advances.sciencemag.org/cgi/content/full/3/5/e1603171/dc1 Supplementary Materials for Carbon dots in zeolites: A new class of thermally activated delayed fluorescence materials with ultralong lifetimes Jiancong Liu, Ning Wang, Yue Yu, Yan Yan, Hongyue Zhang, Jiyang Li, Jihong Yu The PDF file includes: Published 26 May 2017, Sci. Adv. 3, e1603171 (2017) DOI: 10.1126/sciadv.1603171 fig. S1. PXRD patterns. fig. S2. LC-HRMS of dissolved CDs@AlPO-5 composite. fig. S3. The particle diameter distributions of CDs in CDs@zeolite composites. fig. S4. TEM analysis and photoluminescence property of CDs in the diluted mother liquid of CDs@AlPO-5. fig. S5. Structure of 2D-AlPO synthesized by using TTDDA as SDA. fig. S6. TADF properties of CDs@2D-AlPO composite. fig. S7. TADF properties of CDs@MgAPO-5 composite. fig. S8. TADF properties of CDs@zeolite composites after vacuum drying for 12 hours at room temperature. fig. S9. The compositional analysis of the organic species in CDs@AlPO-5 composite. fig. S10. The compositional analysis of the organic species in CDs@2D-AlPO composite. fig. S11. The compositional analysis of the organic species in CDs@MgAPO-5 composite. fig. S12. The time-resolved decay spectrum of the CDs in the diluted mother liquid of CDs@AlPO-5 at room temperature. fig. S13. PXRD and TG characterizations of CDs@AlPO-5 composites vacuumcalcined at different temperatures. fig. S14. TADF properties of CDs@AlPO-5 composites upon vacuum calcination at different temperatures. fig. S15. TADF properties of CDs@zeolite composites kept under ambient conditions for more than half a year. table S1. Crystal data and structure refinement for CDs@2D-AlPO.
table S2. Atomic coordinates ( 10 4 ) and equivalent isotropic displacement parameters (Å 2 10 3 ) for CDs@2D-AlPO. table S3. The photoluminescence emission bands and lifetimes of CDs@zeolite composites after vacuum drying at room temperature. table S4. The photoluminescence emission bands and lifetimes of CDs@AlPO-5 composites after vacuum calcination at different temperatures. table S5. The photoluminescence emission bands and lifetimes of CDs@zeolite composites before and after half a year under ambient conditions. table S6. The multiexponential lifetime (τi) and preexponential for lifetime (Ai) of the CDs@zeolite composites and the diluted mother liquid. Other Supplementary Material for this manuscript includes the following: (available at advances.sciencemag.org/cgi/content/full/3/5/e1603171/dc1) data file S1 (.CIF format). CIF file for CDs@2D-AlPO. data file S2 (.pdf format). CheckCIF file for CDs@2D-AlPO.
fig. S1. PXRD patterns. Powder X-ray diffraction patterns of experimental (A) CDs@AlPO-5, (B) CDs@2D-AlPO and (C) CDs@MgAPO-5 and simulated (A) AFI, (B) 2D-AlPO and (C) AFI.
fig. S2. LC-HRMS of dissolved CDs@AlPO-5 composite. The peak of m/z: 102.1 indicates the existence of C 6H 16N + cations in resultant composite.
fig. S3. The particle diameter distributions of CDs in CDs@zeolite composites. The particle diameter distributions of CDs in (A) CDs@AlPO-5, (B) CDs@2D-AlPO and (C) CDs@MgAPO-5 obtained by counting about 100 particles.
fig. S4. TEM analysis and photoluminescence property of CDs in the diluted mother liquid of CDs@AlPO-5. (A) TEM image of CDs in the mother liquid (inset, HRTEM image of a typical CD that shows a lattice spacing of 0.21 nm). (B) The distribution of CDs particle diameters in mother liquid obtained by counting 100 particles. (C) Excitation-emission two-dimensional plot of the diluted mother liquid of CDs@AlPO-5.
fig. S5. Structure of 2D-AlPO synthesized by using TTDDA as SDA. (A) Thermal ellipsoids of 2D-AlPO given at 50% probability, showing the atomic labelling scheme. (B) The structure of 2D-AlPO viewed along the [001] direction, in which the protonated TTDDA cations are located between the layers.
fig. S6. TADF properties of CDs@2D-AlPO composite. (A) The steady-state photoluminescence spectrum (deep blue line) and delayed photoluminescence spectrum (blue line) of CDs@2D-AlPO excited under 370 nm at room temperature. The emission band of the delayed fluorescence centers at 440 nm, which is similar with that of the prompt fluorescence shown in the steady-state spectrum. (B) The time-resolved decay spectra of CDs@2D-AlPO at room temperature with the long lifetime of 197 ms and short lifetime (inset) of 10.2 ns. (C) Temperature-dependent transient photoluminescence decay of the CDs@2D-AlPO composite. (D) The steady-state photoluminescence spectrum (deep blue line) and delayed photoluminescence spectrum (olive line) of CDs@2D-AlPO excited under 370 nm at 77K. The delayed photoluminescence spectra were collected with the delay time of 1 ms.
