Exotic Carbonate Mineralization Recovered from a Deep Basalt Carbon Storage Demonstration.

Mitigating climate change requires transformational advances for carbon dioxide removal, including geologic carbon sequestration in reactive subsurface environments. The Wallula Basalt Carbon Storage Pilot Project demonstrated that CO injected into >800 m deep Columbia River Basalt Group flow top reservoirs mineralizes on month-year timescales. Herein, we present new optical petrography, micro-computed X-ray tomography, and electron microscopy results obtained from sidewall cores collected two years after CO injection.

Transport of polymer-coated metal-organic framework nanoparticles in porous media.

Injecting fluids into deep underground geologic structures is a critical component to development of long-term strategies for managing greenhouse gas emissions and facilitating energy extraction operations. Recently, we reported that metal-organic frameworks are low-frequency, absorptive-acoustic metamaterial that may be injected into the subsurface to enhance geophysical monitoring tools used to track fluids and map complex structures. A key requirement for this nanotechnology deployment is transportability through porous geologic media without being retained by mineral-fluid interfaces.

Porous Colloidal Nanoparticles as Injectable Multimodal Contrast Agents for Enhanced Geophysical Sensing.

Injecting fluids into underground geologic structures is crucial for the development of long-term strategies for managing captured carbon and facilitating sustainable energy extraction operations. We have previously reported that the injection of metal-organic frameworks (MOFs) into the subsurface can enhance seismic monitoring tools to track fluids and map complex structures, reduce risk, and verify containment in carbon storage reservoirs because of their absorption capacity of low-frequency seismic waves. Here, we demonstrate that water-based Cr/Zn/Zr MOF colloidal suspensions (nanofluids) are multimodal geophysical contrast agents that enhance near-wellbore logging tools.

Manipulating Pore Topology and Functionality to Promote Fluorocarbon-Based Adsorption Cooling.

ConspectusWith the worldwide demand for refrigeration and cooling expected to triple, it is increasingly important to search for alternative energy resources to drive refrigeration cycles with reduced electricity consumption. Recently, adsorption cooling has gained increased attention since energy reallocation in such systems is based on gas adsorption/desorption, which can be driven by waste/natural heat sources. Eco-friendly sorption-based cooling relies on the cyclic transfer of refrigerant gas from a high to low energy state by the pseudocompression effect resulting from adsorption and desorption.

Structure-Property Correlation of Hierarchically Porous Carbons for Fluorocarbon Adsorption.

Although traditional commercially available porous carbon-fluorocarbon working pairs have shown promising applicability for adsorption cooling, advancements in engineered carbons may further improve the performance. Moreover, insights into structure-property relationships that target higher sorption capacities within these synthesized carbons may guide such materials' future design. We utilized hierarchically porous carbons (HPCs), synthesized with colossal microporous and mesoporous content characterized by high surface areas (up to 2689 m/g) and pore volume values (up to 10.

Synergistic Coupling of CO and HO during Expansion of Clays in Supercritical CO-CH Fluid Mixtures.

We used IR and XRD, with supporting theoretical calculations, to investigate the swelling behavior of Na-, NH-, and Cs-montmorillonites (SWy-2) in supercritical fluid mixtures of HO, CO, and CH. Building on our prior work with Na-clay that demonstrated that HO facilitated CO intercalation at relatively low RH, here we show that increasing CO/CH ratios promote HO intercalation and swelling of the Na-clay at progressively lower RH. In contrast to the Na-clay, CO intercalated and expanded the Cs-clay even in the absence of HO, while increasing fluid CO/CH ratios inhibited HO intercalation.

Porous Covalent Organic Polymers for Efficient Fluorocarbon-Based Adsorption Cooling.

Adsorption-based cooling is an energy-efficient renewable-energy technology that can be driven using low-grade industrial waste heat and/or solar heat. Here, we report the first exploration of fluorocarbon adsorption using porous covalent organic polymers (COPs) for this cooling application. High fluorocarbon R134a equilibrium capacities and unique overall linear-shaped isotherms are revealed for the materials, namely COP-2 and COP-3.

Transition-Metal Nitroprussides Examined for Water Harvesting and Sorption Cooling.

