Facile Fabrication of Monodispersed Carbon Sphere: A Pathway Toward Energy-Efficient Direct Air Capture (DAC) Using Amino Acids.

Direct removal of carbon dioxide (CO2 ) from the atmosphere, known as direct air capture (DAC) is attracting worldwide attention as a negative emission technology to control atmospheric CO2 concentrations. However, the energy-intensive nature of CO2 absorption-desorption processes has restricted deployment of DAC operations. Catalytic solvent regeneration is an effective solution to tackle this issue by accelerating CO2 desorption at lower regeneration temperatures. This work reports a one-step synthesis methodology to prepare monodispersed carbon nanospheres (MCSs) using trisodium citrate as a structure-directing agent with acidic sites. The assembly of citrate groups on the surface of MCSs enables consistent spherical growth morphology, reduces agglomeration and enhances water dispersibility. The functionalization-assisted synthesis produces uniform, hydrophilic nanospheres of 100-600 nm range. This work also demonstrates that the prepared MCSs can be further functionalized with strong Brønsted acid sites, providing high proton donation ability. Furthermore, the materials can be effectively used in a wide range of amino acid solutions to substantially accelerate CO2 desorption (25.6% for potassium glycinate and 41.1% for potassium lysinate) in the DAC process. Considering the facile synthesis of acidic MCSs and their superior catalytic efficiency, these findings are expected to pave a new path for energy-efficient DAC.

Engineered assembly of water-dispersible nanocatalysts enables low-cost and green CO2 capture.

Catalytic solvent regeneration has attracted broad interest owing to its potential to reduce energy consumption in CO2 separation, enabling industry to achieve emission reduction targets of the Paris Climate Accord. Despite recent advances, the development of engineered acidic nanocatalysts with unique characteristics remains a challenge. Herein, we establish a strategy to tailor the physicochemical properties of metal-organic frameworks (MOFs) for the synthesis of water-dispersible core-shell nanocatalysts with ease of use. We demonstrate that functionalized nanoclusters (Fe3O4-COOH) effectively induce missing-linker deficiencies and fabricate mesoporosity during the self-assembly of MOFs. Superacid sites are created by introducing chelating sulfates on the uncoordinated metal clusters, providing high proton donation capability. The obtained nanomaterials drastically reduce the energy consumption of CO2 capture by 44.7% using only 0.1 wt.% nanocatalyst, which is a ∽10-fold improvement in efficiency compared to heterogeneous catalysts. This research represents a new avenue for the next generation of advanced nanomaterials in catalytic solvent regeneration.

Water-Dispersible Nanocatalysts with Engineered Structures: The New Generation of Nanomaterials for Energy-Efficient CO2 Capture.

The high energy demand of CO2 absorption-desorption technologies has significantly inhibited their industrial utilization and implementation of the Paris Climate Accord. Catalytic solvent regeneration is of considerable interest due to its low operating temperature and high energy efficiency. Of the catalysts available, heterogeneous catalysts have exhibited relatively poor performances and are hindered by other challenges, which have slowed their large-scale deployment. Herein, we report a facile and eco-friendly approach for synthesizing water-dispersible Fe3O4 nanocatalysts coated with a wide range of amino acids (12 representative molecules) in aqueous media. The acidic properties of water-dispersible nanocatalysts can be easily tuned by introducing different functional groups during the hydrothermal synthesis procedure. We demonstrate that the prepared nanocatalysts can be used in energy-efficient CO2 capture plants with ease-of-use, at very low concentrations (0.1 wt %) and with extra-high efficiencies (up to ∼75% energy reductions). They can be applied in a range of solutions, including amino acids (i.e., short-chain, long-chain, and cyclic) and amines (i.e., primary, tertiary, and primary-tertiary mixture). Considering the superiority of the presented water-dispersible nanocatalysts, this technology is expected to provide a new pathway for the development of energy-efficient CO2 capture technologies.

The electro-Fenton regeneration of Granular Activated Carbons: Degradation of organic contaminants and the relationship to the carbon surface.

