Silver Nanocrystals-Decorated Polyoxometalate Singal-Walled Nanotubes as Nanoreactors for Desulfurization Catalysis at Room Temperature

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1 Electronic Supplementary Material (ESI) for Nanoscale. This journal is The Royal Society of Chemistry 2017 Silver Nanocrystals-Decorated Polyoxometalate Singal-Walled Nanotubes as Nanoreactors for Desulfurization Catalysis at Room Temperature Hao Zhang, Xiaobin Xu, Haifeng Lin, Muhammad Aizaz Ud Din, Haiqing Wang and Xun Wang* Department of Chemistry, Tsinghua University, Beijing , China. Correspondence and requests for materials should be addressed to X.W.. (

Fig S1. The time series in the formation process of POM SWNTs. TEM image of POM SWNTs with various reaction time of (a) 0 min, (b) 15 min, (c) 30 min, (d) 45 min, (e) 120 min and (f) 180 min.

2 Fig S1. The time series in the formation process of POM SWNTs. TEM image of POM SWNTs with various reaction time of (a) 0 min, (b) 15 min, (c) 30 min, (d) 45 min, (e) 120 min and (f) 180 min. The inset in (d) shows a ring in the product, which gives a top view of SWNTs. Scale bar: (a-f), 100 nm; inset of (a), 50 nm. Take a nanoroll from (b) and a nanotube from Fig. 1a to approximately calculate surface area. The surface area of cylinder follows S = πdl, and the nanoroll is calculated by S = 3πdl, for the 3 layers of the nanoroll on each side. It can be calculated that the surface area is about 0.015~0.025 μm 2 for nanoroll and 0.010~0.020 μm 2 for nanotube. The surface area of nanorolls and nanotubes are at the same scale. Considering the error in statistic, the rearrangement process in Scheme 1a can be proved.

3 Fig S2. TEM image of Ag-POM when AgNO 3 concentration is increased to 4 g/l. Scale bar: 50 nm

4 Fig S3. TEM image of Ag-out-POM. The concentration of AgNO 3 is increased to 4 mg/ml and the ratio of EtOH:cyclohexane is 6 ml : 3 ml. Scale bar: 100 nm

5 Fig S4. HRTEM pattern of Ag-POM. Scale bar: 10 nm. POM SWNTs show no lattice fringe in HRTEM pattern for their poor crystallinity. Fig S5. FT-infrared spectroscopy of POM (upper curve) and Ag-POM (lower curve).

6 Fig S6. Powder XRD pattern of POM SWNTs and Ag-POM. Most peaks of both POM SWNTs and Ag-POM are broaden and hard to fit with a certain crystal structure, though a part of peaks labeled by vertical bars can fit some phosphotungstates. The three bars indicate peaks of Na 5 P 3 O 10 6H 2 O (JCPDS: ), (NaPO 3 ) 3 6H 2 O (JCPDS: ) and H 3 PW 12 O 40 (JCPDS: ) nm Theta (deg.) Fig S7. Small angle XRD pattern of Ag-POM shows a periodic distance of 2.51 nm, which indicates the distance of nearby two clusters on the cross section of SWNT. Take the diameter of SWNTs (9 nm) and perimeter equals to πd, the amount of POM clusters can be approximately calculated as: πd n = periodic distance = 11.3

7 0.14 POM Ag-POM TCD signal (a.u.) Temperature ( o C) Fig S8. TPR profile of Ag-POM and POM SWNTs. A flow of 5 vol.% H 2 /Ar is used as carrier gas and heating rate is 5 o C/min.

8 a b Fig S9. TEM image of Ag-POM after recycling process of (a) 1 time and (b) 5 times. Scale bar: 100 nm.

9 200 Relative Concentration (%) 100 A B C D Time (min) Fig S10. The control experiment to reveal the catalytic activity of each component. A: 30 mg POM SWNTs. B: 5 mg Ag NCs supported on 100 mg SiO 2 xh 2 O, C: 30 mg Ag-POM, D: 5 mg Ag NCs. Then 30 μl DPS and 90 μl H 2 O 2 was added into 10 ml n-octane and the reaction temperature is 20 o C.

