Mn-Zn-O active phase promoted Ni-Co nanometal exsolved from MgO-based oxide for photothermal dry reforming of methane

doi:10.1016/S1872-2067(26)65002-4

Abstract

Abstract:

Multicomponent synergistic catalysis offers a promising strategy to address the severe coking in dry reforming of methane (DRM). In this study, a multicomponent Ni_0.05Mn_0.05Co_0.05Zn_0.05Mg_0.8O catalyst was developed, with Zn stabilized MnO (Mn-Zn-O active phase) promotes the DRM performance of exsolved NiCo nanometals from MgO-based oxide. Zn doping improves MnO dispersion and enrichment on MgO support during reduction by forming Mn-Zn-O active phase, in which Mn serves as a redox-active promoter to enhance activation and dissociation of CH₄ and CO₂. The reduction of Mn to a lower valence state can facilitate CO₂ adsorption and dissociation on the surface of catalysts, which also enhanced oxygen mobility to promote CH₄ activation and coke removal. The optimized Ni_0.05Mn_0.05Co_0.05Zn_0.05Mg_0.8O catalyst demonstrates exceptional stability in thermal DRM at 800 °C for 100 h. And in photothermal DRM, the catalyst also achieves outstanding activity under high gas flow rates with well-designed three-dimensional porosity catalytic reactor.

Key words: Mn promoter, NiCo nanometals, MgO, Dry reforming of methane, Coking resistance, Photothermal

Xiaofeng Yan, Yuxuan Meng, Yuefan Tuo, Yao Xue, Qianrui Yang, Zhengkun Luo, Yilong Yan, Meng Lin, Yufei Zhao, Xianguang Meng. Mn-Zn-O active phase promoted Ni-Co nanometal exsolved from MgO-based oxide for photothermal dry reforming of methane[J]. Chinese Journal of Catalysis, 2026, 85: 298-309.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65002-4

https://www.cjcatal.com/EN/Y2026/V85/I6/298

Figures/Tables 9

Table 1 Chemical compositions and abbreviations of the samples.

Catalyst	Abbreviations
Ni/MgO	—
Ni_0.05Mg_0.95O	Ni-MgO
Ni_0.05Zn_0.05Mg_0.9O	NiZn-MgO
Ni_0.05Co_0.05Mg_0.9O	NiCo-MgO
Ni_0.05Mn_0.05Mg_0.9O	NiMn-MgO
Ni_0.05Co_0.05Zn_0.05Mg_0.85O	NiCoZn-MgO
Ni_0.05Zn_0.05Mn_0.05Mg_0.85O	NiZnMn-MgO
Ni_0.05Co_0.05Mn_0.05Mg_0.85O	NiCoMn-MgO
Ni_0.05Co_0.05Zn_0.05Mn_0.05Mg_0.8O	NiCoZnMn-MgO

Fig. 1. (a,b) XRD pattern of as-prepared Ni-MgO, NiMn-MgO, NiCoMn-MgO, and NiCoZnMn-MgO catalysts. (c) H2-TPR profiles of Ni-MgO, NiMn-MgO, NiCoMn-MgO and NiCoZnMn-MgO catalysts. Test conditions: the sample after pre-treatment in He was heated from 50 to 1000 °C at a ramp rate of 10 °C min-1 under a 10% H2/N2 gas mixture, with a flow rate of 50 mL min-1.

Fig. 2. (a,b) XRD patterns of reduced catalysts. SEM images of reduced Ni-MgO (c), NiMn-MgO (d), NiCoMn-MgO (e), and NiCoZnMn-MgO (f) catalysts.

Fig. 3. TEM (a), HRTEM (b) and HAADF-mapping (c,d) images for NiCoZnMn-MgO catalyst after reduction.

Fig. 4. CH4 conversion (a), CO2 conversion (b), and H2/CO ratio (c) of the catalysts for 8-h DRM reaction at 800 °C. Continuous DRM operation of Ni/MgO, NiCo/MgO, NiCoMn-MgO and NiCoZnMn-MgO at 800 °C: CH4 conversion (d) and CO2 conversion (e). Reaction parameters: the GHSV was 24000 mL gcat-1 h-1 (total flow rate = 40 mL min-1), utilizing a feed composition of CH4:CO2 at a ratio of 1:1. The dotted line indicates the equilibrium conversion under the reaction conditions.

Fig. 5. The structural models of catalytic chambers for 3D printing. Photographic images of the corresponding catalyst structures can be found in Fig. S13.

Fig. 6. Conversion and H2/CO ratio of Ni/MgO (a) and NiCoZnMn-MgO (b). Production rate and light-to fuel efficiency of Ni/MgO (c) and NiCoZnMn-MgO (d) for photothermal DRM under different total flow. The total flow rates and GHSV of CH4:CO2 feed with a ratio of 1:1 were: (I) 100 mL min-1, 6000 mL gcat-1 h-1; (II) 250 mL min-1, 15000 mL gcat-1 h-1; (III) 500 mL min-1, 30000 mL gcat-1 h-1; and (IV) 1000 mL min-1, 60000 mL gcat-1 h-1. Temperature profiles at different locations were shown in Fig. S19. Light source: 300 W xenon lamp (with power set to maximum).

Fig. 7. (a) Raman spectra of spent catalysts after thermal DRM. CH4-TPSR (b) and CO2-TPSR (c) profiles of reduced Ni/MgO and NiCoZnMn-MgO. (d) DRIFTs curves for Ni/MgO and NiCoZnMn-MgO at 500 °C under dark and light conditions.

Fig. 8. (a) Schematic of structural changes of Ni-MgO, NiMn-MgO, NiCoMn-MgO and NiCoZnMn-MgO after calcination and after reduction. The gray blocks are metal (Ni/Co/Mn/Zn) doped MgO. (b) The proposed mechanism of the reduction and thermal DRM over NiCoZnMn-MgO.

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