Laser Solid-Phase Synthesis of Robust Single-Atom Catalysts for CO₂ Hydrogenation to Methanol

Abstract

The robustness of single-atom catalysts (SACs) is a critical concern for practical applications, especially for thermal catalysis at elevated temperatures under reductive conditions. In this study, a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time. The resultant catalysts are constructed by Pt single atoms on In₂O₃ supported by Co₃O₄ nanoislands uniformly dispersed in the sea of reduced graphene oxide. The laser process, with a maximum temperature of 2349 K within ~100 μs, produced abundant oxygen vacancies (up to 70.8%) and strong interactions between the Pt single atoms and In₂O₃. The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO₂ hydrogenation to methanol at 300°C with a CO₂ conversion of 30.3%, methanol selectivity of 90.6% and exceptional stability over 48 h without any deactivation, outperforming most of the relevant catalysts reported in the literature. Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged. In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations. It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.

Keywords

CO₂ conversion / CO₂ hydrogenation to methanol / laser synthesis / methanol selectivity / single-atom catalysts / stability

References

[1] L. Wang, D. Wang, and Y. Li, “Single-Atom Catalysis for Carbon Neutrality,” Carbon Energy 4, no. 6 (2022): 1021-1079.

[2] B. Qiao, A. Wang, X. Yang, et al., “Single-Atom Catalysis of CO Oxidation Using Pt₁/FeOx,” Nature Chemistry 3, no. 8 (2011): 634-641.

[3] A. Wang, J. Li, and T. Zhang, “Heterogeneous Single-Atom Catalysis,” Nature Reviews Chemistry 2, no. 6 (2018): 65-81.

[4] H. Qi, J. Yang, F. Liu, et.al, “Highly Selective and Robust Single-Atom Catalyst Ru₁/NC for Reductive Amination of Aldehydes/Ketones,” Nature Chemistry 12, no. 1 (2021): 3295.

[5] J. Li, L. Zhang, K. Doyle-Davis, R. Li, and X. Sun, “Recent Advances and Strategies in the Stabilization of Single-Atom Catalysts for Electrochemical Applications,” Carbon Energy 2, no. 44 (2020): 488-520.

[6] K. Rigby and J.-H. Kim, “Deciphering the Issue of Single-Atom Catalyst Stability,” Current Opinion in Chemical Engineering 40 (2023): 100921.

[7] K. A. Gandionco, J. Kim, L. Bekaert, A. Hubin, and J. Lim, “Single-Atom Catalysts for the Electrochemical Reduction of Carbon Dioxide Into Hydrocarbons and Oxygenates,” Carbon Energy 6, no. 3 (2023): e410.

[8] A. Bruix, Y. Lykhach, I. Matolínová, et al., “Maximum Noble-Metal Efficiency in Catalytic Materials: Atomically Dispersed Surface Platinum,” Angewandte Chemie International Edition 53, no. 3 (2014): 10525-10530.

[9] J. Jones, H. Xiong, A. T. DeLaRiva, et al., “Thermally Stable Single-Atom Platinum-on-Ceria Catalysts via Atom Trapping,” Science 353, no. 6296 (2016): 150-154.

[10] L. DeRita, J. Resasco, S. Dai, et al., “Structural Evolution of Atomically Dispersed Pt Catalysts Dictates Reactivity,” Nature Materials 18, no. 7 (2019): 746-751.

[11] E. J. Peterson, A. T. DeLaRiva, S. Lin, et al., “Low-Temperature Carbon Monoxide Oxidation Catalysed by Regenerable Atomically Dispersed Palladium on Alumina,” Nature Communications 5, no. 1 (2014): 4885.

[12] F. Maurer, J. Jelic, J. Wang, et al., “Tracking the Formation, Fate and Consequence for Catalytic Activity of Pt Single Sites on CeO₂,” Nature Catalysis 3, no. 10 (2020): 824-833.