10 Scheme S1 To confirm the spatial situation of Ag NCs in Ag-POM, suppose that all the NCs are on the outer surface of NTs. For an approximate calculation, the diameter ratio of NCs to NTs is supposed as 1:4. A single NC bind on the outer surface of NTs in a random direction and α stands for the angle of direction (0 α 90). TEM image is taken on a certain direction (top view). To let the outer NCs appears inside NTs in TEM image, α can be calculated as arccos (4/(4+1)) = 36.9 o. That means just 41.0% (=36.9 o /90 o ) NCs are inside NTs in TEM image. However most of NCs are inside NTs and seldom of them is tangent to NTs in figure 1. So it can be ensured that all the NCs are decorated inside the NTs. As a contrast, NCs in figure S3 fixs the 41.0% ratio and thus can be proved outside the NTs. Table S1. ICP-AES data sample W Ag P Na POM SWNTs 36.29% % 3.208% Ag-POM 36.87% 1.528% % % Ag-out-POM 36.56% 1.571% % % precipitate * 32.25% 1.331% % % supernatant ** 1.161% % % % * precipitate and ** supernatant after 5 times recycling. Table S2. The assignment of FTIR spectra Ag-POM POM Assignment* CH2 asym. str CH2 sym. str O-H scissoring CH2N scissoring CH2 scissoring CH3 scissoring P-O asym. str CH2N sym. str W=Od sym. str W-Ob-W sym. str W-Oc-W sym. str CH2 rocking * asym. str., asymmetric stretching; sym. str., symmetric stretching

11 Table S3. TON of other reported ODS catalysts Catalyst Sub. a Temp. b Product TON c Ref. DA-La(PW 11 ) 2 DPS 25 o C sulfone WO 3 DPS 25 o C sulfone (DODA) 3 PW 12 O 40 DPS 50 o C sulfone Chloroperoxidase MPS 37 o C sulfoxide Horseradish peroxidase MPS 37 o C sulfoxide Lactoperoxidase MPS 37 o C sulfoxide Microsome peroxidase MPS 37 o C sulfoxide 3 3. (TBA) 4 Mo 8 O 26 MPS 25 o C sulfoxide (TBA) 2 SeW 2 O 14 MPS 20 o C sulfoxide (Zr 6 O 4 )(AsW 9 O 33 ) 2 MPS 20 o C mixture (Hf 6 O 4 )(AsW 9 O 33 ) 2 MPS 20 o C mixture (HDA) 3 PW 12 O 40 DBT 50 o C sulfone (DODA) 3 PW 12 O 40 DBT 50 o C sulfone (DOHDA) 3 PW 12 O 40 DBT 40 o C sulfone H 3 PW 12 O 40 DBT 50 o C sulfone (STA) 3 PW 12 O 40 DBT 50 o C sulfone (C 18 H 37 ) 2 Me 2 NPW 12 O 40 DBT 60 o C sulfone (DDA) 9 LaW 10 DBT 30 o C sulfone [(C 18 H 37 ) DBT 60 o C sulfone Me 3 N]PV 2 Mo 10 O 40 MoO 2 /C thiophene 70 o C sulfone MoO 3 /Al 2 O 3 thiophene 70 o C sulfone K 8 Fe(PW 9 O 34 ) 2 THT 75 o C sulfoxide a Sub., substrate. b Temp., temperature. c TON, turnover number.

12 Table S4. The reaction condition and convert ratio of DBT ODS reactions. No. Cat. (ml)* Temp. (oc) Time (h) H2O2 (ul) Conversion(%) 0 POM ** POM, POM, POM, Ag-POM, Ag-POM, Ag-POM, Ag-POM, Ag-POM, Ag-POM, Ag-POM, Ag-POM, Ag-POM, * cat., catalyst. 1.0 ml catalyst is amount to 8.5 mg Ag-POM. ** This group uses POM powder instead of nanotubes. Reference 1. Zhao S, Jia Y, Song Y F. Applied Catalysis A General, 2013, 453(1): Nisar A, Lu Y, Zhuang J, et al. Angewandte Chemie, 2011, 123(14): Fernández I, Khiar N. Chemical Reviews, 2003, 103(9): Yang C, Jin Q, Zhang H, et al. Green Chemistry, 2009, 11(9): Kamata K, Hirano T, Ishimoto R, et al. Dalton Transactions, 2010, 39(23): Wallenfels B. Proceedings of the National Academy of Sciences of the United States of America, 1979, 76(7): Nisar A, Zhuang J, Wang X. Advanced Materials, 2011, 23(9): Qi W, Wang Y, Wen L D, et al. Chemistry, 2010, 16(3): Te M, Fairbridge C. Applied Catalysis A General, 2001, 219(1): Huang D, Wang Y J, And L M Y, et al. Industrial & Engineering Chemistry Research, 2011, 45(6):págs Dr C L, Dr Z J, Dr J G, et al. Chemistry, 2004, 10(9): Xu J, Zhao S, Ji Y, et al. Chemistry, 2013, 19(2): Lü H, Gao J, Jiang Z, et al. Chemical Communications, 2006, 2(2): Zhuang L, Li Q, Chen S, et al. Journal of Materials Science, 2014, 49(16): Okun N M, Anderson T M, Hill C L. Journal of the American Chemical Society, 2003, 34(22):

Division of Fuel Cells, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese

Division of Fuel Cells, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supporting information Tuned Depositing Ag clusters on ZrO 2 Nanocrystals from Silver Mirror