fig. S7. TADF properties of CDs@MgAPO-5 composite. (A) The steady-state photoluminescence spectrum (deep blue line) and delayed photoluminescence spectrum (blue line) of CDs@MgAPO-5 excited under 370 nm at room temperature. The emission band of the delayed fluorescence centers at 425 nm, which is consistent with that of the prompt fluorescence shown in the steady-state spectrum. (B) The time-resolved decay spectra of CDs@MgAPO-5 at room temperature with the long lifetime of 216 ms and short lifetime (inset) of 3.2 ns. (C) Temperature-dependent transient photoluminescence decay of the CDs@MgAPO-5 composite. (D) The steady-state photoluminescence spectrum (deep blue line) and delayed photoluminescence spectrum (olive line) of CDs@MgAPO-5 excited under 370 nm at 77K. The delayed photoluminescence spectra were collected with the delay time of 1 ms.
fig. S8. TADF properties of CDs@zeolite composites after vacuum drying for 12 hours at room temperature. The steady-state photoluminescence spectra (deep blue line), delayed photoluminescence spectra (blue line) and time-resolved decay spectra of vacuum dried CDs@AlPO-5 (A, B), CDs@2D-AlPO (C, D) and CDs@MgAPO-5 (E, F) excited under 370 nm at room temperature.
fig. S9. The compositional analysis of the organic species in CDs@AlPO-5 composite. The high resolution XPS spectra of (A) C 1s and (B) N 1s for CDs@AlPO-5. (C) The UV-vis absorption spectrum of CDs@AlPO-5. (D) FTIR spectrum of CDs@AlPO-5.
fig. S10. The compositional analysis of the organic species in CDs@2D-AlPO composite. The high resolution XPS spectra of (A) C 1s and (B) N 1s for CDs@2D-AlPO. (C) The UV-vis absorption spectrum of CDs@2D-AlPO. (D) FTIR spectrum of CDs@2D-AlPO.
fig. S11. The compositional analysis of the organic species in CDs@MgAPO-5 composite. The high resolution XPS spectra of (A) C 1s and (B) N 1s for CDs@MgAPO-5. (C) The UV-vis absorption spectrum of CDs@MgAPO-5. (D) FTIR spectrum of CDs@MgAPO-5. fig. S12. The time-resolved decay spectrum of the CDs in the diluted mother liquid of CDs@AlPO-5 at room temperature. Only short-lived lifetime of 5.1 ns is detected.
fig. S13. PXRD and TG characterizations of CDs@AlPO-5 composites vacuum-calcined at different temperatures. (A) Powder X-ray diffraction patterns of CDs@AlPO-5 composites upon vacuum calcination at different temperatures. (B) TG curves of CDs@AlPO-5 composite and the vacuum calcined CDs@AlPO-5 composites at different temperatures. fig. S14. TADF properties of CDs@AlPO-5 composites upon vacuum calcination at different temperatures. The steady-state photoluminescence spectra (A), delayed photoluminescence spectra (B) and time-resolved decay spectra (C) of raw CDs@AlPO-5 composite and vacuum dried CDs@AlPO-5 composites at different temperatures. Notice that, a broad peak at 500 nm appears in the steady-state photoluminescence spectrum of calcined sample at 500 ºC, suggesting that some new carbon dot species might be formed by pyrolysis.
fig. S15. TADF properties of CDs@zeolite composites kept under ambient conditions for more than half a year. The steady-state photoluminescence spectra (deep blue line), delayed photoluminescence spectra (blue line) and time-resolved decay spectra of CDs@AlPO-5 (A, B), CDs@2D-AlPO (C,D) and CDs@MgAPO-5 (E, F) kept under ambient conditions for over half a year.
