Effective Adsorption of Pd(II), Pt(IV) and Au(III) by Zr- Cluster-Based Metal-Organic Frameworks from Strongly Acidic Solution

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1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 2017 Supporting Information Effective Adsorption of Pd(II), Pt(IV) and Au(III) by Zr- Cluster-Based Metal-Organic Frameworks from Strongly Acidic Solution Shuo Lin, D. Harikishore Kumar Reddy, John Kwame Bediako, Myung-Hee Song, Wei Wei, Jeong-Ae Kim, and Yeoung-Sang Yun* School of Chemical Engineering, Chonbuk National University, Jeonbuk 54896, Republic of Korea Fig. S1. Topological analysis of tetrahedral primitive cells (a, b) and octahedral primitive cell (c, d). Fig. S2. Crystal face exponent (hkl) of cubo-octahedral unit cell. S1

2 Table S1. Lattice parameters of UiO-66 and UiO-66-NH 2 before and Pd(II), Pt(IV) and Au(III) adsorption. The experimental parameters were determined from powder X-ray diffraction and MDI Jade 6.5 (Materials Data Inc.). MOFs a=b (Å) c (Å) α ( ) β ( ) γ ( ) UiO UiO-66-Pd UiO-66-Pt UiO-66-Au UiO-66-NH UiO-66-NH 2 -Pd UiO-66-NH 2 -Pt UiO-66-NH 2 -Au Table S2. Elemental analysis on UiO-66 and UiO-66-NH 2. Complex (Atomic ratio) % Zr % Cl % C % N % O Observed UiO Calculated for Zr 6 O 4 (OH) 4 (BDC) 4 (OH) 2.5 Cl 1.5 (EtOH) Calculated for Zr 6 O 4 (OH) 4 (BDC) 6 Cl Observed UiO-66-NH Calculated for Zr 6 O 4 (OH) 4 (BDC-NH 2 ) 4 (OH) 2.5 Cl 1.5 (EtOH) 5 (H 2 O) Calculated for Zr 6 O 4 (OH) 4 (BDC-NH 2 ) 6 Cl Fig. S3. N 2 isotherms of UiO-66 and UiO-66-NH 2 at 77 K. Solid line shows the observed data, and the dash line shows the Langmuir fitted data. (Only the data from 0 to 0.40 P/P 0 is shown) S2

3 Fig. S4. FE-SEM images for UiO-66 and UiO-66-NH 2 respectively, upon the treatment with acidic Pd(II), Pt(IV) and Au(III) solutions (in 0.1 M HCl solution). S3

4 (a) (b) Fig. S5. N 2 isotherms of UiO-66 (a) and UiO-66-NH 2 (b) after immersion in Pd(II), Pt(IV) and Au(III) solutions (in 0.1 M HCl solution). Inlet shows pore size distributions as determined via DFT. S4

5 Table S3. N 2 uptake, BET surface area, total pore volume and pore width of UiO-66 and UiO-66- NH 2 before and after immersion in Pd(II), Pt(IV) and Au(III) solutions (in 0.1 M HCl solution). N MOFs 2 uptake BET surface Total pore (cm 3 STP/g)) area (m 2 /g) volume (cm 3 Pore width (Å) /g) UiO and 16.1 UiO-66-Pd and 14.7 UiO-66-Pt and 14.7 UiO-66-Au and 14.1 UiO-66-NH and 14.7 UiO-66-NH 2 -Pd and 14.1 UiO-66-NH 2 -Pt and 14.7 UiO-66-NH 2 -Au , 11.8 and 14.7 Table S4. Pd(II), Pt(IV) and Au(III) uptake amounts of various adsorbents including UiO-66 and UiO-66-NH 2 at preliminary adsorption period. Adsorbent ph Pd(II) Pt(IV) Au(III) ph Time ph Time (mg/g) (min) (mg/g) (min) Time (min) (mg/g) Glycine modified crosslinked chitosan resin 1 L-lysine modified crosslinked chitosan resin 2 Graphene Oxide Functionalized silica-gel na na na na na na Chitosan/graphene oxide composites na na na na na na Thiourea-modified chitosan microspheres na na na Collagen-Fiber- Immobilized Tannins 7 na na na na na na Phosphine sulphide-type chelating polymers 8 na na na na na na UiO-66 (This work) UiO-66-NH 2 (This work) na : not available in the reference S5

