Supporting Information for

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1 Supporting Information for Tuning the Pore Structure and Surface Properties of Carbon-Based Acid Catalysts for Liquid-Phase Reactions Isao Ogino,* Yukei Suzuki and Shin R. Mukai Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo, Hokkaido , Japan S1

2 Table S1. Literature Data of the Activity of Sulfonic-Acid Containing Catalysts in Esterification Reactions. reactants reaction conditions catalyst reported rate calculated TOF in mol/(mol-strong acid groups)/s ref. + ethanol + methanol + isoamyl alcohol oleic acid + methanol paltimic acid + methanol + butanol + butanol acrylic acid + butanol 343K, 0.1 mol, 1.0 mol ethanol (10 equiv.), 0.2 g catalyst, no solvent 333 K, 3 M in THF, 6 M methanol (2 equiv.) in THF, g catalyst/ml 333 K, 1:2 molar ratio of and isoamyl alcohol, 5% (w/w) catalyst loading, 368 K, mol oleic acid, 0.16 mol methanol (25 equiv.), g catalyst 358 K, 7.5 mmol paltimic acid + 75 mmol methanol 348 K, 0.66 mol, 0.66 mol butanol, 348 K, 0.66 mol, 0.66 mol butanol sugar-derived carbon-based acid catalyst, 4.9 mmol/g, carbonized at K sugar-derived carbon-based acid catalyst, 0.64 mmol- SO3H/g, carbonized at 673 K Purolite CT-175 (macroporous poly(vinylbenzenesulfonate) resin), 4.9 mmol-so3h/g, median pore diameter = nm sugar-derived carbon acid catalyst Sulfonated hydrothermal carbon (0.59 mmol-so3h/g) Amberlyst-15 (macroporous resin), 4.7 mmmol-so3h/g, average pore diameter = 30 nm p-tsa K Amberlyst min min pre-exponential factor = mol/(g min), activation energy = 47 kj/mol 62% yield in 1 h of the reaction at 368 K (not initial but average value, assume the acid concentration of 1.8 mmol/g) h m 3 /(mol g-cat s) m 3 /(mol g-cat s) kc = exp( /T) mol/(gcat min) S2

3 Figure S1. Experimental setup for the condensation of furfural and 2-methylfuran in a continuous flow reaction system (A) 2000 (B) Quantity adsorbed, V [cm 3 (STP) g -1 ] dv/dlog(r) [cm 3 g -1 ] Relative pressure, P/P Pore radius, r [nm] Figure S2. (A) Nitrogen gas adsorption/desorption isotherms characterizing CMH (, ), CMH (, ), CMH (, ), CMH (, ). The open and closed symbols represent the data for adsorption and desorption branches, respectively. (B) Mesopore size distribution for CMH ( ), CMH ( ), CMH ( ), CMH ( ) as determined by applying the DH method to the adsorption branches. S3

4 Intensity (a.u.) b a ( ) Figure S3. PXRD patterns characterizing (a) CMH SO3H and (b) CMH SO3H TOF/TOF Fraction of Poisoning (Na + /-SO 3 H) Figure S4. Selective poisoning of acid sites of CMH SO3H using NaCl. TOF0 represents the TOF for the unpoisoned CMH SO3H. Reaction conditions: temperature = 333 K; initial molar ratio of acetic acid/ethanol/( SO3H and SO3Na) = 1/1/ S4

-8-9 -10 lnk -11-12 -13-14 3.0 3.2 3.4 1/T 10 3 [K -1 ] Figure S5. Measured rate constants of the esterification of oleic acid with methanol over CMH-SO3H catalysts. Figure S6.

5 lnk /T 10 3 [K -1 ] Figure S5. Measured rate constants of the esterification of oleic acid with methanol over CMH-SO3H catalysts. Figure S6. Reusability test of CMH SO3H in the esterification of oleic acid with methanol in a batch reactor. Oleic acid (6 mmol), methanol (18 mmol). Reaction temperature = 333 K. S5

6 Analysis of the reaction data by the Weisz-Prater criterion The intraparticle mass transfer limitations can be neglected if the Weisz-Prater criterion shown below is satisfied:, 1 where ra,obs is the observed reaction rate in mol (kg-cat) 1 s 1 ; Rp is the radius of a catalyst particle in m; ρp is the density of a catalyst particle kg m 3 ; DeA is the effective diffusivity in m 2 s 1 ; CAs is the reactant concentration at the external surface in mol m 3. Parameters used in the calculation of the Weisz-Prater criterion: The observed reaction rate ra,obs = mol (kg-cat) 1 s 1 The radius of a catalyst particle Rp = m (a half of the maximum thickness of honeycomb wall) The density of a catalyst particle ρp = 45.5 kg m 3 The effective diffusivity DeA = m 2 s 1 (estimated using the equation reported in ref. S8 with λm (ratio of molecular radius to the pore radius) = 0.27 and τp (tortuousty factor) = 4) The reactant concentration at the external surface CAs = mol m 3.(assuming negligible external mass transfer resitance) Using these parameters yields the Weisz-Prater modulus of , which satisfies the criterion. S6

7 References (1) Hara, M.; Yoshida, T.; Takagaki, A.; Takata, T.; Kondo, J. N.; Hayashi, S.; Domen, K. Angew. Chem., Int. Ed. 2004, 43, (2) Mo, X.; Lopez, D. E.; Suwannakarn, K.; Liu, Y.; Lotero, E.; Goodwin, J. G.; Lu, C. Q. J. Catal. 2008, 254, (3) Teo, H.; Saha, B. J. Catal. 2004, 228, (4) Hara, M. Top. Catal. 2010, 53, (5) Fraile, J. M.; García-Bordejé, E.; Pires, E.; Roldán, L. J. Catal. 2015, 324, (6) Peters, T. A.; Benes, N. E.; Holmen, A.; Keurentjes, J. T. F. Appl. Catal., A 2006, 297, (7) Constantino, D. S. M.; Pereira, C. S. M.; Faria, R. P. V.; Ferreira, A. F. P.; Loureiro, J. M.; Rodrigues, A. E. AIChE J. 2015, 61, (8) Anderson, J. L.; Quinn, J. A. Biophys. J. 1974, 14, S7

Synthesis of a Zeolite Column with a Monolithic Microhoneycomb Structure Using the Ice Template Method

Synthesis of a Zeolite Column with a Monolithic Microhoneycomb Structure Using the Ice Template Method Shin R. Mukai, Shinya Murata, Kazufusa Onodera and Izumi Yamada *1 Graduate School of Engineering,