6-6-07, Aoba, Aramaki, Aoba-ku, Sendai , Japan Nakano-machi, Hachioji, Tokyo , Japan

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1 Supporting Information: Performance, Structure and Mechanism of Re x Pd/Ce 2 Catalyst for Simultaneous Removal of Vicinal H Groups with H 2 Nobuhiko ta, [a] Masazumi Tamura, [a, c] Yoshinao Nakagawa,* [a, c] Kazu kumura, [b] [a, c] Keiichi Tomishige* [a] Department of Applied Chemistry, School of Engineering, Tohoku University, , Aoba, Aramaki, Aoba-ku, Sendai , Japan [b] Department of Applied Chemistry, Faculty of Engineering, Kogakuin University, Nakano-machi, Hachioji, Tokyo , Japan [c] Research Center for Rare Metal and Green Innovation, Tohoku University, 468-1, Aoba, Aramaki, Aoba-ku, Sendai , Japan *Corresponding author: Keiichi Tomishige School of Engineering, Tohoku University, , Aoba, Aramaki, Aoba-ku, Sendai, , Japan tomi@erec.che.tohoku.ac.jp *Corresponding author: Yoshinao Nakagawa School of Engineering, Tohoku University, , Aoba, Aramaki, Aoba-ku, Sendai, , Japan yoshinao@erec.che.tohoku.ac.jp

2 Table of Contents i. Figure S1, Screening of active metals (M 1 in M 1 x Pd/Ce 2 ) for simultaneous removal of H groups of 1,4-AHERY... 1 ii. Figure S2, Screening of additives (M 2 in Re x M 2 /Ce 2 ) for simultaneous removal of H groups of 1,4-AHERY... 2 iii. Figure S3, Detail of Figure 4-upper (effect of hydrogen pressure)... 3 iv. Figure S4, Detail of Figure 4-lower (effect of substrate concentration)... 4 v. Table S1, Comparison of hydrogen and 3-pentanol as a reductant in the reaction of 1,4-AHERY over Re x Pd/Ce 2 catalyst... 5 vi. Table S2, Effect of reaction temperature on simultaneous removal of H groups of 1,4-AHERY over Re x Pd/Ce 2 catalyst... 6 vii. Figure S5, X-ray diffraction patterns of Re x Pd/Ce viii. Figure S6, TEM images of calcined Re x Pd/Ce 2 (Re = 2 wt%, Pd/Re = 0.25)... 8 ix. Figure S7, XPS of Re x Pd/Ce 2 in Pd 3d region... 9 x. Figure S8, XPS of reacted catalysts in Re 4f region xi. Figure S9, Relation between white line area and valence of Re xii. Figure S10, Pd K-edge EXAFS spectra xiii. Table S3 and Table S3, Curve fitting results of Pd K-edge EXAFS of Re x Pd/Ce xiv. Figure S11, Ce cluster model for DFT calculation xv. xvi. Figure S12, Calculated energy diagram of DDH of 1,4-AHERY over monomeric Re species on Ce model cluster Figure S13, Raman spectra of Re x Pd/Ce 2, Re x /Ce 2, Pd/Ce 2 after calcination at 773 K for 3 h xvii. Table S4, Suppliers of the reagents xviii. Table S5, Comparison of calculation levels between this and literature studies for methyltrioxorhenium-catalyzed DDH of ethylene glycol... 18

3 Conv. or Sel. / % thers THF Conv. Re W Mo Cr Nb Mn V Active matal (M 1 in M 1 x Pd/Ce 2 ) Figure S1 Screening of active metals (M 1 in M 1 x Pd/Ce 2 ) for simultaneous removal of H groups of 1,4-AHERY. Conditions: 1,4-AHERY 1 g, 1,4-dioxane 4 g, W cat = 150 mg (2 wt% M 1, Pd/M 1 = 0.25), PH 2 = 8 MPa, T = 413 K, t = 4 h. AHERY = anhydroerythritol, THF = tetrahydrofuran. 1

