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Supporting Information - Nature

By Amanda Graham,2014-07-11 21:57
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Supporting Information - NatureSuppor

    Supplementary Information

    An unprecedented (3,4,24)-connected heteropolyoxozincate organic framework as heterogeneous crystalline Lewis acid catalyst for biodiesel production

    11,2114Dong-Ying Du, Jun-Sheng Qin, Zhong Sun, Li-Kai Yan, Michael O'Keeffe,

    1,2311Zhong-Min Su*, Shun-Li Li, Xiao-Hong Wang*, Xin-Long Wang & Ya-Qian

    3Lan*

    1Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal

     University, Changchun 130024, P. R. China. E-mail: zmsu@nenu.edu.cn2State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, P. R. China.

    3Jiangsu Key Laboratory of Biofunctional Materials, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, P. R. China. E-mail: yqlan@njnu.edu.cn

    4Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287, United States.

Contents

    S1. Single-crystal X-ray diffraction S2. Calculations

    S3. Determination of acid strength S4. Catalytic experiments

    S5. Figures in Supplementary Information S6. Tables in Supplementary Information S7. The information for ddy topology

     S2

S1. Single-crystal X-ray diffraction

    Suitable single crystal of IFMC-200 was selected and mounted onto the end of a thin

    glass fiber using Fomblin oil. Single crystal X-ray diffraction data for IFMC-200

    were recorded on a Bruker APEXІІ CCD diffractometer with

    graphite-monochromated Mo Kα radiation (λ = 0.71069 Å) at 293 K. Absorption

    corrections were applied using multi-scan technique. The structure was solved by

    1Direct Method of SHELXS-97 and refined by full-matrix least-squares techniques

    23using the SHELXL-97 program within WINGX.

S2. Calculations

    All the calculations in this work were carried out using the Gaussian 09W program

    45,6package. The hybrid functional B3LYP was used in this work. The LANL2DZ

    basis set associated with the pseudopotential was used to describe the Zn atom, whereas the basis sets of 6-31G for P, C, N, O, and H atoms. The calculated model is formed by carboxyl group-stabilized {PZn} cluster. In order to saturate the 416

    dangling bond in carboxyl group, we select H as counterbalanced atom.

S3. Determination of acid strength

    The acid value was calculated from the following equation:

    acid value = C × V/m

    where C is the molar concentration of aqueous ammonia, V is the volume of aqueous

    ammonia used in the titration procedure, and m is the weight of solid samples.

S4. Catalytic experiments

    Each sample was titrated against 0.1 M KOH using phenolphthalein as an indicator. The acid value (AV) of the sample was defined as follows:

    AV = M × C × V/m W

    where M is the molecular weight of KOH, C is the molar concentration of KOH, V W

     S3

    is the volume of KOH used in the titration procedure, and m is the sample weight.

    After the acid value was determined, the conversion (Con.) of FFAs to fatty acid esters can be calculated by the following equation:

    Con. (%) = (AV ? AV)/AV ×100 00

    where AV is the initial acid value before the esterification reaction. 0

Then, the corresponding turnover frequency (TOF) can be evaluated by the equation

    as follow:

    TOF = [Con. × (m/M)]/[(m/M) × t] 1122

    where m is the sample weight of FFA, m is the catalyst weight, M is the 12n

    corresponding molecular weight, and t is reaction time.

     S4

S5. Figures in Supplementary Information

Figure S1 | The structure of HL ligand. 8

    Figure S2 | The coordination environments of Zn(II) centers. All the hydrogen atoms are omitted for clarity. Symmetry code: #1 0.5-y, 0.5-z, x; #2 z, 0.5-x, 0.5-y; #3 0.5-z, x, 0.5-y; #4 y, 0.5-z, 0.5-x; #5 0.5-z, 0.5-x, y; #6 1-y, x, 0.5-z; #7 0.5+z, y, x; #8 0.5+x, 0.5-z, 0.5-y; #9 1-x, 1-y, z,; #10 1-y, 0.5+z, 0.5-x; #11 0.5+z, 0.5+x, y; #12 y, 1-x, 0.5-z; #13 0.5-z, 1-y, x; #14 0.5-x, 0.5+z, 0.5-y.

     S5

Figure S3 | (a) The calculated model, [Zn(HPO)(HCOO)], and (b) its LUMO 163424

    and HOMO calculated by Gaussian 09W program package.

Figure S4 | The cage structure in IFMC-200.

Figure S5 | The 24-connected node reported in Refs. 7 and 8.

     S6

Figure S6 | The (4,12)-connected structure of IFMC-200: (a) the local connection

    fashion of HL and the four-connected node, (b) the connection fashion of {PZn} 8416

    cluster and the 12-connected node, and (c) the 3D structure and topology.

     S7

Figure S7 | The (4,12)-connected topology comparison of IFMC-200 (left) and the

one reported in Ref. 9 (right).

S8

Figure S8 | The scanning electron microscopy image of IFMC-200.

Figure S9 | The EDS spectrum of IFMC-200.

Figure S10 | The XRPD pattern (red) and simulation pattern (black) of IFMC-200,

    and the XRPD patterns of IFMC-200 after heated in Teflonlined stainless steel container at 65 ?C (blue) and 140?C (green) for 12 h, respectively.

     S9

Figure S11 | The IR spectrum of IFMC-200 (a), and the IR spectra of IFMC-200

    after heated in Teflonlined stainless steel container at 65 ?C (b) and 140?C (c) for 12 h, respectively.

Figure S12 | The IR spectra of IFMC-200 after heated in Teflonlined stainless steel

    container at 65 ?C (a, b) and 140?C (c, d) for 12 h at different pH in KBr pellets from

     S10

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