Supporting information

Lingxiao Lia, Lin Donga, Xiaohui Liua, Yong Guoa, Yanqin Wanga,*

aKey Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and

Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Research Institute of Industrial

Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology,

Shanghai 200237, P. R. China.

* Corresponding authors. E-mail address: guoyong@ecust.edu.cn (Y. Guo); wangyanqin @ecust.edu.cn (Y. Wang).

1. Synthesis of 3-(4-hydroxyphenyl)propanol. In this work, 3-(4-hydroxyphenyl)propanol was used as a model compound of lignin oil and

prepared via a one-step synthesis method. Typically, phloretic acid (2.5 g), lithium aluminum hydride

(4 g) and tetrahydrofuran (60 mL) were added into a three-necked flask equipped with a reflux

condenser. The resulting suspension was heated to reflux under vigorous magnetic stirring in a 70 °C

oil bath for 5 hours. Sequentially, the reaction was carefully quenched using ice water with

anhydrous sodium sulfate (2 g), and the pH value of the white slurry was controlled at 10 ~ 11 by 1

M sodium hydroxide solution, followed by the filtration, evaporated in vacuum to remove the

residual tetrahydrofuran. 0.1 M hydrochloric acid was added portion-wise to adjust the pH value of

the as-evaporated brown solution to 3. Finally, ethyl acetate was used as an extraction agent to

acquire 3-(4-hydroxyphenyl)propanol.

2. Extraction process of Birch Lignin Oil (BLO). The extraction process of birch lignin oil (BLO) was treated via reductive depolymerization

following previously reported procedures [1, 2]. In a typical process, 10 g birch wood residues, 1 g 5

%Pd/C catalyst and 100 mL methanol were added into a 5 L autoclave and pressurized with the

initial H2 pressure of 30 bar, followed by the reductive depolymerization at 225 °C with magnetic

stirring for 6 hours. After reaction, the black slurry was then filtered, concentrated in vacuum and

washed with deionized water for three times to remove sugars, polyols and alcohols. The residues

were again solved in ethanol and evaporated in vacuum for further purification.

Fig. S1. 1H NMR (400 MHz, CDCl3) spectrum of synthesized 3-(4-hydroxyphenyl)propanol.

Fig. S2. 13C NMR (101 MHz, CDCl3) spectrum of synthesized 3-(4-hydroxyphenyl)propanol.

Fig. S3. XRD patterns of reduced Ru/NbO, RuFe/NbO, Fe/NbO and Ru/FeOx catalysts.

Fig. S4. STEM-EDS scanning region (a) and mapping of (b) Ru, (c) Nb, (d) Fe, (e) O, (f) combination of Ru, Fe, Nb, O and (g) EDS spectrum of the 2Ru8Fe/NbO catalyst.

Fig. S5. EDS scanning region (a) and mapping of (b) Ru, (c) Fe, (d) Nb, (e) O, and (f) EDS spectrum

of the 2Ru8Fe/Nb2O5 catalyst.

Fig. S6. H2-TPR profiles of as-prepared Ru/NbO and 2Ru1Fe/NbO catalysts.

Fig. S7. H2-TPR profiles of as-prepared Ru/FeOx catalyst.

Fig. S8. H2-TPD profiles of as-prepared RuFe/NbO catalysts.

Fig. S9. Ru 3d5/2 XPS spectra of as-reduced Ru/NbO and RuFe/NbO catalysts.

Fig. S10. Fe 2p3/2 XPS spectra of as-reduced RuFe/NbO and 10Fe/NbO catalysts.

Fig. S11. Nb 3d5/2 XPS spectra of reduced Ru/NbO, RuFe/NbO and 10Fe/NbO catalysts.

Fig. S12. O 1s XPS spectra of reduced Ru/NbO, RuFe/NbO and 10Fe/NbO catalysts.

Fig. S13. Intermediates tests on the 2Ru8Fe/NbO catalyst. Reaction conditions: 250 °C, 4 bar H2, 1 h; 40 mg catalyst, 0.07 g p-ethylphenol + 0.03 g p-propylphenol, 10 mL water as solvent.

Fig. S14. C-C bond hydrogenolysis test on the 2Ru8Fe/NbO catalyst. Reaction conditions: 250 °C, 4 bar H2, 2 h; 40 mg catalyst, 0.1 g p-propylphenol, 10 mL water as solvent.

