Microwave-Assisted Fabrication of Copper Oxide/N-Doped Carbon Nanocatalyst for Efficient Electrochemical CO2 Conversion to Liquid Fuels.

Electrochemical CO2 reduction reaction (CO2RR), which is driven by electricity generated from renewable energy sources, is a promising technology for sustainably producing carbon-based chemicals or fuels. Several CO2RR catalysts have been explored to date, among which copper-based electrocatalysts are the most widely known for electrochemical CO2RR and are extensively studied for their ability to generate an array of products. Their low selectivity, however, hinders their possibility of being used for practical purposes. In this work, a microwave-assisted one-pot synthesized CuxO/N-doped carbon demonstrates the electrochemical conversion of carbon dioxide into multiple C1 products (mainly formate and methanol), with a maximum Faradaic efficiency of 95% in 0.10 m KHCO3 aqueous solution at a moderately low applied potential of -0.55 V versus RHE (reversible hydrogen electrode). The in-depth theoretical study reveals the key contribution of pyridinic N-based N-doped carbon sites and Cu2O clusters in CO2 adsorption and its subsequent conversion to formate and methanol via an energetically favorable formate pathway. The electrocatalyst continued to demonstrate CO2 reduction to valuable C1 products when a simulated flue gas stream containing 15% CO2 along with 500 ppm SOx and 200 ppm NOx is used as an inlet feed.

Comparative LCA of thermal power plant with CCS and solar PV system: sustainability assessment in Indian context.

The study's objective is to evaluate and compare the sustainability of power production techniques for India's transition to clean power generation. It specifically focuses on coal-based power generation with emission control technologies, flue gas desulfurization (FGD) with carbon capture and storage (CCS), and compares it with solar photovoltaic (PV) systems. The study conducted a life cycle assessment (LCA) to determine the environmental impact of electricity generation in each scenario. Inventory data has been collected for each case through plant visits, emission modelling, and literature searches. The study evaluated midpoint and endpoint impact indicators utilizing the ReCiPe (H) assessment methodology. The economic viability of all the cases was determined by calculating the levelized cost of electricity (LCOE). The results showed that retrofitting an existing power plant with flue gas desulfurization (FGD) and carbon capture and storage (CCS) reduced efficiency by 30%, required 1.2 times more auxiliary power, and increased heat rates. The LCA results showed that the global warming potential (GwP) for FGD and CCS together was 0.614 kg CO2 eq. per kWh of power generation. On the other hand, the GwP for the solar PV system was much lower, at 0.043 kg CO2 eq. per kWh. There were trade-offs in both cases, but solar PV plants are more environmentally friendly than thermal power plants equipped with CCS systems in almost all categories. Furthermore, the LCOE results showed Rs 3.87 per kWh for an on-grid solar PV plant and Rs 5.33 for thermal power, with CCS and FGD showing solar as an economically more feasible option. Retrofitting thermal power facilities with emission control technology is necessary to achieve net zero emissions, but transition to renewable energy sources is inevitable.

Carbon Nanoparticle Oxidation by NO2 and O2: Chemical Kinetics and Reaction Pathways.

Carbon nanoparticle interactions with gases are central to many environmental and technical processes, but the underlying reaction kinetics and mechanisms are not well understood. Here, we investigate the oxidation and gasification of carbon nanoparticles by NO2 and O2 under combustion exhaust conditions. We build on a comprehensive experimental data set and use a kinetic multilayer model (KM-GAP-CARBON) to trace the uptake and release of gas molecules alongside the temporal evolution of particle size and surface composition. The experimental results are captured by a model mechanism that involves different types of carbon atoms (edge/plane-like) and the formation of a reactive oxygen intermediate (activated CO complex) as the rate-limiting step. A transition between distinct chemical regimes driven by NO2 at lower temperatures and O2 at higher temperatures is reflected by an increase in the observable activation energy from ~60 kJ/mol to ~130 kJ/mol. We derive energy profiles for three alternative reaction pathways that involve uni- or bimolecular decomposition of reactive oxygen intermediates.

Improvements in the utilization of calcium carbonate in promoting sustainability and environmental health.

