Supporting Information. Excellent activity and selectivity of one-pot synthesized Cu-SSZ-13 catalyst

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1 Supporting Information Excellent activity and selectivity of one-pot synthesized Cu-SSZ-13 catalyst in the selective catalytic oxidation of ammonia to nitrogen Tao Zhang, Huazhen Chang,*, Yanchen You, Chuanning Shi, Junhua Li School of Environment & Natural Resources, Renmin University of China, Beijing , China State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing, , China * Corresponding authors: address: chz@ruc.edu.cn Tel.: Pages 1 Table 6 Figures page S1

2 Table S1. Review of catalytic performances of different catalysts for selective catalytic oxidation of NH 3 to N 2 Catalysts NH 3 Conversion / Temperature Selectivity to N 2 / Temperature Reaction conditions Ref. Pt(1.2 wt%)/al 2O 3 100% / 200 o C 75% / 200 o C 1.14% NH 3, 8.21% O 2, total flow 74.7 ml min -1, catalyst: 0.2 g 1 Pt Pt(4.0 wt%)/cu(20.0 wt%)/al 2O 3 100% / 200 o C 82% / 200 o C 700 ppm NH 3, 0.5% O 2, total flow 1000 Nml min -1, GHSV: 3000 ml/(min g cat) 2 Pt(0.05 wt%)/mgo-al 2O 3 98% / 300 o C 48% / 300 o C 0.5% NH 3, 2.5% O 2, total flow 40 ml min -1, catalyst: 0.1 g 3 Pt(2.5 wt%)/zsm-5 100% / 250 o C 41% / 250 o C 1000 ppm NH 3, 4%O 2, total flow 100 ml min -1, catalyst: 0.1 g 4 Pd(4.2 wt%)/al 2O 3 84% / 250 o C 97% / 250 o C 1000 ppm NH 3, 4%O 2, total flow 100 ml min -1, catalyst: 0.1 g 4 Pd Pd(0.09 wt%)/mgo-al 2O 3 90% / 300 o C 58% / 300 o C 0.5% NH 3, 2.5% O 2, total flow 40 ml min -1, catalyst: 0.1 g 3 Pd(5.5 wt%)/zsm-5 80% / 250 o C 73% / 250 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.1 g, GHSV: 230,000 h -1 5 Noble metal Rh Pd(2.5 wt%)/y 100% / 250 o C 95% / 250 o C 0.5% NH 3, 2.5% O 2, total flow 40 ml min -1, catalyst: 0.1 g, GHSV: 19,200 h -1 3 Rh(1.2 wt%)/al 2O 3 100% / 200 o C 75% / 200 o C 1.14% NH 3, 8.21% O 2, total flow 74.7 ml min -1, catalyst: 0.2 g 1 Rh(0.09 wt%)/mgo-al 2O 3 25% / 350 o C 90% / 350 o C 0.5% NH 3, 2.5% O 2, total flow 40 ml min -1, catalyst: 0.1 g 3 Rh(2.7 wt%)/zsm-5 9% / 250 o C 95% / 250 o C 1000 ppm NH 3, 4%O 2, total flow 100 ml min -1, catalyst: 0.1 g 4 Ir Ir(1.2 wt%)/al 2O 3 100% / 200 o C 95% / 200 o C 1.14% NH 3, 8.21% O 2, total flow 74.7 ml min -1, catalyst: 0.2 g 1 Au Au(3.0 wt%)/cu(1.0 mol%)/al 2O 3 100% / 327 o C 95% / 327 o C 2% NH 3, 2% O 2, total flow 30 ml min -1 6 Ru Mesoporous RuO 2 100% / 250 o C 78% / 250 o C 1000 ppm NH 3, 2%O 2, total flow 100 ml min -1, catalyst: 0.08 g 7 CuO/ Mesoporous RuO 2 100% / 180 o C 95% / 180 o C 1000 ppm NH 3, 2%O 2, total flow 100 ml min -1, catalyst: 0.08 g 7 Ag powder 100% / 300 o C 72% / 300 o C 1000 ppm NH 3, 10% O 2, total flow 50 ml min -1, catalyst: 0.1 g 8 Ag Ag(10 wt%)/al 2O 3 90% / 200 o C 49% / 200 o C 500 ppm NH 3, 10% O 2, total flow 200 ml min -1, catalyst: 0.2 g 9 Ag(10.0 wt%)/cu(10.0 wt%)/al 2O 3 100% / 200 o C 82% / 200 o C 1% NH 3, 10% O 2, total flow 400N ml min -1, catalyst: 0.8 g 10 Metal oxide Cu Ag(10 wt%)/sio 2 100% / 200 o C 62% / 200 o C 1000 ppm NH 3, 10% O 2, total flow 50 ml min -1, catalyst: 0.1 g 11 CuO(4.6 wt%)/al 2O 3 77% / 325 o C 92% / 325 o C 0.54% NH 3, 8% O 2, total flow 20 ml min -1, catalyst: g 12 CuO(20 wt%)/al 2O 3-ZrO 2 19% / 200 o C 100% / 200 o C 500 ppm NH 3, 5% O 2, total flow 200 ml min -1, catalyst: 0.1 g 13 CuO/carbon nano-tubes 98% / 175 o C 99% / 175 o C 1000 ppm NH 3, 2%O 2, total flow 100 ml min -1, catalyst: 0.1 g 14 CuO(5 mol%)-mg-al 98% / 350 o C 80% / 350 o C 0.5% NH 3, 2.5% O 2, total flow 40 ml min -1, catalyst: 0.1 g 15 Cu(8 mol%)-mg-fe(31 mol%) 80% / 200 o C 93% / 200 o C 0.5% NH 3, 2.5% O 2, total flow 40 ml min -1, catalyst: 0.1 g 16 page S2

