Reaction-Condition-Dependent Active-Site Formation in Mixed-Oxide Catalysts for Syngas Conversion

Wei Ming Tan; Jia Hui Lim; Daniel Kai Chen

Abstract

The active sites of mixed-oxide catalysts often form dynamically under reaction conditions, making their identification difficult by ex situ characterization alone. Herein, first-principles thermodynamics and density functional theory were combined to identify active-site motifs in Zn–Cr–O catalysts for syngas conversion. More than 96 surface models were constructed by varying Zn/Cr ratios, oxygen chemical potential, hydroxyl coverage, and surface vacancy concentration. The results show that partially reduced Zn–O–Cr ensembles are thermodynamically favored under H2-rich conditions and provide lower barriers for CO activation and C–O bond hydrogenation. The calculated barrier for CH3O* formation decreased from 1.21 eV on stoichiometric Cr2O3 to 0.82 eV on Zn-enriched mixed-oxide surfaces. Microkinetic simulations predicted a 2.9-fold increase in oxygenate formation rate when reduced Zn–O–Cr motifs accounted for more than 35% of surface sites. These findings highlight the importance of reaction-induced active-site generation in oxide catalysis.

Keywords

first-principles calculationmixed oxideactive sitesyngas conversionZn–Cr catalystsurface thermodynamics

References

Liang, S., Zhang, X., Du, Y., & Chen, W. (2026). Supply Network Restructuring and Capacity Ramp-Up Limits in the Localized Expansion of High-Performance Computing Equipment Production. Available at SSRN 7339738.
Yapeng, B. E. I., Xing, Y. U., Xianni, B. U., Yuhan, S. U. N., & Peng, G. A. O. (2025). Modified ZnZrOx coupled with ZSM-5 as the catalyst for the hydrogenation of CO2 to aromatics. Journal of Fuel Chemistry and Technology, 53(7), 1038-1049.
Yang, Z., Alexandrova, A. N., & Sautet, P. (2026). Modeling CO2 Hydrogenation to Methanol on an Ensemble of Inverse ZrO2 on Cu Catalytic Sites: Mechanism, Reactivity, and Deactivation. Angewandte Chemie, e5448247.
Belrhazi, I., Sair, S., Ait Ousaleh, H., Kongparakul, S., Samart, C., & Zahouily, M. (2026). Catalytic upgrading of HDPE into aromatic hydrocarbons via in situ and ex situ pyrolysis over metal-impregnated zeolite-based catalysts. Molecular Catalysis, 603, 116288.
Bao, Y., & Wang, H. (2026). Edge-to-Cloud Infrastructure Continuum: A Unified Framework for Optimizing Industrial IoT Systems. Available at SSRN 7185578.
Chen, F., Liang, H., Li, S., Yue, L., & Xu, P. (2025). Design of Domestic Chip Scheduling Architecture for Smart Grid Based on Edge Collaboration.
Kabwe, F. B., Jiang, Q., & Wang, C. (2026). Interfacial Active Sites in Catalysts for Higher Alcohol Synthesis From CO2: A Review. Chemistry–A European Journal, e71373.
Liang, R., Feifan, F. N. U., Liang, Y., & Ye, Z. (2025). Emotion-Aware Interface Adaptation in Mobile Applications Based on Color Psychology and Multimodal User State Recognition. Frontiers in Artificial Intelligence Research, 2(1), 51-57.
Pareras, G., & Rimola, A. (2025). Single-atom iron on silicon carbide surfaces as catalyst of Fischer-Tropsch-type reactions in astrophysical environments. Frontiers in Astronomy and Space Sciences, 12, 1605553.
Du, Y. (2025). Research on Digital Quality Traceability System for Temperature-Controlled Supply Chain of Foreign Trade Wine Driven by Blockchain and IoT. Business and Social Sciences Proceedings, 4, 57-65.
Stamatelos, I., Guo, Z., Pasel, J., & Saei, W. (2026). Oxide-derived metals and alloys: from dynamic reconstruction to function across electrocatalytic reactions. Energy Advances.
Tiwari, J. N., Bhaskaran, G., Kumar, K., Huh, Y. S., & Han, Y. K. (2026). Auto‐Generated Valence States in Electrocatalysts for Boosting Oxygen and Hydrogen Evolution Kinetics in Alkaline Water/Alkaline Seawater/Simulated Seawater/Natural Seawater. Advanced Functional Materials, 36(45), e19158.
Jiao, Y., Zhao, B., Wang, A., & Shi, T. (2026). Construction and Empirical Study of a Modularized Teaching System for Art Courses Based on a Unified Training Pathway.
Yang, J. (2026). Stage‐Coupled Computational Framework for Stratiﬁed Accessibility and Equity Analysis in Community‐Based Elderly Care Services.
Bahou, S., Kosri, C., Ahmed, A. A., Mena, H., Sehrawat, R., Wohlrab, S., ... & Abdel‐Mageed, A. (2026). Regulating Copper Nuclearity in Metal–Organic Frameworks for the Hydrogenation of Carbon Dioxide. Small Methods, e70882.
Wu, J., Wu, D., Zhang, J., & Peng, Y. (2026). Generative AI Feedback in Junior High School Artistic Creation Evaluation. Available at SSRN 7244838.
Bao, Y., Qiu, Y., & Wang, H. (2026, May). Unified Identity Layer for Hyperscale Ecosystems: A Framework for Cross-Platform User Attribution and Experimentation. In 2026 6th International Conference on Machine Learning and Intelligent Systems Engineering (MLISE) (pp. 540-543). IEEE.
Asif, M., Bilal, M., Hakeem, L., Asghar, G., Manzoor, S., Hira, ... & Khan, S. A. (2026). Catalytic Confinement Engineering for CO2 Conversion: From Catalytic Microenvironments to Sustainable Aviation Fuels. Carbon Neutralization, 5(4), e70186.
Gu, X. (2026). Identifying Causal Effects and Analyzing Heterogeneity of User Growth Interventions on Digital Platforms: Evidence from Large-Scale Behavioral Data. Available at SSRN 6809181.
Şahin, Ö., Ekinci, S., İzgi, M. S., & Onat, E. (2025). Effect of different solvents on hydrogen production from hydrolysis of potassium borohydride with a new and active Ni-based catalyst synthesized by green synthesis. International Journal of Hydrogen Energy, 143, 1098-1107.
Shown, B., Gogoi, P., Mitra, S., Shown, I., Bandyopadhyay, R., & Das, A. K. (2026). Emerging trends and future prospects of the catalytic conversion of syngas to higher alcohols. ACS Omega, 11(13), 19963-20001.
You, S. (2026). Verifiable Audit Mechanisms in AI Compliance Automation: Scalability. Available at SSRN 6547458.
Jiao, Y., Shi, T., Zhao, B., & Wang, A. (2026). The Impact of VR Sketching Simulations on the Assessment of Scale and Site Suitability in Public Art Spaces.
Lustemberg, P. G., Yang, C., Wang, Y., Ganduglia-Pirovano, M. V., & Woll, C. (2025). Synergistic effects in low-temperature CO oxidation on cerium oxide surfaces. Journal of the American Chemical Society, 147(8), 6958-6965.

