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S1
Supplementary Information for
Ru nanoparticles deposited on ultrathin TiO2
nanosheets as highly active catalyst for levulinic acid
hydrogenation to γ-valerolactone
Xiaoqing Gaoa,b, Shanhui Zhua,*, Mei Donga, Jianguo Wanga, Weibin Fana,*
aState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese
Academy of Sciences, Taiyuan 030001, PR China.
bUniversity of Chinese Academy of Sciences, Beijing 100039, PR China
S2
Supplementary details on catalyst characterization
N2 adsorption-desorption isotherms were collected on at −196 °C on a
Micromeritics TriStar 3000 instrument. Prior to the measurements, the samples were
pretreated under vacuum at 250 °C for 8 h. The data were analysed by the BET method.
ICP-OES (Optima 2100DV, PerkinElmer) was employed to detect the Ru content.
Prior to the measurement, 0.01g sample was initially treated in 3 mL aqua regia (75
vol.% HCl and 25 vol.% HNO3). The solution was left overnight, and diluted to 100
mL with deionized water in a volumetric flask.
X-ray diffraction (XRD) was carried out in a Rigaku Miniflex II desktop X-ray
diffractometer with a Cu Kα radiation source at 40 kV and 40 mA. Scan speed was set
as 4°/min in the 2θ range of 5° and 90°. The sample was pressed flat and held on the
sample holder.
The low-magnification Transmission electron microscopy (TEM) and high-
resolution transmission electron microscopy (HRTEM) measurements were performed
on a JEOL JEM-2011F instrument operated at 200 kV voltages. Samples were dispersed
onto a carbon coated copper grid after 20 min ultrasonic treatment in ethanol.
X-ray photoelectron spectroscopy (XPS) was performed on a Kratos AXIS
ULTRA DLD spectrometer with Al Kα radiation under ultrahigh vacuum conditions.
The as-prepared catalyst was made into a small tablet (6.0 mm diameter) and held on
the sample holder. The sample was then introduced into the UHV chamber for XPS test
at room temperature. The C 1s peak at 284.8 eV was employed as an internal standard.
S3
Temperature-programmed reduction of hydrogen (H2-TPR) was performed on
Micromeritics Autochem 2920 with a thermal conductivity detector (TCD). For each
run, 0.05 g catalyst sample was loaded in a U-shaped quartz tube. The sample was
initially pretreated on Ar gas at 300 °C for 0.5 h. After the sample was cooled to 30 °C,
the Ar flow was switched to 10 vol% H2/Ar mixed gas. The sampled was heated from
30 °C to 500 °C at a ramp of 5 °/min and the consumed H2 was monitored by a TCD
detector.
S4
Fig. S1. XRD patterns of TiO2 and various supported Ru-based catalysts.
S5
Fig. S2. (a and b) TEM and HRTEM images of Ru/SiO2; (c) Ru nanoparticles size
distribution histogram of Ru/SiO2.
S6
Fig. S3. (a and b) TEM and HRTEM images of Ru/MoS2; (c) Ru nanoparticles size
distribution histogram of Ru/MoS2.
S7
Fig. S4. (a and b) TEM and HRTEM images of Ru/GO; (c) Ru nanoparticles size
distribution histogram of Ru/GO.
S8
Fig. S5. (a and b) TEM and HRTEM images of Ru/C; (c) Ru nanoparticles size
distribution histogram of Ru/C.
S9
Fig. S6. Reusability tests of LA conversion over Ru/TiO2. Reaction conditions: 0.005
g catalyst, 2 mmol LA, 4 MPa H2, 100 °C, 4 mL water, and 30 min.
S10
Table S1 Comparison the catalytic performance of LA hydrogenation to GVL
between the references with our results.
