Abstract
The catalytic performance of inverse oxide–metal systems is strongly influenced by their structural dynamics under reaction conditions. In this study, ab initio molecular dynamics simulations were carried out to investigate temperature-induced restructuring at ZrO2-on-Cu interfaces between 450 and 600 K. The simulations reveal reversible Zr–O bond rearrangements that generate transient low-coordination Zr sites with enhanced Lewis acidity. These dynamically formed sites lower the CO2 activation barrier by up to 0.31 eV compared with static interface models. Time-averaged free energy profiles indicate a 2.7-fold increase in predicted methanol formation rates when dynamic effects are included. In contrast, simulations constrained to static geometries systematically underestimate catalytic activity. The results demonstrate that interface flexibility plays a decisive role in stabilizing key intermediates and should be explicitly considered when modeling inverse catalysts for CO2 hydrogenation
References
Patil, T., Naji, A., Mondal, U., Pandey, I., Unnarkat, A., & Dharaskar, S. (2024). Sustainable methanol production from carbon dioxide: advances, challenges, and future prospects. Environmental Science and Pollution Research, 31(32), 44608-44648.
Medina, O. E., Narváez, P., Amell, A. A., López, D., & Santamaría, A. (2025). Integrating Artificial Intelligence in CO2 Capture and Conversion Processes for Sustainable Energy Solutions. In Artificial Intelligence Applications for a Sustainable Environment (pp. 247-310). Cham: Springer Nature Switzerland.
Peng, H., Dong, N., Liao, Y., Tang, Y., & Hu, X. (2024). Real-Time Turbidity Monitoring Using Machine Learning and Environmental Parameter Integration for Scalable Water Quality Management. Journal of Theory and Practice in Engineering and Technology, 1(4), 29-36.
Kim, J. K., Kim, S., Kim, S., Kim, H. J., Kim, K., Jung, W., & Han, J. W. (2023). Dynamic surface evolution of metal oxides for autonomous adaptation to catalytic reaction environments. Advanced Materials, 35(4), 2203370.
Xu, K., Xu, X., Wu, H., & Sun, R. (2024). Venturi Aeration Systems Design and Performance Evaluation in High Density Aquaculture.
Yang, Z., Kumari, S., Alexandrova, A. N., & Sautet, P. (2025). Catalytic Activity of an Ensemble of Sites for CO2 Hydrogenation to Methanol on a ZrO2-on-Cu Inverse Catalyst. Journal of the American Chemical Society, 147(18), 15294-15306.
Araújo, T. P., Mitchell, S., & Pérez‐Ramírez, J. (2024). Design principles of catalytic materials for CO2 hydrogenation to methanol. Advanced Materials, 36(48), 2409322.
Butera, V., & Barone, G. (2025). Advances in CO 2 capture and utilization: the role of DFT in understanding CO 2 activation and its conversion mechanisms for methanol and cyclic carbonates production. Catalysis Science & Technology, 15(19), 5574-5601.
Xu, K., Xu, X., Wu, H., Sun, R., & Hong, Y. (2023). Ozonation and Filtration System for Sustainable Treatment of Aquaculture Wastewater in Taizhou City. Innovations in Applied Engineering and Technology, 1-7.
Chavez, S., Werghi, B., Sanroman Gutierrez, K. M., Chen, R., Lall, S., & Cargnello, M. (2023). Studying, promoting, exploiting, and predicting catalyst dynamics: the next frontier in heterogeneous catalysis. The Journal of Physical Chemistry C, 127(5), 2127-2146.
Balaish, M., Kim, K. J., Chu, H., Zhu, Y., Gonzalez-Rosillo, J. C., Kong, L., ... & Rupp, J. L. (2025). Emerging processing guidelines for solid electrolytes in the era of oxide-based solid-state batteries. Chemical Society Reviews, 54(19), 8925-9007.
Wang, Y., Wang, Y., Yin, X., Arias, R., & Chen, J. (2026). Research on Dynamic Assessment of Glucose‐Lipid Metabolism and Personalized Drug Response Prediction Based on Wearable Multimodal Sensing.
Yang, W., Abdelfatah, K. E., Kundu, S. K., Rajbanshi, B., Terejanu, G. A., & Heyden, A. (2024). Machine learning accelerated first-principles study of the hydrodeoxygenation of propanoic acid. ACS Catalysis, 14(13), 10148-10163.
Wang, C., & Chakrapani, V. (2023). Photocatalytic generation of reactive oxygen species on Fe and Mn oxide minerals: mechanistic pathways and influence of semiconducting properties. The Journal of Physical Chemistry C, 127(48), 23189-23198.
Fingerhut, J., DeVine, J. A., Yin, R., Bernard, M. E., Bremer, A., Borodin, D., ... & Wodtke, A. M. (2025). The Mechanism and Rate-Determining Step of Catalytic Ammonia Oxidation on Pd (332) at High Temperatures. ACS catalysis, 15, 10521-10530.
Wang, C., & Chakrapani, V. (2023). Environmental Factors Controlling the Electronic Properties and Oxidative Activities of Birnessite Minerals. ACS Earth and Space Chemistry, 7(4), 774-787.
Rehman, M. M., Khan, M., Mutee ur Rehman, H. M., Saqib, M., Iqbal, S., Lim, S. S., ... & Kim, W. Y. (2025). A sustainable and flexible carbon paper-based multifunctional human–machine interface (HMI) sensor. Polymers, 17(1), 98.
Kureljusic, M., & Karger, E. (2024). Forecasting in financial accounting with artificial intelligence–A systematic literature review and future research agenda. Journal of Applied Accounting Research, 25(1), 81-104.
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Copyright (c) 2026 Thomas H. Müller, Andreas Weber, Stefan Klein (Author)