Direct On-Surface Polycondensation

Transcription

1 Supporting Information Synthesis of Well-Ordered COF Monolayers: Surface Growth of Nanocrystalline Precursors vs. Direct On-Surface Polycondensation Jürgen F. Dienstmaier,, Alexander M. Gigler, Andreas J. Goetz, Paul Knochel #, Thomas Bein #, Andrey Lyapin, Stefan Reichlmaier, Wolfgang M. Heckl, and Markus Lackinger,* Deutsches Museum, Museumsinsel 1, Munich (Germany) and Tech. Univ. Munich, TUM School of Education, Schellingstrasse 33, Munich (Germany) and Center for NanoScience (CeNS) Department for Earth- and Environmental Sciences and Center for NanoScience (CeNS), Ludwig-Maximilians-University, Theresienstrasse 41, Munich (Germany) # Department of Chemistry and Center for NanoScience (CeNS), Ludwig-Maximilians-University, Butenandtstrasse 11 (E), 81377, Munich (Germany) Physical Electronics GmbH, Fraunhoferstr. 4, Ismaning, Germany S1

2 Content: Figure S1: STM images of thermally treated BDBA under dry conditions Figure S2: STM image of post-processed COF-1 monolayer, prepared with nonanoic acid Figure S3: STM image of a COF-1 monolayer after verification of its thermal stability Figure S4: PXRD of untreated BDBA, precursor-cofs, and re-hydrolized material Figure S5: Raman spectra of untreated BDBA, precursor-cofs, and re-hydrolized material Figure S6: IR-spectra of untreated BDBA, precursor-cofs, and re-hydrolized material Figure S7: TGA of BDBA Figure S8: Sublimation of unreacted BDBA Figure S9: Molecular mechnics simulation of a hypothetical hydrogen bonded BDBA structure Figure S10: Temperature profile inside the reactor during a thermal treatment S2

3 a) b) Figure S1 STM images a) (58 58 nm²) and b) (35 35 nm²) obtained on HOPG after drop-casting a suspension of BDBA that was thermally treated under dry conditions, i.e. in the absence of H 2 O. The resulting structures are amorphous and only single polymerized chains and smaller covalent aggregates can be discerned but no extended hexagonal networks. S3

4 Figure S2 STM image of an extended 2D COF-1 monolayer (68 68 nm²) acquired under dry conditions. This monolayer was prepared by drop-casting precursor COFs dispersed in nonanoic acid and post-processing under humid conditions. The surface is fully covered and domains with lateral extension of tens of nanometers can be observed with very few defects, like missing BDBA molecules. Also a non-periodic contrast modulation is clearly discernable. S4

5 Figure S3 STM image of an extended 2D COF-1 monolayer (60 60 nm²) acquired under dry conditions after verification of the thermal stability. To this end, an already post-processed sample was exposed to 200 C for almost 14 h (without supplying additional water). The COF-1 monolayer can clearly be observed, and the thermal stability confirms the covalent nature of intermolecular bonds. Yet, the coverage has slightly decreased, which may indicate a slow degradation. S5

6 Figure S4 a) Powder X-ray diffractogram (Mo-K α1 ) of thermally treated BDBA, i.e. pre-polymerization into precursor-cofs (blue curve) b) Simulated curve of a) based on the previously published COF-1 crystal structure (black curve). The Rietveld refinement allows to estimate a precursor-cof crystal size of 7.8 nm in lateral direction and 1.0 nm along the [001] axis (Chi 2 = 3.145). 1-2 c) Difference curve between measured and simulated curve, i.e. (a) (b). The large discrepancy is owed to the extremely small crystal size and the low number of periods especially along the c-axis. Nevertheless, the main features of the experimental diffraction data can be reproduced in the simulation. S6

7 Figure S5 Raman spectra of a) untreated BDBA starting material (red curve), b) after thermal treatment (blue curve), i.e. pre-polymerization into precursor-cofs c) after re-hydrolysis and re-crystallisation of b) from H 2 O (green curve). Although not all modes could be assigned, the modes at ~1097 cm -1 and at ~1378 cm -1 are only observed for untreated and re-hydrolized BDBA and can be attributed to a B-O-H rocking mode and B-O stretching vibrations of the free boronic acid groups, respectively. 3 After thermal treatment the rocking mode at ~1097 cm -1 as well as other, not assigned modes at 770 cm -1 and 310 cm - 1 disappear, while new modes at ~713 cm -1, ~804 cm -1, and ~1004 cm -1 appear. The new mode at ~804 cm -1 corresponds to the breathing mode of boroxine rings, and its presence indicates cyclo-condensation of three boronic acid groups. 4 S7