Calcium carbonate (CaCO3) is an incredibly abundant mineral on Earth, with over 90% of it being found in the lithosphere. To address the CO2 crisis and combat ocean acidification, it is essential to produce more CaCO3 using various synthetic methods. Additionally, this approach can serve as a substitute for energy-intensive processes like cement production. By doing so, we have the potential to not only reverse the damage caused by climate change but also protect biological ecosystems and the overall environment. The key lies in maximizing the utilization of CaCO3 in various human activities, paving the way for a more sustainable future for our planet.

In-field carbon dioxide removal via weathering of crushed basalt applied to acidic tropical agricultural soil.

Enhanced weathering (EW) of silicate rocks such as basalt provides a potential carbon dioxide removal (CDR) technology for combatting climate change. Modelling and mesocosm studies suggest significant CDR via EW but there are few field studies. This study aimed to directly measure in-field CDR via EW of basalt applied to sugarcane on acidic (pH 5.8, 0-0.25 m) Ultisol in tropical northeastern Australia, where weathering potential is high. Coarsely crushed basalt produced as a byproduct of gravel manufacture (<5 mm) was applied annually from 2018 to 2022 at 0 or 50 t ha-1 a-1, incorporated into the soil in 2018 but not in subsequent years. Measurements in 2022 show increased soil pH and extractable Mg and Si at 0-0.25 m depth, indicating significant weathering of the basalt, but showed no increase in crop yield. Soil inorganic carbon content and bicarbonate (HCO3-) flux to deep drainage (1.25 m depth) were measured to quantify CDR in the 2022-2023 wet season (i.e. one year). Soil inorganic carbon was below detection limits. Mean HCO3- flux was 3.15 kmol ha-1 a-1 (±0.40) in the basalt-treated plots and 2.56 kmol ha-1 a-1 (±0.18) in the untreated plots but the difference (0.59 kmol ha-1 a-1 or 0.026 t CO2 ha-1 a-1) was not significant (p = 0.082). Most weathering of the basalt was attributed to acids stronger than carbonic acid. These were, in decreasing order of contribution, surface-bound protons (inherent soil acidity), nitric acid (from nitrification), organic acids, and acids associated with cation uptake by plants. These results indicate in-field CDR via EW of basalt is low where soil and regolith pH is well below the pKa1 of 6.4 for H2CO3. However, increased soil pH, and the consumption of strong acids by weathering will eventually lead to reduced CO2 emission from soil or evasion from rivers, with continued basalt addition.

Unlocking Potential for Low-Carbon Hydrogen Production from U.S. Natural Gas Resources.

Hydrogen will potentially play a key role while transitioning to a net-zero economy. This study addresses resource, environmental, economic, policy, and societal issues related to low-carbon hydrogen production by steam methane reforming with carbon capture and storage in Wyoming and other natural-gas-rich states. For low-carbon hydrogen produced from natural gas and electricity supplies and which stores CO2 in saline reservoirs in Wyoming, the levelized cost of hydrogen (LCOH) ranges from $1.62-2.00/kg H2, and the life cycle emissions range from 3.85-5.74 kg CO2-eq/kg H2. If claimed, the 45Q tax credit decreases the LCOH by 19%. Although the supplies of renewable natural gas feedstock and zero- or low-carbon electricity can lower the carbon footprint to make hydrogen projects qualified for the 45V tax credit, the 45Q tax credit is still a stronger economic incentive. To reduce the supply cost, a hydrogen cluster can be developed in the state by leveraging the colocation and coavailability of multiple natural resources and transport infrastructure. Developing a hydrogen cluster can directly create several thousand construction jobs and several hundred permanent jobs in Wyoming. Low-carbon hydrogen production can also be scaled up in other states across the nation.

Capturing carbon to mitigate climate change: storage or use?

Reducing atmospheric CO2 is vital to combat climate change. Alongside reducing emissions, it is essential to capture atmospheric CO2 and either use it or store it, depending on which option yields the best outcomes. Government policies should coordinate actions in areas such as the bioeconomy and avoid creating perverse incentives.

Simulation of bench-scale CO2 injection using a coupled continuum-discrete approach.

