Correction to: Scientific Reportshttps://doi.org/10.1038/s41598-024-68971-x, published online 13 August 2024 In the original version of this Article a previous rendition of Figure 2B, Figure 4 and Figure 5D was published. The original Figure 2, 4 and 5 and accompanying legends appear below. (Figure presented.) (Figure presented.) (Figure presented.) (A) Representative bubble dynamics for different channel geometries. (B) Universal motion of bubbles within channels with different size, shape and length. The dashed line represents the developed theory, Eq. (2). The marker colors represent the hydraulic diameters (d_h), the shapes represent the cross-section and the facecolor represent the lengths (L). The graphical marker symbols and colors established here are followed throughout this article. The black arrow represents the region of deviation(s) from the expected dynamics. The threshold laser energy absorbed for bubble formation estimated from experiments (E_th,exp) against theory (E_th,theory) presented in Eq. (5). (A,B) Representative dynamic bubble size curves illustrating the emergence of instabilities. The zones of the instabilities are highlighted using a shaded rectangular area. The arrows represent if the instabilities occur before or after X_max. (A) Illustrates the experimental data for different d_h with similar oscillation time. The instabilities emerge with increasing d_h. (B) Illustrates the data for d_h = 200 µm with increasing laser energies. The instabilities disappear with increasing E_abs. (C) Flow stability diagram with the transition line at W_o = 734. The markers represent the experiments and the lines represent the analytical estimate. The numbers correspond to the channel hydraulic diameters (in µm) with the dashed and solid lines representing the channel lengths L = 25 and 50 mm, respectively. (D) The dimensionless convective timescale against the L/d_h aspect ratio. The partition line is a linear relation between the x and y axes with 45 × 10⁻⁶ as the slope and the origin as the intercept. The original Article has been corrected.

@en

The maritime sector accounts for approximately 3% of the global emissions, and to limit these emissions, a transition towards alternative fuels is ongoing. In this work, a novel circular bunkering process for marine vessels is considered, such that a renewable fuel economy for the maritime industry can be realised. The proposed bunkering process is shown in Figure 1, and uses sodium borohydride (NaBH4) as the fuel, due to its favourable gravimetric and volumetric energy density compared to other alternatives [1]. NaBH4 is fed into a reactor during vessel operation, where it reacts with water to form hydrogen and sodium metaborate (NaBO2). While the hydrogen can be used in e.g. fuel cells to power the ship, the NaBO2, also referred to as spent fuel, has to be stored for the remainder of the voyage. Both NaBH4 and NaBO2 are bulk solids with a particle size distribution ranging from a hundred micrometres to several millimetres.
To this moment, NaBH4 has predominantly been used in the chemical industry as a reducing agent [2], and consequently, the mechanical characteristics and the effects of operational conditions such as humidity, temperature, and stress on the behaviour of the material are virtually unknown. However, this knowledge is essential to be able to design the required storage and handling equipment to realise the aforementioned circular bunkering process. Therefore, this work focuses on acquiring the relevant data using experiments. While most experiments show that NaBH4 is initially free-flowing, particular combinations of operational conditions show a significant change in the materials flow characteristics, some results showing very cohesive material or even non-flowing characteristics. Using the acquired experimental data, the Discrete Element Method (DEM) will be used to calibrate, verify, and validate material models, such that the flow characteristics of this novel fuel can be captured numerically. These models can then be used to conceptualise the bunkering process in a virtual environment. Finally, an outlook on how to use the gained insights to develop and design the storage and handling equipment for the proposed circular bunkering process is presented.

References
[1]: M.C. van Benten, J.T. Padding, and D.L. Schott. “Towards Hydrogen-Fuelled Marine Vessels using Solid Hydrogen Carriers”. In: The 14th International Conference on Bulk Materials Storage, Handling and Transportation. Wollongong, Australia, July 2023
[2]: Kaiqiang Zhang et al. “Recent Advances in the Nanocatalyst-Assisted NaBH 4 Reduction of Nitroaromatics in Water”. DOI: 10.1021/acsomega.8b03051
@en

Reducing the use of fossil fuels in shipping requires new, alternative maritime fuels. Hydrogen carriers offer a safe and energy-dense solution for storing hydrogen, a zero-emission alternative fuel. This research focuses on ammonia borane, NaBH4, n-ethylcarbazole and dibenzyltoluene. Applying hydrogen carriers influences ship design significantly, as they require additional specialised equipment to remove hydrogen from the hydrogen carrier. This research estimates the size of the equipment. As this equipment will need to be stored and maintained on the ship, the exact sizing and sequence of the additional equipment will likely influence ship design. Results show that the reactor size is significant for all hydrogen carriers. The mixing tank is considerably sized for NaBH4 and ammonia borane, while the heat exchangers are large for dibenzyltoluene and n-ethylcarbazole.@en

In flow-by capacitive deionization (CDI) brackish water flows between two electrodes that capacitively remove salt. We assume low inlet concentrations so “salt shocks” appear in the electrodes and the process becomes diffusion-limited. For unit charge efficiency, a simplified model is derived consisting of two coupled partial differential equations. We obtain approximations, and exact solutions in terms of the Lambert W function, for the salt concentration as a function of time and space and for the equilibrium charge-voltage relation. These surprisingly simple solutions compare well with the results from comprehensive two-dimensional simulations. Useful analytical expressions are obtained for optimal geometrical and operational parameters that maximize the productivity and minimize the specific energy losses. By making cells much thinner the productivity can be increased an order of magnitude compared to typical values in the literature. The optimal electrode is found to be roughly six times thinner than the spacer. The associated pressure drop is around 0.4 bar per 1 mM of inlet salt concentration, making our recommendations practically feasible only for relatively low concentrations. The obtained model and analytical expressions provide useful guidance to strongly improve the design process.