4 Conv. or Sel. / % H H 100 1,4-AHTHR H 1-BuH thers DHF None Co Ni Cu Ru Rh Pd Ir Pt Additives (M 2 in Re x M 2 /Ce 2 ) THF Figure S2 Screening of additives (M 2 in Re x M 2 /Ce 2 ) for simultaneous removal of H groups of 1,4-AHERY. Conditions: 1,4-AHERY 1 g, 1,4-dioxane 4 g, W cat = 150 mg (2 wt% Re, M 2 /Re = 0.25), PH 2 = 8 MPa, T = 413 K, t = 4 h. AHERY = anhydroerythritol, THF = tetrahydrofuran, BuH = butanol, AHTHR = anhydrothreitol, DHF = dihydrofuran. 2

5 Amount of THF / mmol Amount of THF / mmol Amount of THF / mmol Amount of THF / mmol 2.0 (a) 2.0 (b) y = x R² = Time / h (c) y = x R² = Time / h (d) y = x R² = y = x R² = Time / h Time / h Figure S3 Detail of Figure 4-upper (effect of hydrogen pressure). Conditions: 1,4-AHERY 0.5 g, 1,4-dioxane 2 g, W cat = 50 mg (2 wt% Re, 0.3 wt% Pd), PH 2 = MPa, T = 413 K. (a) PH 2 = 0.5 MPa, (b) PH 2 = 1 MPa, (c) PH 2 = 4 MPa, (d) PH 2 = 8 MPa. 3

6 Amount of THF / mmol Amount of THF / mmol Amount of THF / mmol Amount of THF / mmol 2.0 (a) 2.0 (b) y = x R² = y = x R² = Time / h (c) Time / h 2.0 (d) y = x R² = y = x R² = Time / h Time / h Figure S4 Detail of Figure 4-lower (effect of substrate concentration). Conditions: 1,4-AHERY 0.5 g, 1,4-dioxane g, W cat = 50 mg (2 wt% Re, 0.3 wt% Pd), PH 2 = 8 MPa, T = 413 K. (a) C = 5 wt%, (b) C = 10 wt%, (c) C = 15 wt%, (d) C = 20 wt%. 4

7 Table S1: Comparison of hydrogen and 3-pentanol as a reductant in the reaction of 1,4-AHERY over Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) catalyst. Entry Reductant Conv. / % Selectivity / % Tetrahydrofuran Dihydrofurans thers 1 hydrogen 38 >99 <1 <1 2 a 3-pentanol 2 <1 27 b 73 Conditions: 1,4-AHERY 1 g, 1,4-dioxane 4 g, W cat = 150 mg (2 wt% Re, 0.3 wt% Pd), PH 2 = 8 MPa, T = 413 K, t = 4 h. a 3-pentanol 4 g (as a solvent and reductant), P Ar = 4 MPa (at room temperature). b Ratio of 2,3-dihydrofuran/2,5-dihydrofuran=1/3. 5

8 Table S2: Effect of reaction temperature on simultaneous removal of H groups of 1,4-AHERY over Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) catalyst. Entry Reaction temp. /K Conv. / % Selectivity / % 3-Hydroxy- Tetrahydrofuran BuDs BuHs Tetrahydrofuran 1,4-Anhydrothreitol >99 <1 <1 <1 <1 < >99 <1 <1 <1 <1 < <1 >99 <1 <1 <1 <1 <1 thers Conditions: 1,4-AHERY 0.5 g, 1,4-dioxane 2 g, W cat = 50 mg, PH 2 = 8 MPa, t = 2 h. BuD = bunanediol, BuH = butanol. 6

