreted through urine and can end up in wastewater. Water remediation from pharmaceuticals, such as acetaminophen, is required before reaching the environment. This work demonstrates that Fe–BiOBr using the solar photo-Fenton process eliminates acetaminophen at mild pH in aqueous media. Fe-BiOBr is produced using microwave-assisted solvothermal synthesis, and the formation of the BiOBr phase is confirmed with XRD. SEM and TEM demonstrated the flower-like morphology, in which crystallite size reduces as a function of the Fe loading. The chemical environment at the surface of Fe–BiOBr is investigated with XPS. The results are connected with Raman analysis, which suggests the presence of oxygen vacancies in Fe–BiOBr. Furthermore, the effect of Fe in BiOBr is assessed by determining the optical band gap with UV–Vis. The Fe-BiOBr functionality is assessed during acetaminophen degradation. Fe-BiOBr revealed excellent performance in degrading acetaminophen in the first minutes (Q = 10 kJ m −2) under natural sunlight. Results reveal that 1% Fe content in BiOBr can degrade acetaminophen and its main byproduct (30 min, Q = 50 kJ m −2) at pH 5 and using 0.25 gL -1 of catalyst. A synergistic mechanism between heterogeneous photocatalysis and Fenton processes with primary superoxide ( •O 2 –) radical, followed by hydroxyl ( •OH) radical and photogenerated holes (h +), is proposed. Our research contributes to the degradation of pharmaceuticals under mild conditions and sunlight irradiation.</p

Alternative nano-lithographic tools for shell-isolated nanoparticle enhanced Raman spectroscopy substrates

Chemically synthesized metal nanoparticles (MNPs) have been widely used as surface-enhanced Raman spectroscopy (SERS) substrates for monitoring catalytic reactions. In some applications, however, the SERS MNPs, besides being plasmonically active, can also be catalytically active and result in Raman signals from undesired side products. The MNPs are typically insulated with a thin (∼3 nm), in principle pin-hole-free shell to prevent this. This approach, which is known as shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), offers many advantages, such as better thermal and chemical stability of the plasmonic nanoparticle. However, having both a high enhancement factor and ensuring that the shell is pin-hole-free is challenging because there is a trade-off between the two when considering the shell thickness. So far in the literature, shell insulation has been successfully applied only to chemically synthesized MNPs. In this work, we alternatively study different combinations of chemical synthesis (bottom-up) and lithographic (top-down) routes to obtain shell-isolated plasmonic nanostructures that offer chemical sensing capabilities. The three approaches we study in this work include (1) chemically synthesized MNPs + chemical shell, (2) lithographic substrate + chemical shell, and (3) lithographic substrate + atomic layer deposition (ALD) shell. We find that ALD allows us to fabricate controllable and reproducible pin-hole-free shells. We showcase the ability to fabricate lithographic SHINER substrates which report an enhancement factor of 7.5 × 103 ± 17% for our gold nanodot substrates coated with a 2.8 nm aluminium oxide shell. Lastly, by introducing a gold etchant solution to our fabricated SHINER substrate, we verified that the shells fabricated with ALD are truly pin-hole-free.</p

Enabling high-quality transparent conductive oxide on 3D printed ZrO2 architectures through atomic layer deposition

The conformal atomic layer deposition of a transparent conductive oxide composed of Al-doped ZnO (AZO) over three-dimensional (3D) shaped ZrO2 microarchitectures produced using two-photon lithography (TPL) is reported here for the first time. The effect of ZrO2 morphology, surface roughness, and crystallographic phase (tetragonal and monoclinic) on the quality and properties of the deposited ZnO and AZO thin films is investigated. No discontinuities, domains, or areas differing from the desired chemical composition have been found in films grown over the 3D structures. Three different Al dopant concentrations (4.0 %, 4-5 %, and 5.0 % Al doping cycles) are examined and compared to undoped ZnO. AZO and ZnO optical and electrical properties are studied using cathodoluminescence (CL) and Hall effect measurements. The CL study confirms that the observed emissions from the ZnO and AZO films are associated with the near band emission of ZnO and defects, i.e., zinc and oxygen vacancies and interstitial oxygen. The AZO films exhibit n-type semiconductor behavior, and a minimum resistivity of 1.2 x 10-3 Ω cm is achieved. From a broad perspective, AZO deposition on 3D microarchitectures opens a new route towards dimensionally refined optoelectronic devices in which the ZrO2/AZO can serve a key enabling role for the production of electrodes

Modular approach for bimodal antibacterial surfaces combining photo-switchable activity and sustained biocidal release

Photo-responsive antibacterial surfaces combining both on-demand photo-switchable activity and sustained biocidal release were prepared using sequential chemical grafting of nano-objects with different geometries and functions. The multi-layered coating developed incorporates a monolayer of near-infrared active silica-coated gold nanostars (GNS) decorated by silver nanoparticles (AgNP). This modular approach also enables us to unravel static and photo-activated contributions to the overall antibacterial performance of the surfaces, demonstrating a remarkable synergy between these two mechanisms. Complementary microbiological and imaging evaluations on both planktonic and surface-attached bacteria provided new insights on these distinct but cooperative effects