@en

The local conditions inside a gas diffusion electrode (GDE) pore, especially in the electrical double layer (EDL) region, influence the charge transfer reactions and the selectivity of desired CO₂ER products. Most GDE computational models ignore the EDL or are limited in their applicability at high potentials. In this work, we present a continuum model to describe the local environment inside a catalytic pore at varying potentials, electrolyte concentrations and pore diameters. The systems studied in this work are based on an Ag catalyst in contact with KHCO₃ solution. Our study shows that steric effects dominate the local environment at high cathodic potentials (≪−25 mV vs pzc at the OHP), leading to a radial drop of CO₂ concentration. We also observe a drop in pH value within 1 nm of the reaction plane due to electrostatic repulsion and attraction of OH⁻ and H⁺ ions, respectively. We studied the influence of pore radii (1-10 nm) on electric field and concentrations. Pores with a radius smaller than 5 nm show a higher mean potential, which lowers the mean CO₂ concentration. Pores with a favourable local environment can be designed by regulating the ratio between the pore radius and Debye length.

@en

Greenhouse gas emissions drive global warming, posing significant risks to ecosystems and human society. The maritime sector contributes approximately 3% of global emissions, leading the International Maritime Organization (IMO) to target a 40% reduction in emissions by 2030 and 70% by 2050, compared to 2008 levels. This reduction can be achieved by improving vessel efficiency or adopting alternative fuels such as hydrogen. Traditionally, hydrogen is stored as a gas, liquid, or cryocompressed, but these methods have drawbacks, including high pressure and energy demands. A promising alternative is sodium borohydride (NaBH4), a solid hydrogen carrier that offers high volumetric energy density and safe storage at ambient conditions. When used in maritime vessels, NaBH4 reacts with water to produce hydrogen and a byproduct, which is stored and later regenerated onshore. Both NaBH4 and its spent fuel are granular materials, requiring specific handling equipment. This paper aims to identify the mechanical characteristics of NaBH4 and its spent fuel to design appropriate storage and handling systems using the Discrete Element Method (DEM).@en

Sodium borohydride (NaBH₄) has a high hydrogen (H₂ ) gravimetric capacity of 10.7 wt %. NaBH₄ releases H₂ through a hydrolysis reaction in which aqueous NaB(OH)₄ is formed as a byproduct. NaB(OH)₄ strongly influences the thermophysical properties of aqueous solutions (i.e., densities, viscosities, and electrical conductivities) and the hydrolysis reaction kinetics and conversion of NaBH₄. Here, molecular dynamics (MD) simulations are performed to compute viscosities, electrical conductivities, and self-diffusivities of H₂ , Na⁺, and B(OH)₄^- for a temperature and concentration range of 298-353 K and 0-5 mol NaB(OH)₄/kg water, respectively. Continuous fractional component Monte Carlo (CFCMC) simulations are used to compute the solubilities of H₂ and activities of water in aqueous NaB(OH)₄ solutions for the same temperature and concentration range. A new force field is developed (Delft force field of B(OH)₄^-: DFF/B(OH)₄^-) in which B(OH)₄^- is modeled as a tetrahedral structure with a scaled charge of −0.85. The OH group in B(OH)₄^- is modeled as a single interaction site. This force field is based on TIP4P/2005 water and the Madrid-2019 Na⁺ force field. The MD simulations can accurately capture the densities and viscosities within 2.5% deviation from available experimental data at 298 K up to a concentration of 5 mol NaB(OH)₄/kg water. The computed electrical conductivities deviate by ca. 10% from experimental data at 298 K for the same concentration range. Based on the molecular simulations results, engineering equations are developed for shear viscosities, self-diffusivities of H₂, Na⁺, and B(OH)₄^-, and solubilities of H₂, which can be used to design and model NaBH₄ hydrolysis reactors.

