Smart Energy and Sustainable Environment , ISSN 2668-957X
2026, Volume 29, Issue 1
Pages 33-44

https://doi.org/10.46390/j.smensuen.29126.465

A CONCISE ANALYSIS FOR REACTION MECHANISMS REGARDING THE GREEN METHANOL SYNTHESIS USING Copper-Based Catalysts

Abstract

Methanol synthesis is an essential component of the chemical industry and a promising direction for sustainable fuel production, especially through CO₂ hydrogenation. Due to their high intrinsic activity, selectivity toward methanol, and cost-effectiveness, copper-based catalysts remain highly relevant in industrial applications. Knowledge of their metal-support interactions, as well as the structural and electronic properties of these catalysts, is essential for optimizing their performance under different reaction conditions. This review presents the development, characterization, and performance of copper-based catalytic systems for methanol synthesis. Thermodynamic and kinetic concepts, reaction mechanisms for methanol production from both syngas and CO₂ reduction are also presented. Conventional Cu/ZnO/Al₂O₃ catalysts are analyzed in terms of particle size, dispersion and active site models. Advanced catalytic formulations, including Cu supported on ZrO₂, CeO₂ and other metal oxides, as well as bimetallic systems, are evaluated in terms of activity, selectivity and stability of these chemical catalysts. The influence of preparation methods and operating parameters on catalytic performance is also discussed. The paper concludes by presenting current challenges for improving future research in the field of catalysis.

References

K.A. Ali, A. Zuhairi, A.R. Mohamed, “Recent development in catalytic technologies for methanol synthesis from renewable sources: a critical review”, Renewable and Sustainable Energy Reviews, 2015, 44, 508-518.

T.P. Araújo, S. Mitchell & J. Pérez‐Ramírez, “Design Principles of Catalytic Materials for CO₂ Hydrogenation to Methanol”, Advanced Materials, 2024, 36(48), 2470385.

N.J. Azhari, D. Erika, S. Mardiana, T. Ilmi,M. L. Gunawan, I. G. B. N. Makertihartha & G.T. Kadja, “Methanol synthesis from CO₂: A mechanistic overview”, Results in Engineering, 2022, 16, 100711.

H. Bahrami, A. Faghri, “Review and advances of direct methanol fuel cells: Part II: Modeling and numerical simulation”, Journal of Power Sources, 2013, 230, 303-320.

B. Balopi & P. Agachi, “Methanol synthesis chemistry and process engineering aspects-a review with consequence to Botswana chemical industries”, Procedia Manufacturing, 2019, 35, 367-376.

N.H. Berahim, N. A. M. Zabidi, “Catalytic conversion of CO₂ into methanol”, Carbon Dioxide Capture and Conversion, 2022, 129-162, Elsevier.

P. Borisut, A. Nuchitprasittichai, “Methanol production via CO₂ hydrogenation: sensitivity analysis and simulation—based optimization”, Frontiers in Energy Research, 2019, 7, 81.

A. Boretti, “Renewable hydrogen to recycle CO₂ to methanol”, International Journal of Hydrogen Energy, 2013, 38(4), 1806-1812.

M. Bowker, “Methanol Synthesis from CO₂ hydrogenation”, ChemCatChem, 2019, 11, 4238-4246.

G. Bozzano, & F. Manenti, “Efficient methanol synthesis: Perspectives, technologies and optimization strategies”, Progress in Energy and Combustion Science, 2016, 56, 71-105.

X. Cui, S.K. Kær, “A comparative study on three reactor types for methanol synthesis from syngas and CO₂”, Chemical Engineering Journal, 2020, 393, Article 124632.

S. Dang, H. Yang, P. Gao, H. Wang, X. Li, W. Wei, Y. Sun, “A review of research progress on heterogeneous catalysts for methanol synthesis from carbon dioxide hydrogenation”, Catalysis Today, 2019, 330, 61-75.

