Unraveling the superiority of Ni1-MoS2 single-atom catalyst in CO2 hydrogenation to methanol: A DFT combined microkinetic study

doi:10.1016/S1872-2067(26)65027-9

Abstract

Abstract:

Converting CO₂ to methanol presents a crucial pathway for achieving carbon neutrality, yet designing highly active and selective nano catalysts remain challenging. In this work, we report a combined density functional theory and microkinetic study screening 26 transition metal single atoms (Sc-Zn, Y-Cd, Ta-Au) atomically dispersed in MoS₂ nanosheet (M₁-MoS₂) for CO₂ hydrogenation to methanol. Among these, Ni₁-MoS₂ was identified as a promising candidate, exhibiting excellent stability and hydrogen dissociation capability. The reaction proceeds through a dissociative hydrogenation mechanism via key intermediates including *COOH, *C(OH)₂, *CH(OH)₂, *CHOH, and *CH₂OH. Microkinetic simulations reveal that Ni₁-MoS₂ significantly outperforms the experimentally validated Pt₁-MoS₂, demonstrating a 26.76-fold enhancement in formation rate and high selectivity under industrial relevant conditions (210 °C, 8 bar CO₂, 24 bar H₂). This work not only highlights Ni₁-MoS₂ as a highly efficient and cost-effective catalyst but also provides a mechanistic and kinetic framework for accelerating the design of single-atom catalysts for CO₂ conversion.

Key words: Density functional theory, Microkinetic analysis, Single metal atom doped MoS₂, CO₂ hydrogenation, Methanol

Lanlan Chen, Li Sheng, Yanan Zhou, Qiquan Luo, Zhenyu Li, Wenhua Zhang, Jinlong Yang. Unraveling the superiority of Ni₁-MoS₂ single-atom catalyst in CO₂ hydrogenation to methanol: A DFT combined microkinetic study[J]. Chinese Journal of Catalysis, 2026, 85: 143-152.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65027-9

https://www.cjcatal.com/EN/Y2026/V85/I6/143

Figures/Tables 7

Fig. 1. The calculated formation energy (Ef), adsorption energy of one adsorbed H (E1H) over twenty-six kinds of doped-MoS2, the catalyst in blue region represents six-coordinated structures, the catalysts in gray and orange region represent tetra-coordinated structures, and the doped catalysts in the orange region are the selected catalysts.

Fig. 2. The profile distributions of the highest occupied molecular orbital (a-i) and the lowest unoccupied molecular orbital of pure (j-r), Co (b,k), Ni (c,l), Cu (d,m), Zn (e,n), Rh (f,o), Pd (g,p), Ir (h,q) and Pt (i,r) doped MoS2. The isosurface value is set as 0.03 e Å-3. The yellow, cyan and white spheres represent S, Mo and H atoms, respectively.

Fig. 3. The adsorption structures of Hα (a), Hβ (b), 2H-1 (c), 2H-2 (d), 2H-3 (e), 2H-4 on M1-MoS2 (f). M represent the doped Co, Ni, Cu, Zn, Rh, Pd, Ir and Pt atoms, respectively. (g) The energy profile for H2 dissociation and Hα transformation over Cu1-MoS2. The yellow, cyan, white, blue, salmon spheres represent S, Mo, H, M and Cu atoms, respectively.

Table 1 The energies (eV) involved in the H2 dissociation and atomic hydrogen transformation process on the Co1(Ni1, Cu1, Zn1, Rh1, Pd1, Pt1)-MoS2. Ea (∆E) and E’a (∆E’) are the energy barriers (reaction energies) of H2 dissociation processes and atomic hydrogen atom transformation process.

Elementary step	(eV)	Co₁	Ni₁	Cu₁	Zn₁	Rh₁	Pd₁	Pt₁
H₂(g)→2H_α-in(2H-3)	∆E	0.42	0.22	-0.55	-0.12	0.34	0.15	-0.24
H₂(g)→2H_α-in(2H-3)	E_a	1.47	1.09	0.79	0.95	1.01	1.08	0.97
2H_α-in→H_α-in+ H_α-out(2H-2)	∆E’	—	-0.39	-0.35	-0.42	-0.41	-0.31	-0.33
2H_α-in→H_α-in+ H_α-out(2H-2)	E’_a	—	0.67	0.61	0.37	0.45	0.65	0.55

Fig. 4. The energy profile of CO2 reduction pathway along CO2, *COOH, *C(OH)2, *CH(OH)2, *CHOH, *CH2OH with Hα (a) and Hβ (b) on Ni1, Cu1, Zn1, Rh1, Pd1 and Pt1-MoS2. The numbers are the corresponding reaction barriers for each step.

Fig. 5. The results of microkinetic simulations. (a) Turnover frequency at T = 483.15 K, PCO2: PH2 = 8: 4 bar, activation energy for CH3OH formation on Ni1, Pt1, Rh1, Zn1, Pd1, Cu1-MoS2. The calculated ln(TOF) for CH3OH formation on Ni1 (b), Pt1 (c), Rh1 (d), Zn1 (e), Pd1 (f), and Cu1-MoS2 (g) at a temperature range of 300-600 K and a total pressure of 1-100 bar.

Fig. 6. The geometric structures of initial states (IS) and transition states (TS) of each elementary step along the optimal energy profiles on Ni1-MoS2: I’ (* + *CO2 + 2Hα ? * + *COOH + Hα), II’ (* + *COOH + Hα ? * + *C(OH)2), III (* + *C(OH)2 + Hβ ? * + *CH(OH)2), IV (* + *CH(OH)2 + Hβ ? * + *CHOH + H2O), V (* + *CHOH + Hβ ? * + *CH2OH), VI (* + *CH2OH + Hβ ? * + *CH3OH). The yellow, cyan, white, red, gray, blue spheres represent S, Mo, H, O, C, Ni atoms, respectively.

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Unraveling the superiority of Ni₁-MoS₂ single-atom catalyst in CO₂ hydrogenation to methanol: A DFT combined microkinetic study

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