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Carbon capture is one of the essential low-carbon technologies required to achieve societal climate goals at the lowest cost. Covalent organic frameworks (COFs) are promising adsorbents for CO2 capture because of their well-defined porosity, large surface area, and high stability. Current COF-based CO2 capture is mainly based on a physisorption mechanism, exhibiting smooth and reversible sorption isotherms. In the present study, we report unusual CO2 sorption isotherms featuring one or more tunable hysteresis steps with metal ion (Fe3+, Cr3+, or In3+)-doped Schiff-base two-dimensional (2D) COFs (Py-1P, Py-TT, and Py-Py) as adsorbents. Synchrotron X-ray diffraction, spectroscopic and computational studies indicate that the sharp adsorption steps in the isotherm originate from the insertion of CO2 between the metal ion and the N atom of the imine bond on the inner pore surface of the COFs as the CO2 pressure reaches threshold values. As a result, the CO2 adsorption capacity of the ion-doped Py-1P COF is increased by 89.5% compared with that of the undoped Py-1P COF. This CO2 sorption mechanism provides an efficient and straightforward approach to enhancing the CO2 capture capacity of COF– based adsorbents, yielding insights into developing chemistry for CO2 capture and conversion. [ABSTRACT FROM AUTHOR]

This paper investigates the challenging problem of diagnosing novel faults whose fault mechanisms and relevant historical data are not available. Most existing fault diagnosis systems are incapable to explain root causes for unanticipated, novel faults, because they rely on either models or historical data of known faulty conditions. To address this issue we propose a new framework for novel fault diagnosis, which integrates causal reasoning on signed digraph models with multivariate statistical process monitoring. The prerequisites for our approach include historical data of normal process behavior and qualitative cause--effect relationships that can be derived from process flow diagrams. In this new approach, a set of candidate root nodes is identified first via qualitative reasoning on signed digraph; then quantitative local consistency tests are implemented for each candidate based on multivariate statistical process monitoring techniques; finally, using the resulting multiple local residuals, diagnosis is performed based on the exoneration principle. The cause--effect relationships in the digraph enable automatic variable selection and the local residual interpretations for statistical monitoring. The effectiveness of this new approach is demonstrated using numerical examples based on the Tennessee Eastman process data. [ABSTRACT FROM AUTHOR]

Two-dimensional covalent organic frameworks (2D COFs) have been widely viewed as rigid porous materials with smooth and reversible gas sorption isotherms. In the present study, we report an unusual hysteresis step in the CO 2 adsorption isotherm of a 2D COF, TAPB-OMeTA. In situ powder X-ray diffraction (PXRD) measurements, computational modeling, and Pawley refinement indicate that TAPB-OMeTA experiences slight interlayer shifting during the CO 2 adsorption process, resulting in a new structure that is similar but not identical to the AA stacking structure, namely, a quasi-AA stacking structure. This interlayer shifting is responsible for the step in its CO 2 adsorption isotherm. We attribute the interlayer shifting to the interactions between COF and CO 2 , which weaken the attraction strength between adjacent COF layers. Notably, the repulsion force between the methoxy groups on the backbone of TAPB-OMeTA is essential in facilitating the interlayer shifting process. After further increasing the size of side groups by grafting poly(N-isopropylacrylamide) oligomers to the TAPB-OMeTA backbone via surface-initiated atom transfer radical polymerization (SI-ATRP), we observed a second interlayer shifting and two adsorption steps in the CO 2 adsorption isotherm, suggesting tunability of the interlayer shifting process. Density functional theory (DFT) calculations confirm that the quasi-AA stacking structure is energetically preferred over AA stacking under a CO 2 atmosphere. These findings demonstrate that 2D COFs can be "soft" porous materials when interacting with gases, providing new opportunities for 2D COFs in gas storage and separation.

We describe a versatile and scalable strategy toward long-range and periodically ordered mesoporous alumina (Al 2 O 3 ) structures by evaporation-induced self-assembly of a structure-directing ABA triblock copolymer (F127) mixed with aluminum tri- sec -butoxide-derived sol additive. We found that the separate preparation of the alkoxide sol-gel reaction before mixing with the block copolymer enabled access to a relatively unexplored parameter space of copolymer-to-additive composition, acid-to-metal molar ratio, and solvent, yielding ordered mesophases of two-dimensional (2D) lamellar, hexagonal cylinder, and 3D cage-like cubic lattices, as well as multiscale hierarchical ordered structures from spinodal decomposition-induced macro- and mesophase separation. Thermal annealing in air at 900 °C yielded well-ordered mesoporous crystalline γ-Al 2 O 3 structures and hierarchically porous γ-Al 2 O 3 with 3D interconnected macroscale and ordered mesoscale pore networks. The ordered Al 2 O 3 structures exhibited tunable pore sizes in three different length scales, <2 nm (micropore), 2-11 nm (mesopore), and 1-5 μm (macropore), as well as high surface areas and pore volumes of up to 305 m 2 /g and 0.33 cm 3 /g, respectively. Moreover, the resultant mesoporous Al 2 O 3 demonstrated enhanced adsorption capacities of carbon dioxide and Congo red dye. Such hierarchically ordered mesoporous Al 2 O 3 are well-suited for green environmental solutions and urban sustainability applications, for example, high-temperature solid adsorbents and catalyst supports for carbon dioxide sequestration, fuel cells, and wastewater separation treatments.