M. J. Da Silva, “Synthesis of methanol from methane: Challenges and advances on the multi-step (syngas) and one-step routes (DMTM)”, Fuel Processing Technology, 2016, 145, 42-61.

S. Devakirubakaran, C. Bharatiraja, T. Narasimha Prasad, B. Praveen Kumar, & Shitharth, S., “Optimal power generation of proton exchange membrane fuel cell using ANFIS based MPPT algorithm”, Scientific Reports, 2024, 14, 26455.

M. Dore, C. Peinado, S. Rojas, J.M. Campos-Martin, D. Liuzzi, & S. Morales-de la Rosa, “Influence of Mg loadings in copper-based catalysts for CO₂ hydrogenation to methanol”, Catalysis Today, 2025, 459, 115425.

L.Z. Gao, & C.T. Au, “CO₂ hydrogenation to methanol on a YBa₂Cu₃O₇ catalyst”, Journal of Catalysis, 2000, 189(1), 1-15.

L.C. Grabow, M. Mavrikakis, “Mechanism of methanol synthesis on Cu through CO₂ and CO hydrogenation”, ACS Catalysis, 2011, 1(4), 365-384.

R. Guil-López, N. Mota, J. Llorente, E. Millán, B. Pawelec, J. L. G. Fierro, R. M. Navarro, “Methanol synthesis from CO2: a review of the latest developments in heterogeneous catalysis”, Materials, 2019, 12(23), 3902.

A. Han, J. Ding, & Q. Zhong, “Role of single-atom Pd in Cu/ZrO₂ catalysts for CO₂ hydrogenation to methanol”, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 641, 128535.

C. Han, Y. Gao, L. Qin, Y. Cao, S. Wang, & J. Li, “Modulating electronic structure and exposed surface area of Cu-based catalysts by Pd doping for enhanced CO₂ hydrogenation to methanol”, Separation and Purification Technology, 2025, 354, 128852.

M.P. Hogarth, & G. A. Hards, “Direct methanol fuel cells”, Platinum Metals Review, 1996, 40(4), 150-159.

S.G. Jadhav, P.D. Vaidya, B.M. Bhanage, J.B. Joshi, “Catalytic carbon dioxide hydrogenation to methanol: a review of recent studies”, Chemical Engineering Research and Design, 2014, 92, 2557-2567.

Y. Jeong, I. Kim, J. Y. Kang, H. Jeong, J. K. Park, J. H. Park, J. C. Jung, “Alcohol-assisted low temperature methanol synthesis from syngas over Cu/ZnO catalysts: Effect of pH value in the co-precipitation step”, Journal of Molecular Catalysis A: Chemical, 2015, 400, 132-138.

H. Liang, G. Zhang, Z. Li, Y. Zhang, P. Fu, "Catalytic hydrogenation of CO to methanol over Cu-based catalysts: Active sites profiling and regulation strategy as well as reaction mechanisms exploration”, Fuel Processing Technology, 2014, 252, 107995.

X. Jiang, X. Nie, X. Guo, C. Song, J. G. Chen, “Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis”, Chemical reviews, 2020, 120(15), 7984-8034.

X. Li, J. Huang, M. Yuan, Y. Zhao, M. Li, J. Du, ... & Z. You, “Unveiling a Synergistic ZrO₂-Ga₂O₃ Promotion Strategy for Copper Catalysts: Enhanced Methanol Synthesis from CO₂ via Improved Hydrogenation of Formate Intermediate”, Applied Catalysis B: Environment and Energy, 382, 2026, 125970.

D.S. Marlin, E. Sarron, Ó. Sigurbjörnsson, “Process advantages of direct CO₂ to methanol synthesis”, Frontiers in Chemistry, 2018, 6, 446.

U. Mondal, G. D. Yadav, “Methanol economy and net zero emissions: critical analysis of catalytic processes, reactors and technologies”, Green Chemistry, 23, 8361-8405 (2021).

