1. Enhanced direct deoxygenation of anisole to benzene on SiO2-supported Ni-Ga alloy and intermetallic compound.
- Author
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Zheng, Ying, Zhao, Ning, and Chen, Jixiang
- Subjects
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DEOXYGENATION , *METHANATION , *INTERMETALLIC compounds , *BENZENE , *SCISSION (Chemistry) , *ALLOYS , *ELECTRON density - Abstract
Graphical abstract Highlights • Ga geometrically and electronically modify Ni in Ni-Ga alloy and IMC. • Direct deoxygenation (DDO) was more preferential on Ni-Ga alloy and IMC than Ni. • Benzene hydrogenation, C C cleavage and methanation was suppressed on alloy and IMC. • H 2 was generated from anisole via methanol decomposition on Ni-Ga alloy and IMC. • There was a synergetic effect between Ni and Ga on alloy and IMC for HDO. Abstract Herein, Ni/SiO 2 and bimetallic Ni x Ga/SiO 2 (Ni/Ga atomic ratio x = 6 and 3) catalysts were prepared by the impregnation method followed by reduction at 550 °C and tested in the vapor hydrodeoxygenation of anisole at 0.1 MPa and 300 °C. Ni-Ga alloy and Ni 3 Ga intermetallic compound (IMC) formed in Ni 6 Ga/SiO 2 and Ni 3 Ga/SiO 2 , respectively, where the Ga atoms break contiguous Ni ones reducing the ensembles of Ni atoms and the H 2 uptakes. Also, a charge transfer from Ga to Ni increased the electron density of Ni, and hydrogen spill-over occurred on Ni x Ga/SiO 2. In contrast to Ni/SiO 2 , Ni x Ga/SiO 2 improved not only the hydrodeoxygenation activity but also the selectivity to benzene. At the similar anisole conversion (˜31%), the selectivity to benzene was 75.2%, 83.0% and 92.6% on Ni/SiO 2 , Ni 6 Ga/SiO 2 and Ni 3 Ga/SiO 2 , respectively. Reactivity evaluation, anisole-TPD and TPSR results show that the direct C Ar OCH 3 bond cleavage (C Ar represents the carbon in benzene ring) to benzene was more preferential on Ni x Ga/SiO 2 than on Ni/SiO 2. Isotope tracing experiment indicates that the spilt-over hydrogen at the interface between the Ni 3 Ga particles and support participated in the reaction. We suggest that the synergetic effect between Ni and Ga facilitated the direct C Ar O bond cleavage. Moreover, Ni x Ga/SiO 2 were less active for benzene hydrogenation and C C bond hydrogenolysis than Ni/SiO 2 , contributing to higher selectivity to benzene. Significantly, methanol, derived from the direct the C Ar OCH 3 bond cleavage, dominatingly decomposed to CO and H 2 and methanation scarcely occurred on Ni x Ga/SiO 2 , however, it was mainly converted to methane on Ni/SiO 2. Low activities for benzene hydrogenation, C C bond hydrogenolysis and methanation on Ni x Ga/SiO 2 (especially Ni 3 Ga/SiO 2) are attributed to the geometric and electronic effects of Ga in alloy and IMC. The finding is significant in rationally designing the catalyst with high benzene yield and low H 2 consumption. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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