Supporting Information

Transcription

1 Supporting Information Improving the Loading Capacity of Metal-Organic-Framework Thin Films by Using Optimized Linkers Wei Guo 1,, Meiqin Zha 3, Zhengbang Wang 1, Engelbert Redel 1, Zhengtao Xu 3, Christof Wöll 1* 1 Karlsruhe Institute of Technology, Institute of Functional Interfaces (IFG), Hermann-von-Helmholtz-Platz 1, 73 Eggenstein-Leopoldshafen, Germany christof.woell@kit.edu; Fax: +9-(0) ; Tel: +9-(0) State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Ruoshi Road 1#, Wuhan 30070, PR China 3 Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, PR China 1

2 X-ray Diffraction (XRD): Each sample was characterized by using a Bruker D8 Advance equipped with a Si-strip detector (PSD Lynxeye ; position sensitive detector) with Cu K α1, radiation (λ = nm) in θ θ geometry, variable slit on primary circle. Scans were run over various ranges with step width of 0.0 θ and 8 seconds, for higher order peaks up to 33 seconds per step. The θ angle scanning range to observe corresponding peak to deposited film is picked up from 5 to 0. Infrared reflection absorption spectroscopy(irras): IRRAS were measured using the infrared spectrometer (Bruker VERTEX 80) purged with dried air. The spectra were recorded in grazing incidence reflection mode at a fixed angle of incidence of 80 relative to the surface normal using mercury cadmium telluride (MCT) detector. Predeuterated hexadecanethiol SAM on Au/Ti/Silicon substrates were used for reference measurements. The UV-Vis spectra were recorded in the range of 00 nm to 800 nm by means of a Cary5000spectrometer with a UMA unit from Agilent. The UV-Vis spectra of the SURMOFs on the quartz substrate were measured in transmission mode. Quartz Crystal Microbalance (QCM): A quartz crystal microbalance (QCM) was employed to growth an SURMOF thin film on a QCM sensor in a clean and well-controlled manner to further perform the uptake metal ions experiments. The QCM sensor was placed in a flow cell (Q-Sense E). Infiltration with guest molecules was achieved via a stream of liquid through the cell. The grown SURMOF QCM sensor was grown directly on gold wafer, which was functionalization with a11-mercapto-1-undecanol (MUD, 99%, Aldrich) self-assembled monolayer. SURMOF growth was carried out in situ in the QCM flow cell by alternating between the metal source solution (1 mm copper(ii) acetate), a solution of 0. mm ligand in ethanol and pure ethanol as described previously.

3 Figure S-1 Schematic of quartz crystal microbalance (QCM) method for SURMOF preparation. Cu sensor Cu sensor Normalized Intensity θ / o Figure S- X-ray diffraction patterns recorded for Cu (atbdc) (black) and Cu (BDC) (red) of SURMOFs on QCM sensor. 0. Cu (atbdc) Cu (BDC) 0.1 Absorbance / a.u Wavenumber / cm -1 Figure S-3 IR spectrum for Cu (atbdc) (black) and Cu (BDC) (red) of SURMOFs. Table S-1 Band assignment for the IR spectrum of Cu (atbdc) and Cu (BDC) on MHDA SAM. 3

4 Cu (atbdc) Cu (BDC) Absorption band (cm -1 ) Assignment 18 (COO - ) asymm. Stretching 197, 17, 137 (CH )(from dabco) 103, 1, 1097 (CH )(from CH -S-) 93 (-C-H) (from CH=CH ) Cu (atbdc) Cu (BDC) Absorbance λ / nm Figure S- UV-Vis spectrum for Cu (atbdc) (black) and Cu (BDC) (red) of SURMOFs.

5 8 Cu (BDC) 5 layers 8 Cu (atbdc) 5 layers Uptake / µg cm - BDC Cu(Ac) Uptake / µg cm - BDC Cu(Ac) Figure S-5 Layer-by-layer growth of the Cu (BDC) (left) and Cu (atbdc) (right) SURMOF on the QCM sensor with 5 cycles. The inset is a magnification of the layer-by-layer growth of the SURMOF. Fe-complex uptake Pd-complex uptake uptake m / / molec per pore uptake uptake m / molec per pore 0 Cu (atbdc) Sim ulation uptake m / molec / per per pore Cu (atbdc) Sim ulation D= m s -1 0 D= m s Cu (BDC) Simulation uptake m molec per pore uptake / molec per pore.5 Cu (BDC).0 Sim ulation D= m s D= m s Figure S- Quartz crystal microbalance (QCM) uptake data of Fe 3+ (left) and Pd + (right)for Cu (atbdc) (up) and Cu (BDC) (down). 5

6 Figure S-7 XRD patterns of Cu (atbdc) SURMOF (black), after loading Fe(NO 3 ) 3 (up red) and after loading Pd(NO 3 ) (down red).