Electronic Supplementry Mteril (ESI) for Ctlysis Science & Technology. This journl is The Royl Society of Chemistry 2017 Supporting informtion PdAu imetllic nnoprticles nchored on mine-modified mesoporous ZrSBA- 15 for dehydrogention of formic cid t mient conditions Zhenzhen Wng, Xiufeng Ho, Dinwen Hu, Lin Li, Xiojing Song, Wenxing Zhng, nd Mingjun Ji, * College of Chemistry, Jilin University, Chngchun 130012, Chin Stte Key Lortory of Inorgnic Synthesis nd Preprtive Chemistry, Jilin University, Chngchun 130012, Chin * Corresponding uthor: Tel: (+86)431-85155390; Fx: (+86)431-85168420. Emil ddress: jimj@jlu.edu.cn (M. Ji)
Fig. S1 SEM imge of ZrSBA-15.
Fig. S2 SEM imge of SBA-15.
Quntity dsored (mmol/g) 50 A 40 30 20 10 c 0 0.0 0.2 0.4 0.6 0.8 1.0 Reltive pressure (P/P0 ) dv/dd (cm 3 g -1 nm -1 ) 8 6 4 2 0 B 5 10 15 20 25 30 Pore dimeter (nm) c Fig. S3 The N 2 dsorption-desorption isotherms (A) nd the pore size distriutions (B) of ZrSBA-15 (), ZrSBA-15-AP () nd Pd 60 Au 40 / ZrSBA-15-AP (c).
Volume of gs generted (ml) 100 80 60 40 20 0 0 1 2 3 4 5 6 7 Time (min) Fig. S4 The volume of generted gs versus time for the dditive-free dehydrogention of FA (0.2 M, 10 ml) t 298 K in the presence of Pd 60 Au 40 /ZrSBA- 15-AP () nd Pd 60 Au 40 /SBA-15-AP (), respectively.
H 2 Intensity (. u.) CO c 0 1 2 3 4 5 6 7 Time (min) Fig. S5 Gs chromtogrphy nlysis results of pure CO (), pure H 2 () nd generted gs for Pd 60 Au 40 /ZrSBA-15-AP ctlyzed dditive-free dehydrogention of FA (0.2 M, 10 ml) (c).
Volume of gs generted (ml) 100 80 60 40 20 0 0.0 0.5 1.0 1.5 2.0 2.5 Time (min) Fig. S6 The volume of generted gs versus time for Pd 60 Au 40 /ZrSBA-15-AP ctlyzed dditive-free dehydrogention of FA (0.2 M, 10 ml) t 298 K in the sence () or presence () of NOH trp.
Volume of H 2 + CO 2 (ml) 100 80 60 40 20 0 0 10 20 30 40 50 60 Time (min) Fig. S7 The volume of generted gs mixture versus time for the dehydrogention of FA (0.2 M, 10 ml) over Pd 60 Au 40 /ZrSBA-15-AP ctlyst t 288 K () nd 275 K ().
e d Asornce c 300 400 500 600 700 800 Wvelength (nm) Fig. S8 UV-Vis spectr of the queous solution contining different orgnic mines: () AP, () AEAP, (c) AEAEAP, (d) MAP, nd (e) DMAP.
Fig. S9 The photos of the mixed solution contining different orgnic mines nd the metl precursors (PdCl 4 2-, AuCl 4- ) t room temperture.