Electrochemical regeneration of Granular Activated Carbon is an emerging treatment option to restore adsorption capacity in systems designed to remove organic contaminants from aqueous solutions. The electro-Fenton process is one such electrochemical process and it is reviewed along with other members of its family including Photoelectro-Fenton and Heterogeneous electro-Fenton and electro-Fenton like reactions, for its ability to regenerate Granular Activated Carbons contaminated with organics. The behaviour of critical operating parameter such as pH, current, catalyst concentration and initial contaminant concentration are reviewed to find optimal operating conditions. The relationship between electro-Fenton regeneration and the chemical and physical surface of the carbon is also explored. Understanding regeneration mechanisms and the optimal operating conditions enables these technologies to be used commercially and to be scaled-up and treat contaminated waters more efficiently.

Assessment of the electro-Fenton pathway for the removal of naphthalene from contaminated waters in remote regions.

This work investigates the effectiveness of the electro-Fenton reaction for the treatment of wastewaters contaminated with petroleum hydrocarbons. More specific attention was given to field deployment applications in remote regions, such as the sub-Antarctic, where there is a need for low-cost technologies that can aid in remediation efforts. Naphthalene, a high priority pollutant for removal within these regions, was chosen as a model contaminant and treated with inexpensive graphite electrodes to promote the electro-Fenton pathway. Results show that naphthalene can be fully removed from a near-saturated solution, 20 mg/L, in less than 3 h of treatment. The underlying removal mechanisms were identified, and a kinetic model is presented that can accurately predict treatment outcomes at varying operating conditions of applied electric currents, 0-5 mA, and iron(II) concentrations, 0-2.0 mM. Optimal operating conditions for the electro-Fenton pathway were found to be at an applied current of 5 mA and an iron(II) concentration of 0.06 mM; this resulted in a specific energy consumption of 5.6 kWhr/kg of naphthalene removed, low enough to be operated in remote regions via sustainable energy sources.

Electrochemical removal of naphthalene from contaminated waters using carbon electrodes, and viability for environmental deployment.

This work assesses the potential of electrochemical technologies for the treatment of groundwaters contaminated with petroleum hydrocarbons. Specific consideration was given to deployment in Antarctic regions where numerous fuel spills have occurred over the last two centuries, and resources and manual labour for remediation efforts are limited. The polycyclic aromatic hydrocarbon, naphthalene, was a used as a model contaminant and was treated with low-cost, active carbon electrodes to promote the active chlorine degradation pathway. Results showed that 20 mg/L naphthalene solutions could be treated to sufficient standards in less than 3 h of treatment, and that the formation of toxic and chlorinated by-products is not an issue of concern if the appropriate timeframes are used (4 h of treatment). The effects of the applied current (0-160 mA) and electrolyte concentration (0.01-0.1 M NaCl) were evaluated and a dynamic kinetic model proposed and found to be in good agreement with the experimental results. The energy consumption is an important limitation in remote environmental regions where resources are scarce. It was found that an energy usage of 104 kW h/kg of naphthalene removed could be achieved.

Data in brief on CO2 absorption-desorption of aqueous-based amino acid solvents with phase change behaviour.

The data presented in this paper are related to the published research article "Development of aqueous-based phase change amino acid solvents for energy-efficient CO2 capture: The role of antisolvent" [1]. The raw and analyzed data include the equilibrium and kinetics of CO2 absorption, the density and concentration of different CO2-containing species at upper and lower liquid phases, and particle size distribution of solid particles precipitated during CO2 absorption of aqueous and aqueous-based amino acid solvents. In addition, the SEM images of solid precipitates at the end of CO2 absorption are presented. The detailed values of this phase change amino acid solvent are crucial for large-scale implementation of CO2 capture systems with phase change behavior.

The electrochemical regeneration of granular activated carbons: A review.