Fig. S15. (a) Comparison with physical mixture, (b) influence of reduction temperature. Reaction conditions: 250 °C, 4 bar H2, 4 h; 40 mg catalyst, 0.1 g 3-(4-hydroxyphenyl)propanol, 10 mL water as solvent.

Fig. S16. Product distributions and RAPs during the stability test over the 2Ru1Fe/Nb2O5 catalyst. Reaction conditions: 300 °C, 10 bar H2, 15 h, 20 mg catalyst, 0.1 g BLO, 10 mL water as the solvent.

Table S1. Aromatic monomers in lignin oil produced via reductive depolymerisation.

Lignin Oil

Yield of Monomers (wt %)Selectivity

toAr-C3H6OH

(%)

Distribution of

Ar-C3H6OH(%)

Birch 0.3 1.4 1.1 4.5 80.9 79.7

Table S2. Element mass concentration obtained from FESEM-EDS spectrum of the 2Ru8Fe/NbO catalyst.

Element Weight % Atom % Net intensity % ErrorsO K 9.2 36.89 1082.03 0Fe L 1.06 1.21 75.65 0.02Nb L 87.84 60.68 8626.12 0Ru L 1.91 1.21 136.59 0.06

Table. S3. H2 consumptions of as-prepared Ru/NbO and RuFe/NbO catalysts.

Catalyst Atom ratio(Ru:Fe)

H2 consumption of the 1st

peak (μmol·g-1)Total H2 consumption

(μmol·g-1)2Ru/NbO - 331.1 331.1

2Ru1Fe/NbO 1:0.9 403.5 445.2

2Ru2Fe/NbO 1:1.8 506.8 550.2

2Ru4Fe/NbO 1:3.6 533.6 728.0

2Ru8Fe/NbO 1:7.2 567.1 821.8

2Ru12Fe/NbO 1:10.8 621.7 907.6

10Fe/NbO - 761.5 761.5

2Ru/FeOx - 635.6 2041.3

Table. S4. Catalytic conversion of 3-(4-hydroxyphenyl)propanol over Ru/NbO and RuFe/NbO.

Cat.Con./%

Yield /% C7%

C8%

C9%

SA%

1a 2a 3a 1b 2b 3b 1c 2c 3c 1d 2d 3d

2Ru 99.9 2.2 14.3 4.5 9.1 53.2 14.1 0.1 0.3 0.2 - 0.4 - 11.6 69.1 19.2 98.6

2Ru1Fe 99.9 8.2 62.5 17.2 - - - 0.2 1.6 0.3 - 0.2 - 9.3 71.3 19.4 97.4

2Ru2Fe 99.9 6.3 65.2 16.3 - 0.7 0.4 0.4 1.3 0.4 - 0.3 - 7.4 74.0 18.7 97.5

2Ru4Fe 99.9 5.9 58.1 12.1 0.8 14.2 3.1 0.2 0.9 0.4 - 0.9 - 7.1 76.8 16.2 97.5

2Ru8Fe 99.9 6.1 45.4 7.2 - 29.9 - 0.3 1.5 0.2 - 0.9 - 7.0 84.9 8.1 96.9

2Ru12Fe 99.9 3.7 40.1 7.4 - 33.5 1.1 0.4 1.4 0.5 - 3.2 - 4.4 85.7 9.9 94.0

2RuFeOx 99.9 - 0.8 - 0.9 83.0 9.9 - 0.1 - - - - 0.9 88.6 10.5 99.9

10Fe unreacted

Reaction conditions: 250 °C, 4 bar H2, 40 mg catalyst, 0.1 g 3-(4-hydroxyphenyl)propanol, 10 mL water as solvent.

Table. S5. Catalytic conversion of Birch Lignin Oil (BLO) over 2Ru/NbO and 2Ru1Fe/NbO.

Ent. Cat.Yield (Distribution) /% Total

yield /%1 2 3 4 5 6 7 8 9

1 2Ru/NbO 0.9(6.6) 3.2(23.2) 2.2(15.9) 0.1(0.9) 0.8(5.6) 0.4(3.2) 0.2(1.1) 4.1(30.3) 1.8(13.2) 13.7

2 2Ru1Fe/NbO 1.0(8.0) 8.2(63.4) 1.4(10.5) 0.1(1.1) 0.9(6.7) 0.5(3.7) 0.2(1.3) 0.5(3.7) 0.2(1.6) 13.0

Reaction conditions: 300 °C, 10 bar H2, 15 h, 20 mg catalyst, 0.1 g BLO, 10 mL water as solvent.

References

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