Boosting co-thermal coupled in-situ reduction of morphology- engineered carbonate via preparing distinct crystalline phases

doi:10.1016/S1872-2067(26)65039-5

Abstract

Abstract:

Co-thermal coupled in-situ hydrogenation of carbonates represents a promising strategy for producing metal oxide coupling syngas, facilitating the CO₂ conversion into value-added chemicals while reducing thermal decomposition temperatures. Nevertheless, the impact of CaCO₃ morphological modulation on hydrogenation performance and mechanisms has yet to be elucidated. Herein, we first report the morphology-controlled synthesis of CaCO₃ with distinct crystalline phases (e.g., rhombohedral calcite, spherical vaterite, and rod-shaped aragonite). This engineered morphology significantly enhances co-thermal coupled in-situ reduction, simultaneously lowering the decarboxylation temperature and promoting syngas formation. Compared with rhombohedral calcite, spherical vaterite exhibits superior CO selectivity and formation rate during reduction processes across various temperatures, reaching 96% and 0.80 mmol min^-1 at 700 °C, respectively. Notably, rod-shaped aragonite achieves an exceptional CO selectivity of 86%, surpassing both rhombohedral calcite and spherical vaterite, and the CO formation rate (0.46 mmol min^-1) is more than 2.3 times that of spherical vaterite at 550 °C. Moreover, combination of temperature programmed reduction-mass spectrometry and in-situ diffuse reflectance infrared Fourier transformed experiments reveals temperature-dependent hydrogenation mechanisms for different morphologies of CaCO₃: direct hydrogenation dominates at relatively low temperatures, while at elevated temperatures, the dual mechanism combining direct hydrogenation and reverse water-gas shift reaction (HCOO* as the key intermediate) prevails. This study presents a novel strategy demonstrating high efficiency and low carbon for sustainable carbonate hydrogenation systems, offering significant scientific merit and industrial potential.

Key words: Inorganic carbonate, Morphology-engineering, Crystalline phase, In-situ reduction, Energy-saving, Emission reduction, Syngas

Shaokang Yu, Meng Dong, Ming Xu, Yijia Lv, Zhiyang Peng, Weitao Zhang, Dabing Guo, Yixie Wang, Zhen Xue, Yusen Yang, Hao Li, Mingfei Shao. Boosting co-thermal coupled in-situ reduction of morphology- engineered carbonate via preparing distinct crystalline phases[J]. Chinese Journal of Catalysis, 2026, 86: 149-159.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65039-5

https://www.cjcatal.com/EN/Y2026/V86/I7/149

Figures/Tables 6

Fig. 1. The hydrogenation performance of CaCO3 with different morphologies. The selectivity and formation rate of CO and CO2 during reductive calcination of rhombohedral calcite (a,b), spherical vaterite (c,d) and rod-shaped aragonite (e,f) under a pure hydrogen atmosphere. Reaction conditions: CaCO3 (300 mg), 1 bar, H2: 100 mL min-1, space velocity: 20000 mL gCaCO3-1 h-1.

Fig. 2. Structural characterizations of rhombohedral calcite, spherical vaterite, and rod-shaped aragonite after hydrogenation. SEM images of rhombohedral calcite (a), spherical vaterite (b), and rod-shaped aragonite (c). (d) XRD patterns of CaCO3 in different crystalline phases. XRD patterns of rhombohedral calcite (e), spherical vaterite (f), and rod-shaped aragonite (g) after hydrogenation at different temperatures. (h) Nitrogen adsorption-desorption isotherms of CaCO3 with different morphologies after hydrogenation at 700 °C, the inset shows the pore size distribution derived from the desorption branch of the isotherm using the BJH method. Reaction conditions: 300 mg sample, 100 mL min-1, H2, 700 °C.

Fig. 3. Morphology characterization of rhombohedral calcite, spherical vaterite and rod-shaped aragonite after hydrogenation. HRTEM, HAADF-STEM and corresponding EDS mapping of CaO obtained through hydrogenation of rhombohedral calcite (a-c), spherical vaterite (d-f), and rod-shaped aragonite (g-i) at 700 °C. Reaction conditions: 300 mg sample, 100 mL min-1, H2, 700 °C.

Fig. 4. SEM images of rhombohedral calcite (a-c), spherical vaterite (d-f), and rod-shaped aragonite (g-i) after hydrogenation at different temperatures. Reaction conditions: 300 mg sample, 100 mL min-1, H2, 500, 600, and 700 °C.

Fig. 5. DTA, TG, and DTG curves of rhombohedral calcite (a), spherical vaterite (b), and rod-shaped aragonite (c) during temperature evolution under an argon atmosphere. MS signals from TPR experiments of rhombohedral calcite (d), spherical vaterite (e), and rod-shaped aragonite (f) under H2 flow.

Fig. 6. CO2 conversion (a), CO selectivity (b), and reaction rate (c) of CaO for the RWGS reaction, derived from the hydrogenation of CaCO3 with different morphologies at 700 ℃. In-situ DRIFTS spectra of rhombohedral calcite (d), spherical vaterite (e), and rod-shaped aragonite (f) during hydrogenation.

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