The electrochemical treatment of exhausted granular activated carbon (GAC) has been identified as an effective alternative to traditional adsorbent regeneration methods (e.g. thermal, chemical, and microbial). However, despite its proven potential and initial investigation over two decades ago, the development of this technology has been progressing slowly, hindering its deployment in industrial applications. Thus, a review has been conducted that aims to present the fundamentals of GAC electrochemical regenerative methods, what research has been conducted to develop the technology to the present day, and lastly, identify limitations and future prospects associated with electrochemical methods. The regenerative mechanism is firstly discussed, followed by a presentation of the varying reactor configurations and operating parameters utilized during the electrochemical treatment of GAC materials exhausted with a broad range of wastewater contaminants. Finally, emerging electrochemical technologies used for the commercial treatment of exhausted adsorbent materials and contaminated soils are discussed.

Liquid marble formation and solvent vapor treatment of the biodegradable polymers polylactic acid and polycaprolactone.

Liquid Marbles were produced by rolling aqueous droplets on a powder bed of biodegradable polymers, namely polylactic acid (PLA), polycaprolactone (PCL) and blends of these. Solvent vapor treatment was subsequently applied with dichloromethane (DCM). This treatment aligned the polymer chains in order to form a smooth polymeric shell with enhanced mechanical and barrier properties. Whilst a wide range of potential applications for Liquid Marbles exists, the aim here is to encapsulate a solution containing a fertilizer, i.e. urea to produce a controlled release fertilizer. The influences of droplet volume, polymer particle size and solvent vapor treatment time on the liquid marble properties were investigated. Crystallinity and thermal properties were analyzed by differential scanning calorimetry (DSC), surface characteristics and shell thickness by scanning electron microscopy (SEM), mechanical strength and elasticity by compression tests and evaporation rates by thermogravimetric analysis (TGA).

From urban municipalities to polar bioremediation: the characterisation and contribution of biogenic minerals for water treatment.

Minerals of biological origin have shown significant potential for the separation of contaminants from water worldwide. This study details the contribution of biologically derived minerals to water treatment operations, with a focus on filtration media from urban municipalities and remote cold regions. The results support biofilm-embedded iron and manganese to be the building blocks of biogenic mineral development on activated carbon and nutrient-amended zeolites. The presence of similar iron and manganese oxidising bacterial species across all filter media supports the analogous morphologies of biogenic minerals between sites and suggests that biological water treatment processes may be feasible across a range of climates. This is the first time the stages of biogenic mineral formation have been aligned with comprehensive imaging of the biofilm community and bacterial identification; especially with respect to cold regions. Where biogenic mineral formation occurs on filter media, the potential exists for enhanced adsorption for a range of organic and inorganic contaminants and improved longevity of filter media beyond the adsorption or exchange capacities of the raw material.

Permeable bio-reactive barriers to address petroleum hydrocarbon contamination at subantarctic Macquarie Island.

A reliance on diesel generated power and a history of imperfect fuel management have created a legacy of petroleum hydrocarbon contamination at subantarctic Macquarie Island. Increasing environmental awareness and advances in contaminant characterisation and remediation technology have fostered an impetus to reduce the environmental risk associated with legacy sites. A funnel and gate permeable bio-reactive barrier (PRB) was installed in 2014 to address the migration of Special Antarctic Blend diesel from a spill that occurred in 2002, as well as older spills and residual contaminants in the soil at the Main Power House. The PRB gate comprised of granular activated carbon and natural clinoptilolite zeolite. Petroleum hydrocarbons migrating in the soil water were successfully captured on the reactive materials, with concentrations at the outflow of the barrier recorded as being below reporting limits. The nutrient and iron concentrations delivered to the barrier demonstrated high temporal variability with significant iron precipitation observed across the bed. The surface of the granular activated carbon was largely free from cell attachment while natural zeolite demonstrated patchy biofilm formation after 15 months following PRB installation. This study illustrates the importance of informed material selection at field scale to ensure that adsorption and biodegradation processes are utilised to manage the environmental risk associated with petroleum hydrocarbon spills. This study reports the first installation of a permeable bio-reactive barrier in the subantarctic.

The performance of ammonium exchanged zeolite for the biodegradation of petroleum hydrocarbons migrating in soil water.

