Designing materials for electrochemical carbon dioxide recycling

Electrochemical carbon dioxide recycling provides an attractive approach to synthesizing fuels and chemical feedstocks using renewable energy. On the path to deploying this technology, basic and applied scientific hurdles remain. Integrating catalytic design with mechanistic understanding yields scientific insights and progresses the technology towards industrial relevance. Catalysts must be able to generate valuable carbon-based products with better selectivity, lower overpotentials and improved current densities with extended operation. Here, we describe progress and identify mechanistic questions and performance metrics for catalysts that can enable carbon-neutral renewable energy storage and utilization

Microstructure and carbon storage capacity of hydrated magnesium carbonates synthesized from different sources and conditions

Recently, the mineral carbonation via the reaction of CO2 with saline aquafers received much attention as one of the most promising ways for geologic CO2 storage. This paper reports microstructure and carbon storage capacity of hydrated magnesium carbonates (HMCs) synthesized from different sources, i.e., reject brine and commercial Mg(OH)2 slurry, and under different conditions, i.e., pH (8–14) and Mg(OH)2:CO2 molar ratio (1:1–1:7). Results show that dypingite (Mg5(CO3)4(OH)2·5H2O) is the main phase forming at lower Mg(OH)2:CO2 ratios. An increase in the Mg(OH)2:CO2 ratio and/or pH leads to the precipitation of nesquehonite (MgCO3·3H2O). A unique “house of cards” texture, involving formation of the rosette-like dypingite flakes on the surface of nesquehonite needles, is discovered under elevated pH and Mg(OH)2:CO2 ratios. HMCs synthesized from reject brine exhibit a much higher carbon storage capacity of 82.6% than that produced from the commercial Mg(OH)2 slurry (43.7%). Findings from this study advance understanding of mineral recovery from reject brine and the capture and long-term storage of CO2 in the form of HMCs

Investigation of the properties of MgO recovered from reject brine obtained from desalination plants

In addition to its use in various applications such as those in the agriculture, pharmaceutical and refractory industries, MgO is being investigated as a cement binder due to the low calcination temperatures used during its production and its ability to gain strength by absorbing CO2in construction products. Similar to the dry-route, the reactivity of MgO synthesized from waste water or reject brine via the calcination of the precipitated Mg(OH)2depends on the calcination conditions. This study investigated the influence of two bases, namely ammonia solution (NH4OH) and sodium hydroxide (NaOH), on the properties of Mg(OH)2precipitated and consequently the characteristics of MgO produced under different calcination conditions. The energy consumption of the production of reactive MgO from reject brine via the addition of NH4OH and NaOH was also reported and compared with the industrial production routes to assess the sustainability of the production procedure. The final products were characterized in terms of their specific surface area (SSA) and microstructure. Results indicated that Mg(OH)2synthesized via the addition of NH4OH into reject brine generated a more porous, flake-like morphology than those obtained via the use of NaOH. The SSA and reactivity of NH4OH-based MgO demonstrated a sharper decrease with increasing temperature and duration compared to NaOH-based MgO. Out of all samples, NH4OH-based MgO calcined at 500 °C for 2 h revealed the highest reactivity (SSA of 78.8 m2/g), which was higher than NaOH-based MgO (SSA of 51.4 m2/g)

Effectiveness of preoperative planning in the restoration of balance and view in ankylosing spondylitis

Object. The object of this study was to assess the effectiveness of preoperative planning in the restoration of balance and view angle in patients treated with lumbar osteotomy in ankylosing spondylitis (AS). Methods. The authors prospectively analyzed 8 patients with a thoracolumbar kyphotic deformity due to AS that was treated using a closing wedge osteotomy (CWO) of the lumbar spine to correct sagittal imbalance and horizontal view. Preoperative planning to predict postoperative balance, defined by the sagittal vertical axis (SVA) and the sacral endplate angle (SEA), and the view angle, defined by the chin-brow to vertical angle (CBVA), was performed using the ASKyphoptan computational program. Results. All patients were treated with a CWO at level L-4 and improved in balance and view angle. The mean correction angle was 35° (range 24-47°). The postoperative SEA improved from 21 to 36° for a mean correction of 15°. In addition, the SVA and CBVA improved significantly. Note, however, that the postoperative results did not exactly reflect the predicted values of the analyzed parameters. Conclusions. Preoperative planning for the restoration of balance and view angle in AS improves understanding of the biomechanical and clinical effects of a correction osteotomy of the lumbar spine. The adaptation of basic clinical and biomechanical principles to restore balance is advised in such a way that the individual SEA is corrected by 15° (maximum 40°) in relation to the horizon and C-7 is balanced exactly above the posterosuperior corner of the sacrum

