Identification of stable and selective nickel alloy catalyst for acceptorless dehydrogenation of ethane

doi:10.1016/S1872-2067(24)60229-9

Abstract

Abstract:

Modifying the electronic density of states and the synergistic effect of the active centers by introducing a second metal present an efficient strategy to tune physi/chemi-sorption, probably lead to improving catalytic performances. Herein, bimetallic Ni₃Mo/Al₂O₃ catalyst was demonstrated and exhibited over 5 times more active than Pt/Al₂O₃ toward the ethane dehydrogenation (EDH) as well as 2-10 times activity enhancement compared with their monometallic Ni and Mo counterparts and other Ni-based bimetallic nanoparticles. Kinetic studies revealed that the activation energy over Ni₃Mo/Al₂O₃ (111 kJ mol^-1) was much lower than that of Ni (157 kJ mol^-1) and Mo (171 kJ·mol^-1). DFT calculations showed ethane was adsorbed on the Ni or Mo surface in a more parallel configuration, whereas over Ni₃Mo it adopted an inclined configuration. This change promoted ethane adsorption and pre-activation of the C-H bond, thereby benefiting the ethane dehydrogenation process on the Ni₃Mo surface.

Key words: Acceptorless dehydrogenation, Bimetallic nanoparticle, Catalyst, Olefin, Mechanism

Guomin Li, Teng Li, Bin Wang, Yong Ding, Xinjiang Cui, Feng Shi. Identification of stable and selective nickel alloy catalyst for acceptorless dehydrogenation of ethane[J]. Chinese Journal of Catalysis, 2025, 70: 322-332.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60229-9

https://www.cjcatal.com/EN/Y2025/V70/I3/322

Figures/Tables 8

Fig. 1. High-magnification TEM image of the Ni3Mo, Ni and Mo NPs on the Al2O3 support and Intensity profile recorded from the area indicated by the yellow rectangular box in panel: (a,b) Ni3Mo/Al2O3; (c,d) Ni/Al2O3; (e,f) Mo/Al2O3. (g) The HAADF-STEM imaging of Ni3Mo/Al2O3 catalyst. (h) EDS line scan analysis of intensity profiles of Ni (K) and Mo (L) components in the Ni3Mo/Al2O3 (along the red line in g). (i) EDS mapping of the Ni3Mo/Al2O3 shown in g, with the signals attributed to the different elements shown as Ni, Mo and Al.

Fig. 2. Characterizations of catalysts. Normalized XANES spectra of Ni (a) and Mo (b) for Ni3Mo/Al2O3-fresh, Ni3Mo/Al2O3-used, Ni/Al2O3-fresh and Mo/Al2O3-fresh. (c) Fourier transforms of k3-weighted EXAFS of Ni K-edge for Ni2O3, Ni foil and Ni3Mo/Al2O3-used, respectively. (d) Fourier transforms of k3-weighted EXAFS of Mo K-edge for MoO3, Mo foil and Ni3Mo/Al2O3-used. (e) Ni 2p XPS spectra of Ni/Al2O3 and Ni3Mo/Al2O3 catalysts before reaction. (f) Mo 3d XPS spectra of Mo/Al2O3 and Ni3Mo/Al2O3 catalysts before reaction.

Fig. 3. (a) Initial ethylene selectivity versus ethane conversion for Ni-M/Al2O3 catalysts in the ethane dehydrogenation reaction at 600 °C. (b) Ethane conversion and ethylene selectivity with Ni/Al2O3, Mo/Al2O3 and Ni3Mo/Al2O3. (c) Effect of the ratio of Ni to Mo on the EDH. (d) Effect of calcinating temperature on ethane conversion and ethylene selectivity. (e) The formation rate of ethylene over Ni3Mo/Al2O3 catalyst at different space velocities at 600 °C (active metal surface area: 0.148 m2 g-1). (f) Effect of the supports on the EDH. Reaction temperature: 600 °C, 1 atm, 8% H2, 20% C2H6/Ar, 0.5 g catalyst, reaction time: 10 min.

Fig. 4. (a) Catalytic performance of Ni3Mo/Al2O3, Pt/Al2O3 and PtSn/Al2O3 catalysts at 600 °C. (b) Recycling performance of Ni3Mo/Al2O3 catalyst in catalytic EDH. In situ FTIR spectra of ethane adsorption and reaction on Ni3Mo/Al2O3 catalyst at 550 °C: the adsorption of ethane (c) and ethane (d).

Fig. 5. (a) Flow rate test: The trend of ethane conversion with reaction flow rate. (Ni3Mo/Al2O3, Reaction temperature: 600 °C, WHSV = 13.66 h-1). (b) Particle size test: The trend of ethane conversion with catalyst particle size. (No limitation from interphase diffusion in a, mcat.: 0.2 g). (c) Arrhenius plots for the activation energies (Ea) of the EDH reaction on Ni/Al2O3, Mo/Al2O3 and Ni3Mo/Al2O3 catalysts. C2H6-TPSR profiles on Ni/Al2O3 (d), Mo/Al2O3 (e) and Ni3Mo/Al2O3 (f) catalysts.

Table 1 Ethane conversion of Ni3Mo/Al2O3 in kinetic experiments.

Reaction temperature (K)	Equilibrium conversion^a (%)	Equilibrium constant K (10^-2)^a	Experimental conversion (%)	Reaction quotient Q (10^-3)	Frac. Appr. to Equil. ^b (%)
853	14.46	1.79	2.10	1.81	10.11
863	17.02	2.26	2.56	2.24	9.91
873	19.83	2.85	3.12	2.78	9.75
883	22.86	3.56	3.74	3.40	9.55
893	26.10	4.44	4.16	3.83	8.63

Fig. 6. Adsorption structures and the charge density differences (isovalue of ±0.0006 electron ??3) of ethane on Ni (111) (a,d,g), Mo (110) (b,e,h) and Ni3Mo (100) (c,f,i) surfaces. ∠A is the angle of C?C bond with respect to surface plane.

Fig. 7. Energy profiles of ethane dehydrogenation on Ni(111) (a), Mo(110) (b) and Ni3Mo(100) (c) surfaces. (d) Comparison of the apparent barrier of ethane dehydrogenation. (e) The energy difference between desorption energy and energy barrier for further dehydrogenation of ethylene on Ni(111), Mo(110) and Ni3Mo(100) surfaces.

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