Bimetallic Copper-Cerium-Based Metal-Organic Frameworks for Selective Carbon Dioxide Capture.

Metal-organic frameworks (MOFs) are highly regarded as valuable adsorbent materials in materials science, particularly in the field of CO2 capture. While numerous single-metal-based MOFs have demonstrated exceptional CO2 adsorption capabilities, recent advancements have explored the potential of bimetallic MOFs for enhanced performance. In this study, a CuCe-BTC MOF was synthesized through a straightforward hydrothermal method, and its improved properties, such as high surface area, smaller pore size, and larger pore volume, were compared with those of the bare Ce-BTC. The impact of the Cu/Ce ratio (1:4, 1:2, 1:1, and 3:2) was systematically investigated to understand how adding a second metal influences the CO2 adsorption performance of the Ce-BTC MOF. Various characterization techniques, including scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and N2 BET surface area analysis, were employed to assess the physical and chemical properties of the bare Ce-BTC and CuCe-BTC samples. Notably, CuCe-BTC-1:2 exhibited superior surface area (133 m2 g-1), small pore size (3.3 nm), and large pore volume (0.14 cm3 g-1) compared to the monometallic Ce-BTC. Furthermore, CuCe-BTC-1:2 demonstrated a superior CO2 adsorption capacity (0.74 mmol g-1), long-term stability, and good CO2/N2 selectivity. This research provides valuable insights into the design of metal-BTC frameworks and elucidates how introducing a second metal enhances the properties of the monometallic Ce-BTC-MOF, leading to improved CO2 capture performance.

Mercury-bearing wastes: Sources, policies and treatment technologies for mercury recovery and safe disposal.

Due to the lenient environmental policies in developing economies, mercury-containing wastes are partly produced as a result of the employment of mercury in manufacturing and consumer products. Worldwide, the presence of mercury as an impurity in several industrial processes leads to significant amounts of contaminated waste. The Minamata Convention on Mercury dictates that mercury-containing wastes should be handled in an environmentally sound way according to the Basel Convention Technical Guidelines. Nevertheless, the management policies differ a great deal from one country to another because only a few deploy or can afford to deploy the required technology and facilities. In general, elemental mercury and mercury-bearing wastes should be stabilized and solidified before they are disposed of or permanently stored in specially engineered landfills and facilities, respectively. Prior to physicochemical treatment and depending on mercury's concentration, the contaminated waste may be thermally or chemically processed to reduce mercury's content to an acceptable level. The suitability of the treated waste for final disposal is then assessed by the application of standard leaching tests whose capacity to evaluate its long-term behavior is rather questionable. This review critically discusses the main methods employed for the recovery of mercury and the treatment of contaminated waste by analyzing representative examples from the industry. Furthermore, it gives a complete overview of all relevant issues by presenting the sources of mercury-bearing wastes, explaining the problems associated with the operation of conventional discharging facilities and providing an insight of the disposal policies adopted in selected geographical regions.

CeO2-Decorated ?-MnO2 Nanotubes: A Highly Efficient and Regenerable Sorbent for Elemental Mercury Removal from Natural Gas.

CeO2 nanoparticle-decorated ?-MnO2 nanotubes (NTs) were prepared and tested for elemental mercury (Hg0) vapor removal in simulated natural gas mixtures at ambient conditions. The composition which had the largest surface area and a relative Ce/Mn atomic weight ratio of around 35% exhibited a maximum Hg0 uptake capacity exceeding 20 mg?g?1 (2 wt %), as determined from measurements of mercury breakthrough which corresponded to 99.5% Hg0 removal efficiency over 96 h of exposure. This represents a significant improvement in the activity of pure metal oxides. Most importantly, the composite nanosorbent was repeatedly regenerated at 350 ?C and retained the 0.5% Hg0 breakthrough threshold. It was projected to be able to sustain 20 regeneration cycles, with the presence of acid gases, CO2, and H2S, not affecting its performance. This result is particularly important, considering that pure CeO2 manifests rather poor activity for Hg0 removal at ambient conditions, and hence, a synergistic effect in the composite nanomaterial was observed. This possibly results from the addition of facile oxygen vacancy formation at ?-MnO2 NTs and the increased amount of surface-adsorbed oxygen species.

Role of Ceria in the Design of Composite Materials for Elemental Mercury Removal.

The necessity to drastically act against mercury pollution has been emphatically addressed by the United Nations. Coal-fired power plants contribute a great deal to the anthropogenic emissions; therefore, numerous sorbents/catalysts have been developed to remove elemental mercury (Hg0 ) from flue gases. Among them, ceria (CeO2 ) has attracted significant interest, due to its reversible Ce3+ /Ce4+ redox pair, surface-bound defects and acid-base properties. The removal efficiency of Hg0 vapor depends among others, on the flue gas composition and temperature. CeO2 can be incorporated into known materials in such a way that the abatement process can be effective at different operating conditions. Hence, the scope of this account is to discuss the role of CeO2 as a promoter, active phase and support in the design of composite Hg0 sorbents/catalysts. The elucidation of each of these roles would allow the integration of CeO2 advantageous characteristics to such degree, that tailor-made environmental solution to complex issues can be provided within a broader application scope. Besides, it would offer invaluable input to theoretical calculations that could enable the materials screening and engineering at a low cost and with high accuracy.

Mercury in natural gas streams: A review of materials and processes for abatement and remediation.

The role of natural gas in mitigating greenhouse gas emissions and advancing renewable energy resource integration is undoubtedly critical. With the progress of hydrocarbons exploration and production, the target zones become deeper and the possibility of mercury contamination increases. This impacts on the industry from health and safety risks, due to corrosion and contamination of equipment, to catalyst poisoning and toxicity through emissions to the environment. Especially mercury embrittlement, being a significant problem in LNG plants using aluminum cryogenic heat exchangers, has led to catastrophic plant incidents worldwide. The aim of this review is to critically discuss the conventional and alternative materials as well as the processes employed for mercury removal during gas processing. Moreover, comments on studies examining the geological occurrence of mercury species are included, the latest developments regarding the detection, sampling and measurement are presented and updated information with respect to mercury speciation and solubility is displayed. Clean up and passivation techniques as well as disposal methods for mercury-containing waste are also explained. Most importantly, the environmental as well as the health and safety implications are addressed, and areas that require further research are pinpointed.