8 Figure S6 IR spectra of a) untreated BDBA starting material (red curve); b) after thermal treatment, i.e. pre-polymerization into precursor-cofs (blue curve); c) after re-hydrolysis and re-crystallisation of b) from H 2 O (green curve). The dotted square marks a region with weak peaks that can be attributed to BO 2 rocking vibrations in the free boronic acid BDBA. 5 Notice their diminishment in the prepolymerized sample b).the IR spectrum of the pre-polymerized product is also in excellent agreement with the results reported for solvothermally synthesized COF-1. 6 In particular, the absorption maxima in the IR spectra of thermally treated samples at 701 cm -1 and 1605 cm -1 were also found for solvothermally synthesized COF-1, and indicate the presence of boroxine rings. 6 The first mode belongs to out-of-plane deformation of the boroxine unit, and the second mode arises from boronic acid (B(OH) 2 ) end groups in asymmetrically substituted benzenes. This mode is attributed to free boronic acid groups which are still present on the surface of nanocrystals. S8

9 Figure S7 Thermal Gravimetric Analysis (TGA) of previously untreated BDBA (rate: 10 C / minute, quantity: mg). The weight loss due to the condensation is almost completed at ~250 C. The change of slope at temperatures above 250 C may indicate the onset of thermal degradation. S9

10 Degree of completion of the thermal polymerization In order to detect the presence of residual unreacted BDBA after thermal treatment, the prepolymerized product was introduced in an effusion cell operated in high vacuum. The crucible aims at a highly sensitive quartz crystal microbalance (QCMB), thus allowing to measure effusion rates as a function of crucible temperature. 7 However, heating the precursor-cof up to 200 C did not result in a detectable deposition of unreacted BDBA monomers on the QCMB chip, although the experiment features monolayer sensitivity. In contrast, the sublimation onset of untreated BDBA starting material can already be detected at ~100 C, and the sublimation rate increases with temperature according to an Arrhenius law (see below, Figure S8). From these experiments we conclude that the amount of residual unreacted BDBA in the thermally treated material is extremely low. a) b) Figure S8 Characterization of the sublimation of untreated BDBA by means of an effusion cell and a Quartz Crystal Micro Balance (QCMB). 7 a) Frequency shift f of the QCMB as a function of time for different crucible temperatures (indicated next to each curve). The linear dependence indicates a constant effusion rate. b) Arrhenius plot of the data in a), where for each crucible temperature T the slope of the respective frequency vs. time curve f/ t was used. These measurements demonstrate that the free boronic acid can be sublimed, whereas form thermally treated BDBA (precursor-cofs) no sublimation could be detected for crucible temperatures up to 200 C, hinting towards an extremely low amount of unreacted BDBA. S10

11 Figure S9 Molecular Mechanics (MM) calculation of a hypothetic porous hexagonal BDBA monolayer structure on a graphite substrate (not shown for clarity) based on the Dreiding force field. The graphite substrate was approximated by two layers, and the atomic positions of the second one were fixed. The BDBA molecules were arranged flat on the surface without constraints. The structure is stabilized by cyclic intermolecular hydrogen bonds (indicated by dotted lines). Note that there are no boroxine rings present here. The distance between adjacent pores, i.e. the lattice parameter of this hypothetical selfassembled structure corresponds to 2.05 nm. Colour code: C = gray; B = pink; O = red; H = white. S11

12 Figure S10 Temperature profile inside the reactor during the thermally induced ripening process of precursor-cof layers into well-ordered 2D COF-1 monolayers with large domains. The oven was preheated to 120 C. While the reactor remained inside the oven for 60 minutes its interior temperature reached 107 C before it was removed and allowed to cool down. The temperature inside the reactor remained above 100 C for ~30 minutes. References 1. Larson, A. C.; von Dreele, R. B., General Structure Analysis System (GSAS), Los Alamos National Laboratory Report LAUR Toby, B. H., EXPGUI, A Graphical User Interface for GSAS. J. Appl. Crystallog. 2001, 34, Krishnan, K., The Raman Spectrum of Boric Acid. Proc. Indian. Acad. Sci. (Math. Sci.) 1963, 57, Goubeau, J.; Keller, H., Raman-Spektren und Struktur von Boroxol-Verbindungen. Z. Anorg. Allg. Chem. 1953, 272 (5-6), Faniran, J. A.; Shurvell, H. F., Infrared Spectra of Pheynlboronic Acid (Normal and Deuterated) and Diphenyl Phenylboronate. Can. J. Chemistry. 1968, 46 (12), Cote, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keeffe, M.; Matzger, A. J.; Yaghi, O. M., Porous, Crystalline, Covalent Organic Frameworks. Science 2005, 310 (5751), Gutzler, R.; Heckl, W. M.; Lackinger, M., Combination of a Knudsen Effusion Cell with a Quartz Crystal Microbalance: In Situ Measurement of Molecular Evaporation Rates with a Fully Functional Deposition Dource. Rev. Sci. Instrum. 2010, 81 (1), S12