Unintended releases of CO2 from carbon capture and storage operations presents the risk of atmospheric emissions and groundwater or surface water quality impacts. Given the potential impacts, it is valuable to have tools capable of predicting groundwater concentrations and likely pathways of CO2 migration in the subsurface. Traditional multiphase flow models struggle to simulate the discontinuous flow expected at leakage sites. This work applied a coupled continuum-discrete model, ET-MIP, to simulate a bench-scale injection of CO2. Results demonstrate the capability of ET-MIP to accurately capture gas fingering behaviour, and the complexity of multicomponent mass transfer observed in the experiment. Simulations were computationally efficient, allowing for the use of multiple displacement pressure realizations. CO2 migration in the subsurface was shown to be sensitive to mass transfer, as i) increased groundwater velocity can dissolve leaked CO2 prior to reaching the surface and ii) background dissolved gases in the subsurface can impact the rate of upwards gas movement, gas distribution, and the composition and persistence of the gas phase. The sensitivity to mass transfer suggests it may be preferable to monitor for low-solubility gases in the source mixture rather than CO2. These findings are applicable to other gases in the subsurface, such as hydrogen or methane migrating from geoenergy wells.

Integration of Moving Bed Biofilm Reactor (MBBR) and algal PhotoBioReactors (aPBR) for achieving carbon neutrality in wastewater treatment.

Carbon neutrality is a primary goal for wastewater treatment plants (WWTPs), as they are responsible for significant greenhouse gas (GHG) emissions as well as unpleasant odour emissions. The paper shows a new modular biotechnology that enables simultaneous treatment of gaseous emissions and biofixation of CO2. A comparative assessment of system performances in removing target pollutants (toluene, p-xylene and hydrogen sulphide) was implemented. Results showed that the highest removal efficiency (RE) was recorded for the toluene, equaling 99.9 ± 0.1 %, for an inlet load (IL) of 9.91 ± 3.44 g m-3 d-1. During the experimental tests regarding hydrogen sulphide removal, the system recorded the highest CO2 assimilation, equal to -3.03 ± 0.93 g m-3 d-1. However, this assimilation rate did not correspond to the maximum volumetric biomass productivity (MVBP), equal to 1.3 g L-1 d-1, recorded with toluene treatment, with a maximum lipid productivity (MLP) of 450 mg L-1 d-1. The results demonstrated the complete adaptability of the investigated system, which can help to fill the gaps in the current technological landscape, providing an innovative biotechnology that can be directly implemented and environmentally sustainable.

CO2 capture enhancement by metal oxides impregnated coal fly ash: a breakthrough adsorption study.

Coal fired power plants are significant contributors to CO2 emissions and produce solid waste in the form of coal fly ash, posing severe environmental challenges. This study explores the application of dry-impregnated coal fly ash for CO2 capture from gas stream. The modification of coal fly ash was achieved using alkaline earth metal oxides, specifically CaO and MgO, to alter its physical and chemical properties. Characterization techniques like X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and BET (Brunauer-Emmett-Teller) analysis were employed for physio-chemical changes in the adsorbent. Breakthrough experiments were conducted using a laboratory-scale fixed packed-bed reactor to assess the influence of temperature and gas flow rate on CO2 adsorption. Among the synthesized sorbents, calcium oxide-impregnated ash showed the highest CO2 uptake capacity, achieving 9.41 mg/g at 30 °C and a flow rate of 20 L/hr under atmospheric pressure. Isotherm modeling indicated a heterogeneous adsorbent surface, with the data best fitting the Sips isotherm model. Furthermore, the adsorption data conformed well to the Yoon-Nelson and Thomas kinetic models, affirming their relevance in characterizing the adsorption process under varying conditions. This research emphasizes the potential of coal fly ash-an abundant, cost-free material-as an effective CO2 adsorbent, contributing to both CO2 mitigation and landfill waste reduction.

Isolation and Whole-genome analysis of Desmodesmus sp. SZ-1: Novel acid-tolerant carbon-fixing microalga.

