Electrochemically mediated amine regeneration (EMAR) was recently developed to avoid the use of thermal means to release CO2 captured from postcombustion flue gas in the benchmark amine process. To address concerns related to the high vapor pressure of ethylenediamine (EDA) as the primary amine used in EMAR, a mixture of EDA and aminoethylethanolamine (AEEA) was investigated. The properties of the mixed amine systems, including the absorption rates, electrolyte pH and conductivity, and CO2 capacity, were evaluated in comparison with those of solely EDA. The mixed amine system had similar properties to that of EDA, indicating no significant changes would be necessary for the future implementation of the EMAR process with mixed amines as opposed to that with just EDA. The electrochemical performance of the mixed amines in terms of the cell voltage, gas desorption rate, electron utilization, and energetics was also investigated. A 50/50 mixture of EDA and AEEA displayed the lowest energetics: ∼10% lower than that of 100% EDA. With this mixture, a continuous EMAR process, in which the absorption column was connected to the electrochemical cell as the desorption stage, was tested over 100 h. The cell voltage was very stable and there was a steady gas output close to theoretical values. The desorbed gas was further analyzed and found to be 100% CO2, confirming no evaporation of the amine. The mixed absorbent composition was also characterized using titration and nuclear magnetic resonance (NMR) spectroscopy, and the results showed no amine degradation. These findings that demonstrate a stable, low vapor pressure absorbent with improved energetics are promising and could be a guideline for the future development of EMAR for CO2 capture from flue gas and other sources.
For the effective reduction of global CO2 emissions, it is essential to develop and deploy efficient and cost-effective technologies for CO2 capture, especially from large point sources. We recently developed an electrochemically mediated amine regeneration (EMAR) system to replace traditional thermal desorption for the capture of CO2 from post-combustion flue gases. Despite EMAR effectiveness on a laboratory scale, concerns regarding the high gas-to-liquid ratio in the electrochemical cell and long-term instability of the electrodes need to be addressed before further scale-up of the process to a pilot plant and beyond can be entertained. Accordingly, we investigated the effect of using sodium dodecyl sulfate (SDS) as an anionic surfactant and dodecyltrimethylammonium bromide (DTAB) as a cationic surfactant on the process operation. It was found that it is advantageous to use an anionic surfactant for a system such as EMAR that contains hydrophilic electrodes and a positively charged electrochemically active species. The overall cell resistance was notably reduced when SDS anionic surfactant was used. The precipitation of copper particles observed in the anode outlet when no surfactant was used was effectively avoided when SDS was added to the electrolyte, resulting in electrode stability. In addition, smaller gas bubbles were produced in the presence of the SDS surfactant, which resulted in less blockage of the electrode by the gas with a resultant lower cell potential under constant current conditions, driving more efficient CO2 desorption. This led to an approximate 25% reduction in the electrochemical energy requirement, the lowest ever achieved experimentally for the EMAR process. Overall, the addition of a very low concentration of SDS resulted in the successful circumvention of the important problems faced by the EMAR system regarding further scale-up.
The development of sustainable CO2 capture technologies is critical to address issues associated with global warming. In this context, the concept of an electrochemically driven proton concentration process is developed for the capture of CO2 based on modulation of the proton concentration in an electrochemical cell by a proton intercalating MnO2 electrode. The pH sensitivity of CO2 hydration is leveraged such that CO2 is absorbed as bicarbonate and carbonate ions at high pH values and desorbed as gas at low pH values. The electrochemical work requirement for the proposed proton concentration process to desorb CO2 captured from a flue gas stream is estimated to be 33.2 kJe/mol CO2, suggesting that this process is competitive with other similar electrochemical-based approaches. The experimental results show that the generated current in a symmetrical electrochemical cell with fabricated electrodes is effectively translated into proton intercalation/deintercalation reactions through reversible cycles, resulting in modulated proton concentrations.