table S1. Crystal data and structure refinement for CDs@2D-AlPO. Identification code CDs@2D-AlPO Empirical formula C 10H 27Al 2N 2O 15P 3 Formula weight 562.21 Temperature 293(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2 1/c Unit cell dimensions a = 9.2188(9) Å α = 90 b = 28.760(3) Å β = 112.73 c = 9.2188(9) Å γ = 90 Volume 2254.4(4) Å 3 Z, Calculated density 4, 1.656 Mg/m 3 Absorption coefficient 0.416 mm -1 F(000) 1168 Crystal size 0.23 0.21 0.20 mm Theta range for data collection 1.42 to 28.26 Limiting indices -12 h 12, -38 k 36, -7 l 12 Reflections collected / unique 16458 / 5561 [R int = 0.1548] Completeness to theta = 28.26 99.20% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9214 and 0.9103 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5561 / 36 / 292 Goodness-of-fit on F 2 0.956 Final R indices [I> 2σ (I)] a R 1 = 0.0784, wr 2 = 0.2103 R indices (all data) R 1 = 0.1012, wr 2 = 0.2295 Largest diff. peak and hole 1.254 and -1.246 e. Å -3 a R 1=Σ( F/Σ(Fo)); wr 2=(Σ[w(F o2 -F c2 )])/ Σ[w(F o2 ) 2 ] 1/2, w=1/[σ 2 (F o2 )+(0.1411P) 2 +0.0000P] where P=(Fo 2 +2Fc 2 )/3
table S2. Atomic coordinates ( 10 4 ) and equivalent isotropic displacement parameters (Å 2 10 3 ) for CDs@2D-AlPO. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Al(1) 6387(1) 2732(1) 4633(1) 21(1) Al(2) 1886(1) 2709(1) 4911(1) 22(1) P(1) 9898(1) 2876(1) 6968(1) 24(1) P(3) 4130(1) 3510(1) 4804(1) 25(1) P(2) 4848(1) 2060(1) 6085(1) 20(1) O(1) 11106(2) 2905(1) 6224(2) 38(1) O(2) 10431(2) 2512(1) 8259(2) 48(1) O(3) 8362(1) 2695(1) 5732(2) 36(1) O(4) 5424(2) 2228(1) 4816(1) 28(1) O(5) 3311(2) 2303(1) 5853(2) 40(1) O(6) 6074(1) 2781(1) 2670(1) 32(1) O(7) 5632(1) 3221(1) 5212(2) 30(1) O(8) 2736(2) 3183(1) 4383(2) 37(1) O(9) 9752(2) 3345(1) 7580(2) 44(1) O(10) 4620(2) 1542(1) 6018(1) 31(1) O(11) 4279(2) 3832(1) 6110(2) 38(1) O(12) 3889(2) 3798(1) 3294(2) 38(1) O(13) 7849(3) 71(1) 3777(3) 97(1) O(14) 8026(4) 354(1) 899(3) 134(2) O(15) 8570(2) 870(1) -2134(2) 60(1) N(1) 7362(2) -1185(1) 6876(2) 36(1) N(2) 7562(2) 1128(1) -6899(2) 48(1) C(1) 7582(5) -689(1) 6642(4) 95(1) C(2) 7589(9) -524(1) 5388(5) 223(3) C(3) 7533(6) -21(1) 5045(4) 153(2) C(4) 6899(6) -88(1) 2319(5) 140(3) C(5) 7612(6) -99(1) 1180(5) 116(2) C(6) 7764(6) 464(2) -473(4) 152(2) C(7) 8280(4) 913(1) -810(3) 74(1) C(8) 9198(4) 1291(1) -2484(3) 82(1) C(9) 9203(3) 1265(1) -4059(3) 70(1) C(10) 7611(3) 1255(1) -5336(3) 53(1)
table S3. The photoluminescence emission bands and lifetimes of CDs@zeolite composites after vacuum drying at room temperature. Compounds PL (nm) PL dried (nm) τ TADF (ms) τ TADF-dried (ms) CDs@AlPO-5 430 430 350 357 CDs@2D-AlPO 440 440 197 188 CDs@MgAPO-5 425 425 216 226 table S4. The photoluminescence emission bands and lifetimes of CDs@AlPO-5 composites after vacuum calcination at different temperatures. Compounds CDs@AlPO-5 CDs@AlPO-5 200 ºC calcined CDs@AlPO-5 500 ºC calcined Prompt PL (nm) 430 430 430, 500 Delayed PL (nm) 430 430 -- τ TADF (ms) 350 266 -- Quantum yield (%) 15.53 3.98 0.78 table S5. The photoluminescence emission bands and lifetimes of CDs@zeolite composites before and after half a year under ambient conditions. Compounds PL (nm) PL half a year (nm) τ TADF (ms) τ TADF-half a year (ms) CDs@AlPO-5 430 430 350 344 CDs@2D-AlPO 440 440 197 205 CDs@MgAPO-5 425 425 216 213 table S6. The multiexponential lifetime (τ i) and preexponential for lifetime (A i) of the CDs@zeolite composites and the diluted mother liquid. Compounds τ p (ns) τ TADF (ms) τ 1 A 1 τ 2 A 2 τ 3 A 3 τ 1 A 1 τ 2 A 2 CDs@AlPO-5 14.4 0.0025 3.6 0.015 0.3 0.57 151.4 2172 423.7 2094 CDs@2D-AlPO 17.9 0.023 7.7 0.068 2.3 0.095 65.5 4376 316.9 989 CDs@MgAPO-5 12.9 0.0088 3.6 0.025 0.2 2.03 127.5 4835 256.8 5275 Mother liquid of CDs@AlPO-5 10.5 0.019 3.5 0.089 0.7 0.19 - - - -