Seawater electrodeposition is gaining renewed interest in the context of sustainable development, both to build climate-resilient coastal infrastructure and for ocean-based decarbonization applications. Most of the applications benefit from CaCO₃-rich deposits, but constant-voltage electrodeposition results in a mixture of CaCO₃ and Mg(OH)₂, especially at higher voltages where precipitation rates are more desirable. The use of pulse voltages can help control interfacial pH that dictates the precipitation reactions. Here, we explore the use of pulse electrodeposition as a function of pulse frequency and duty cycle to control deposit composition. The most CaCO₃-rich deposits were obtained under 10 Hz frequency and 10% duty cycle conditions for the voltage window investigated (−0.8 V to −1.2 V vs. SCE). While pulsing the voltage increases the amount of CaCO₃ deposited, the energy required per gram of CaCO₃ is significantly higher (14.5×) when compared to the base case of applying a constant voltage of −0.8 V vs. SCE. Further optimization of pulse conditions, electrode materials, and system configuration could lead to finding parameters that result in exclusively carbonate deposits without compromising precipitation rates, which may prove to be more useful for corrosion protection, coastal infrastructure, and other applications in sustainable development.

Global production of nickel (Ni) and ferronickel (FeNi) alloys, critical to battery materials and stainless steel alloys, is limited to a few countries due to the distribution of laterite ores. To meet the growing demand, an alternative supply of Ni and FeNi alloys needs to be established. Laterite ores result from olivine (Mg_xFe_2−xSiO₄) weathering under tropical conditions, making olivine a promising alternative source to consider; however, the lower Ni concentration of olivine makes it less economical. One approach to lowering the process costs is using waste chemical inputs in place of expensive commodity chemicals. In this study we evaluate the feasibility of using such waste byproducts generated by a demonstration-scale electrochemical marine carbon dioxide removal system to extract Ni from olivine (0.27 wt% Ni) as FeNi alloy. Bipolar membrane electrodialysis (BPMED) technology used for ocean alkalinity enhancement generates acidic, desalinated, and basic streams using seawater and electricity. The acid stream is a waste product, and we show that it is 37% better than equal-strength commercial HCl for leaching of Ni from olivine at room temperature. A small volume of the alkaline product from BPMED is used to increase the pH of the olivine leachate to remove all dissolved silicon and the majority of the dissolved iron, while retaining most of the dissolved Ni (65%) and Mg (84%). This enriched solution is used for Ni recovery via electroplating while the spent electrolyte, rich in Mg, is suitable as an additional source of alkalinity for marine CO₂ removal. We demonstrate the recovery of Ni as a FeNi alloy with an Fe to Ni molar ratio of 1.37 : 1 and evaluate the cost-benefit of the process for various possible scenarios. Preliminary assessment indicates an overall net economic benefit from recovering Ni from olivine using the proposed method and the net benefit is expected to further increase if the overall recovery rate of Ni is improved, the price of the Ni product is increased, and the value of CO₂ credit is included.

Magnetic separations present a promising approach for the recovery of rare earth (RE) elements from mixtures, particularly when coupled with precipitation techniques that enhance process efficiency and selectivity. However, the magnetic properties of RE materials typically encountered in the separations industry are not well characterized. Here, we synthesized a series of RE materials, combining four REs – praseodymium (Pr), neodymium (Nd), terbium (Tb), and dysprosium (Dy) – with three precipitating agents – hydroxide, oxalate, and dibutyl phosphate. All materials showed typical paramagnetic behavior consistent with the Curie-Weiss law. At low temperatures, we observed weak antiferromagnetic correlations, which were more pronounced for the lighter RE ions (Pr, Nd). Particle morphology and crystallography analyses showed that the dibutyl phosphates were well-ordered metal-organic frameworks, the oxalates were crystals with mixed hydration states, and the hydroxides were mostly amorphous. Regardless of the degree of crystallinity, the effective magnetic moments aligned well with theoretical estimates based on Hund's rules and 4f electron configurations of the corresponding RE ions. For a given RE ion, the magnetophoretic response was thus determined by the size of the particles rather than specific metal-ligand coupling, with dibutyl phosphate promoting the formation of larger crystals that were the most strongly attracted to magnets.