[13] M. Moliner, J. E. Gabay, C. E. Kliewer, et al., “Reversible Transformation of Pt Nanoparticles Into Single Atoms Inside High-Silica Chabazite Zeolite,” Journal of the American Chemical Society 138, no. 48 (2016): 15743-15750.

[14] X. Li, X. I. Pereira-Hernández, Y. Chen, et al., “Functional CeOx Nanoglues for Robust Atomically Dispersed Catalysts,” Nature 611, no. 7935 (2022): 284-288.

[15] Z. Li, B. Li, and Q. Li, “Single-Atom Nano-Islands (SANIs): A Robust Atomic-Nano System for Versatile Heterogeneous Catalysis Applications,” Advanced Materials 35, no. 20 (2023): 2211103.

[16] M. Zhao, X. Wang, J. Xu, et al., “Strengthening the Metal-Acid Interactions by Using CeO₂ as Regulators of Precisely Placing Pt Species in ZSM-5 for Furfural Hydrogenation,” Advanced Materials 36, no. 21 (2024): e2313596.

[17] J. Fang, H. Wang, Q. Dang, et al., “Atomically Dispersed Iridium on Mo₂C as an Efficient and Stable Alkaline Hydrogen Oxidation Reaction Catalyst,” Nature Communications 15, no. 1 (2024): 4236.

[18] Y. Peng, J. Cao, Y. Sha, W. Yang, L. Li, and Z. Liu, “Laser Solid-Phase Synthesis of Single-Atom Catalysts,” Light, Science & Applications 10, no. 1 (2021): 168.

[19] Y. Sha, F. Moissinac, M. Zhu, et al., “Laser Synthesis of Nonprecious Metal-Based Single-Atom Catalysts for Oxygen Reduction Reaction,” ACS Applied Materials & Interfaces 15, no. 44 (2023): 51004-51012.

[20] M. M. Shahid, P. Rameshkumar, W. J. Basirunc, et al., “An Electrochemical Sensing Platform of Cobalt Oxide@Gold Nanocubes Interleaved Reduced Graphene Oxide for the Selective Determination of Hydrazine,” Electrochimica Acta 259 (2018): 606-616.

[21] W. A. Spieker, J. Liu, X. Hao, J. T. Miller, A. J. Kropf, and J. R. Regalbuto, “An EXAFS Study of the Coordination Chemistry of Hydrogen Hexachloroplatinate (IV),” Applied Catalysis, A: General 243, no. 1 (2003): 53-66.

[22] L. Li, B. Yang, B. Gao, et al., “CO₂ Hydrogenation Selectivity Shift Over in-Co Binary Oxides Catalysts: Catalytic Mechanism and Structure-Property Relationship,” Chinese Journal of Catalysis 43, no. 3 (2022): 862-876.

[23] R. Su, Y. Gao, L. Chen, et al., “Utilizing the Oxygen-Atom Trapping Effect of Co₃O₄ With Oxygen Vacancies to Promote Chlorite Activation for Water Decontamination,” Proceedings of the National Academy of Sciences of the United States of America 121, no. 11 (2024): e2319427121.

[24] Y. Zhao, P. V. Kumar, X. Tan, et al., “Modulating Pt-O-Pt Atomic Clusters With Isolated Cobalt Atoms for Enhanced Hydrogen Evolution Catalysis,” Nature Communications 13, no. 1 (2022): 2430.

[25] W. Han, W. Ling, P. Gao, F. Dong, and Z. Tang, “Engineering Pt Single Atom Catalyst With Abundant Lattice Oxygen by Dual Nanospace Confinement Strategy for the Efficient Catalytic Elimination of VOCs,” Applied Catalysis, B: Environmental 345 (2024): 123687.

[26] A. Cao, Z. Wang, H. Li, and J. K. Nørskov, “Relations Between Surface Oxygen Vacancies and Activity of Methanol Formation From CO₂ Hydrogenation Over In₂O₃ Surfaces,” ACS Catalysis 11, no. 3 (2021): 1780-1786.