9 Intensity / counts Ce 2 (e) (d) (c) (b) (a) degree / 2q Figure S5 X-ray diffraction patterns of Re x Pd/Ce 2. (a) Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) after calcination, (b) Re x Pd/Ce 2 (10 wt% Re, 1.5 wt% Pd) after calcination, (c) Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) after reduction in H 2 flow (30 cc/min) at 423 K for 1 h (at a heating rate 10 K/min), (d) Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) after reaction, (e) Re x Pd/Ce 2 (10 wt% Re, 1.5 wt% Pd) after reduction in H 2 flow (30 cc/min) at 423 K for 1 h (at a heating rate 10 K/min) 7

10 Figure S6 TEM images of calcined Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd). 8

11 Intensity / a.u. Pd II 3d 5/2 Pd 0 3d 5/2 a b c Binding Energy / ev Figure S7 XPS of Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) in Pd 3d region. (a) Re x Pd/Ce 2 before stoichiometric reaction (Reduction temp. = 423 K), (b) Re x Pd/Ce 2 after stoichiometric reaction (Reaction temp. = 353 K, t = 4 h), (c) Re x Pd/Ce 2 after reaction (Reaction temp. = 413 K, t = 4 h). Raw XPS data (black solid line), calculated data (black dotted line). Reference: C 1s = ev. Normalized by area of Ce 3d XPS. 9

12 Intensity / a.u. Re VII Re VI 4f 7/2 4f 7/2 Re IV 4f 7/2 Re 0 4f 7/2 a Valence of Re from XPS 5.0 b Binding Energy / ev 38 Figure S8 XPS of reacted catalysts in Re 4f region. (a) Re x Pd/Ce 2 after reaction (2 wt% Re, 0.3 wt% Pd, Reaction temp. = 413 K, t = 4 h), (b) Re x Pd/Si 2 after reaction (2 wt% Re, 0.3 wt% Pd, Reaction temp. = 413 K, t = 4 h). Raw XPS data (black solid line), calculated data (black dotted line). Reference: C 1s = ev. 10

13 White line area / a.u (e) (f) (c) (d) (b) (a) Valence of Re Figure S9 Relation between white line area and valence of Re. (a) Re powder, (b) Re 2, (c) Re 3, (d) Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) after reduction in H 2 flow (30 cc/min) at 423 K for 1 h, (e) Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) after stoichiometric reaction for 4 h, (f) Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) after catalytic use under the standard conditions. 11

14 k 3 χ(k) k 3 χ(k) F(r). (I) 20. (II) 20 c 5 c b b a a k / 10 nm -1.. (III) Distance / 0.1 nm. c k / 10 nm -1. Figure S10 Pd K-edge EXAFS spectra. (I) k 3 -Weighted EXAFS oscillations. (II) Fourier transform of k 3 -weighted Pd K-edge EXAFS, FT range: nm 1. (III) Fourier filtered EXAFS data (solid line) and calculated data (dotted line), Fourier filtering range: nm. (a)pd, (b) Pd foil, (c) Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd) after catalytic use under standard conditions. 12

15 Table S3: Curve fitting results of Pd K-edge EXAFS of Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd). Sample Shells CN a R / 10-1 nm b / 10-1 nm c E 0 / ev d R f / % e Re x Pd/Ce 2 after catalytic use under the standard conditions Pd Pd 3.1± ± ± ± Pd Re 1.6± ± ± ±0.9 Pd foil Pd Pd a CN = Coordination number, b R = Bond distance, c = Debye-Waller factor, d E 0 = Difference in origin of photoelectron energy between the reference and the sample, e R f = Residual factor. Table S3 : Curve fitting results of Pd K-edge EXAFS of Rex Pd/Ce2 (2 wt% Re, 0.3 wt% Pd) after catalytic use under the standard conditions. Model Shells CN a R / 10-1 nm b / 10-1 nm c E 0 / ev d R f / % e Two shells model Pd Pd Pd Re ne shell model Pd Pd a CN = Coordination number, b R = Bond distance, c = Debye-Waller factor, d E 0 = Difference in origin of photoelectron energy between the reference and the sample, e R f = Residual factor. The value of Residual factor on one shell model is unacceptably high. Therefore, the curve fitting analysis of Pd K-edge EXAFS is conducted using two shells model. 13

(a) Top view (b) Side view (c) Front view (d) Model construction scheme (2.5,2.5,5) (2.5,5,2.5) (2.5,5,2.5) (2.5,3.75,3.75) (3.75,2.5.3.75) (1.