A thorough experimental investigation of a bench-scale apparatus of the proton concentration process with two symmetrical MnO2 electrodes is presented, with the aim of continuous desorption of CO2 from a K2CO3 solution. The electrodes were fabricated through cathodic deposition, and their chemical states, morphology, and microstructural architecture were characterized with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Successful formation of MnO2 film was confirmed by XPS analysis, and the SEM images showed a uniform distribution of the film across the carbon substrate surface and along the strand, with an average thickness of ∼500 nm, thus making proton ion diffusion possible. Continuous and efficient desorption of CO2 from a K2CO3 solution was obtained when electrodeposited MnO2 electrodes were used in a flow-based proton concentration process. The amount of CO2 desorbed per area of the electrode was 12-fold higher than that of a similar system. The electrochemical nature of the proton concentration process offers substantial practical advantages for the future, especially if electricity can be sustainably produced from renewable sources.
In this Opinion, the importance of public awareness to design solutions to mitigate climate change issues is highlighted. A large-scale acknowledgment of the climate change consequences has great potential to build social momentum. Momentum, in turn, builds motivation and demand, which can be leveraged to develop a multi-scale strategy to tackle the issue. The pursuit of public awareness is a valuable addition to the scientific approach to addressing climate change issues. The Opinion is concluded by providing strategies on how to effectively raise public awareness on climate change-related topics through an integrated, well-connected network of mavens (e.g., scientists) and connectors (e.g., social media influencers).
The electrochemically-mediated amine regeneration (EMAR) process uses electrons to modulate amine capacity to achieve CO2 separation from flue gas as an alternative to the traditional thermal regeneration process for CO2 capture. The EMAR separation scheme is validated in a batch system designed to evaluate efficiency losses. Current and voltage responses of the electrochemical process were analyzed in a flow system operated continuously for up to 50 h. An isothermal EMAR system can achieve separation efficiencies above 80% from a 15% CO2 feed, which is representative of the CO2 composition in a flue gas. This bench scale continuous system can operate at 40–80 kJe/molCO2 with an amine regeneration of between 0.12 and 0.62 molCO2/molamine. The ability to separate CO2 at high electron utilization and moderate electrical energy consumption will prompt future research into optimization of the electrochemical separation unit to obtain long-term and stable operations for flue gas scrubbing.
Low-grade heat from geothermal sources and industrial plants is a significant source of sustainable power that has great potential to be converted to electricity. The two main approaches that have been extensively investigated for converting low-grade heat to electrical energy, organic Rankine cycles and solid-state thermoelectrics, have not produced high power densities or been cost-effective for such applications. Newer, alternative liquid-based technologies are being developed that can be categorized by how the heat is used. Thermoelectrochemical cells (TECs), thermo-osmotic energy conversion (TOEC) systems, and thermally regenerative electrochemical cycles (TRECs) all use low-grade heat directly in a device that generates electricity. Other systems use heat sources to prepare solutions that are used in separate devices to produce electrical power. For example, low-temperature distillation methods can be used to produce solutions with large salinity differences to generate power using membrane-based systems, such as pressure-retarded osmosis (PRO) or reverse electrodialysis (RED); or highly concentrated ammonia solutions can be prepared for use in thermally regenerative batteries (TRBs). Among all these technologies, TRECs, TOEC, and TRBs show the most promise for effectively converting low-grade heat into electrical power mainly due to their high power productions and energy conversion efficiencies.
Thermally regenerative ammonia batteries (TRABs) have shown great promise as a method to convert low-grade waste heat into electrical power, with power densities an order of magnitude higher than other approaches. However, previous TRABs based on copper electrodes suffered from unbalanced anode dissolution and cathode deposition rates during discharging cycles, limiting practical applications. To produce a TRAB with stable and reversible electrode reactions over many cycles, inert carbon electrodes were used with silver salts. In continuous flow tests, power production was stable over 100 discharging cycles, demonstrating excellent reversibility. Power densities were 23 W m−2-electrode area in batch tests, which was 64% higher than that produced in parallel tests using copper electrodes, and 30 W m−2 (net energy density of 490 Wh m−3-anolyte) in continuous flow tests. While this battery requires the use a precious metal, an initial economic analysis of the system showed that the cost of the materials relative to energy production was $220 per MWh, which is competitive with energy production from other non-fossil fuel sources. A substantial reduction in costs could be obtained by developing less expensive anion exchange membranes.