Transition-metal pentacyanonitrosylferrates, commonly known as nitroprussides, have a long and documented history. Here, we synthesize cobalt and nickel nitroprussides (NPs) in order to probe their use as sorbents for water and fluorocarbon uptake for potential water harvesting and cooling applications. These NPs show stable and reversible equilibrium sorption isotherms at room temperature with peak uptake values of ∼40 wt % for HO and ∼30 wt % for fluorocarbon R134a.

Quantification of CO Mineralization at the Wallula Basalt Pilot Project.

In 2013, the Pacific Northwest National Laboratory led a geologic carbon sequestration field demonstration where ∼1000 tonnes of CO was injected into several deep Columbia River Basalt zones near Wallula, Washington. Rock core samples extracted from the injection zone two years after CO injection revealed nascent carbonate mineralization that was qualitatively consistent with expectations from laboratory experiments and reactive transport modeling. Here, we report on a new detailed analysis of the 2012 pre-injection and 2015 post-injection hydrologic tests that capitalizes on the difference in fluid properties between scCO and water to assess changes in near-field, wellbore, and reservoir conditions that are apparent approximately two years following the end of injection.

Metal-Organic Framework-Based Microfluidic Impedance Sensor Platform for Ultrasensitive Detection of Perfluorooctanesulfonate.

The growing global concerns to public health from human exposure to perfluorooctanesulfonate (PFOS) require rapid, sensitive, detection where current, state-of-the-art techniques are yet to adequately meet sensitivity standards of the real world. This work presents, for the first time, a synergistic approach for the targeted affinity-based capture of PFOS using a porous sorbent probe that enhances detection sensitivity by embedding it on a microfluidic platform. This novel sorbent-containing platform functions as an electrochemical sensor to directly measure PFOS concentration through a proportional change in electrical current (increase in impedance).

Molecular Insight into Fluorocarbon Adsorption in Pore Expanded Metal-Organic Framework Analogs.

The rapid growth in the global energy demand for space cooling requires the development of more efficient environmental chillers for which adsorption-based cooling systems can be utilized. Here, in this contribution, we explore sorbents for chiller use via a pore-engineering concept to construct analogs of the 1-dimensional pore metal-organic framework MOF-74 by using elongated organic linkers and stereochemistry control. The prepared pore-engineered MOFs show remarkable equilibrium adsorption of the selected fluorocarbon refrigerant that is translated to a modeled adsorption-based refrigeration cycle.

Understanding Time Dependence on Zinc Metal-Organic Framework Growth Using in Situ Liquid Secondary Ion Mass Spectrometry.

The abundance of novel metal-organic framework (MOF) materials continues to increase as more applications are discovered for these highly porous, well-ordered crystalline structures. The simplicity of constituents allows for the design of new MOFs with virtue of functionality and pore topology toward target adsorbates. However, the fundamental understanding of how these frameworks evolve during nucleation and growth is mostly limited to speculation from simulation studies.

Enhanced elasticity in poly(acrylic acid) gels via synthesis in the presence of high concentrations of select salts.

Poly(acrylic acid) (PAA) gels synthesized via free-radical polymerization of acrylic acid, N,N'-methylenebisacrylamide and high molarities of salts in water exhibit properties markedly different from PAA gels synthesized without salt, even when the latter are incubated in high-molarity salt solutions after gelation. Particularly noteworthy is unusual mechanical behaviour that includes substantially increased elongation, increased modulus, and rapid recovery after strain. The greatest enhancement in viscoelastic behaviour is evident in 2 M LiCl and ZnCl samples, with LiCl samples having a modulus of 39 kPa and reaching an extension ratio of 10 and a fracture stress of 135 kPa, and ZnCl samples having a modulus of 43 kPa and reaching an extension ratio of 8.

Insight into Fluorocarbon Adsorption in Metal-Organic Frameworks via Experiments and Molecular Simulations.

The improvement in adsorption/desorption of hydrofluorocarbons has implications for many heat transformation applications such as cooling, refrigeration, heat pumps, power generation, etc. The lack of chlorine in hydrofluorocarbons minimizes the lasting environmental damage to the ozone, with R134a (1,1,1,2-tetrafluoroethane) being used as the primary industrial alternative to commonly used Freon-12. The efficacy of novel adsorbents used in conjunction with R134a requires a deeper understanding of the host-guest chemical interaction.

Anomalously low activation energy of nanoconfined MgCO precipitation.

