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Seawater electrolysis enables Mg(OH) 2 production and CO 2 mineralization
A method for producing one or more hydroxide solids includes providing a catholyte comprising an electrolyte solution; contacting the catholyte with an electroactive mesh cathode to electrolytically generate hydroxide ions, thereby precipitating the one or more hydroxide solid(s); and removing the one or more hydroxide solids from the surface of the mesh where they may deposit.
2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid
Efficiently transforming CO 2 into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non-toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO 2 (CO 2 RR) on conventional carbon black-supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp $d_{z^2}$, $d_{yz}$, $d_{xz}$ orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO 2 reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemical reactions through the electronic mixing of metal and other p-block elements.
Stabilizing Transition Metal Vacancy Induced Oxygen Redox by Co 2+ /Co 3+ Redox and Sodium-Site Doping for Layered Cathode Materials
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Regional Assessment for the CO 2 Storage Potential in the Northern Niagaran Pinnacle Reef Trend
The Midwest Regional Carbon Sequestration Partnership (MRCSP) was founded in 2003 as part of the U.S. Department of Energy’s (DOE’s) Regional Carbon Sequestration Partnership initiative. Since its founding, MRCSP has made significant strides toward making CCUS a viable option for states in the region. The public/private consortium, funded through the DOE Regional Carbon Sequestration Initiative, brings together nearly 40 industry partners and 10 states. Battelle, as the project lead, oversees research, development and operations and coordinates activities among the partners. The incremental, phased approach has built a valuable knowledge base for the industry and paved the way for commercial-scale adoption of CCUS technologies. From 2008 to 2020, MRCSP Phase III focused on the development of large-scale injection projects. This report is part of a series of reports prepared under the Midwestern Regional Carbon Sequestration Partnership (MRCSP) Phase III (Development Phase). These reports summarize and detail the findings of the work conducted under the Phase III project. The report describes the regional analysis of the Northern Niagaran Pinnacle Reef Trend (NNPRT) in Northern Michigan as part of the MRCSP programs Regional Assessment goals. The goal of this task was to perform an initial assessment of the geologic storage capacity and injectivity of the Northern Fairway of Michigan’s Niagaran Reef Trend. This was achieved through three main objectives: 1) development of a reef atlas, 2) understanding the regional trends in geology, and 3) estimating CO 2 and CO 2 -EOR resources. Data collected across multiple subtasks were integrated into a mappable database that could be accessed from many of the leading software. The reef atlas was used to map the reefs and associated characteristics across the entire NNPRT. Several methodologies were explored to estimate the CO 2 and CO 2 -EOR resources across the trend which included three scenarios: 1) storage only using fluid substitution and volumetric estimations, 2) CO 2 -EOR which applied proximity analysis concepts and measured performance metrics from the Core Energy reefs to predict performance at all oil reefs, and 3) enhanced storage scenario which combined CO 2 -EOR with fluid substitution to represent maximized storage after completion of CO 2 -EOR.
Reaction Diffusion Modelling of 3D Pillar Electrodes in Single-Catalyst CO 2 Reduction Cascades
Effective electrochemical CO 2 reduction to liquid fuels requires that the local catalytic environment facilitates the desired reactivity, yet a microscopic understanding of this environment is difficult to achieve from experiment alone. In this work, a 3D reaction-diffusion model was developed to explore the effects of electrode surface area and local geometry on the performance of a heterogeneous catalyst that performs a two-step CO 2 reduction cascade reaction to CO and then CH 3 OH under aqueous conditions. Kinetic parameters for the model were inspired by experimental results using a cobalt phthalocyanine (CoPc) catalyst. Three-dimensional architectures composed of arrays of square pillars with varying dimensions and either smooth or periodically modulated surfaces were tested, revealing the extent to which geometry modulates the performance of the cascade reactions. Although structural variations modulate local concentration gradients, we find that electrochemically active surface area predominantly governs the overall cascade reaction. Moreover, the results suggest that supersaturation of CO, with concentrations up to ten-fold higher than the equilibrium solubility limit, might be critical for more efficient conversion to CH 3 OH. For any given geometry, the spatially averaged ratio of [CO] to [CO 2 ] is dictated by the electrochemically active surface area and determines the yield of CH 3 OH. For a fixed surface area, geometries that spatially confine the electrolyte yield moderate local [CO] to [CO 2 ] ratios within small volumes. In contrast, less confining geometries result in a broader distribution of local ratios spread over larger volumes, with both configurations yielding the same spatially averaged [CO] to [CO 2 ] ratio. These insights provide valuable design principles—highlighting the critical importance of surface area and possibly CO supersaturation—for engineering advanced electrode architectures that leverage intermediate trapping and CO supersaturation to enhance overall performance in tandem CO 2 reduction systems.