Nitrogen deficiency has been identified as the main inhibiting factor for biodegradation of petroleum hydrocarbons in low nutrient environments. This study examines the performance of ammonium exchanged zeolite to enhance biodegradation of petroleum hydrocarbons migrating in soil water within laboratory scale flow cells. Biofilm formation and biodegradation were accelerated by the exchange of cations in soil water with ammonium in the pores of the exchanged zeolite when compared with natural zeolite flow cells. These results have implications for sequenced permeable reactive barrier design and the longevity of media performance within such barriers at petroleum hydrocarbon contaminated sites deficient in essential soil nutrients.

Application of controlled nutrient release to permeable reactive barriers.

The application of controlled release nutrient (CRN) materials to permeable reactive barriers to promote biodegradation of petroleum hydrocarbons in groundwater was investigated. The longevity of release, influence of flow velocity and petroleum hydrocarbon concentration on nutrient release was assessed using soluble and ion exchange CRN materials; namely Polyon™ and Zeopro™. Both CRN materials, assessed at 4 °C and 23 °C, demonstrated continuing release of nitrogen, phosphorus and potassium (N-P-K) at 3500 bed volumes passing, with longer timeframes of N-P-K release at 4 °C. Zeopro™-activated carbon mixtures demonstrated depletion of N-P-K prior to 3500 bed volumes passing. Increased flow velocity was shown to lower nutrient concentrations in Polyon™ flow cells while nutrient release from Zeopro™ was largely unchanged. The presence of petroleum hydrocarbons, at 1.08 mmol/L and 3.25 mmol/L toluene, were not shown to alter nutrient release from Polyon™ and Zeopro™ across 14 days. These findings suggest that Polyon™ and Zeopro™ may be suitable CRN materials for application to PRBs in low nutrient environments.

A permeable reactive barrier (PRB) media sequence for the remediation of heavy metal and hydrocarbon contaminated water: A field assessment at Casey Station, Antarctica.

A field trial was conducted at Casey Station, Antarctica to assess the suitability of a permeable reactive barrier (PRB) media sequence for the remediation of sites containing both hydrocarbon and heavy metal contamination. An existing PRB was modified to assess a sequence consisting of three sections: (i) Nutrient release/hydrocarbon sorption using ZeoPro™ and granular activated carbon; (ii) Phosphorus and heavy metal capture by granular iron and sand; (iii) Nutrient and excess iron capture by zeolite. The media sequence achieved a greater phosphorus removal capacity than previous Antarctic PRB configurations installed on site. Phosphorus concentrations were reduced during flow through the iron/sand section and iron concentrations were reduced within the zeolite section. However, non-ideal flow was detected during a tracer test and supported by analysis of media and liquid samples from the second summer of operation. Results indicate that the PRB media sequence trialled might be appropriate for other locations, especially less environmentally challenging contaminated sites.

The specific reactive surface area of granular zero-valent iron in metal contaminant removal: Column experiments and modelling.

A series of dynamic-flow kinetic experiments were conducted to assess the removal rates of aqueous Cu(2+) and Zn(2+) ions by zero-valent iron (ZVI), a promising material for inclusion in cold-climate remediation applications. The influence of experimental parameters on contaminant removal rates, including aqueous flow rate, operating temperature, and the concentrations of ZVI, salt and dissolved oxygen, was investigated. A mass transport model has been developed that accounts (i) aqueous-phase dispersion processes, (ii) film diffusion of contaminant ions to the reactive ZVI surface and (iii) the reactive removal mechanism itself. Regression to the experimental data indicated that when oxygen is present in the solution feed Cu(2+) and Zn(2+) removal processes were limited by film diffusion. In de-aerated solutions film diffusion still controls Cu(2+) removal but a first-order surface reaction provides a better model for Zn(2+) kinetics. Using air as the equilibrium feed gas, the reactive proportion of the total surface area for contaminant removal was calculated to be 97% and 64% of the active spherically-assumed geometric area associated with ZVI media for Cu(2+) and Zn(2+), respectively. Relative to a gas absorption area, determined in previous studies, the reactive proportion is less than 0.41% of the unreacted ZVI total surface area. These findings suggest that only part of the iron oxyhydroxide surface is reacting during ZVI based metal contaminant removal.