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1 Electronic Supplementary Material (ESI) for Catalysis Science & Technology. This journal is The Royal Society of Chemistry 2017 Supporting formation Selective Hydrogenation of Unsaturated Carbonyls by - based Alloy Catalysts Wahyu Satpriyo Putro, [a] Takashi Kojima, [a] Takayoshi Hara, [a] Nobuyuki Ichikuni, [a] and Shogo Shimazu* [a] [a] Chiba University, Graduate School of Engineering, 1-33 Yayoi, age, Chiba , Japan. -Al(1.0)HT -Ga(1.0)HT Co -Co(1.0)HT -Ti(1.0)HT -(1.0)HT Al Al Al Ga 2 Ga Ga 2 Ga Ti Co Ti (1.0)HT Co Ti Ce 2 -/Al 2 3 -/Ce 2 -/Hydrotalcite -/Taeniolite -/Si 2 -(2.0)HT / degree 2degree Fi gure S1. XRD patterns of -M (M =, Ti, Co,, Ga, Al) HT-673 catalysts, and - (2)(wt. 25%) supported on M x y (M x y = Si 2, Taeniolite, Hydrotalcite, Ce 2, and Al 2 3 ) catalysts. : : 2 4 : 2 3 (d) (c) 2degree) Figure S2. XRD patterns of -(2) without hydrothermal and H 2 treatment, -(2) hydrothermal at 423 K, without H 2 treatment, (c) -(2) without hydrothermal, H 2 treatment at 573 K, (d) -(2) hydrothermal at 423 K and H 2 treatment at 573 K. Page 1 of 5

2 with (2:1) hydrothermal HT-573 Yield60 of FFalc 40 (%) Time (min) - without (2:1) HT-573 hydrothermal w/o H2(T) -(2) with - hydrothermal (2:1) w/o H2(T) at 423 K -(2) without - hydrothermal (2:1) H2 (373 K) Figure S3. Effect of hydrothermal for catalytic performance of - alloy catalysts. Reaction conditions: C SUBS = M; W CAT = 50 mg (substrate/= 2); V iso-prh = 3 ml; P H2 = 10 bar; and T= 423 K. Yield determined by GC using an internal standard technique. Adsorbed amount, cm3/g -(2) -(2)HT-523 -(2)HT-623 -(2)HT-673 -(2)HT-723 Adsorbed -(5%)/ amount, cm3/g-(10%)/ Relative Relative Figure S4. Typical N 2 adsorption-desorption isotherm for -(2); with various temperatures of H 2 treatment, loaded on with various loading amounts of - alloy. Page 2 of 5

3 _ _ (2)HT-623 = 66.7 = 33.3 Rp = 4.2 = 66.9 = 33.1 Rp = 4.9 -(2)HT-673 -(2)HT-723 Pm3m = 84.5 = 15.5 Rp = 16.6 Pm3m = 67.0 = 33.0 Rp = 8.1 Figure S5. Multi-Rietveld analysis program LH-Riet profiles of powder XRD data of -(2) alloy catalysts with various temperatures of H 2 treatment. Data points (black line); calculated line, (red line); difference line, (green line); marker points (blue vertical line) Yield 60 of FFalc 40 (%) 20 Substrate/ ratio: Time Figure S6. Effect of Substrate/ ratios on the yield of furfuryl alcohol (FFalc) by using - (2)HT-573 catalysts. Reaction conditions: C SUBS = M; V iso-prh = 3 ml; P H2 = 10 bar; and T= 423 K. Yield determined by GC using an internal standard technique. Page 3 of 5

4 : : (e) (cps) (d) (c) 2degree) Figure S7. XRD patterns of bulk and supported - alloy with various loading amounts of -. bulk -(2)HT-673, -(wt. 50%)/, (c) -(wt. 25%)/, (d) - (wt. 10%)/, (e) -(wt. 5%)/. Yield of FFalc (%) Yield of FFalc VS Reaction Time -(25%)/ -(5%)/ -(50%)/ -(10%)/ -(2) 0 50Reaction 100Time 150 (min) Selectivity of FFalc (%) Selectivity VS Reaction Time -(2) -(25%)/ -(5%)/ -(10%)/ -(50%)/ Reaction Time (min) Figure S8. Time profile investigation of various loading amount of - alloy supported on. Reaction conditions: C SUBS = 73.4 mm; W CAT = 10 mg (Substrate/= 2); V iso-prh = 3 ml; P H2 = 10 bar; and T= 423 K. Page 4 of 5

5 (formation rate) (formation rate) ln (H Figure S9. Effect of initial H 2 pressure and furfural concentration over bulk -(2)HT alloy catalysts. Table S1. Comparison data for liquid-phase chemoselective hydrogenation of unsaturated carbonyls + + H Catalyst P H2 (MPa) T (K) t (min) Conv. (%) Sel. of 1 (%) Ref. Pt-Cu hollow-core [1] 7.5%Pt@g-C 3 N >99 [2] Pd-Cu/Mg [3] Cu(3):Zn(2):Cr(1):Zr(4) [4] Co/SBA [5] -Cu/Al [6] () 4 -Si [7] -Sn(3-2)HT [8] -(2-1)HT This Work H References [1] S. Huang, N. Yang, S. Wang, Y. Sun, Y. Zhu, Nanoscale 2016, 8, [2] X. Chen, L. Zhang, B. Zhang, X. Guo, X. Mu, Sci. Rep. 2016, 6, [3] K. Fulajtárova, T. Soták, M. Hronec, I. Vávra, E. Dobročka, M. mastová, Appl. Catal. A Gen. 2015, 502, [4] R. V. Sharma, U. Das, R. Sammynaiken, A. K. Dalai, Appl. Catal. A Gen. 2013, 454, [5] M. Audemar, C. Ciotonea, K. De liveira Vigier, S. Royer, A. Ungureanu, B. Dragoi, E. Dumitriu, F. Jérôme, ChemSusChem 2015, 8, [6] S. A. Khromova, M. V. Bykova,. A. Bulavchenko, D. Y. Ermakov, A. A. Saraev, V. V. Kaichev, R. H. Venderbosch, V. A. Yakovlev, Top. Catal. 2016, 59, [7] A. Halilu, T. H. Ali, A. Y. Atta, P. Sudarsanam, S. K. Bhargava, S. B. Abd Hamid, Energy & Fuels 2016, 30, [8] Rodiansono, S. Khairi, T. Hara, N. Ichikuni, S. Shimazu, Catal. Sci. Technol. 2012, 2, Page 5 of 5