Supporting Information

Relationship between surface property and catalytic application

of amorphous NiP/Hβ catalyst for n-hexane isomerization

Jinshe Chen, ZunBin Duan, ZhaoYang Song, Lijun Zhu, Yulu Zhou, Yuzhi Xiang, and

Daohong Xia*

State Key Laboratory of Heavy Oil Processing, China University of Petroleum,

Qingdao 266580, People’s Republic of China

*Corresponding Author: xiadh@upc.edu.cn.

List of contents:

The synthesis of crystalline Ni2P.

The preparation of Ni2P/Hβ catalyst.

Figures:

Figure S1. Pore size distribution curves of Hβ (Carrier) and NiP/Hβ(3-30 wt％).

The range of pore diameter (A):0-20nm and (B):0-2nm (magnification).

Figure S2. XRD patterns of (A) Ni2P dried at 70℃ and (B) Hβ (Carrier), 10wt.

％Ni2P/Hβ and 30wt.％Ni2P/Hβ.

Figure S3. TEM micrographs of the samples: (A) 3 wt.％ NiP/Hβ, (B) 5 wt.％ NiP/Hβ, (C) 20 wt.％ NiP/Hβ, (D) 30 wt.％ NiP/Hβ.

Figure S4. DSC curves of Pure NiP and 10 wt.％ NiP/Hβ.

Figure S5. The effect of different sulfur concentrations of ethanethiol on the (A) the

conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).

Figure S6. The effect of different sulfur concentrations of ethyl sulfide on the (A) the

conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).

Figure S7. The effect of different sulfur concentrations of thiophene on the (A) the

conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).

Figure S8. The effect of different sulfur concentrations of dimethyl disulfide on the

(A) the conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).

Figure S9. N2 adsorption-desorption isotherms for fresh and test samples.

Figure S10. Pore size distribution curves of fresh and test samples. The range of pore diameter (A):0-20nm and (B):0-2nm (magnification).

Figure S11. SEM-mappings of test by S sample.

Figure S12. SEM-mappings of test by water sample.

Figure S13. FT-IR spectra of pyridine absorbed on of fresh and test samples. Absorbance peaks characteristic of hydrogen-bound pyridine (H), Brønsted (B), weak Lewis (WL), and strong Lewis (SL) sites are indicated.

Figure S14. NH3-TPD profiles of fresh and test samples.

Figure S15. The effect of N2 and H2 on (A) the conversion of n-hexane and (B)

the yield of iso-alkanes(i-C5 and i-C6).

Reaction conditions: T=300℃, P=2.0 MPa, WHSV=1.0h-1, Reaction time= 3h, H2-to-

n-hexane molar ratio=4.0

Figure S16. The stability of catalyst.

Tables:

Table S1. The molar ratios of elemental Ni and P characterized by depth profile XPS with sputtering time.

Table S2. Textural properties of samples before and after test by S and water.

Table S3. EDX results of test by S sample.

The synthesis of crystalline Ni2P.

Nickel chloride hexahydrate (9.70 g) and sodium hypophosphite (6.43 g) were

dissolved in 40.0 mL deionized water. The solution was dried at 80 for 12 h and ℃

then a yellow solid was obtained. Afterwards the yellow solid was treated at 300 ℃

for 0.5 h under nitrogen atmosphere, after which the product was cooled to ambient

temperature under nitrogen atmosphere and washed further with deionized water to

remove ion impurities. In the end, the wet substance was dried at 120 for 2 h.℃

The preparation of Ni2P/Hβ catalyst.

The Ni2P/Hβ catalysts were prepared using the same method, which was adopted

in the preparation of amorphous NiP/Hβ catalyst (2.2. Preparation of catalysts).

Figures:

Figure S1. Pore size distribution curves of Hβ (Carrier) and NiP/Hβ(3-30 wt％).

The range of pore diameter (A):0-20nm and (B):0-2nm (magnification).

Figure S2. XRD patterns of (A) Ni2P dried at 70℃ and (B) Hβ (Carrier), 10wt.

％Ni2P/Hβ and 30wt.％Ni2P/Hβ.

BA

Figure S3. TEM micrographs of the samples: (A) 3 wt.％ NiP/Hβ, (B) 5 wt.％ NiP/Hβ, (C) 20 wt.％ NiP/Hβ, (D) 30 wt.％ NiP/Hβ.

Figure S4. DSC curves of Pure NiP and 10 wt.％ NiP/Hβ.

C D

Figure S5. The effect of different sulfur concentrations of ethanethiol on the (A) the conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).

Figure S6. The effect of different sulfur concentrations of ethyl sulfide on the (A)

the conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).

Figure S7. The effect of different sulfur concentrations of thiophene on the (A) the conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).

Figure S8. The effect of different sulfur concentrations of dimethyl disulfide on the (A) the conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).

Figure S9. N2 adsorption-desorption isotherms for fresh and test samples.

Figure S10. Pore size distribution curves of fresh and test samples. The range of pore diameter (A):0-20nm and (B):0-2nm (magnification).

Figure S11. SEM-mappings of test by S sample.

Figure S12. SEM-mappings of test by water sample.

Figure S13. FT-IR spectra of pyridine absorbed on of fresh and test samples. Absorbance peaks characteristic of hydrogen-bound pyridine (H), Brønsted (B), weak Lewis (WL), and strong Lewis (SL) sites are indicated.

Figure S14. NH3-TPD profiles of fresh and test samples.

Figure S15. The effect of N2 and H2 on (A) the conversion of n-hexane and (B) the yield of iso-alkanes(i-C5 and i-C6).Reaction conditions: T=300℃, P=2.0 MPa, WHSV=1.0h-1, reaction time =3 h, H2-to-n-hexane molar ratio=4.0.

Figure S16. The stability of catalyst.

Tables:

Table S1

The molar ratios of elemental Ni and P characterized by depth profile XPS with sputtering time.

Sputtering time /min The molar ratio of elemental Ni/P1 2.72 2.83 2.84 3.15 2.76 2.77 2.78 2.89 2.810 3.111 2.9

Table S2

Textural properties of samples before and after test by S and water.

samples BET (m2/g) Vmp.a (cm3/g) VT.b (cm3/g)Fresh catalyst 411.10 0.14 0.30

Deactivation test by S 409.15 0.13 0.29Deactivation test by H2O 408.01 0.13 0.29

a Micropore volume as determined by t-plot and normalized per gram of support.

b Total pore volume.

Table S3

EDX results of test by S sample.

Element At %P 8.1Ni 17.0S 0.0

Au 74.9