Publication details

Journal: Journal of Artificial Intelligence and Interdisciplinary Research
Volume: 1 (2026)
Article number: aji20260004
License: CC BY 4.0

[1] Liang, S., Zhang, X., Du, Y., & Chen, W. (2026). Supply Network Restructuring and Capacity Ramp-Up Limits in the Localized Expansion of High-Performance Computing Equipment Production. Available at SSRN 7339738.

[2] Yapeng, B. E. I., Xing, Y. U., Xianni, B. U., Yuhan, S. U. N., & Peng, G. A. O. (2025). Modified ZnZrOx coupled with ZSM-5 as the catalyst for the hydrogenation of CO2 to aromatics. Journal of Fuel Chemistry and Technology, 53(7), 1038-1049.

[3] Yang, Z., Alexandrova, A. N., & Sautet, P. (2026). Modeling CO2 Hydrogenation to Methanol on an Ensemble of Inverse ZrO2 on Cu Catalytic Sites: Mechanism, Reactivity, and Deactivation. Angewandte Chemie, e5448247.

[4] Belrhazi, I., Sair, S., Ait Ousaleh, H., Kongparakul, S., Samart, C., & Zahouily, M. (2026). Catalytic upgrading of HDPE into aromatic hydrocarbons via in situ and ex situ pyrolysis over metal-impregnated zeolite-based catalysts. Molecular Catalysis, 603, 116288.

[5] Bao, Y., & Wang, H. (2026). Edge-to-Cloud Infrastructure Continuum: A Unified Framework for Optimizing Industrial IoT Systems. Available at SSRN 7185578.

[6] Chen, F., Liang, H., Li, S., Yue, L., & Xu, P. (2025). Design of Domestic Chip Scheduling Architecture for Smart Grid Based on Edge Collaboration.