@en

Electrochemical reduction of CO2 heavily depends on the reaction conditions found near the electrode surface. These local conditions are affected by phenomena such as electric double layer formation and steric effects of the solution species, which in turn impact the passage of CO2 molecules to the catalytic surface. Most models for CO2 reduction ignore these effects, leading to an incomplete understanding of the local electrode environment. In this work, we present a modeling approach consisting of a set of size-modified Poisson–Nernst–Planck equations and the Frumkin interpretation of Tafel kinetics. We introduce a modification to the steric effects inside the transport equations which results in more realistic concentration profiles. We also show how the modification lends the model numerical stability without adopting any separate stabilization technique. The model can replicate experimental current densities and faradaic efficiencies till −1.5 vs. SHE/V of applied electrode potential. We also show the utility of this approach for systems operating at elevated CO2 pressures. Using Frumkin-corrected kinetics gels well with the theoretical understanding of the double layer. Hence, this work provides a sound mechanistic understanding of the CO2 reduction process, from which new insights on key performance controlling parameters can be obtained.@en

Crystallization abounds in nature and industrial practice. A plethora of indispensable products ranging from agrochemicals and pharmaceuticals to battery materials are produced in crystalline form in industrial practice. Yet, our control over the crystallization process across scales, from molecular to macroscopic, is far from complete. This bottleneck not only hinders our ability to engineer the properties of crystalline products essential for maintaining our quality of life but also hampers progress toward a sustainable circular economy in resource recovery. In recent years, approaches leveraging light fields have emerged as promising alternatives to manipulate crystallization. In this review article, we classify laser-induced crystallization approaches where light-material interactions are utilized to influence crystallization phenomena according to proposed underlying mechanisms and experimental setups. We discuss nonphotochemical laser-induced nucleation, high-intensity laser-induced nucleation, laser trapping-induced crystallization, and indirect methods in detail. Throughout the review, we highlight connections among these separately evolving subfields to encourage the interdisciplinary exchange of ideas.

@en

Optofluidic devices have revolutionized the manipulation and transportation of fluid at smaller length scales ranging from micrometers to millimeters. We describe a dedicated optical setup for studying laser-induced cavitation inside a microchannel. In a typical experiment, we use a tightly focused laser beam to locally evaporate the solution laced with a dye resulting in the formation of a microbubble. The evolving bubble interface is tracked using high-speed microscopy and digital image analysis. Furthermore, we extend this system to analyze fluid flow through fluorescence-Particle Image Velocimetry (PIV) technique with minimal adaptations. In addition, we demonstrate the protocols for the in-house fabrication of a microchannel tailored to function as a sample holder in this optical setup. In essence, we present a complete guide for constructing a fluorescence microscope from scratch using standard optical components with flexibility in the design and at a lower cost compared to its commercial analogues.@en

At the beginning of the second half of the twentieth century, Proudman and Pearson (J. Fluid. Mech.,2(3), 1956, pp.237–262) suggested that the functional form of the drag coefficient (C_D) of a single sphere subjected to uniform fluid flow consists of a series of logarithmic and power terms of the Reynolds number (Re). In this paper, we will explore the validity of the above statement for Reynolds numbers up to 10⁶ by using a symbolic regression machine learning method. The algorithm is trained by available experimental data and data from well-known correlations from the literature for Re ranging from 0.1 to 2×10⁵. Our results show that the functional form of C_D contains powers of log(Re), plus the Stokes term. The logarithmic C_D expressions can generalize (extrapolate) better beyond the training data than pure power series of Re and are the first in the literature to predict with acceptable accuracythe onset of the rapid decrease (drag crisis) of C_D at high Re, but also to follow the right behaviour towards zero Re. We also find a connection between the root of the Re-dependent terms in the C_D expression and the first point of laminar separation. The generalization behaviour of power-based drag coefficient equations is worse than logarithmic-based ones, especially towards the zero Re regime in which they give non-physical results. The logarithmic based C_D correctly describes the physics from the low Re regime to the onset of the drag crisis. Also, by applying a minor modification in the logarithmic based equations, we can predict the drag coefficient of an oblate spheroid in the high Re regime.

@en

We demonstrate that a cavitation bubble initiated by a Nd:YAG laser pulse below breakdown threshold induces crystallization from supersaturated aqueous solutions with supersaturation and laser-energy-dependent nucleation kinetics. Combining high-speed video microscopy and simulations, we argue that a competition between the dissipation of absorbed laser energy as latent and sensible heat dictates the solvent evaporation rate and creates a momentary supersaturation peak at the vapor-liquid interface. The number and morphology of crystals correlate to the characteristics of the simulated supersaturation peak.

@en

Green hydrogen combined with PEM fuel cell systems is a viable option to meet the demand for alternative maritime fuels. However, hydrogen storage faces challenges, including low volumetric density, fire and explosion risks and transport challenges. We assessed over fifteen hydrogen carriers based on their maritime performance characteristics to determine their suitability for shipboard use. Evaluation criteria included energy density, locally zero-emission, circularity of process, safety, dehydrogenation process, logistic availability and handling. Thus, excluding ammonia and methanol because of these constraints, we found that borohydrides, liquid organic hydrogen carriers and ammoniaborane are the most promising hydrogen carriers to use on ships with PEM fuel cells. Borohydrides, specifically sodium borohydride, have high energy densities but face regeneration issues. The liquid organic hydrogen carrier dibenzyltoluene has a lower energy density but exhibits easy hydrogenation and good handling. Given varying operational demands, we developed a framework to assess the suitability of hydrogen carriers for use in different ship categories. Evaluating the three types of hydrogen carriers, using our framework and considering current practices, shows that these are viable options for almost all ship types. Thus, we have identified three types of hydrogen carriers, which should be the focus of future research.

@en