The cluster is sculpted from the 5x5x5 supercell of Ce 2 crystal with fluorite structure.

The atoms on the boundary are included except the 6 cerium atoms at the vertexes of the octahedron, because these cerium atoms have a too

16 (a) Top view (b) Side view (c) Front view (d) Model construction scheme (2.5,2.5,5) (2.5,5,2.5) (2.5,5,2.5) (2.5,3.75,3.75) (3.75, ) (1.25,3.75,2.5) (2.5,1.25,1.25) (5,2.5,2.5) (0,2.5,2.5) (5,2.5,2.5) (1.25,2.5,1.25) (3.75,1.25,3.75) (2.5,0,2.5) (2.5,2.5,0) (2.5,2.5,0) Figure S11 Ce cluster model for DFT calculation. The cluster is sculpted from the 5x5x5 supercell of Ce 2 crystal with fluorite structure. First, an octahedron composed of (111) surface is sculpted from the supercell by cutting down the vertexes of the supercell. The atoms on the boundary are included except the 6 cerium atoms at the vertexes of the octahedron, because these cerium atoms have a too low (4) coordination number. Next, the octahedron is cut in half. The cross section becomes a large (111) surface which is used as the model surface. 14

17 Re IV Re VI Re IV Re IV Re Re IV Figure S12 Calculated energy diagram of DDH of 1,4-anhydroerythritol over monomeric Re species on Ce model cluster. Energies are shown in kj/mol. sub = Doubly deprotonated 1,4-anhydroerythritol. Calculation level: PW91/DND-3.5+DSPP, gas phase. Note 1: Although the four states shown in the right side are in high energy level, the Re species of these states are coordinated with only one oxygen atom on the Ce 2 surface. These states can be somewhat stabilized by adsorption of another alcoholic molecule (substrate) on the unoccupied oxygen site which was occupied in Re 2 /Ce 2. Adsorption of methanol on the Ce model cluster is calculated to be exothermic by 56 kj/mol. Note 2: Because a pure GGA-DFT (PW91) was used, the calculated activation barriers will be lower by ~30% than those calculated with more common B3LYP functional. See Table S5 for the comparison using model system with methyltrioxorhenium catalyst. Note 3: Re 2 /Ce 2 with only one Re bond was calculated to be in much higher energy level (+186 kj/mol) than the standard structure with two Re bonds as shown above. Structure of Re 3 /Ce 2 with two Re bonds was not found; geometry optimization leads to the structure with one Re bond as shown above. 15

18 Intensity / a.u. Intensity / a.u. a b c d e f g / Raman Shift / cm -1 Raman Shift / cm -1 Figure S13 Raman spectra of Re x Pd/Ce 2, Re x /Ce 2, Pd/Ce 2 after calcination at 773 K for 3 h. The intensity was normalized by that of Ce 2 -derived 464 cm -1 peak. (a) Ce 2 (after calcination at 873 K for 3 h), (b) Re x Pd/Ce 2 (10 wt% Re, 1.5 wt% Pd), (c) Re x Pd/Ce 2 (4 wt% Re, 0.6 wt% Pd), (d) Re x Pd/Ce 2 (2 wt% Re, 0.3 wt% Pd), (e) Re x Pd/Ce 2 (0.5 wt% Re, 0.07 wt% Pd), (f) Re x /Ce 2 (2 wt% Re), (g) Pd/Ce 2 (0.3 wt% Pd) 16