Tle S1 Comprison of the ctlytic performnce of Pd 60 Au 40 /ZrSBA-15-AP presented in this work with the recently reported heterogeneous ctlyst systems for the FA dehydrogention in the sence of ny dditives t room temperture. Ctlyst T (K) TOF initi l (h -1 ) Con. (%) E kj mol -1 Ref. Pd 60 Au 40 /ZrSBA-15-AP 298 1185 95 42.5 This work Pd/CN x 298 639 98 48.8 S1 Ag@Pd/C 298 157 43 - S2 AgPd/C 298 274 46 22.0 S3 AuPd/C 298 41 24 28.0 S4 CoAuPd/C 298 54 91 - S5 NiAuPd/C 298 20 73 - S6 AgAuPd/rGO 298 95 100 - S7 CoAuPd/r-GO 298 63 51 - S8 CoAuPd/DNA-rGO 298 130 96 - S8 AuPd/N-mrGO 298 39 93 - S9 Au@Pd/N-mrGO 298 111 98 - S9 AuPd/N-rGO 298 17 57 - S10 AuPd-CeO 2 /N-rGO 298 68 98 - S10 AuPd/ZIF-8-rGO 298 532 83 - S11 AuPd-MnO x /ZIF-8-rGO 298 764 94 - S11 PdAg-MnO x /N-SiO 2 298 482 99 72.4 S12 CrAuPd/N-SiO 2 298 707 87 49.8 S13 PdAu/N-SiO 2 298 164 76 26.2 S14 PdAu-MnO x /N-SiO 2 298 981 92 26.2 S14 AgPd@MIL-100(Fe) 298 58 37 - S15 Pd/SBA-15-NH 2 298 127 28 - S16 The initil TOF vlues of some literture reported ctlysts hve een reclculted on the sis of the conversion of formic cid fter recting 20 min in order to mke comprison. References S1 Q. Y. Bi, J. D. Lin, Y. M. Liu, H. Y. He, F. Q. Hung nd Y. Co, Angewndte. Chem. Int. Edit., 2016, 55, 11849-11853. S2 K. Tedsree, T. Li, S. Jones, C. W. A. Chn, K. M.K. Yu, P. A. J. Bgot, E. A. Mrquis, G. D. W. Smith nd S. C. E. Tsng, Nt. Nnotechnol., 2011, 6, 302-307. S3 S. Zhng, Ö. Metin, D. Su nd S. Sun, Angew. Chem. Int. Edit., 2013, 52, 3681-3684. S4 Ö. Metin, X. Sun nd S. Sun, Nnoscle, 2013, 5, 910-912. S5 Z. L. Wng, J. M. Yn, Y. Ping, H. L. Wng, W. T. Zheng nd Q. Jing, Angew. Chem. Int. Edit., 2013, 52, 4406-4409. S6 Z. L. Wng, Y. Ping, J. M. Yn, H. L. Wng nd Q. Jing, Int. J. Hydrogen Energ., 2014, 39, 4850-4856.
S7 S. j. Li, Y. Ping, J. M. Yn, H. L. Wng, M. Wu nd Q. Jing, J. Mter. Chem. A, 2015, 3, 14535-14538. S8 Z. L. Wng, H. L. Wng, J. M. Yn, Y. Ping, S. I. O, S. J. Li nd Q. Jing, Chem. Commun., 2014, 50, 2732-2734. S9 Z. L. Wng, J. M. Yn, H. L. Wng, Y. Ping nd Q. Jing, J. Mter. Chem. A, 2013, 1, 12721-12725. S10 Z. L. Wng, J. M. Yn, Y. F. Zhng, Y. Ping, H. L. Wng nd Q. Jing, Nnoscle, 2014, 6, 3073-3077. S11 J. M. Yn, Z. L. Wng, L. Gu, S. J. Li, H. L. Wng, W. T. Zheng nd Q. Jing, Adv. Energy Mter., 2015, 5, 1500107. S12 A. Bulut, M. Yurderi, Y. Krts, Z. Sy, H. Kivrk, M. Ky, M. Gulcn, E. Ozensoy nd M. Zhmkirn, ACS Ctl., 2015, 5, 6099-6110. S13 M. Yurderi, A. Bulut, N. Cner, M. Celei, M. Ky, M. Zhmkirn, Chem. Commun., 2015, 51, 11417-11420. S14 Y. Krts, A. Bulut, M. Yurderi, I.E. Erts, O. All, M. Gulcn, M. Celei, H. Kivrk, M. Ky nd M. Zhmkirn, Appl. Ctl. B: Environ., 2016, 180, 586-595. S15 F. Ke, L. Wng nd J. Zhu, Nnoscle, 2015, 7, 8321-8325. S16 K. Koh, J. E. Seo, J. H. Lee, A. Goswmi, C. W. Yoon nd T. Asef, J. Mter. Chem. A, 2014, 2, 20444-20449.
Clcultion method of initil TOF vlue: The initil TOF vlue ws clculted sed on the molr mount of nole metl Pd nd Au toms ccording to the following eqution: TOF = P 0 V/2RT n metl t wherein P 0 is the tmospheric pressure (101325 P), V is the volume of (H 2 + CO 2 ) relesed t 20% conversion of FA (m 3 ), R is the universl gs constnt (8.3145 m 3 P mol -1 K -1 ), T is the room temperture (298 K), n metl is the totl mole numer of nole metl toms in ctlyst, nd t is the rection time (h) when 20% conversion of FA is reched.