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Reaction pathways & configurations to upcycle aqueous biomass oxygenates and large amounts of low value calcium & magnesium bearing sources over Ni and Pt catalyst to produce high value H₂with inherent CO₂removal in a single step was explored. 

Scalable efforts to remove anthropogenic CO 2 via the formation of durable carbonates require us to harness siliceous nanoporous geologic materials for carbon storage. While calcium carbonate formation has been extensively reported in bulk fluids, there is a limited understanding of the influence of nanoconfined fluids on the formation of specific stable and metastable polymorphs of calcium carbonates in siliceous materials that are abundant in subsurface environments. To address this challenge, silica nanochannels with diameters of 3.7 nm are architected and the formation of specific calcium carbonate phases is investigated using X-ray diffraction (XRD), and molecular dynamics (MD) simulations. The formation of stable calcium carbonate (or calcite) is noted in silica nanochannels. The presence of fewer water molecules in the first hydration shell of calcium ions in confinement compared to in bulk fluids contributes to stable calcium carbonate formation. These studies show that nanoporous siliceous environments favor the formation of stable calcium carbonate formation. 

Achieving reversible and tunable assembly of silica nanoparticles at liquid–liquid interfaces is vital for a wide range of scientific and technological applications including sustainable subsurface energy applications, catalysis, drug delivery and material synthesis. In this study, we report the mechanisms controlling the assembly of silica nanoparticles (dia. 50 nm and 100 nm) at water–heptane and water–toluene interfaces using sodium dodecyl sulfate (SDS) surfactant with concentrations ranging from 0.001–0.1 wt% using operando ultrasmall/small-angle X-ray scattering, cryogenic scanning electron microscopy imaging and classical molecular dynamics simulations. The results show that the assembly of silica nanoparticles at water–hydrocarbon interfaces can be tuned by controlling the concentrations of SDS. Silica nanoparticles are found to: (a) dominate the interfaces in the absence of interfacial SDS molecules, (b) coexist with SDS at the interfaces at low surfactant concentration of 0.001 wt% and (c) migrate toward the aqueous phase at a high SDS concentration of 0.1 wt%. Energetic analyses suggest that the van der Waals and electrostatic interactions between silica nanoparticles and SDS surfactants increase with SDS concentration. However, the favorable van der Waals and electrostatic interactions between the silica nanoparticles and toluene or heptane decrease with increasing SDS concentration. As a result, the silica nanoparticles migrate away from the water–hydrocarbon interface and towards bulk water at higher SDS concentrations. These calibrated investigations reveal the mechanistic basis for tuning silica nanoparticle assembly at complex interfaces.