Utilizing microalgae to capture flue gas pollutants is an effective strategy for mitigating greenhouse gas emissions. However, existing carbon-fixing microalgae exhibit poor tolerance towards acidic flue gas. In this study, the Desmodesmus sp. SZ-1, which can thrive in acidic environments and efficiently sequester CO2, was isolated. Desmodesmus sp. SZ-1 exhibited strong acid tolerance ability, with an average carbon fixation rate of 497.6 mg/L/d under 10 % CO2 and pH 3.5. Physiological analysis revealed that SZ-1 responded to high CO2 by increasing chlorophyll levels while coping with acidic stress by activating antioxidant enzymes. Genome analysis revealed a large number of carbon fixation and acid adaptation genes, involved in membrane lipid biosynthesis, H+ pumps, molecular chaperones, peroxidase system, amino acid synthesis, and carbonic anhydrase. This study provides a novel algal resource for mitigating acid gas emissions and a comprehensive genetic database for genetically modifying microalgae.

Physicochemical Modulations in MXenes for Carbon Dioxide Mitigation and Hydrogen Generation: Tandem Dialogue between Theoretical Anticipations and Experimental Evidences.

The dawn of MXenes has fascinated researchers under their intriguing physicochemical attributes that govern their energy and environmental applications. Modifications in the physicochemical properties of MXenes pave the way for efficient energy-driven operations such as carbon capture and hydrogen generation. The physicochemical modulations such as interface engineering through van der Waals coupling with homo/hetero-junctions render the tunability of optoelectronic variables driving the photochemical and electrochemical processes. Herein, we have reviewed the recent achievements in physicochemical properties of MXenes by highlighting the role of intercalants/terminal groups, atomic defects, surface chemistry and few/mono-layer formation. Recent findings of MXenes-based materials are systematically surveyed in a tandem manner with the future outlook for constructing next-generation multi-functional catalytic systems. Theoretical modelling of MXenes surface engineering proffers the mechanistic comprehension of surface phenomena such as termination, interface formation, doping and functionalization, thereby enabling the researchers to exploit them for targeted applications. Therefore, theoretical anticipations and experimental evidences of electrochemical/photochemical carbon dioxide reduction and hydrogen evolution reactions are synergistically discussed.

A new carbon-negative hydrogen production cycle for better sustainability.

Carbon dioxide removal is considered by many as an essential piece to achieve global net zero targets which was also mentioned by the third working group of Intergovernmental Panel on Climate Change. On top of this, green hydrogen is badly needed to achive carbon-free society long-term sustainability. This study proposes a new five-step sodium hydroxide thermochemical cycle for simultaneous hydrogen production and carbon dioxide removal, which is driven by the heat at least 400 °C. The proposed integrated cycle can be driven by clean energy sources that can be utilized to generate heat at required temperatures. The proposed system is designed and analyzed by using energy and exergy approaches of thermodynamics. A case study is also developed in order to understand the effects of changing parameters on system performance. A thermochemical hydrogen production cycle is designed with an unequilibrium reaction where the respective heat capacity calculation models are employed. According to the calculations, more than half of the energy content of process heat can be converted into hydrogen, where maximum energy and exergy efficiencies of the thermochemical cycle are found as 50.05% and 76.61% when the separation reaction is carried out at 400 °C. According to the case study results, a parabolic trough collector type concentrated solar energy system with 295 kW of heat sink capacity, can generate 5216.65 kg of hydrogen and capture 19,991.97 kg of carbon dioxide in a location where 1500.11 kWh of solar energy is reached per m2 of area in a typical year.

Nanoscale Understanding on CO2 Diffusion and Adsorption in Clay Matrix Nanopores: Implications for Carbon Geosequestration.

Carbon capture and storage (CCS) in subsurface reservoirs represents a highly promising and viable strategy for mitigating global carbon emissions. In the context of CCS implementation, it is particularly crucial to understand the complex molecular diffusive and adsorptive behaviors of anthropogenic carbon dioxide (CO2) in the subsurface at the nanoscale. Yet, conventional molecular models typically represent only single-slit pores and overlook the complexity of interconnected nanopores. In this work, finite kaolinite lamellar assemblages with abundant nanopores (r < 2 nm) were used. Molecular dynamics simulations were performed to quantify the spatial distribution correlations, adsorption preference, diffusivity, and residence time of the CO2 molecules in kaolinite nanopores. The movement of the CO2 molecules primarily occurs in the central and proximity regions of the siloxane surfaces, progressing from larger to smaller nanopores. CO2 prefers smaller nanopores over larger ones. The diffusion coefficients increase, while residence times decrease, with the pore size increasing, differing from typical slit-pore models due to the pore shape and interconnectivity. The perspectives in this study, which would be challenging in conventional slit-pore models, will facilitate our comprehension of the CO2 molecular behaviors in the complex subsurface clay sediments for developing quantitative estimation techniques throughout the CCS project durations.

