Ni nanoparticle coupled surface oxygen vacancies for efficient synergistic conversion of palmitic acid into alkanes

doi:10.1016/S1872-2067(23)64401-8

Abstract

Abstract:

The catalytic transformation of renewable biomass oil (mainly comprising fatty acids and triglycerides) into high-value alkanes is a versatile technique, and Ni-based catalysts are considered to be the most suitable substitutes for precious metals. Ni nanoparticles supported on CeO₂ carriers, prepared by hydrothermal synthesis (Ni/H-CeO₂) with abundant oxygen vacancies, exhibited superior catalytic activity compared to precious metal catalysts. For the hydrodeoxygenation of palmitic acid, the Ni/H-CeO₂catalyst converted palmitic acid into pentadecane with a 94.8% selectivity under mild reaction conditions. The outstanding catalytic performance of Ni/H-CeO₂ can be attributed to the synergistic effect between the Ni nanoparticles for activating hydrogen and the abundant oxygen vacancies for adsorbing oxygen from palmitic acid. The abundant oxygen vacancies of Ni/H-CeO₂improved the interaction between the Ni metal and CeO₂ support, as confirmed by density functional theory calculations. Therefore, the abundant oxygen vacancies were more conducive to the dispersion of Ni, resulting in the formation of Ni nanoparticles, which enhanced the potential for hydrogen activation due to the increased number of exposed Ni and electronic effects. The high pentadecane selectivity was governed by small Ni nanoparticles. This study provides a novel strategy to obtain an efficient hydrodeoxygenation catalyst for converting biomass oil into biofuel.

Key words: Hydrodeoxygenation, Oxygen vacancy, Ni nanoparticle, Palmitic acid conversion, Biofuel

Yan Zeng, Hui Wang, Huiru Yang, Chao Juan, Dan Li, Xiaodong Wen, Fan Zhang, Ji-Jun Zou, Chong Peng, Changwei Hu. Ni nanoparticle coupled surface oxygen vacancies for efficient synergistic conversion of palmitic acid into alkanes[J]. Chinese Journal of Catalysis, 2023, 47: 229-242.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64401-8

https://www.cjcatal.com/EN/Y2023/V47/I4/229

Figures/Tables 13

Fig. 1. N2 isothermal adsorption and desorption curves of the C-CeO2, P-CeO2, and H-CeO2 carriers (a) and Ni/C-CeO2, Ni/P-CeO2, and Ni/H-CeO2 catalysts (b); and the pore size distributions of the C-CeO2, P-CeO2, and H-CeO2 carriers (c), and Ni/C-CeO2, Ni/P-CeO2, and Ni/H-CeO2 catalysts (d).

Table 1 Physicochemical properties of the carriers and fresh catalysts.

Samples	Surface area^a (m² g^-1)	Pore volume (cm³ g^-1)	Pore diameter^b (nm)	XRD phase (s)	Crystal size ^c (nm)	Ni content (wt%) ^d	Metal dispersion (%) ^e
C-CeO₂	8.2	0.04	21.6	CeO₂	21.3	—	—
P-CeO₂	59.9	0.10	6.5	CeO₂	14.0	—	—
H-CeO₂	24.4	0.14	20.7	CeO₂	21.3	—	—
Ni/C-CeO₂	5.6	0.04	29.7	CeO₂+Ni	26.7, 52.2	9.9	1.93
Ni/P-CeO₂	42.3	0.08	7.8	CeO₂+Ni	14.7, 36.5	9.7	2.76
Ni/H-CeO₂	18.7	0.10	21.8	CeO₂+Ni	30.7, 25.3	9.5	3.99

Fig. 2. (a) XRD patterns of the C-CeO2, P-CeO2, and H-CeO2 carriers, and Ni/C-CeO2, Ni/P-CeO2, and Ni/ H-CeO2 catalysts. (b) XRD patterns at 27°-30°.

Fig. 3. (a) EPR and XPS spectra of Ce 3d (b), and O 1s (c) of C-CeO2, P-CeO2, and H-CeO2; (d) XPS spectra of Ce 3d; O 1s (e), and Ni 2p (f) of the Ni/C-CeO2, Ni/P-CeO2, and Ni/H-CeO2 catalysts, respectively.

Table 2 Surface element content of carriers and catalysts and FD/F2g of different catalysts.

Sample	C_Ce³⁺/(C_Ce³⁺ + C_Ce⁴⁺) (%)	O_sur/(O_sur+ O_L) (%)	Ni⁰ 2p_3/2 (eV)	Ni⁰/(Ni⁰ + Ni²⁺) (%)	F_D/F_2g
C-CeO₂	8.4	19.7	—	—	—
P-CeO₂	10.1	28.1	—	—	—
H-CeO₂	12.0	43.7	—	—	—
Ni/C-CeO₂	8.5	26.4	852.0	21.38	0.24
Ni/P-CeO₂	10.4	30.6	851.9	18.22	0.26
Ni/H-CeO₂	13.0	67.0	851.7	8.57	0.28

Fig. 4. Raman spectra of the C-CeO2, P-CeO2, and H-CeO2 carriers (a), Ni/C-CeO2 (b), Ni/P-CeO2 (c), and Ni/H-CeO2 (d) catalysts.