Thermally regenerative ammonia-based batteries (TRABs) have been developed to harvest low-grade waste heat as electricity. To improve the power production and anodic coulombic efficiency, the use of ethylenediamine as an alternative ligand to ammonia was explored here. The power density of the ethylenediamine-based battery (TRENB) was 85 ± 3 W m−2-electrode area with 2 M ethylenediamine, and 119 ± 4 W m−2 with 3 M ethylenediamine. This power density was 68% higher than that of TRAB. The energy density was 478 Wh m−3-anolyte, which was ∼50% higher than that produced by TRAB. The anodic coulombic efficiency of the TRENB was 77 ± 2%, which was more than twice that obtained using ammonia in a TRAB (35%). The higher anodic efficiency reduced the difference between the anode dissolution and cathode deposition rates, resulting in a process more suitable for closed loop operation. The thermal-electric efficiency based on ethylenediamine separation using waste heat was estimated to be 0.52%, which was lower than that of TRAB (0.86%), mainly due to the more complex separation process. However, this energy recovery could likely be improved through optimization of the ethylenediamine separation process.
Thermally regenerative ammonia-based batteries (TRABs) can be used to harvest low-grade waste heat as electrical power. To improve TRAB performance, a series of benzyltrimethyl quaternary ammonium-functionalized poly(phenylene oxide) anion exchange membranes (BTMA-AEMs) were examined for their impact on performance relative to a commercial AEM (Selemion AMV). The synthesized AEMs had different degrees of functionalization (DF; 25% and 40%), and thicknesses (50, 100 and 150 μm). Power and energy densities were shown to be a function of both DF and membrane thickness. The power density of TRAB increased by 31% using a BTMA-AEM (40% DF, 50 μm thick; 106 ± 7 W m−2) compared to the Selemion (81 ± 5 W m−2). Moreover, the energy density increased by 13% when using a BTMA-based membrane (25% DF, 150 μm thick; 350 Wh m−3) compared to the Selemion membrane (311 Wh m−3). The thermal-electric conversion efficiency improved to 0.97% with the new membrane compared to 0.86% for the Selemion. This energy recovery was 7.0% relative to the Carnot efficiency, which was 1.8 times greater than the highest previously reported value of a system used to capture low-grade waste heat as electricity.
A thermally regenerative ammonia battery (TRAB) recently developed for electricity generation using waste heat was adapted and used here as a treatment process for solutions containing high concentrations of copper ions. Copper removal reached a maximum of 77% at an initial copper concentration (Ci) of 0.05 M, with a maximum power density (P) of 31 W m−2-electrode area. Lowering the initial copper concentration decreased the percentage of copper removal from 51% (Ci = 0.01 M, P = 13 W m−2) to 2% (Ci = 0.002 M, P = 2 W m−2). Although the final solution may require additional treatment, the adapted TRAB process removed much of the copper while producing electrical power that could be used in later treatment stages. These results show that the adapted TRAB can be a promising technology for removing copper ions and producing electricity by using waste heat as a highly available and free source of energy at many industrial sites.
Salinity gradient energy can be directly converted to electrical power using reverse electrodialysis (RED) and other technologies, but reported power densities have been too low for practical applications. Here, the RED stack performance was improved by using 2,6-dihydroxyanthraquinone and ferrocyanide as redox couples. These electrolytes were then used in a flow battery, to produce an integrated RED stack and flow battery (RED-FB) system capable of capturing, storing, and discharging salinity gradient energy. Energy captured from the RED stack was discharged in the flow battery at a maximum power density of 3.0 kW/m2-anode, which was similar to the flow batteries charged by electrical power and could be used for practical application. Salinity gradient energy captured from the RED stack was recovered from the electrolytes as electricity with a 30% efficiency, and the maximum energy density of the system was 2.4 kWh/m3-anolyte. The combined RED-FB system overcomes many limitations of previous approaches to capture, store, and use salinity gradient energy from natural or engineered sources.
In this study, for the first time a statistical analysis based on the response surface methodology (RSM) was employed to investigate individual and interaction effects of key operating parameters of the photocatalytic degradation under visible-light irradiation using Ag-S/PEG/TiO2. Ag-S/PEG/TiO2 is a visible-light-driven photocatalyst and was synthesized (based on earlier research) by co-doping of TiO2 with silver and sulphur and addition of polyethylene glycol (as a reagent template). In addition, the model pollutant was methylene orange (MO) and the studied operating parameters included the photocatalyst loading, initial concentration of the pollutant, and pH of the solution. The statistics-based experimental design and RSM was utilized to find a quadratic model as a functional relationship between the degradation efficiency and the three operating parameters. The regression analysis with R2 value of 0.9678 showed a close fit between the model prediction and experimental data of the degradation efficiency. The analysis of variance based on the model indicated that pH of the solution was the most influential factor, while the two other operating parameters were also significant. The efficiency of MO degradation reached 94.0% under the optimum conditions (i.e. photocatalyst loading of 1.20 g/L, MO concentration of 5 mg/L, and pH of 2).