Magnesite (MgCO3) precipitation within the nanoconfined space of adsorbed H2O films (∼5 monolayers) was determined to have an apparent activation energy of only 36 ± 6 kJ mol-1, suggesting that Mg2+ under nanoconfinement adopts a hydration configuration that mimics that of aqueous Ca2+, at least energetically, if not also specifically in hydration structure.

Probing the Sorption of Perfluorooctanesulfonate Using Mesoporous Metal-Organic Frameworks from Aqueous Solutions.

One approach to reduce increasing concentrations of toxic per- and polyfluoroalkyl substances (PFAS) involves the capture of PFAS from aqueous media using porous materials. The use of highly porous, tunable metal organic framework (MOF) materials is appealing for targeted liquid phase sorption. In this work, we demonstrate the excellent capture of perfluorooctanesulfonate (PFOS) using both the chromium and iron analogs of the MIL-101 framework.

Natural, incidental, and engineered nanomaterials and their impacts on the Earth system.

Nanomaterials are critical components in the Earth system's past, present, and future characteristics and behavior. They have been present since Earth's origin in great abundance. Life, from the earliest cells to modern humans, has evolved in intimate association with naturally occurring nanomaterials.

Molecular Simulation of the Catalytic Regeneration of BuLi through a Hydrometalation Route.

Efficient regeneration of organolithium compounds is a challenging aspect in the process of novel organometathetical catalytic cycles. One of these catalytic cycles is a newly suggested method for Mg production from seawater that capitalizes on the rich chemistry of Grignard reagents. The proposed three-step catalytic cycle with Cp MCl L catalyst ( M = Ti, Zr; L = select organic ligands) requires the regeneration of BuLi from Li(s), butene, and H.

Microporous and Flexible Framework Acoustic Metamaterials for Sound Attenuation and Contrast Agent Applications.

The low-frequency (100-1250 Hz) acoustic properties of metal-organic framework (MOF) materials were examined in impedance tube experiments. The anomalously high sound transmission loss of HKUST-1, FeBTC, and MIL-53(Al) quantitatively demonstrated that these prototypical MOFs are absorptive acoustic metamaterials. To the best of our knowledge, this is the first example of MOFs that have been demonstrated to be acoustic metamaterials.

Tunable Manipulation of Mineral Carbonation Kinetics in Nanoscale Water Films via Citrate Additives.

We explored the influence of a model organic ligand on mineral carbonation in nanoscale interfacial water films by conducting five time-resolved in situ X-ray diffraction (XRD) experiments at 50 °C. Forsterite was exposed to water-saturated supercritical carbon dioxide (90 bar) that had been equilibrated with 0-0.5 m citrate (CHO) solutions.

Dynamic Adsorption of CO/N on Cation-Exchanged Chabazite SSZ-13: A Breakthrough Analysis.

Alkali-exchanged SSZ-13 adsorbents were investigated for their applicability in separating N from CO in flue gas streams using a dynamic breakthrough method. In contrast to IAST calculations based on equilibrium isotherms, K exchanged SSZ-13 was found to yield the best N productivity, comparable to Ni-MOF-74, under dynamic conditions where diffusion properties play a significant role. This was attributed to the selective, partial blockage of access to the chabazite cavities, enhancing the separation potential in a 15/85 CO/N binary gas mixture.

Synthesis of nanometer-sized fayalite and magnesium-iron(II) mixture olivines.

Olivines are divalent orthosilicates with important geologic, biological, and industrial significance and are typically comprised of mixtures of Mg and Fe ranging from forsterite (MgSiO) to fayalite (FeSiO). Investigating the role of Fe(II) in olivine reactivity requires the ability to synthesize olivines that are nanometer-sized, have different percentages of Mg and Fe, and have good bulk and surface purity. This article demonstrates a new method for synthesizing nanosized fayalite and Mg-Fe mixture olivines.

Reduced Magnetism in Core-Shell Magnetite@MOF Composites.

The magnetic susceptibility of synthesized magnetite (FeO) microspheres was found to decline after the growth of a metal-organic framework (MOF) shell on the magnetite core. Detailed structural analysis of the core-shell particles using scanning electron microscopy, transmission electron microscopy, atom probe tomography, andFe-Mössbauer spectroscopy suggests that the distribution of MOF precursors inside the magnetic core resulted in the oxidation of the iron oxide core.

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO.

Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of HO is well-known to be systematically correlated with the hydration free energy of the interlayer cation, particularly in environments dominated by nonpolar solvents (i.e.