19 Table S4: Suppliers of the reagents. Reagent Supplier NH 4 V 3 Cr(N 3 ) 3 9H 2 Mn(N 3 ) 2 6H 2 (NH 4 ) 6 Mo H 2 (NH 4 )Nb(C 2 4 ) 2 xh 2 Aldrich Co., Ltd. (NH 4 ) 6 H 2 W xh 2 Strem Chemicals Inc. NH 4 Re 4 Soekawa Chemicals Co., Ltd. Pd(N 3 ) 2 N.E. Chemcat Corp. Co(N 3 ) 2 6H 2 Ni(N 3 ) 2 6H 2 Cu(N 3 ) 2 3H 2 Ru(N)(N 3 ) 3-x (H) x Aldrich Co., Ltd. RhCl 3 3H 2 H 2 IrCl 6 Furuya Metals Co., Ltd. H 2 PtCl 6 6H 2 Soekawa Chemicals Co., Ltd. Ce 2 Daiichi Kigenso Co., Ltd. Si 2 Fuji Silysia Chemical Ltd. 1,4-anhydroerythritol Aldrich Co., Ltd. 1,4-dioxane hydrogen Showa Denko K.K. 1,4-anhydrothreitol Astatech, Inc. cis-1,2-cyclopentanediol Frinton Laboratories, Inc. trans-1,2-cyclopentanediol Aldrich Co., Ltd. cis-1,2-cyclohexanediol Sigma Aldrich, Co. LLC. trans-1,2-cyclohexanediol Tokyo Chemical Industry Co., Ltd. 2,3-butanediol Tokyo Chemical Industry Co., Ltd. 3-hydroxytetrahydrofuran Tokyo Chemical Industry Co., Ltd. tetrahydrofuran 1,2-butanediol 1,4-butanediol 1,3-butanediol 1,2-hexanediol erythritol 1,2-dimethoxyethane dodecane 1-pentanol 3-pentanol 17

20 Table S5: Comparison of calculation levels between this and literature [S1] studies for methyltrioxorhenium(mt)-catalyzed DDH of ethylene glycol (EG) Parameters (lengths in Å; energies in kj/mol) This study Program: DMol 3 Functional: PW91 Basis set & ECP: DND3.5, DSPP Solvent: none Program: DMol 3 Functional: B3LYP Basis set & ECP: DND3.5, DSPP Solvent: none Ref. S1 Program: Gaussian09 Functional: B3LYP Basis set & ECP: 6-31G(d), LanL2DZ Solvent: C 6 H 6 (CPCM) Structure of EG diolate of reduced MT Re- 1 : 1.93, Re- 2 : C: 1.46, 2-2 C: 1.46 C- 2 C: 1.52 Re- 1 : 1.93, Re- 2 : C: 1.43, 2-2 C: 1.43 C- 2 C: 1.51 Re- 1 : 1.92, Re- 2 : C: 1.44, 2-2 C: 1.44 C- 2 C: 1.53 Re- 3 : 1.72 Re- 3 : 1.71 Re- 3 : 1.70 Structure of TS of Re- 1 : 1.81, Re- 2 : 1.80 Re- 1 : 1.79, Re- 2 : 1.79 Re- 1 : 1.78, Re- 2 : 1.79 DDH (MT catalyst) 1-1 C: 1.81, 2-2 C: C: 1.86, 2-2 C: C: 1.83, 2-2 C: C- 2 C: C- 2 C: C- 2 C: 1.42 Re- 3 : 1.73 Re- 3 : 1.73 Re- 3 : 1.72 Activation barrier (MT catalyst) Structure of EG diolate of reduced MT + H 2 Ea: 49 Ea: 91 Ea: 74 Ga: 65 (298 K, 1 atm) Re- 1 : 1.95, Re- 2 : 1.94 Re- 1 : 1.97, Re- 2 : 1.94 Re- 1 : 1.94, Re- 2 : C: 1.44, 2-2 C: C: 1.42, 2-2 C: C: 1.43, 2-2 C: C- 2 C: C- 2 C: C- 2 C: 1.53 Re- 3 : 1.72 Re- 3 : 1.70 Re- 3 : 1.70 Re- 4 : 2.27 Re- 4 : 2.21 Re- 4 : 2.16 Structure of TS of Re- 1 : 1.81, Re- 2 : 1.82 Re- 1 : 1.79, Re- 2 : 1.82 Re- 1 : 1.78, Re- 2 : 1.78 DDH (MT + H C: 1.83, 2-2 C: C: 1.92, 2-2 C: C: 1.90, 2-2 C: 1.89 catalyst) 1 C- 2 C: C- 2 C: C- 2 C: 1.41 Re- 3 : 1.74 Re- 3 : 1.73 Re- 3 : 1.72 Re- 4 : 2.42 Re- 4 : 2.33 Re- 4 : 2.33 Activation barrier (MT + H 2 catalyst) Ea: 86 Ea: 141 Ea: 129 Ga: 113 (298 K, 1 atm) Continues to next page [S1] Liu, P.; Nicholas, K. M. rganometallics 2013, 32,