3 Fe 2O 3(5 wt%)-al 2O 3 68% / 350 o C 80% / 350 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.2 g 17 Fe 2O 3(5 wt%)-sio 2 47% / 350 o C 79% / 350 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.2 g 17 Fe Fe 2O 3(5 wt%)-tio 2 65% / 350 o C 78% / 350 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.2 g 17 Fe 2O 3(5 wt%)-zro 2 62% / 350 o C 80% / 350 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.2 g 17 Fe(4.6 mol%)-mg-al 22% / 350 o C 88% / 350 o C 0.5% NH 3, 2.5% O 2, total flow 40 ml min -1, catalyst: 0.1 g 18 Co Co(5 mol%)-mg-al 48% / 350 o C 60% / 350 o C 0.5% NH 3, 2.5% O 2, total flow 40 ml min -1, catalyst: 0.1 g 15 V Mn V 2O 5(5 wt%)/tio 2 77% / 350 o C 89% / 350 o C 1000 ppm NH 3, 4%O 2, total flow 100 ml min -1, catalyst: 0.1 g 4 V 2O 5(2 wt%)-ceo (10 wt%)/tio 2 98% / 275 o C 75% / 275 o C 200 ppm NH 3, 8%O 2, 6% moisture, total flow 500 ml min -1, GHSV: 60,000 h MnO 2 96% / 200 o C 67% / 200 o C 500 ppm NH 3, 3%O 2, total flow 1000 ml min -1, catalyst: 2 g 20 Mn 2O 3 100% / 200 o C 70% / 200 o C 500 ppm NH 3, 3%O 2, total flow 1000 ml min -1, catalyst: 2 g 5 Cu(4.3 wt%) 48% / 250 o C 95% / 250 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.1 g 5 Fe(2.0 wt%) 63% / 250 o C 92% / 250 o C 500 ppm NH 3, 2% O 2, total flow 200 ml min -1, catalyst: 0.1 g 5 ZSM-5 Co(1.2 wt%) 58% / 250 o C 73% / 250 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.1 g 5 Zeolite Beta Mn(1.0 wt%) 68% / 250 o C 77% / 250 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.1 g 5 Ni(0.9 wt%) 39% / 250 o C 69% / 250 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.1 g 5 Cu(6.6 wt%) 100% / 350 o C 96% / 350 o C 0.54% NH 3, 8% O 2, total flow 200 ml min -1, W/F: g s ml, catalyst: g 21 Fe 13% / 250 o C 95% / 250 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.1 g 22 Y Fe(2.0 wt%) 29% / 350 o C 61% / 350 o C 500 ppm NH 3, 2% O 2, total flow 200 ml min -1, catalyst: 0.1 g 23 MOR Fe 26% / 250 o C 88% / 250 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.1 g 22 FER Fe 18% / 350 o C 95% / 350 o C 1000 ppm NH 3, 2%O 2, total flow 500 ml min -1, catalyst: 0.1 g 22 SSZ-13 Cu(4.08%) 94% / 200 o C 97% / 200 o C 500 ppm NH 3, 5%O 2, total flow 200 ml min -1, catalyst: 0.05 g, GHSV: 160,000 h -1 This work page S3

4 100 (A) 100 NH 3 Conversion / % (B) GHSV = 160,000 h -1 Cu-SSZ-13-O Cu-SSZ-13-O-H GHSV = 320,000 h -1 Cu-SSZ-13-O Cu-SSZ-13-O-H Temperature / o C N 2 Selectivity / % Figure S1. (A) NH 3 conversion and (B) N 2 selectivity over two samples under different GHSVs. page S4

5 Cu-SSZ-13-O Intensity / a.u. α β Cu-SSZ-13-O-H Magnetic Field / G Figure S2. EPR spectra of Cu-SSZ-13 catalysts. page S5

