*3.1. Chemicals and Mterials*

Potassium hydroxide pellets (85%) and ammonium nitrate were purchased from Merck (Darmstadt, Germany). Colloidal silica HS-40 was supplied by Sigma-Aldrich (Darmstadt, Germany). Aluminium sulfate hexadecahydrate (Al2(SO4)3. 16H2O, 97%) was obtained from BDH Chemical Ltd, (Poole, UK). All chemicals were used without further purification. For the catalytic tests, the following chemicals have been utilized: glucose (Sigma-Aldrich, >99%), fructose (Sigma-Aldrich, >99%) and calcium chloride (VWR, Radnor, PA, USA, 97%). Deionized water and methyl isobutyl ketone (MIBK, VWR, 98%) have been used as solvents.

### *3.2. Synthesis of L-Type Zeolites*

Short-rod shape L-type zeolite was synthesized by dissolving KOH (3.018 g) and Al2(SO4)3.16H2O (1.442 g) with distilled water (18.208 g) in a polypropylene (PP) bottle. The mixture was magnetically stirred at room temperature to form a slightly cloudy solution. A clear silicate solution was prepared by mixing HS-40 (6.875 g) with distilled water (9.958 g) under stirring for 5 min. To avoid gelation, the silicate solution was added dropwise into the aluminate solution under vigorous stirring for 5 min. The solution with a final molar ratio of 10.0 K2O:1 Al2O3:20 SiO2:800 H2O was further aged at room temperature for 18 h under stirring prior to crystallization at 180 ◦C for 3 days. The solid product was then filtered and purified with distilled water until pH 7 prior to freeze-drying. The zeolite powder in K-form (3.000 g) was then ion exchanged with ammonium nitrate (1.5 M, 100 mL) at 25 ◦C for 18 h before subjecting calcination at 480 ◦C for 4 h to produce protonated L-type zeolite (ROD-LTL). Similar procedures were used for preparing L-type zeolites with other morphologies (needle and cylinder) but using hydrogels of different molar compositions as stated in Table 4. The protonated L-type zeolite crystalline solids with short-rod, cylindrical and needle shapes were denoted as ROD-LTL, CYL-LTL and NEEDLE-LTL, respectively.

**Table 4.** Experimental conditions for the synthesis of L-type zeolites with different morphologies.


### *3.3. Characterization of LTL Zeolites*

XRD patterns were recorded using an AXS D8 di ffractometer (Bruker, Rheinstetten, Germany) operating at 40 kV and 10 mA (Cu Kα radiation, λ = 0.15418 nm). The surface morphology of samples was observed using a JSM-6701F FESEM microscope (JEOL, Tokio, Japan). The infrared (IR) spectra were acquired using a System 2000 instrument (Perkin-Elmer, Waltham, MA, USA) using the KBr method (sample:KBr ratio = 1:50). The chemical composition of zeolites was also determined with an Optima 8300 inductively coupled plasma-optical emission spectrometer (ICP-OES). Textural properties were determined by an ASAP 2010 nitrogen adsorption analyzer (Micrometrics, Norcross, GA, USA) at –196 ◦C. First, the sample (ca. 0.08 g) was degassed under vacuum at 300 ◦C overnight. The surface area and pore size distribution of samples were estimated using the Langmuir and DFT models, respectively. The total pore volume of the solids was determined from the nitrogen adsorbed volume at P/Po = 0.990.

The FTIR spectra after pyridine adsorption were acquired using a 2000 FTIR spectrometer (Nicolet, Thermo Fisher Scientific, Waltham, MA, USA). Initially, the zeolite powder (ca. 0.01 g) was ground and pressed into a self-supporting wafer (area 2 cm2) at 6.0 ton. The wafer was introduced into an IR vacuum cell and activated at 400 ◦C for 5 h under vacuum (10-<sup>3</sup> mbar). The sample was cooled to 25 ◦C before the background spectrum of zeolite was recorded. Pyridine vapor was adsorbed onto the sample for 3 min before the excess pyridine vapor was evacuated. The FTIR spectra were recorded at 25 ◦C using 200 scans with a resolution of 6 cm<sup>−</sup>1. The wafer was then heated at 150 ◦C for 1 h to remove weakly bound pyridine before the second IR spectrum was recorded. The wafer was heated again to 300 ◦C for 1 h before it was cooled to 25 ◦C and scanned again with an IR spectrometer. The concentration of Lewis and Brönsted acid sites were calculated by using the molar integral extinction coe fficients of εBrönsted = 3.03 cm μmol−<sup>1</sup> and εLewis = 3.80 cm μmol−<sup>1</sup> [36].

X-ray photoelectron spectra were obtained with a PHI 5700 spectrometer (Physical Electronics, Eden Prairie, Minnesota, USA) with non-monochromatic Mg K α radiation (300 W, 15 kV, and 1253.6 eV) with a multi-channel detector. Spectra were recorded in the constant pass energy mode at 29.35 eV, using a 720 μm diameter analysis area. Charge referencing was measured against adventitious carbon (C 1s at 284.8 eV). The PHI ACCESS ESCA-V6.0 F software package was used for acquisition and data analysis. A Shirley-type background was subtracted from the signals. Recorded spectra were always fitted using Gaussian–Lorentzian curves in order to determine accurately the binding energies of the di fferent element core levels.

27Al MAS-NMR experiments were performed on an AV-400 (9.4 T) spectrometer (Bruker, Rheinstetten, Germany), using a BL-4 probe with zirconia rotors. The spectra were obtained using a spinning speed of vR = 10 kHz, a pulse width of 1 μs corresponding to a π/12 rad. Pulse length, a relaxation delay of 1 s, and typically 1200 scans. The temperature-programmed desorption of ammonia (NH3-TPD) was carried out to evaluate the total surface acidity of catalysts. After cleaning of catalysts (0.08 g) with helium up to 550 ◦C and subsequent adsorption of ammonia at 100 ◦C, the NH3-TPD was performed by raising the temperature from 100 to 550 ◦C, under a helium flow of 40 mL min−1, with a heating rate of 10 ◦C min−<sup>1</sup> and maintained at 550 ◦C for 15 min. The evolved ammonia was analyzed by using a TCD detector of a gas chromatograph (Shimadzu GC-14A).

Thermogravimetric analyses (TGA) were performed with a TGA/DSC model 1 instrument (Mettler-Toledo, Columbus, OH, USA) heating from room temperature until 900 ◦C with a heating ramp of 10 ◦C min−<sup>1</sup> under air flow of 50 mL min−1. The carbon content of spent catalysts was measured with a CHNS 932 analyzer (LECO, Madrid, Spain).