Salinity-gradient energy (SGE) technologies produce carbon-neutral and renewable electricity from salinity differences between seawater and freshwater. Capacitive mixing (CapMix) is a promising class of SGE technologies that captures energy using capacitive or battery electrodes, but CapMix devices have produced relatively low power densities and often require expensive materials. Here, we combined existing CapMix approaches to develop a concentration flow cell that can overcome these limitations. In this system, two identical battery (i.e., faradaic) electrodes composed of copper hexacyanoferrate (CuHCF) were simultaneously exposed to either high (0.513 M) or low (0.017 M) concentration NaCl solutions in channels separated by a filtration membrane. The average power density produced was 411 ± 14 mW m–2 (normalized to membrane area), which was twice as high as previously reported values for CapMix devices. Power production was continuous (i.e., it did not require a charging period and did not vary during each step of a cycle) and was stable for 20 cycles of switching the solutions in each channel. The concentration flow cell only used inexpensive materials and did not require ion-selective membranes or precious metals. The results demonstrate that the concentration flow cell is a promising approach for efficiently harvesting energy from salinity differences.
Mixing entropy batteries (MEBs) are a new approach to generate electricity from salinity differences between two aqueous solutions. To date, MEBs have only been prepared from solutions containing chloride salts, owing to their relevance in natural salinity gradients created from seawater and freshwater. We hypothesized that MEBs could capture energy using ammonium bicarbonate (AmB), a thermolytic salt that can be used to convert waste heat into salinity gradients. We examined six battery electrode materials. Several of the electrodes were unstable in AmB solutions or failed to produce expected voltages. Of the electrode materials tested, a cell containing a manganese oxide electrode and a metallic lead electrode produced the highest power density (6.3 mW m−2). However, this power density is still low relative to previously reported NaCl-based MEBs and heat recovery systems. This proof-of-concept study demonstrated that MEBs could indeed be used to generate electricity from AmB salinity gradients.
Large amounts of low-grade waste heat (temperatures <130 °C) are released during many industrial, geothermal, and solar-based processes. Using thermally-regenerative ammonia solutions, low-grade thermal energy can be converted to electricity in battery systems. To improve reactor efficiency, a compact, ammonia-based flow battery (AFB) was developed and tested at different solution concentrations, flow rates, cell pairs, and circuit connections. The AFB achieved a maximum power density of 45 W m−2 (15 kW m−3) and an energy density of 1260 Wh manolyte−3, with a thermal energy efficiency of 0.7 % (5 % relative to the Carnot efficiency). The power and energy densities of the AFB were greater than those previously reported for thermoelectrochemical and salinity-gradient technologies, and the voltage or current could be increased using stacked cells. These results demonstrated that an ammonia-based flow battery is a promising technology to convert low-grade thermal energy to electricity.
A new photocatalyst (Ag−S/PEG/TiO2) was synthesized by adding polyethylene glycol (PEG) to an efficient Ag−S/TiO2 photocatalyst, to obtain a photocatalyst that is highly active under visible light. In addition to Ag−S/PEG/TiO2, Ag−S/TiO2 and pure TiO2 were prepared to compare their properties and activities. Specifically, the morphologies and microstructures of the nanophotocatalysts were characterized by means of powder X-ray diffraction (XRD), N2 adsorption−desorption measurements, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) microanalysis, transmission electron microscopy (TEM), UV−visible diffuse reflectance spectroscopy (DRS), photoluminescence (PL) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Moreover, to evaluate their activities, the synthesized powders were used for the degradation of acid orange 7 (AO7) and methylene blue (MB) azo dyes in aqueous solution under low-voltage lightemitting diodes (LEDs) as the visible-light source. It was found that addition of PEG to Ag−S/TiO2 increases the photodegradation of AO7 and MB by about 28.82% and 24.24%, respectively, in comparison with Ag−S/TiO2 without PEG addition.