6 (A) O ads O 1s Intensity / a.u. O latt O ads /O latt Binding Energy / ev (B) Cu 2p Cu 2p 3/2 Intensity / a.u. b Satellite Cu 2p 1/2 a Binding Energy / ev Figure S3. (A) O 1s and (B) Cu 2p XPS spectra of (a) Cu-SSZ-13-O and (b) Cu-SSZ-13-O-H. The Cu 2p XPS spectra of Cu-SSZ-13-O and Cu-SSZ-13-O-H are shown in Figure S2B. Cu 2p 3/2 and Cu 2p 1/2 peaks were observed in the ranges of and ev, respectively. The Cu 2p3/2 peak around ev and the satellite peak around ev is regarded as a characteristic to determine Cu page S6

7 4 3 (A) o C Intensity / a.u o C 300 o C 250 o C 200 o C 150 o C 100 o C Wavenumber / cm (B) o C Intensity / a.u o C 300 o C 250 o C 200 o C 150 o C 100 o C Wavenumber / cm -1 Figure S4. DRIFTS spectra of chemisorbed 500 ppm NH 3 on Cu-SSZ-13-O-H at 100 C followed by purge in (A) N 2 or (B) 5%O 2 /N 2 at different temperatures. page S7

8 Absorbance / a.u Cu-SSZ-13-O-H 1619 HSSZ Wavenumber / cm -1 Figure S5. DRIFTS spectra of chemisorbed 500 ppm NH 3 on H-SSZ-13 and Cu-SSZ-13-O-H at 100 C. page S8

9 100 (A) NH 3 Conversion / % Cu-SSZ-13-O-H CuO/Cu-SSZ-13-O-H Temperature / o C ln (NH 3 TOF) [mol NO / mol Cu / s] (B) E a ~ 93 kj/mol lna ~ / T (K -1 ) Cu-SSZ-13-O-H CuO/Cu-SSZ-13-O-H E a ~ 109 kj/mol lna ~ 27.8 Figure S6. (A) NH 3 conversion as function of temperature over Cu-SSZ-13-O-H and CuO/Cu-SSZ-13-O-H. (B) Arrhenius plots of NH 3 conversion (in TOF, mol NH 3 / mol Cu / s) over Cu-SSZ-13-O-H and CuO/Cu-SSZ-13-O-H catalysts. TOFs were calculated using reaction data shown in Figure S6A. Reaction conditions: [NH 3 ] = 500 ppm, [O 2 ] = 5%, N 2 balance, total flow rate 200 ml min -1 and GHSV = 320,000 h -1. The catalytic performances of Cu-SSZ-13-O-H and CuO/Cu-SSZ-13-O-H catalysts were page S9

10 evaluated and the results are shown in Figure S6A. Furthermore, NH 3 turnover frequencies (TOF) on a per mole of Cu basis were calculated using the reaction data shown in Figure S6A, and Arrhenius plots are depicted in Figure S6B. Note that for Cu-SSZ-13-O-H, the ion-exchange level is 82.7%. Although partial ion-exchanged sites in Cu-SSZ-13-O-H are still remained, Cu 2+ ions are hard to be exchanged onto them. This is due to the small pore openings and limitation of ion-exchanged capacity of SSZ-13 zeolite. Therefore, the Cu species introduced onto Cu-SSZ-13-O-H mainly exsited as CuO. Compared with Cu-SSZ-13-O-H, TOF for CuO/Cu-SSZ-13-O-H decreased obviously with loading CuO, suggesting that Cu 2+ ions were more active than CuO in the NH 3 -SCO reaction over Cu-SSZ-13 catalyst. In addition, Cu-SSZ-13-O-H showed a relatively higher E a of 109 kj mol -1 in comparison with CuO/Cu-SSZ-13-O-H, indicating that fewer pore diffusion limitations existing in the former. 25 References [1] Gang, L.; Anderson, B. G.; van Grondelle J.; van Santen R. A. NH 3 oxidation to nitrogen and water at low temperatures using supported transition metal catalysts. Catal. Today 2001, 61 (1-4), [2] Olofsson, G.; Wallenberg, L. R.; Andersson, A. Selective catalytic oxidation of ammonia to nitrogen at low temperature on Pt/CuO/Al 2 O 3. J. Catal. 2005, 230 (1), [3] Jablonska, M.; Krol, A.; Kukulska-Zajac, E.; Tarach, K.; Chmielarz, L.; Gora-Marek, K. Zeolite Y modified with palladium as effective catalyst for selective catalytic oxidation of ammonia to nitrogen. J. Catal. 2014, 316, [4] Li, Y. J.; Armor, J. N. Selective NH 3 oxidation to N 2 in a wet stream. Appl. Catal. B 1997, 13 (2), page S10

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