[7] Kabwe, F. B., Jiang, Q., & Wang, C. (2026). Interfacial Active Sites in Catalysts for Higher Alcohol Synthesis From CO2: A Review. Chemistry–A European Journal, e71373.

[8] Liang, R., Feifan, F. N. U., Liang, Y., & Ye, Z. (2025). Emotion-Aware Interface Adaptation in Mobile Applications Based on Color Psychology and Multimodal User State Recognition. Frontiers in Artificial Intelligence Research, 2(1), 51-57.

[9] Pareras, G., & Rimola, A. (2025). Single-atom iron on silicon carbide surfaces as catalyst of Fischer-Tropsch-type reactions in astrophysical environments. Frontiers in Astronomy and Space Sciences, 12, 1605553.

[10] Du, Y. (2025). Research on Digital Quality Traceability System for Temperature-Controlled Supply Chain of Foreign Trade Wine Driven by Blockchain and IoT. Business and Social Sciences Proceedings, 4, 57-65.

[11] Stamatelos, I., Guo, Z., Pasel, J., & Saei, W. (2026). Oxide-derived metals and alloys: from dynamic reconstruction to function across electrocatalytic reactions. Energy Advances.

[12] Tiwari, J. N., Bhaskaran, G., Kumar, K., Huh, Y. S., & Han, Y. K. (2026). Auto‐Generated Valence States in Electrocatalysts for Boosting Oxygen and Hydrogen Evolution Kinetics in Alkaline Water/Alkaline Seawater/Simulated Seawater/Natural Seawater. Advanced Functional Materials, 36(45), e19158.

[13] Jiao, Y., Zhao, B., Wang, A., & Shi, T. (2026). Construction and Empirical Study of a Modularized Teaching System for Art Courses Based on a Unified Training Pathway.

[14] Yang, J. (2026). Stage‐Coupled Computational Framework for Stratiﬁed Accessibility and Equity Analysis in Community‐Based Elderly Care Services.

[15] Bahou, S., Kosri, C., Ahmed, A. A., Mena, H., Sehrawat, R., Wohlrab, S., ... & Abdel‐Mageed, A. (2026). Regulating Copper Nuclearity in Metal–Organic Frameworks for the Hydrogenation of Carbon Dioxide. Small Methods, e70882.

[16] Wu, J., Wu, D., Zhang, J., & Peng, Y. (2026). Generative AI Feedback in Junior High School Artistic Creation Evaluation. Available at SSRN 7244838.

[17] Bao, Y., Qiu, Y., & Wang, H. (2026, May). Unified Identity Layer for Hyperscale Ecosystems: A Framework for Cross-Platform User Attribution and Experimentation. In 2026 6th International Conference on Machine Learning and Intelligent Systems Engineering (MLISE) (pp. 540-543). IEEE.

[18] Asif, M., Bilal, M., Hakeem, L., Asghar, G., Manzoor, S., Hira, ... & Khan, S. A. (2026). Catalytic Confinement Engineering for CO2 Conversion: From Catalytic Microenvironments to Sustainable Aviation Fuels. Carbon Neutralization, 5(4), e70186.

[19] Gu, X. (2026). Identifying Causal Effects and Analyzing Heterogeneity of User Growth Interventions on Digital Platforms: Evidence from Large-Scale Behavioral Data. Available at SSRN 6809181.

[20] Şahin, Ö., Ekinci, S., İzgi, M. S., & Onat, E. (2025). Effect of different solvents on hydrogen production from hydrolysis of potassium borohydride with a new and active Ni-based catalyst synthesized by green synthesis. International Journal of Hydrogen Energy, 143, 1098-1107.

[21] Shown, B., Gogoi, P., Mitra, S., Shown, I., Bandyopadhyay, R., & Das, A. K. (2026). Emerging trends and future prospects of the catalytic conversion of syngas to higher alcohols. ACS Omega, 11(13), 19963-20001.

[22] You, S. (2026). Verifiable Audit Mechanisms in AI Compliance Automation: Scalability. Available at SSRN 6547458.

[23] Jiao, Y., Shi, T., Zhao, B., & Wang, A. (2026). The Impact of VR Sketching Simulations on the Assessment of Scale and Site Suitability in Public Art Spaces.

[24] Lustemberg, P. G., Yang, C., Wang, Y., Ganduglia-Pirovano, M. V., & Woll, C. (2025). Synergistic effects in low-temperature CO oxidation on cerium oxide surfaces. Journal of the American Chemical Society, 147(8), 6958-6965.