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1 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 , Chin Stte Key Lortory of Inorgnic Synthesis nd Preprtive Chemistry, Jilin University, Chngchun , Chin * Corresponding uthor: Tel: (+86) ; Fx: (+86) Emil ddress: jimj@jlu.edu.cn (M. Ji)
2 Fig. S1 SEM imge of ZrSBA-15.
3 Fig. S2 SEM imge of SBA-15.
4 Quntity dsored (mmol/g) 50 A c Reltive pressure (P/P0 ) dv/dd (cm 3 g -1 nm -1 ) B 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).
5 Volume of gs generted (ml) 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.
6 H 2 Intensity (. u.) CO c 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).
7 Volume of gs generted (ml) 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.
8 Volume of H 2 + CO 2 (ml) 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 ().
9 e d Asornce c Wvelength (nm) Fig. S8 UV-Vis spectr of the queous solution contining different orgnic mines: () AP, () AEAP, (c) AEAEAP, (d) MAP, nd (e) DMAP.
10 Fig. S9 The photos of the mixed solution contining different orgnic mines nd the metl precursors (PdCl 4 2-, AuCl 4- ) t room temperture.
11 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 This work Pd/CN x S1 Ag@Pd/C S2 AgPd/C S3 AuPd/C S4 CoAuPd/C S5 NiAuPd/C S6 AgAuPd/rGO S7 CoAuPd/r-GO S8 CoAuPd/DNA-rGO S8 AuPd/N-mrGO S9 Au@Pd/N-mrGO S9 AuPd/N-rGO S10 AuPd-CeO 2 /N-rGO S10 AuPd/ZIF-8-rGO S11 AuPd-MnO x /ZIF-8-rGO S11 PdAg-MnO x /N-SiO S12 CrAuPd/N-SiO S13 PdAu/N-SiO S14 PdAu-MnO x /N-SiO S14 AgPd@MIL-100(Fe) S15 Pd/SBA-15-NH 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, 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, S3 S. Zhng, Ö. Metin, D. Su nd S. Sun, Angew. Chem. Int. Edit., 2013, 52, S4 Ö. Metin, X. Sun nd S. Sun, Nnoscle, 2013, 5, S5 Z. L. Wng, J. M. Yn, Y. Ping, H. L. Wng, W. T. Zheng nd Q. Jing, Angew. Chem. Int. Edit., 2013, 52, S6 Z. L. Wng, Y. Ping, J. M. Yn, H. L. Wng nd Q. Jing, Int. J. Hydrogen Energ., 2014, 39,
12 S7 S. j. Li, Y. Ping, J. M. Yn, H. L. Wng, M. Wu nd Q. Jing, J. Mter. Chem. A, 2015, 3, 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, S9 Z. L. Wng, J. M. Yn, H. L. Wng, Y. Ping nd Q. Jing, J. Mter. Chem. A, 2013, 1, S10 Z. L. Wng, J. M. Yn, Y. F. Zhng, Y. Ping, H. L. Wng nd Q. Jing, Nnoscle, 2014, 6, 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, S12 A. Bulut, M. Yurderi, Y. Krts, Z. Sy, H. Kivrk, M. Ky, M. Gulcn, E. Ozensoy nd M. Zhmkirn, ACS Ctl., 2015, 5, S13 M. Yurderi, A. Bulut, N. Cner, M. Celei, M. Ky, M. Zhmkirn, Chem. Commun., 2015, 51, 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, S15 F. Ke, L. Wng nd J. Zhu, Nnoscle, 2015, 7, S16 K. Koh, J. E. Seo, J. H. Lee, A. Goswmi, C. W. Yoon nd T. Asef, J. Mter. Chem. A, 2014, 2,
13 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 ( P), V is the volume of (H 2 + CO 2 ) relesed t 20% conversion of FA (m 3 ), R is the universl gs constnt ( 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.
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