The thermodynamic factor in diffusion in the L1_2-type non-stoichiometricintermetallic compounds Ni_3Ga and Pt_3In was derived from the experimentally measured activities ofGa and In, respectively. The results show th...The thermodynamic factor in diffusion in the L1_2-type non-stoichiometricintermetallic compounds Ni_3Ga and Pt_3In was derived from the experimentally measured activities ofGa and In, respectively. The results show that the thermodynamic factor in diffusion in the Ni_3Gaand Pt_3In compounds exhibits the maximum near the stoichiometric composition with the variation ofcomposition over the compound region. The values indicate strong interaction between Ni and Gaatoms, as well as Pt and In atoms, respectively, as expected in ordered alloys.展开更多
Ni/Si O_2 and bimetallic Ni_xGa/SiO_2 catalysts with different Ni/Ga atomic ratios(x = 10～2) were investigated for the selective hydrogenation of acetylene.It was found that Ni_xGa/SiO_2 showed higher selectivity to ...Ni/Si O_2 and bimetallic Ni_xGa/SiO_2 catalysts with different Ni/Ga atomic ratios(x = 10～2) were investigated for the selective hydrogenation of acetylene.It was found that Ni_xGa/SiO_2 showed higher selectivity to ethylene than Ni/Si O_2.This is attributed to the formation Ni-Ga alloy and Ni3 Ga intermetallic compound(IMC) where there was a charge transfer from Ga to Ni,which is favorable for reducing the adsorption strength and amount of ethylene on Ni atoms.As a result,the over-hydrogenation,the C–C bond hydrogenolysis and the polymerization were suppressed,and subsequently the selectivity to ethylene was enhanced.With the decrease of Ni/Ga atomic ratio,the activity and stability of the Ni_xGa/SiO_2 catalysts increased first and then decreased,while the ethylene selectivity tended to increase.Ni_5 Ga/SiO_2 exhibited the best performance.Under the conditions of 180 °C,0.1 MPa,and a reactant(1.0 vol% acetylene,5.0 vol% H_2 and 94 vol% N_2) with the space velocity of 36,000 m L h^(-1) g^(-1),the acetylene conversion maintained at 100% on Ni_5 Ga/SiO_2 during 120 h time on stream and the selectivity to ethylene was 75%～81%after reaction for 68 h.It was also found that the formation of Ni-Ga alloy and Ni_3 Ga IMC suppressed the incorporation of carbon to form NiCx,subsequently enhancing the catalyst stability.Additionally,with increasing the Ga content,the catalyst acid amount and strength tended to increase,which promoted the polymerization and carbon deposition and so the catalyst deactivation.展开更多
基金This project is jointly supported by the National Natural Science Foundation of China (No. 29871005) the Science Foundation of Austria (No. P12962-CHE).
文摘The thermodynamic factor in diffusion in the L1_2-type non-stoichiometricintermetallic compounds Ni_3Ga and Pt_3In was derived from the experimentally measured activities ofGa and In, respectively. The results show that the thermodynamic factor in diffusion in the Ni_3Gaand Pt_3In compounds exhibits the maximum near the stoichiometric composition with the variation ofcomposition over the compound region. The values indicate strong interaction between Ni and Gaatoms, as well as Pt and In atoms, respectively, as expected in ordered alloys.
基金supported by the National Natural Science Foundation of China (21576193)
文摘Ni/Si O_2 and bimetallic Ni_xGa/SiO_2 catalysts with different Ni/Ga atomic ratios(x = 10～2) were investigated for the selective hydrogenation of acetylene.It was found that Ni_xGa/SiO_2 showed higher selectivity to ethylene than Ni/Si O_2.This is attributed to the formation Ni-Ga alloy and Ni3 Ga intermetallic compound(IMC) where there was a charge transfer from Ga to Ni,which is favorable for reducing the adsorption strength and amount of ethylene on Ni atoms.As a result,the over-hydrogenation,the C–C bond hydrogenolysis and the polymerization were suppressed,and subsequently the selectivity to ethylene was enhanced.With the decrease of Ni/Ga atomic ratio,the activity and stability of the Ni_xGa/SiO_2 catalysts increased first and then decreased,while the ethylene selectivity tended to increase.Ni_5 Ga/SiO_2 exhibited the best performance.Under the conditions of 180 °C,0.1 MPa,and a reactant(1.0 vol% acetylene,5.0 vol% H_2 and 94 vol% N_2) with the space velocity of 36,000 m L h^(-1) g^(-1),the acetylene conversion maintained at 100% on Ni_5 Ga/SiO_2 during 120 h time on stream and the selectivity to ethylene was 75%～81%after reaction for 68 h.It was also found that the formation of Ni-Ga alloy and Ni_3 Ga IMC suppressed the incorporation of carbon to form NiCx,subsequently enhancing the catalyst stability.Additionally,with increasing the Ga content,the catalyst acid amount and strength tended to increase,which promoted the polymerization and carbon deposition and so the catalyst deactivation.
