An investigation of the structural and electronic origins of enhanced chemical looping air separation performance of B-site substituted SrFe1-xCoxO3-δ perovskites.

Chemical looping air separation (CLAS) is a promising process intensification technology for extracting oxygen from air for oxygen enrichment in process streams. Co-doped strontium ferrites (SrFe1-xCoxO3-δ) have been found to have outstanding activities for CLAS processes. In this study, we explore the underlying factors driving the enhancement in oxygen uptake and release performance of perovskite structured SrFe1-xCoxO3-δ oxygen carriers for CLAS. Phase-pure perovskites, with B site substituted by up to 75 mol% Co, were prepared by a sol-gel method and systematically investigated through a wide range of well controlled experimental and computational approaches. While all SrFe1-xCoxO3-δ oxygen carriers showed excellent cyclic stability and structural reversibility over CLAS cycles, increased B site occupancy by Co resulted in monotonic decrease in onset temperature for oxygen release and increase in oxygen carrying capacity. These experimental trends can be fundamentally explained by an increase in the structural tolerance factor, an elevation in transition metal d-band, as well as an increased degree of hybridization between the metal d-band and the O p band. Therefore, these ab initio structural and electronic descriptors are useful design rationales for the hypothesis-driven synthesis of high-performing oxygen carriers for CLAS.

Harnessing Ash for Sustainable CO2 Absorption: Current Strategies and Future Prospects.

This review explores the potential of using different types of ash, namely fly ash, biomass ash, and coal ash etc., as mediums for CO2 capture and sequestration. The diverse origins of these ash types - municipal waste, organic biomass, and coal combustion - impart unique physicochemical properties that influence their suitability and efficiency in CO2 absorption. This review first discusses the environmental and economic implications of using ash wastes, emphasizing the reduction in landfill usage and the transformation of waste into value-added products. Then the chemical/physical treatments of ash wastes and their inherent capabilities in binding or reacting with CO2 are introduced, along with current methodologies utilize these ashes for CO2 sequestration, including mineral carbonation and direct air capture techniques. The application of using ash wastes for CO2 capture are highlighted, followed by the discussion regarding challenges associated with ash-based CO2 absorption approach. Finally, the article projects into the future, proposing innovative approaches and technological advancements needed to enhance the efficacy of ash in combating the increasing CO2 levels. By providing a comprehensive analysis of current strategies and envisioning future prospects, this review aims to contribute to the field of sustainable CO2 absorption and environmental management.

Defect Engineering of Low-Coordinated Metal-Organic Frameworks (MOFs) for Improved CO2 Access and Capture.

While metal-organic frameworks (MOFs) are promising gas adsorbents, their tortuous microporous structures cause additional resistance for gas diffusion, thus hindering the accessibility of interior active sites. Here, we present a practical strategy to incorporate missing cluster defects into a representative low-coordinated MOFs structure, Mg-MOF-74, while maintaining the stability of a defect-rich structure. In this proposed method, graphene oxide (GO) is employed as modulator, and crystallization time is varied to promote defect formation by altering the nucleation and crystal growth processes. The best performing GO-modified Mg-MOF-74 sample (MOF@GO 40 h) achieved 18% and 15% improvement in surface area and total pore volume, respectively, over pristine Mg-MOF-74. The reduced diffusion resistance to gas flow translates to increased accessibility for gas molecules to active Mg adsorption sites inside the MOFs, leading to enhanced CO2 capture performance; the CO2 uptake quantity of MOF@GO 40 h arrives at 6.06 mmol/g at 0.1 bar and at 9.17 mmol/g at 1 bar and 25 °C, 19.29% and 16.37% higher, respectively, than that of the pristine Mg-MOF-74, with a CO2/N2 selectivity around 17.36% greater than that of pristine Mg-MOF-74. Our study demonstrates a facile approach for incorporating defects into MOFs systems with low coordination environments, thus expanding the library of defect-rich MOFs beyond the current highly coordinated MOF systems.

Synthesizing High-Volume Chemicals from CO2 without Direct H2 Input.

Decarbonizing the chemical industry will eventually entail using CO2 as a feedstock for chemical synthesis. However, many chemical syntheses involve CO2 reduction using inputs such as renewable hydrogen. In this review, chemical processes are discussed that use CO2 as an oxidant for upgrading hydrocarbon feedstocks. The captured CO2 is inherently reduced by the hydrocarbon co-reactants without consuming molecular hydrogen or renewable electricity. This CO2 utilization approach can be potentially applied to synthesize eight emission-intensive molecules, including olefins and epoxides. Catalytic systems and reactor concepts are discussed that can overcome practical challenges, such as thermodynamic limitations, over-oxidation, coking, and heat management. Under the best-case scenario, these hydrogen-free CO2 reduction processes have a combined CO2 abatement potential of approximately 1 gigatons per year and avoid the consumption of 1.24 PWh renewable electricity, based on current market demand and supply.