P.S. Murthy, W. Liang, Y. Jiang, J. Huang, “Cu-Based nanocatalysts for CO₂ hydrogenation to Methanol”, Energy Fuels, 2021, 35, 8558-8584.

S. Pang, X. Dou, W. Zhao, S. Bai, B. Wan, T. Wang, & J. H. Yang, “A Review on the Design Strategies of Copper-Based Catalysts for Enhanced Activity and Stability in Methanol Reforming to Hydrogen”, Nanomaterials, 2025, 15(14), 1118.

N. Park, M.J. Park, Y.J. Lee, K.S. Ha, K.W. Jun, “Kinetic modeling of methanol synthesis over commercial catalysts based on three-site adsorption”, Fuel Processing Technol., 2014, 125, 139-147.

N. Radenahmad, A. Afif, P. I. Petra, M. H. Rahman, G. S.-Eriksson, A. K. Azad, “Proton-conducting electrolytes for direct methanol and direct urea fuel cells—A state-of-the-art review”, Renewable and Sustainable Energy Reviews, 2016, 57, 1347-1358.

X. San, X. Li, Q. Jin, B. Dai, L. Zhang, D. Meng, & J. Qi, “Comprehensive insight into Cu-based catalysts for CO₂ hydrogenation to methanol”, Sustainable Materials and Technologies, 2025, 45, e01437.

C. S. Santana, L.S. Shine, L. H. Vieira, R. J. Passini, E. A. Urquieta-Gonzalez, E. M. Assaf, ... & J. M. Assaf, “Effect of the synthesis method on physicochemical properties and performance of Cu/ZnO/Nb₂O₅ catalysts for CO₂ hydrogenation to methanol”, Industrial & Engineering Chemistry Research, 2021, 60(51), 18750-18758.

S.K. Saw, S. Datta, P.D. Chavan, P.K. Gupta, S. Kumari, G. Sahu, & V. Chauhan, “Significance and influence of various promoters on Cu‐based catalyst for synthesizing methanol from syngas: a critical review”, Journal of Chemical Technology & Biotechnology, 2023, 98(5), 1083-1102.

S. Simon Araya, V. Liso, X. Cui, N. Li, J. Zhu, S. L. Sahlin, ... & S. K. Kær, “A review of the methanol economy: the fuel cell route”, Energies, 2020, 13(3), 596.

P. J. Smith, S. A. Kondrat, P. A. Chater, B. R. Yeo, G. M. Shaw, L. Lu, G. J. Hutchings, “A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by co-precipitation”, Chemical Science, 2017, 8(3), 2436-2447.

X. Tang, Y. Wu, Z. Fang, X. Dong, Z. Du, B. Deng & X. Li, “Syntheses, catalytic performances and DFT investigations: a recent review of copper-based catalysts of methanol steam reforming for hydrogen production”, Energy, 2024, 295, 131091.

M. Thommes, K. Kaneko, A. V. Neimark, J. P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K. S. Sing, “Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)”, Pure and applied chemistry, 2015, 87(9-10), 1051-1069.

A. Ullah, N. A. Hashim, M. F. Rabuni, & M. U. Mohd Junaidi, “A review on methanol as a clean energy carrier: roles of zeolite in improving production efficiency”, Energies, 2023, 16(3), 1482.

J.C. Védrine, “Heterogeneous catalysis on metal oxides”, Catalysts, 2017, 7(11), 341.

Z. Xia, X. Zhang, H. Sun, S. Wang, G. Sun, “Recent advances in multi-scale design and construction of materials for direct methanol fuel cells”, Nano Energy, 2019, 65, 104048.

Y. Yang, M.G. White, P. Liu, “Theoretical study of methanol synthesis from CO₂ hydrogenation on metal-doped Cu (111) surfaces”, The Journal of Physical Chemistry C, 2012, 116, 248-256.