Gradient Amine Sorbents for Low Vacuum Swing CO 2 Capture at Ambient Temperature
The growing concerns over CO 2 emissions have led to the development of various methods for CO 2 capture. CO 2 capture by amine-based sorbents has been achieved by temperature (thermal) swing adsorption (TSA) process, pressure swing adsorption (PSA) process, and temperature pressure or vacuuming swing adsorption (TPSA or TVSA) process for CO 2 capture. Amine sorbents for energy-efficient TSA, PSA, VSA, TPSA or TVSA CO 2 capture should possess a capability which allow adsorbed CO 2 to desorb and amine sorbent to be regenerated at low temperatures or low vacuums. Development of such amine sorbents would significantly decrease energy consumption and sorbent degradation during the regeneration step. The objective of this project is to develop a low vacuum swing adsorption (VSA) process for the capture of CO 2 from air. The focus is on the development of amine sorbent which allows CO 2 to adsorb in the form of weakly adsorbed CO 2 . The weakly adsorbed CO 2 species can be collected from the sorbent by applying a low vacuum at ambient temperature. Specifically, no heating (i.e., thermal energy) is needed for regeneration of amine sorbents. This novel sorbent allows VSA to be operated at ambient temperature without a significant energy demand. This process eliminates the energy-intensive heating and cooling process in temperature swing adsorption (TSA) process. Ambient temperature operation could prolong the lifetime of sorbent and minimize the maintenance cost. Extensive sorbent studies with in-situ infrared spectroscopy have revealed the modifications of conventional amine sorbents with additives can increase the fraction of weakly adsorbed CO 2 . The amine sorbents with loaded CO 2 can be regenerated in part by the following approaches: (i) mild heating to temperatures below 70 °C, (ii) flowing purging gas over modified amine sorbents at temperatures below 40 °C, (iii) vacuuming at pressure below 0.2 atm and temperatures below 40 °C. The performance of these modified amine sorbents has been tested in a 60 grams VSA unit at ambient temperatures. The results show that weakly adsorbed CO 2 which can be desorbed from modified amine sorbents with purging gas at 100 cc/min can also be evacuated at a vacuum of 1 psia at room temperature. A preliminary techno- economic analysis indicates the major cost of the VSA process with modified amine sorbents stems from the operation of vacuum pumps. Thus, developing an excellent sealing with minimum leakage for the VSA unit is the most critical task for further the development of this VSA technology.
Probing Electrolyte Influence on CO 2 Reduction in Aprotic Solvents
Selective CO 2 capture and electrochemical conversion are important tools in the fight against climate change. Industrially, CO 2 is captured using a variety of aprotic solvents due to their high CO 2 solubility. However, most research efforts on electrochemical CO 2 conversion use aqueous media and are plagued by competing hydrogen evolution reaction (HER) from water breakdown. Fortunately, aprotic solvents can circumvent HER, making it important to develop strategies that enable integrated CO 2 capture and conversion. However, the influence of ion solvation and solvent selection within nonaqueous electrolytes for efficient and selective CO 2 reduction is unclear. In this work, we show that the bulk solvation behavior within the nonaqueous electrolyte can control the CO2 reduction reaction and product distribution occurring at the catalyst-electrolyte interface. We study different tetrabutylammonium (TBA) salts in two electrolyte systems with glyme ethers (e.g., 1,2 dimethoxyethane or DME) and dimethyl sulfoxide (DMSO) as a low and high dielectric constant medium, respectively. Using spectroscopic tools, we quantify the fraction of ion pairs that forms within the electrolyte. Also, we show how ion pair formation is prevalent in DME and is dependent on the anion type. More importantly, we show that as ion pair formation decreases within the electrolyte, CO 2 current densities increase, and a higher CO Faradaic efficiency is observed at low overpotentials. Meanwhile, in an electrolyte medium where the ion pair fraction does not change with the anion type (such as in DMSO), a smaller influence of solvation is observed on CO 2 current densities and product distribution. By directly coupling bulk solvation to interfacial reactions and product distribution, we showcase the importance and utility of controlling the reaction microenvironment in tuning the electrocatalytic reaction pathways. Insights gained from this work will enable novel electrolyte designs for efficient and selective CO 2 conversion to desired fuels and chemicals.