Towards a high-rate operation of contact stabilization process: A microscopic view of carbon capture properties.

Carbon capture performance is a key factor determining the chemical energy recovery potential of the high-rate contact stabilization (HiCS) process. However, the mechanisms of organic carbon capture are complex, involving surface adsorption, extracellular adsorption, and intracellular storage. A unique characteristic of the HiCS process is its low sludge residence time (SRT). Unfortunately, the influence of SRT on carbon capture has not been thoroughly studied, especially in terms of the underlying mechanisms. In this study, the microscopic changes in carbon capture performance during the transition from a conventional contact stabilized (CS) system to a high-rate mode of operation were demonstrated using intracellular carbon sources, extracellular polymeric substances (EPS), signaling molecules, and microbial community assays. The results showed that the extracellular carbon adsorption and intracellular carbon storage performance increased, and the microbial community structure changed significantly with converting the CS system to the high-rate operation mode. The enhancement of extracellular carbon adsorption performance mainly relied on the growth of EPS, which was accomplished by the strong growth of the relative abundance of the dominant bacterial group Cloacibacterium within the HiCS system, offsetting the negative effect produced by the decline of acyl-homoserine lactones. 98 mgCOD/gSS, 343 mgCOD/gSS, and 500 mgCOD/gSS of polyhydroxyalkanoates (PHAs) per sludge unit were obtained at SRT-24d, 8d, and 2d, respectively, suggesting that the HiCS system is more advantageous for rapid PHAs production.

Separation and concentration of CO2 from air using a humidity-driven molten-carbonate membrane.

Separation processes are substantially more difficult when the species to be separated is highly dilute. To perform any dilute separation, thermodynamic and kinetic limitations must be overcome. Here we report a molten-carbonate membrane that can 'pump' CO2 from a 400 ppm input stream (representative of air) to an output stream with a higher concentration of CO2, by exploiting ambient energy in the form of a humidity difference. The substantial H2O concentration difference across the membrane drives CO2 permeation 'uphill' against its own concentration difference, analogous to active transport in biological membranes. The introduction of this H2O concentration difference also results in a kinetic enhancement that boosts the CO2 flux by an order of magnitude even as the CO2 input stream concentration is decreased by three orders of magnitude from 50% to 400 ppm. Computational modelling shows that this enhancement is due to the H2O-mediated formation of carriers within the molten salt that facilitate rapid CO2 transport.

Optimizing large-scale CO2 pipeline networks using a geospatial splitting approach.

CO2 transport infrastructure is the backbone of carbon capture and storage (CCS) technology for the mitigation of carbon emissions and project deployment viability. In conventional large-scale CO2 pipeline network designs, the storage sites are generally assumed as the centroids of the major geologic basins, however, this approach might provide suboptimal solutions since the large extension of some storage formations significantly increases the length of the CO2 transportation networks. To address this situation and obtain optimal pipeline routes, we present a novel geospatial splitting framework that partitions large basins into multiple sub-sinks. In our approach, we used a large number of reservoir models varying petrophysical properties and CO2 injection rates to compute pressure plumes through numerical simulations, leading to the calculation of the number of subregions for each basin as a function of the extension of pressure interference areas and boundaries. Finally, we applied K-means clustering and Voronoi polygon algorithms to partition large basins into subregions and obtain their sink coordinates. To demonstrate the capability of the developed workflow, we investigated two CO2 pipeline network modeling case studies using our splitting approach: one regional case study focusing on the Intermountain West (I-West) region and one nationwide case study covering the lower 48 states in the U.S. In both case studies, we compared the optimal pipeline routes using the original and new storage locations and examined the major differences. The use of the developed geospatial approach resulted in both cases in a shortening of the total pipeline network length by 13% and 10%, compared to the pipeline modeling with the original basins, leading to cost reductions of 25% and 17%, respectively, demonstrating that the location of point sinks has a critical impact on the length and expenses of pipelines to efficiently transport CO2 to distant storage sites. Therefore, the workflow presented here contributes to the proper and realistic modeling of case studies that support decision-making in CCS deployment.