Sulfur-Modulated Tin Sites Enable Highly Selective Electrochemical Reduction of CO2 to Formate

Electrochemical reduction of carbon dioxide (CO2RR) to formate provides an avenue to the synthesis of value-added carbon-based fuels and feedstocks powered using renewable electricity. Here, we hypothesized that the presence of sulfur atoms in the catalyst surface could promote undercoordinated sites, and thereby improve the electrochemical reduction of CO2 to formate. We explored, using density functional theory, how the incorporation of sulfur into tin may favor formate generation. We used atomic layer deposition of SnSx followed by a reduction process to synthesize sulfur-modulated tin (Sn(S)) catalysts. X-ray absorption near-edge structure (XANES) studies reveal higher oxidation states in Sn(S) compared with that of tin in Sn nanoparticles. Sn(S)/Au accelerates CO2RR at geometric current densities of 55 mA cm−2 at −0.75 V versus reversible hydrogen electrode with a Faradaic efficiency of 93%. Furthermore, Sn(S) catalysts show excellent stability without deactivation (<2% productivity change) following more than 40 hours of operation. With rapid advances in the efficient and cost-effective conversion of sunlight to electrical power, the development of storage technologies for renewable energy is even more urgent. Using renewable electricity to convert CO2 into formate simultaneously addresses the need for storage of intermittent renewable energy sources and the need to reduce greenhouse gas emissions. We report an increase of greater than 4-fold in the current density (hence the rate of reaction) in formate electrosynthesis compared with relevant controls. Our catalysts also show excellent stability without deactivation (<2% productivity change) following more than 40 hours of operation. The electrochemical reduction of carbon dioxide (CO2RR) offers a compelling route to energy storage and high-value chemical manufacture. The presence of sulfur atoms in catalyst surfaces promotes undercoordinated sites, thereby improving the electrochemical reduction of CO2 to formate. The resulting sulfur-modulated tin catalysts accelerate CO2RR at geometric current densities of 55 mA cm−2 at −0.75 V versus RHE with a Faradaic efficiency of 93%

Deformation of the Fermi surface in the extended Hubbard model

The deformation of the Fermi surface induced by Coulomb interactions is investigated in the t-t'-Hubbard model. The interplay of the local U and extended V interactions is analyzed. It is found that exchange interactions V enhance small anisotropies producing deformations of the Fermi surface which break the point group symmetry of the square lattice at the Van Hove filling. This Pomeranchuck instability competes with ferromagnetism and is suppressed at a critical value of U(V). The interaction V renormalizes the t' parameter to smaller values what favours nesting. It also induces changes on the topology of the Fermi surface which can go from hole to electron-like what may explain recent ARPES experiments.Comment: 5 pages, 4 ps figure

Recovery of reactive MgO from reject brine via the addition of NaOH

© 2017 Elsevier B.V. Reject brine, generated as a waste at the end of the desalination process, presents a useful source for the extraction of valuable resources. This study investigated the recovery of reactive MgO from reject brine obtained from a local desalination plant. This was enabled via the reaction of Mg2 + present within reject brine with an alkali source (NaOH), which led to the precipitation of Mg(OH)2, along with a small amount of CaCO3. The determination of the optimum NaOH/Mg2 + ratio led to the production of the highest amount of yield. The synthesized Mg(OH)2 was further calcined under a range of temperatures (500–700 °C) and durations (2 − 12h) to produce reactive MgO. A detailed characterization of MgO obtained under these conditions was presented in terms of its reactivity, specific surface area (SSA), composition and microstructure. While an increase in the calcination temperature and duration decreased the reactivity and SSA of MgO, samples calcined at 500 °C for 2 h revealed the highest reactivity, which was reflected by their SSA of 51.4 m2/g.This project is funded by the National Research Foundation (NRF), Prime Minister's Office, Singapore under its Campus for Research Excellence and Technological Enterprise (CREATE) program

Synthesis of reactive MgO from reject brine via the addition of NH4_{4}OH

Reactive magnesia (MgO) with a high purity and reactivity is used in several high-end applications. This study reports the feasibility of synthesizing high reactivity MgO from reject brine with the use of NH$_{4}$OH. The molar amount of NH$_{4}$OH was optimized at a NH$_{4}$OH/Mg$^{2 +}$ molar ratio of 6 to provide maximum magnesium oxide yield and purity. This led to the synthesis of Mg(OH)$_{2}$ with a purity of 93.5%, which was further calcined at 500 °C for 2 h to produce reactive MgO with a SSA of 78.8 m2/g. This study shed light on the significant potential of reject brine in the recovery of Mg$^{2 +}$ and the synthesis of reactive MgO with a wide range of potential applications.The authors would like to acknowledge research scholarship from Energy Research Institute at Nanyang Technological University