Large magnetic anisotropy of a decorated spin-chain system K 2 Co 3 (MoO 4 ) 3 (OH) 2
The magnetic structure of K 2 Co 3 (MoO 4 ) 3 (OH) 2 is studied in detail. The material has a half-sawtooth one-dimensional (1-D) structure containing two unique Co 2+ ions, one in the chain backbone and one on the apex of the sawtooth creating a series of isosceles triangles along the b-axis. These triangles can be a source of magnetic frustration. The ability to grow large single crystals enables detailed magnetic measurements with the crystals oriented in a magnetic field along the respective axes. It has a Curie–Weiss temperature θ CW of 5.3(2) K with an effective magnetic moment of 4.8(3)μ B /Co. The material is highly anisotropic with a sharp antiferromagnetic ordering transition at 7 K with a metamagnetic transition at 2 kOe. Neutron diffraction was used to determine the magnetic structure and revealed a magnetic structure with canted spins along the backbone of the chain while spins along the sawtooth caps maintained a colinear orientation, arranging antiferromagnetically relative to the backbone spins. In conclusion, the parallel chains arrange antiferromagnetically relative to each other along the c-axis and ferromagnetically along the a-axis.
Operando X-ray Absorption Spectroscopy Study of SnO 2 Nanoparticles for Electrochemical Reduction of CO 2 to Formate
Tin–based electrocatalysts exhibit a remarkable ability to catalyze CO 2 to formate selectively. Understanding the size-property relationships and exploring the evolutions of active size still lack complete understanding. Herein, we prepared SnO 2 nanoparticles (NPs) with controllable size supported on commercial carbon spheres (SnO 2 /C–n, n=1,2,3) by a simple low-temperature annealing method. The transmission electron microscopy(TEM)/scanning transmission electron microscope (STEM) images and fitting results of the small angle X-ray scattering (SAXS) profile confirm the increased size of SnO 2 NPs as the increase of SnO 2 loading. The catalytic performance of SnO 2 has proved the size-dependent effect during CO 2 reduction reaction process. The as-prepared SnO 2 /C–1 displayed the maximum Faradic efficiency of formate (FE HCOO– ) of 82.7% at –1.0 V vs. RHE. In contrast, SnO 2 /C–2 and SnO 2 /C–3 with larger particle sizes achieved lower maximum FE HCOO– and larger overpotential. Moreover, we employed operando XAS to study the evolution of the oxidation state and local coordination environment of SnO 2 under working conditions. In addition to the observed the shifts of rising edge of Sn K-edge X-ray absorption near edge structure (XANES) spectra to lower energy side as the applied voltage decreases, the decreased coordination number of Sn in the Sn-O scattering path and the presence of Sn mental contribution in extended X-ray absorption fine structure (EXAFS) spectra verify the reduction of SnO 2 to SnO x and metallic Sn.
Synthesis of a planar, multicomponent catalytic surface of Na 2 CO 3 /MnO
Here, O 2 adsorption on MnO(100) precovered with sodium (Na) multilayers was investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Deposition of Na multilayers leads to a first monolayer of oxidic Na followed by metallic Na island growth. XPS results for the oxidation of the metallic Na islands indicate an incomplete oxidation of Na at 125 K. Oxidation at 350 K completely oxidizes the metallic islands producing a mixture of Na 2 O and Na 2 O 2 . Thermal evolution of the oxidation products was examined. After oxidation at 350 K and flashing to 750 K, Na 2 O and Na 2 O 2 are the primary oxides on MnO(100). After flashing to 850 K, a solid state reaction of Na 2 O 2 /Na 2 O and the MnO(100) substrate forms a NaMnO 2 -like surface compound which decomposes above 850 K. Oxygen exchange between CO 2 and Na oxides is observed. The strong interaction between CO 2 and Na oxide islands forms Na 2 CO 3 on MnO(100). Heating the Na 2 CO 3 covered MnO(100) surface to 600 K for 10 min drives oxidic Na in the first monolayer into the MnO subsurface, and produces a surface exposing islands of Na 2 CO 3 on MnO(100).
Identifying Critical Electrode Metrics for Efficient, Selective CO 2 Electrochemical Conversion
Low-temperature electrochemical CO 2 reduction (CO 2 R) in zero-gap membrane electrode assembly (MEA) reactors presents a scalable route to fuels and carbon utilization. However, performance at industrially relevant current densities hinges on mesoscale catalyst layer integration, particularly at the ionomer|catalyst interface. Here, we demonstrate a generalizable in situ electrochemical impedance spectroscopy (EIS) method. We utilize this technique to decouple electrode-level parameters that are correlated to the overall MEA performance. By performing this ex situ EIS method on CO 2 -to-CO catalyst-coated membranes with systematically varied ionomer-to-catalyst (I:C) ratios, we reveal a pronounced dependence of performance, ion transport resistance, and catalyst utilization on the I:C ratio as well as the electrode conditioning. We demonstrate that an optimal I:C ratio exists at which ion transport resistance is minimized and Faradaic efficiency for CO production is maximized. Beyond the electrodes examined, here we compare ion transport resistance to MEA selectivity/Faradaic efficiency obtained in prior studies, revealing a clear correlation between the two. These results suggest that ion transport resistance within the catalyst layer may be a quantitative predictor of MEA performance which underscores the importance of mesoscale integration in achieving scalable CO 2 R technologies.