Exploitation of Pore Structure for Increased CO2 Selectivity in Type 3 Porous Liquids.

CO2 capture requires materials with high adsorption selectivity and an industrial ease of implementation. To address these needs, a new class of porous materials was recently developed that combines the fluidity of solvents with the porosity of solids. Type 3 porous liquids (PLs) composed of solvents and metal-organic frameworks (MOFs) offer a promising alternative to current liquid carbon capture methods due to the inherent tunability of the nanoporous MOFs. However, the effects of MOF structural features and solvent properties on CO2-MOF interactions within PLs are not well understood. Herein experimental and computational data of CO2 gas adsorption isotherms were used to elucidate both solvent and pore structure influences on ZIF-based PLs. The roles of the pore structure including solvent size exclusion, structural environment, and MOF porosity on PL CO2 uptake were examined. A comparison of the pore structure and pore aperture was performed using ZIF-8, ZIF-L, and amorphous-ZIF-8. Adsorption experiments here have verified our previously proposed solvent size design principle for ZIF-based PLs (1.8× ZIF pore aperture). Furthermore, the CO2 adsorption isotherms of the ZIF-based PLs indicated that judicious selection of the pore environment allows for an increase in CO2 selectivity greater than expected from the individual PL components or their combination. This nonlinear increase in the CO2 selectivity is an emergent behavior resulting from the complex mixture of components specific to the ZIF-L + 2'-hydroxyacetophenone-based PL.

Effect of phytohormones on the carbon sequestration performance of CO2 absorption-microalgae conversion system under low light restriction.

Microalgae have the potential to fix CO2 into valuable compounds. Low photosynthetic efficiency caused by low light was one of the challenges faced by microalgae carbon sequestration. In this study, Melatonin (MT) and indole-propionic acid (IPA) were used to alleviate the growth inhibition of Spirulina in CAMC system under low light restriction. The results showed that MT and IPA increased biomass and carbon fixation capacity. 10 mg/L IPA group achieved the maximum biomass and carbon fixation capacity, which were 17.11% and 21.46% higher than control. MT and IPA promoted the synthesis of chlorophyll, which in turn captured more light energy for microalgae growth. The increase of superoxide dismutase (SOD), catalase (CAT) and glutathione reductase (GR) activities enhanced the resistance of microalgae to low light stress. MT and IPA promoted the secretion of extracellular polymeric substances (EPS) which was benefit to protect cells. The maximum phycocyanin content and yield was found in 10 mg-IPA group, which was 20.67% and 46.67% higher than control. MT and IPA improved the synthesis of carbohydrates and proteins and increased carbohydrates and proteins yield. This indicated that adding phytohormones was an effective method to alleviate the growth of microalgae restricted by low light stress, which provided a theoretical guidance for the application of CAMC system in CO2 capture and resource utilization.

Efficient Dynamic Phase Splitting Driven by Centrifugal Force for CO2 Capture from Flue Gas using Biphasic Solvents.

Carbon dioxide (CO2) chemisorption using biphasic solvents has been regarded as a promising approach, but challenges remain in achieving efficient dynamic phase-splitting during practical implementation. To address this, the centrifugal force was innovatively adopted to enhance the coalescence and separation of immiscible fine droplets within the biphasic solvent. The comprehensive evaluation demonstrates that centrifugal phase-splitting shows outstanding separation efficiency (>95%) and excellent applicability for various solvents. Correlation analysis reveals a strong relationship between the rich phase's viscosity, lean phase's residual CO2, and the phase separation efficiency. The time-profile behavior of immiscible droplets, observed through microscope images of phase-splitting, enables the estimation of the growth and coalescence rates of the discrete phase. Industrial-scale process simulation for technical and economic analysis confirms that the total capture cost ($ 42.5/t CO2) can be reduced by ∼22% with the use of biphasic solvents and a centrifugal separator compared to conventional methods. This study introduces a fresh perspective on polarity-induced cluster generation and coagulation-induced separation, offering an effective solution to address the challenges associated with dynamic phase-splitting in biphasic solvents during practical applications.