Fig. 5. H2-TPR curves of different CeO2 carriers (a), and Ni/C-CeO2, Ni/P-CeO2, and Ni/H-CeO2 precursors (b).

Fig. 6. (a) HAADF-STEM images of Ni/C-CeO2. (b) HR-TEM images of Ni/C-CeO2. (c) HAADF-STEM images and corresponding elemental mapping images of Ni/C-CeO2. (d) HAADF-STEM images of Ni/P-CeO2. (e) HR-TEM images of Ni/P-CeO2. (f) HAADF-STEM images and corresponding elemental mapping images of Ni/P-CeO2. (g) HAADF-STEM images of Ni/H-CeO2. (h) HR-TEM images of Ni/H-CeO2 catalysts. (i) HAADF-STEM images and corresponding elemental mapping images of Ni/H-CeO2 catalysts.

Fig. 7. (a) Top and side views of CeO2 (111) and CeO2-OV (111) surface structures (white and red balls for Ce and O atoms. Circles denote the OVs), and (b) optimized Ni13 adsorption structures on CeO2 (111) and CeO2-OV (111) surface (white, red, and blue balls denote Ce, O, and Ni atoms).

Fig. 8. Product yield on the C-CeO2 (a), P-CeO2 (b) and H-CeO2 (c) carriers. (d) Conversion of palmitic acid on the C-CeO2, P-CeO2, and H-CeO2 carriers. Reaction conditions: palmitic acid (1.0 g), heptane (100 mL), carriers (0.2 g), temperature (270 °C), pressure (2 MPa H2), and time (6 h).

Fig. 9. Catalytic performance of Ni/C-CeO2 (a,b), Ni/P-CeO2 (c,d), and Ni/H-CeO2 (e,f) catalysts for palmitic acid conversation at 270 °C for 10 h. Reaction conditions: palmitic acid (1.0 g), heptane (100 mL), catalyst (0.2 g), temperature (270 °C), pressure (2 MPa H2), and time (10 h).

Table 3 Comparison of the catalytic performance of noble catalysts in the literature.

Catalyst	Reactor	Raw material	Reaction solvent	Reaction condition	Ratio of reactant/catalyst	Activity Performance	Ref.
5% Pd/CNTs	150 mL autoclave batch reactor	palmitic acid	50 mL decane	280 °C, 4 MPa H₂, 4 h	2:1	95.8% conversion, 78.3% pentadecane selectivity	[59]
Pd/C	300 mL reactor	59% palmitic and 40% stearic acids	50 mL dodecane	300 °C, 17.5 bar 5% H₂/Ar, 5 h	1.3:1	100% conversion, approximately 47.5% alkane selectivity	[60]
5% Pd/C	300 mL reactor	stearic acid	dodecane	600 kPa He, 300 °C, 6 h	4.5:1	100% conversion, 95% heptadecane selectivity	[61]
5% Pt/C	300 mL reactor	stearic acid	dodecane	600 kPa He, 300 °C, 6 h	4.5:1	86% conversion, 87% heptadecane selectivity	[61]
Ir/SiO₂	50 mL Parr reactor	stearic acid	10 mL cyclohexane	180 °C, 2 MPa H₂, 1 h	5:1	0.4% conversion, 49% octadecane selectivity, 37% heptadecane selectivity	[62]
Ru/La(OH)₃	50 mL Parr reactor	stearic acid	20 mL n-hexane	200 °C, 4 MPa H₂, 4 h	1.4:1	100% conversion, 95.9% heptadecane selectivity	[63]
Ru/ZrO₂	50 mL Parr reactor	stearic acid	20 mL n-hexane	200 °C, 4 MPa H₂, 4 h	1.4:1	82.8% conversion 60.6% heptadecane selectivity	[63]
5 wt% Pd/C	300 mL reactor	lauric acid	100 mL hexadecane	300 °C, 2 MPa H₂, 5 h	10:1	65% conversion, 86.2% undecane selectivity	[64]
Pt/OMSMS-700	100 mL stainless-steel tank reactor	oleic acid	—	340 °C, 2 MPa CO₂, 3 h	8:1	78% C8-C17 alkanes yield	[65]
Ni/H-CeO₂	300 mL Parr reactor	palmitic acid	100 mL heptane	270 °C, 2 MPa H₂, 10 h	5:1	100% conversion, 94.8% pentadecane selectivity	This study

Scheme 1. Schematic of the palmitic acid conversion on C-CeO2 (a), Ni/C-CeO2 (b), and Ni/H-CeO2 (c).

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