6 Table S5. Pd(II), Pt(IV) and Au(III) maximum uptake amounts of various adsorbents including UiO-66 and UiO-66-NH 2. Pd(II) Pt(IV) Au(III) Adsorbent ph ph ph (mg/g) (mg/g) (mg/g) Glycine modified crosslinked chitosan resin L-lysine modified crosslinked chitosan resin Graphene Oxide Functionalized silica-gel na na na na Chitosan/graphene oxide composites na na na na Thiourea-modified chitosan microspheres na na Collagen-Fiber- Immobilized Tannins 7 na na na na Phosphine sulphide-type chelating polymers 8 na na na na UiO-66 (This work) UiO-66-NH 2 (This work) Table S6. Number of Pd, Pt and Au ions adsorbed per node in UiO-66 and UiO-66-NH 2. MOFs UiO-66 UiO-66-NH 2 Items (mg/g) per Node (mg/g) per Node Maximum adsorption per node Actual adsorption per node Pd(II) Pt(IV) Au(III) Pd(II) Pt(IV) Au(III) S6

7 Table S7. Zeta potentials of various adsorbents including UiO-66 and UiO-66-NH 2. Zeta potential Zeta potential Target Adsorbent ph ph (mv) (mv) adsorbate Activated carbon Methylene blue Graphene Sb(II) Graphene oxide nanocomposite Cd(II) Ceria nanoparticles supported on carbon nanotubes As(III) Fe Mn binary oxide Phosphate Amino-functionalized nanoparticles Cr(VI), Pd(II) and Au(III) NH 2 -MCM Au(III) Fe Al Ce trimetal oxide Fluoride UiO-66 (This work) Pd(III), Pt(IV) and Au(III) UiO-66-NH 2 (This work) Pd(III), Pt(IV) and Au(III) Fig. S6. FT-IR spectra from 3650 to 3050 cm -1 and 1650 to 1350 cm -1 of (1) pristine UiO-66 and after adsorption, (2) UiO-66-Pd, (3) UiO-66-Pt, (4) UiO-66-Au; (5) pristine UiO-66-NH 2 and after adsorption (6) UiO-66-NH 2 -Pd, (7) UiO-66-NH 2 -Pt and (8) UiO-66-NH 2 -Au. S7

8 Fig. S7. XPS N 1s spectra of (1) pristine UiO-66 and after adsorption, (2) UiO-66-Pd, (3) UiO-66- Pt and (4) UiO-66-Au; XPS Pd 3d, Pt 4f and Au 4f spectra of UiO-66 after adsorption, (5) UiO- 66-Pd, (6) UiO-66-Pt and (7) UiO-66-Au. Fig. S8. XRD patterns (from 35 to 80 degree) of the pristine UiO-66-NH 2 and after Au adsorption (left). Image of falcon tube containing precipitated gold after adsorption in 800 and 1600 mg / L Au(III) solution (right). S8

9 (a) (b) Fig. S9. s of various metals by UiO-66 (a) and UiO-66-NH 2 (b) mixed metal solutions containing Co(II), Ni(II), Cu(II), Zn(II), and precious metal ions with their respective concentrations of 100 mg / L. The mixed metal solutions were prepared by dissolving metal salts of CoCl 2 6H 2 O, NiCl 2 6H 2 O, CuCl 2 and ZnCl 2 as well as precious metal salts in 0.1 M HCl solution. In each case, 10 mg of MOF was exposed to mixed solutions at ph 1.0 for 24 h. S9

10 (a) (b) Fig. S10. Adsorption-desorption cycles of UiO-66 (a) and UiO-66-NH 2 (b) for Pd(II) (blue column), Pt(IV) (red column) and Au(III) (green column). S10

11 Fig. S11. PXRD patterns of UiO-66 and UiO-66-NH 2 after five cycles of adsorption-desorption. S11

12 (a) (b) Fig. S12. The effect of solution ph on the adsorption of Pd(II), Pt(IV) and Au(III) onto UiO-66 (a) and UiO-66-NH 2 (b). In each case, 10 mg of MOF was exposed to 100 mg / L Pd(II), Pt(IV) and Au(III). As seen in the figure, all the uptakes of Pd(II), Pt(IV) and Au(III) onto the UiO-66 and UiO-66-NH 2 generally decreased with the increasing of solution ph. These were due to the positively charged functional groups in the UiO-66 and UiO-66-NH 2 and the species of Pd(II), Pt(IV) and Au(III) significantly influenced by the solution ph. As the solution ph increased, the charge of the functional groups would tend to neutral. In addition, the PdCl 4 2-, PtCl 6 2- and AuCl 4 - species of Pd(II), Pt(IV) and Au(III) would turn to PdO, PtO 2 and Au(OH) 3, respectively (the fraction of each species of metals was simulated by Medusa software). This is likely the reason why the adsorption capacity decreased with the increasing of the solution ph. S12

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