Development of Mixed Matrix Membranes by Using NH 2 ‐Functionalized UiO‐66 and [APTMS][AC] Ionic Liquid for the Separation of CO 2
The ever‐escalating CO 2 concentration in the atmosphere calls for accelerated development and deployment of carbon capture processes to reduce emissions. Mixed matrix membranes (MMMs), which are fabricated by incorporating the beneficial properties of highly selective inorganic fillers into a polymer matrix, have exhibited significant progress and the ability to enhance the performance of a membrane for gas separation. In this research, an amine‐based ionic liquid (IL) [APTMS][AC] was prepared, which has greater CO 2 affinity and greater solubility due to its amine moiety. The metal–organic framework (MOF) UiO‐66 with a multidimensional crystalline structure was used as a filler due to its appropriate porosity and tunable properties, and it was functionalized with NH 2 . MOFs were further modified with an IL to prepare UiO‐66@IL and UiO‐66‐NH 2 @IL, and MMMs incorporating each MOF were fabricated with the polymer Pebax‐1657. All the prepared membranes and MOFs were characterized to predict their separation efficiency. Several characterization techniques, namely, FTIR spectroscopy, XRD, and SEM, were used to successfully synthesize UiO‐66@IL and UiO‐66‐NH 2 @IL composites and confirmed proper dispersion and excellent polymer‒filler compatibility at filler loadings ranging from 0 to 30 wt.%. The separation performances were investigated, and the results showed that the incorporation of RTIL with the highly crystalline structure and large surface area of UiO‐66 enhanced the separation efficiency of the membrane. The permeability of CO 2 for all fabricated membranes continuously increased with increasing filler concentration, wherein the permeability was comparatively high for the UiO‐66‐NH 2 MMMs. The CO 2 /CH 4 selectivity improved by 35%, 54%, and 60%, respectively, for UiO‐66@IL, UiO‐66‐NH 2 , and UiO‐66‐NH 2 @IL MMMs compared to simple UiO‐66 for CO 2 /CH 4 and by 28%, 36%, and 63%, respectively, for CO 2 /N 2 , with an increase in filler loading in the MMMs.
2‐Aminobenzenethiol‐Functionalized Silver‐Decorated Nanoporous Silicon Photoelectrodes for Selective CO 2 Reduction
Abstract A molecularly thin layer of 2‐aminobenzenethiol (2‐ABT) was adsorbed onto nanoporous p‐type silicon (b‐Si) photocathodes decorated with Ag nanoparticles (Ag NPs). The addition of 2‐ABT alters the balance of the CO 2 reduction and hydrogen evolution reactions, resulting in more selective and efficient reduction of CO 2 to CO. The 2‐ABT adsorbate layer was characterized by Fourier transform infrared (FTIR) spectroscopy and modeled by density functional theory calculations. Ex situ X‐ray photoelectron spectroscopy (XPS) of the 2‐ABT modified electrodes suggests that surface Ag atoms are in the +1 oxidation state and coordinated to 2‐ABT via Ag−S bonds. Under visible light illumination, the onset potential for CO 2 reduction was −50 mV vs. RHE, an anodic shift of about 150 mV relative to a sample without 2‐ABT. The adsorption of 2‐ABT lowers the overpotentials for both CO 2 reduction and hydrogen evolution. A comparison of electrodes functionalized with different aromatic thiols and amines suggests that the primary role of the thiol group in 2‐ABT is to anchor the NH 2 group near the Ag surface, where it serves to bind CO 2 and also to assist in proton transfer.
Skin CO 2 sniffing for wearable metabolic monitoring
CO 2 is a key physiological parameter used to assess hypoventilation and to estimate metabolic rates. However, current CO 2 monitoring relies on bulky breath-analysis systems that are impractical for continuous use in daily life. Here, we present a wearable on-skin gas-sniffing system that quantifies skin-emitted CO 2 and establishes its physiological relevance through direct correlation with exhaled CO 2 and metabolic rate. Participant studies demonstrate strong correlations between CO 2 flow rates from the skin and breath during both rest and exercise, with skin-emitted CO 2 approximately four orders of magnitude lower than exhaled CO 2 . Skin-emitted CO 2 also correlates with metabolic rate, suggesting its potential as a surrogate for breath-based indirect calorimetry. With its wearable form factor and physiological relevance, this skin gas sniffing system enables continuous, noninvasive metabolic monitoring and opens opportunities for studying skin gas exchange.