21 Table S5 (continued) Parameters This study (lengths in Å; energies Program: DMol 3 in kj/mol) Functional: PW91 Basis set & ECP: DND3.5, DSPP Solvent: none Structure of MT Re- 1 : 1.73, Re- 2 : 1.73 Re- 3 : 1.73 Program: DMol 3 Functional: B3LYP Basis set & ECP: DND3.5, DSPP Solvent: none Re- 1 : 1.73, Re- 2 : 1.73 Re- 3 : 1.72 Ref. S1 Program: Gaussian09 Functional: B3LYP Basis set & ECP: 6-31G(d), LanL2DZ Solvent: C 6 H 6 (CPCM) Re- 1 : 1.71, Re- 2 : 1.71 Re- 3 : 1.71 Structure of MT + Re- 1 : 1.74, Re- 2 : 1.74 Re- 1 : 1.74, Re- 2 : 1.74 Re- 1 : 1.72, Re- 2 : 1.72 H 2 Re- 3 : 1.73 Re- 3 : 1.73 Re- 3 : 1.71 Re- 4 : 2.64 Re- 4 : 2.58 Re- 4 : 2.64 E of coordination of MT with H 2 Structure of EG C- 2 C: C- 2 C: C- 2 C: C- 1 : C- 1 : C- 1 : C- 2 : C- 2 : C- 2 : 1.43 Structure of EG diolate Re- 1 : 1.99, Re- 2 : 1.93 Re- 1 : 1.98, Re- 2 : 1.92 Re- 1 : 1.97, Re- 2 : 1.91 of MT 1-1 C: 1.43, 2-2 C: C: 1.47, 2-2 C: C: 1.42, 2-2 C: C- 2 C: C- 2 C: C- 2 C: 1.52 Re- 3 : 1.73, Re- 4 : 1.73 Re- 3 : 1.72, Re- 4 : 1.72 Re- 3 : 1.71, Re- 4 : 1.70 E of diolate formation from MT and EG Structure of EG diolate of MT + H Re- 1 : 2.02, Re- 2 : 1.93 Re- 1 : 2.01, Re- 2 : 1.91 Re- 1 : 2.01, Re- 2 : C: 1.43, 2-2 C: C: 1.42, 2-2 C: C: 1.42, 2-2 C: C- 2 C: C- 2 C: C- 2 C: 1.53 Re- 3 : 1.72, Re- 4 : 1.74 Re- 5 : 2.69 Re- 3 : 1.71, Re- 4 : 1.73 Re- 5 : 2.69 Re- 3 : 1.72, Re- 4 : 1.70 Re- 5 : 2.59 E of diolate formation from MT + H 2 and EG [S1] Liu, P.; Nicholas, K. M. rganometallics 2013, 32,

Characterization of Re-Pd/SiO 2 catalysts for hydrogenation of stearic acid

Supporting Information: Characterization of Re-Pd/SiO 2 catalysts for hydrogenation of stearic acid Yasuyuki Takeda, [a] Masazumi Tamura, [a] Yoshinao Nakagawa, [a] Kazu Okumura, [b] and Keiichi Tomishige*