[27] A. Tsoukalou, P. M. Abdala, D. Stoian, et al., “Structural Evolution and Dynamics of an In₂O₃ Catalyst for CO₂ Hydrogenation to Methanol: An Operando XAS-XRD and In Situ TEM Study,” Journal of the American Chemical Society 141, no. 34 (2019): 13497-13505.

[28] G. Xie, X. Wang, X. Li, Y. Fang, R. Zhang, and Zj Wang, “Oxygen Vacancy-Boosted Thermocatalytic CO₂ Hydrogenation: Engineering Strategies, Promoting Effects and Mediating Mechanisms,” Journal of Energy Chemistry 99 (2024): 393-408.

[29] J. Ye, C. Liu, D. Mei, and Q. Ge, “Active Oxygen Vacancy Site for Methanol Synthesis From CO₂ Hydrogenation on In₂O₃ (110): A DFT Study,” ACS Catalysis 3, no. 6 (2013): 1296-1306.

[30] K. Sun, N. Rui, Z. Zhang, Z. Sun, Q. Ge, and C.-J. Liu, “A Highly Active Pt/In₂O₃ Catalyst for CO₂ Hydrogenation to Methanol With Enhanced Stability,” Green Chemistry 22, no. 115 (2020): 5059-5066.

[31] A. E. Schweizer and G. T. Kerr, “Thermal Decomposition of Hexachloroplatinic Acid,” Inorganic Chemistry 17, no. 8 (1978): 2326-2327.

[32] D. Glass, E. Cortés, S. Ben-Jaber, et al., “Dynamics of Photo-Induced Surface Oxygen Vacancies in Metal-Oxide Semiconductors Studied Under Ambient Conditions,” Advanced Science 6, no. 22 (2019): 1901841.

[33] F. Chang, Z. Zhang, Y. Zhang, et al., “Synergistic Modulation of Valence State and Oxygen Vacancy Induced by Surface Reconstruction of the CeO₂/CuO Catalyst Toward Enhanced Electrochemical CO₂ Reduction,” Carbon Energy 6, no. 12 (2024): e588.

[34] L. Liu, J. Liu, G. Li, et al., “Exceptional CO₂ Hydrogenation to Ethanol via Precise Single-Atom Ir Deposition on Functional P Islands,” Angewandte Chemie International Edition 64 (2025): e202422744.

[35] C. Shen, Q. Bao, W. Xue, et al., “Synergistic Effect of the Metal-Support Interaction and Interfacial Oxygen Vacancy for CO₂ Hydrogenation to Methanol Over Ni/In₂O₃ Catalyst: A Theoretical Study,” Journal of Energy Chemistry 65 (2022): 623-629.

[36] H. Zhao, X. Liu, C. Zeng, W. Liu, and L. Tan, “Thermochemical CO₂ Reduction to Methanol Over Metal-Based Single-Atom Catalysts (SACs): Outlook and Challenges for Developments,” Journal of the American Chemical Society 146, no. 34 (2024): 23649-23662.

[37] A. Pustovarenko, A. Dikhtiarenko, A. Bavykina, et al., “Metal-Organic Framework-Derived Synthesis of Cobalt Indium Catalysts for the Hydrogenation of CO₂ to Methanol,” ACS Catalysis 10, no. 9 (2020): 5064-5076.

[38] D. Lin, Q. Shen, Y. Tang, et al., “In₂O₃ Crystal Phase Variation on In₂O₃/Co₃O₄ to Boost CO₂ Hydrogenation to Methanol,” Molecular Catalysis 557 (2024): 113998.

[39] H. Zhou, Z. Chen, A. V. López, et al., “Engineering the Cu/Mo₂CTx (MXene) Interface to Drive CO₂ Hydrogenation to Methanol,” Nature Catalysis 4, no. 10 (2021): 860-871.

RIGHTS & PERMISSIONS

2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.