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      PVBA-UiO-66 using a flexible PVBA with multi-coordination groups as mixed ligands and their super adsorption towards methylene blue

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          Abstract

          A series of poly-vinyl benzoic acid (PVBA) and UiO-66 materials (PVBA-UiO-66) were prepared by a mixed-linker approach.

          Abstract

          A series of poly-vinyl benzoic acid (PVBA) and UiO-66 materials (PVBA-UiO-66) were prepared by a mixed-linker approach. Using a flexible PVBA with multi-coordination groups as mixed ligands, mesopores and uncoordinated benzoic groups were introduced into the UiO-66 crystal structures, thus leading to a special structure and functionality. The structure of the PVBA-UiO-66 was characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and nitrogen gas adsorption measurements. The adsorption property toward methylene blue (MB) of PVBA-UiO-66 was studied. The adsorption of MB by UiO-66 and PVBA (43%)-UiO-66 fit the Langmuir model and Freundlich model well. The result showed that PVBA (43%)-UiO-66 has super adsorption capacity as high as 909 mg g −1 for MB owing to the mesopores and the uncomplexed carboxyl groups which were caused by the long PVBA involved in coordination. The adsorption kinetics of MB onto PVBA (43%)-UiO-66 can be well fitted to the pseudo-second-order model. The process of adsorption MB onto PVBA-UiO-66 is spontaneous and thermodynamically favorable at 303, 313 and 323 K.

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          Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance

          Sunkyu Park, John Baker, Michael Himmel … (2010)
          Although measurements of crystallinity index (CI) have a long history, it has been found that CI varies significantly depending on the choice of measurement method. In this study, four different techniques incorporating X-ray diffraction and solid-state 13C nuclear magnetic resonance (NMR) were compared using eight different cellulose preparations. We found that the simplest method, which is also the most widely used, and which involves measurement of just two heights in the X-ray diffractogram, produced significantly higher crystallinity values than did the other methods. Data in the literature for the cellulose preparation used (Avicel PH-101) support this observation. We believe that the alternative X-ray diffraction (XRD) and NMR methods presented here, which consider the contributions from amorphous and crystalline cellulose to the entire XRD and NMR spectra, provide a more accurate measure of the crystallinity of cellulose. Although celluloses having a high amorphous content are usually more easily digested by enzymes, it is unclear, based on studies published in the literature, whether CI actually provides a clear indication of the digestibility of a cellulose sample. Cellulose accessibility should be affected by crystallinity, but is also likely to be affected by several other parameters, such as lignin/hemicellulose contents and distribution, porosity, and particle size. Given the methodological dependency of cellulose CI values and the complex nature of cellulase interactions with amorphous and crystalline celluloses, we caution against trying to correlate relatively small changes in CI with changes in cellulose digestibility. In addition, the prediction of cellulase performance based on low levels of cellulose conversion may not include sufficient digestion of the crystalline component to be meaningful.
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            Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption.

            Hui Wu, Yong Shen Chua, Vaiva Krungleviciute … (2013)
            UiO-66 is a highly important prototypical zirconium metal-organic framework (MOF) compound because of its excellent stabilities not typically found in common porous MOFs. In its perfect crystal structure, each Zr metal center is fully coordinated by 12 organic linkers to form a highly connected framework. Using high-resolution neutron power diffraction technique, we found the first direct structural evidence showing that real UiO-66 material contains significant amount of missing-linker defects, an unusual phenomenon for MOFs. The concentration of the missing-linker defects is surprisingly high, ∼10% in our sample, effectively reducing the framework connection from 12 to ∼11. We show that by varying the concentration of the acetic acid modulator and the synthesis time, the linker vacancies can be tuned systematically, leading to dramatically enhanced porosity. We obtained samples with pore volumes ranging from 0.44 to 1.0 cm(3)/g and Brunauer-Emmett-Teller surface areas ranging from 1000 to 1600 m(2)/g, the largest values of which are ∼150% and ∼60% higher than the theoretical values of defect-free UiO-66 crystal, respectively. The linker vacancies also have profound effects on the gas adsorption behaviors of UiO-66, in particular CO2. Finally, comparing the gas adsorption of hydroxylated and dehydroxylated UiO-66, we found that the former performs systematically better than the latter (particularly for CO2) suggesting the beneficial effect of the -OH groups. This finding is of great importance because hydroxylated UiO-66 is the practically more relevant, non-air-sensitive form of this MOF. The preferred gas adsorption on the metal center was confirmed by neutron diffraction measurements, and the gas binding strength enhancement by the -OH group was further supported by our first-principles calculations.
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              Adsorptive removal of methyl orange and methylene blue from aqueous solution with a metal-organic framework material, iron terephthalate (MOF-235).

              Enamul Haque, Jong Jun, Sung Jhung (2011)
              An iron terephthalate (MOF-235), one of the metal-organic frameworks (MOFs), has been used for the removal of harmful dyes (anionic dye methyl orange (MO) and cationic dye methylene blue (MB)) from contaminated water via adsorption. The adsorption capacities of MOF-235 are much higher than those of an activated carbon. The performance of MOF-235 having high adsorption capacity is remarkable because the MOF-235 does not adsorb nitrogen at liquid nitrogen temperature. Based on this study, MOFs, even if they do not adsorb gases, can be suggested as potential adsorbents to remove harmful materials in the liquid phase. Adsorption of MO and MB at various temperatures shows that the adsorption is a spontaneous and endothermic process and that the entropy increases (the driving force of the adsorption) with adsorption of MO and MB. Copyright © 2010 Elsevier B.V. All rights reserved.
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                Author and article information

                Journal
                Journal ID (publisher-id): ICHBD9
                Title: Dalton Transactions
                Abbreviated Title: Dalton Trans.
                Publisher: Royal Society of Chemistry (RSC)
                ISSN (Print): 1477-9226
                ISSN (Electronic): 1477-9234
                Publication date Created: 2018
                Publication date (Electronic): 2018
                Volume: 47
                Issue: 18
                Pages: 6538-6548
                Affiliations
                [1 ]Institute of Polymer Science and Engineering
                [2 ]Hebei University of Technology
                [3 ]Tianjin 300130
                [4 ]P. R. China
                Article
                DOI: 10.1039/C8DT00184G
                SO-VID: 9d4f15f9-257f-4e2c-b9c3-5f73b5745486
                Copyright © © 2018
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                http://rsc.li/journals-terms-of-use

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