Supplementary Information. Donor-Acceptor Porous Conjugated Polymers for Photocatalytic Hydrogen. Production: The Importance of Acceptor Comonomer

Transcription

1 S1 Supplementary Information Donor-Acceptor Porous Conjugated Polymers for Photocatalytic Hydrogen Production: The Importance of Acceptor Comonomer Lianwei Li, Wai-yip Lo, Zhengxu Cai, Na Zhang, and Luping Yu 1, * Department of Chemistry and the James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, IL 60637, USA.

2 S2 Unless otherwise stated, all chemicals obtained from commercial suppliers were used without further purification. Monomers M12-M15 were prepared according to literatures. 1-4 Iridium-catalyzed direct tetraborylation of 4,8-di(thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene was carried out to synthesize monomer DBD according to our previous procedure. 5,6 Solid-state 13 C-NMR spectra were recorded on a Bruker DRX-500 spectrometer. Elemental analysis was performed by Midwest MicroLab. TGA measurement of the polymers was performed using a TA Q600 instrument over the temperature range 50 to 800 C under nitrogen with a heating rate of 15 C/min. FTIR spectra were recorded on Nicolet is 10 FTIR Spectrometer as KBr pellets. UV vis absorption spectra were measured on a Shimadzu UV-3600 device. Diffuse reflectance accessory was used for the measurement of solid samples. SEM images were recorded on FEI NanoSEM. Each sample was carefully milled in mortar with 100 ul of acetone, and then a drop of suspension was deposited onto conductive substrate and air-dried before measurement. Wide angle powder X-ray diffraction (XRD) patterns were collected using a Bruker D8 diffractometer with a Cu Kα X-ray source (λ = nm) operating at 40 kv and 40 ma by depositing fine-powder on glass substrate. Metal content was determined by inductively coupled plasma mass spectrometry (ICP-MS), where the sample was first digested by H2SO4/H2O2 (0.8 ml/0.2 ml) solvent at 60 ºC for 12 h. The molecular geometries of the molecules were optimized, and their orbital energies and charge distributions calculated using the B3LYP DFT function with basis set 6-31G* as implemented in Gaussian 09.

3 N % S % C % H % S Theory THF Tol Dio DMF Theory THF DMF Dio Tol Theory THF Tol Dio DMF Theory THF DMF Dio Tol Figure 1. Elemental analysis of photocatalysts prepared in different reaction solvents, where the theoretical mass fraction for CHNS is 68.85%, 3.35%, 8.45% and 19.35%, respectively. DMF B O O Dio Tol THF / ppm Figure S2. Solid-state 1 H- 13 C CP/MAS NMR spectra of prepared in different reaction solvents.

4 S4 PCP1 PCP4 PCP2 PCP3 PCP5 PCP9 PCP7 PCP8 PCP11 Figure S3. FTIR spectra of PCP1-11 prepared in DMF.

5 S5 1.0 W/W PCP1 PCP2 PCP T / C W/W 0 Transmittance / % PCP4 PCP5 PCP7 PCP T / C W/W PCP9 PCP Figure S4. TGA spectra of the -11 in nitrogen T / C Transmittance / % 400 nm-longpass filter 100 Bandpass filter nm 550 nm 600 nm 450 nm 400 nm Wavelength / nm Wavelength / nm Figure S5. UV-vis absorption spectra of the 400 nm-longpass and bandpass filters used in this study

6 H 2,visible / mol Normalized Absorbance Normalized Absorbance Normalized Absorbance H 2 / ( mol/h) S PCP1 PCP2 PCP3 PCP4 PCP5 PCP7 PCP8 PCP9 PCP11 Figure S6. Photocatalytic hydrogen production rates of -11 under visible light irradiation for 2 h. before reaction 1.0 Before reaction After reaction after reaction 0.5 before reaction Wavelength / nm 1.0 Before reaction After reaction after reaction 0.5 before reaction Wavelength / nm Before reaction After reaction after reaction Wavelength / nm Figure S7. FTIR and UV-vis spectra of, and before and after 2 h photoreaction Time / min Figure S8. Reaction time dependence of PHP amount for under visible-light illumination within 14 h.

7 S7 HOMO LUMO HOMO LUMO HOMO LUMO PCP1 PCP1 PCP2 PCP2 PCP3 PCP3 PCP4 PCP4 PCP5 PCP5 PCP7 PCP7 PCP8 PCP8 PCP9 PCP9 PCP11 PCP11 Figure S9. Molecular orbital diagrams of fragmental structures (pentamer) of -11. PCP Debye 1.65 Debye PCP Debye 1.48 Debye PCP Debye Figure S10. Calculated dipole moments for repeating units of PCP1,, PCP9, and PCP11 by DFT calculations.

8 20 nm S8 4 ml 24 ml Figure S11. Photographs of PCP1-11 in triethylamine/water (2/8, v/v) solution after stopping stirring for 10 min PCP1 PCP2 PCP3 20 um 5 um 4 um 1 um 1 um Figure S12. SEM images of -3 prepared in DMF.

9 S9 PCP4 PCP5 PCP7 PCP8 30 um or 40 um 5 um 1 um Figure S13. SEM images of PCP4-8 prepared in DMF.

10 S10 PCP9 PCP11 30 um or 40 um 5 um 1 um Figure S14. SEM images of PCP9-11 prepared in DMF.

11 H 2 / ( mol/h) S11 + M PCP PCP12 PCP13 PCP14 M 12 M 13 PCP15 M 14 Figure S15. FTIR spectra of PCP M M M M 12 M PCP12 PCP13 PCP14 PCP15 Figure S16. PHP rates of PCP12-15 under full-arc irradiation.

12 Normalized Absorbance S PCP12 PCP13 PCP14 PCP Wavelength / nm Figure S17. Diffuse reflectance UV vis absorption spectra of PCP12-15.

13 S13 Supplementary References. 1. Ren, S.; Dawson, R.; Adams, D.; Cooper, A. Polymer Chemistry 2013, 4, Balandier, J.; Quist, F.; Amato, C.; Bouzakraoui, S.; Corni,l J.; Sergeyev, S.; Geerts, Y. Tetrahedron 2010, 66, Battagliarin, G.; Zhao, Y.; Li, C.; Müllen, K. Organic Letters 2011, 13, Sander,s G.; Vandijk, M.; Vanderplas, H. Heterocycles 1981, 15, Li, L.; Cai, Z.; Wu, Q.; Lo, W.-Y.; Zhang, N.; Chen, L. X.; Yu, L. Journal of the American Chemical Society 2016, 138, Wu, Q.; Zhao, D.; Schneider, A.; Chen, W.; Yu, L. Journal of the American Chemical Society 2016, 138, 7248.