Organic Additive‐derived Films on Cu Electrodes Promote Electrochemical CO 2 Reduction to C 2+ Products Under Strongly Acidic Conditions
Abstract Electrochemical CO 2 reduction (CO 2 R) at low pH is desired for high CO 2 utilization; the competing hydrogen evolution reaction (HER) remains a challenge. High alkali cation concentration at a high operating current density has recently been used to promote electrochemical CO 2 R at low pH. Herein we report an alternative approach to selective CO 2 R (>70 % Faradaic efficiency for C 2+ products, FE C2+ ) at low pH (pH 2; H 3 PO 4 /KH 2 PO 4 ) and low potassium concentration ([K + ]=0.1 M) using organic film‐modified polycrystalline copper (Modified‐Cu). Such an electrode effectively mitigates HER due to attenuated proton transport. Modified‐Cu still achieves high FE C2+ (45 % with Cu foil /55 % with Cu GDE) under 1.0 M H 3 PO 4 (pH≈1) at low [K + ] (0.1 M), even at low operating current, conditions where HER can otherwise dominate.
Modeling diurnal and annual ethylene generation from solar-driven electrochemical CO 2 reduction devices
Integrated solar fuels devices for CO 2 reduction (CO 2 R) are a promising technology class towards reducing carbon emissions. Designing integrated CO 2 R solar fuels devices requires careful co-design of electrochemical and photovoltaic components as well as consideration of the diurnal and seasonal effects of solar irradiance, temperature, and other meteorological factors expected for ‘on-sun’ deployment. Using a photovoltaic-electrochemical (PV-EC) platform, we developed a temperature and potential-dependent diurnal and annual model using experimentally-determined CO 2 R performance of Cu-based electrocatalysts, local meteorological data from the National Solar Radiation Database (NSRD), and modeled performance of commercial c-Si PVs. Here we simulated gaseous diurnal product outputs with and without the effects of ambient temperature. From these outputs, we observed seasonal variation in gaseous product generation, with up to two-fold increases in ethylene productivity between the Winter and Summer, analyzed the consequences of dynamic cloud coverage, and identified periods where device cooling/heating mechanisms could be implemented to maximize ethylene generation. Finally, we modeled the annual ethylene generation for a scaled 1 MW solar farm at three different locations (Beijing, CN; Sydney, AUS; Barstow, CA) to determine the consequences of local meteorological climates on PV-EC CO 2 R product output, recording a maximum ethylene output of 18.5 tonne per year at Barstow. Overall, this model presents a critical tool for streamlining the translation of experimental solar-driven electrochemical research to real-world implementation.
Polystyrene sulfonate (PSS) stabilized polyethylenimine (PEI) membranes fabricated by spray coating for highly effective CO 2 /N 2 separation
Greenhouse effect, largely caused by CO 2 emission, has become a major concern for global climate change. Post-combustion CO 2 capture is one of the critical strategies to mitigate this issue. Membrane technology for carbon capture has drawn significant attention because of the cost and energy efficiency and scalability. Many membranes for CO 2 capture are limited by the trade-off between CO 2 permeability and CO 2 /N 2 selectivity and the long-term stability under practical operating conditions. Facilitated transport membranes with efficient CO 2 carriers have demonstrated potential to surpass the permeability-selectivity trade-off, but these carriers are often lost under operational conditions. In this work, we designed and fabricated a polystyrene sulfonate (PSS) stabilized polyethylenimine (PEI) membrane by a facile and scalable spray-coating method. The deposited defect-free selective layer, in which the amine carriers in PEI can be stabilized electrostatically by PSS, exhibited superior CO 2 separation performance with good long-term stability under practical operating conditions. The separation performance was optimized by spray-coating cycles, CNT network loading, and PSS loading. Our membrane showed CO 2 permeance ranging from 820 to 1,770 GPU and CO 2 /N 2 selectivity varying from 395 to 460 under vacuum operation mode in the temperature range between 80 and 90 °C. Furthermore, the membrane was successfully scaled up to 200 cm 2 with good uniformity. These results might suggest a novel membrane structure and a scalable approach for fabrication of highly efficient CO 2 separation membranes.