Entry Catalyst Reaction
temperature (°C)
Reaction
pressure
(MPa)
TOF value
(h−1)
rGVL
(molGVLgmetal−1·h−1)f
Reference
1 Ru-NPs 130 2.5 143.3 1.4 [1]
2 Ru/ZrO2 130 2.4 180 1.7 [2]
3 5% wt%Ru/C 130 1.2 133.2 1.1 [3]
4 Ru0.9Ni0.1-OMC 150 4.5 2501 24.8 [4]
5 Ru40@Meso-SiO2 150 1.0 6555 1.0 [5]
6 Pt/HAPa 275 0.1 8352 63.8 [6]
7 Ru/HAPa 275 0.1 10440 84.7 [6]
8 Ru18/Sn5/C 180 3.5 50.4 9.2 [7]
9 1wt%Ru/OMSb 100 3.0 3420 37.8 [8]
10 5%Ru/NOMCc 120 1.3 438 3.4 [9]
11 Ru/ZrO2@C 140 1.0 612 9.5 [10]
12 3Cs-Ru/Al2O3 220 1.4 2844 18.0g [11]
13 3K-Ru/C 220 1.4 2016 15.8g [12]
14 AuPd/TiO2 200 4.0 360 2.0 [13]
15 CuZn120MLDd 240 1.0 11.2 0.04 [14]
16 NiZr-Al2O3/NFe 250 0.1 41.3 0.2 [15]
17 Ni-MoOx/C 250 5.0 206 3.6 [16]
18 20%Mo2C/CNT 100 3.0 4.8 0.02 [17]
19 Ir@ZrO2@C 180 4.0 122.4 42.9 [18]
20 Ru/TiO2(P25) 150 3.0 1044 2.9 [19]
21 Ru/H-β 200 4.0 1450.8 4.7 [20]
22 CePO4/Co2P 90 4.0 2196 0.01h [21]
23 Ru/TiO2 100 4.0 19045 152.8 this work
ahydroxyapatite
S11
boctahedral molecular sieve
cN-doped ordered mesoporous carbon
dmolecular layer deposition
enickel-foam
f rGVL =
𝑀𝑜𝑙𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝐺𝑉𝐿
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡𝑜𝑡𝑎𝑙 𝑎𝑐𝑡𝑖𝑣𝑒 𝑚𝑒𝑡𝑎𝑙 𝑎𝑡𝑜𝑚𝑠 ×𝑟𝑒𝑎𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒
gBecause the yield of GVL is not provided, the consumed amount of LA is used to
calculate rGVL.
hThe total catalyst mass is used to calculate rGVL.
S12
Table S2 Adsorption configuration and adsorption energy of the most stable species
on Ru (002) facet optimized by DFT calculation.
Species Binding mode Ead (eV) Side view Top view
LA η2μ3 (O, O) −0.18
CH3COHCH2CH2COOH η2μ2 (O, C) −1.23
CH3CHOCH2CH2COOH η2μ3 (O, O) −2.68
HPA η1μ1 (O) −0.40
CH3CHOHCH2CH2CO η3μ3 (O, C, O) −2.47
CH3CHOCH2CH2CO η3μ5 (O, C, O) −2.19
GVL η2μ2 (O, O) −0.13
GVL−OH η1μ1 (O) −2.65
H2 η2μ1 (H, H) −0.50
S13
H η1μ3 (H) −2.88
OH η1μ3 (O) −3.37
H2O η1μ1 (O) −0.42
S14
Table S3 Adsorption configuration and adsorption energy of the most stable species
on Ru10/TiO2 optimized by DFT calculation.
Species Binding mode Ead (eV) Side view Top view
LA η2μ2 (O, O)
−0.90
CH3COHCH2CH2COOH η1μ2 (O)
−1.56
CH3CHOCH2CH2COOH η1μ2 (O)
−2.62
HPA η1μ1 (O)
−0.46
CH3CHOHCH2CH2CO η2μ2(O, C)
−2.36
CH3CHOCH2CH2CO η3μ3 (O, O, C)
−1.95
GVL η2μ2 (O, O)
−0.65
S15
GVL−OH η2μ2 (O, O)
−2.23
H2 η2μ1 (H, H)
−0.46
H η1μ1 (H)
−2.85
OH η1μ2 (O)
−3.74
H2O η1μ1 (O)
−0.54
S16
TS1 TS2 TS3
TS4 TS5 TS6
TS7 TS8 TS9
TS10 TS11
Fig. S6. The TS configurations of LA hydrogenation to GVL on Ru (0 0 2) surface.
S17
TS1 TS2 TS3
TS4 TS5 TS6
TS7 TS8 TS9
TS10 TS11
Fig. S7. The TS configurations of LA hydrogenation to GVL on Ru10/TiO2 surface.
S18
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