CO₂ Hydrogenation Catalysis Series Research: Precise Regulation Practices and High-Value Conversion Breakthroughs by Professor Liang Bing’s Team from Shenyang University of Chemical Technology and Academician Noritaka Tsubaki’s Team from the University of

Against the backdrop of the “Dual Carbon” strategy, the efficient conversion of CO₂ into high-value hydrocarbons (liquefied petroleum gas, aromatics, light olefins, etc.) is a key pathway to achieving carbon cycling. However, its core challenges lie in breaking through the Anderson-Schulz-Flory (ASF) distribution limit, precisely regulating product selectivity, and improving conversion efficiency. From 2024 to 2025, Professor Liang Bing’s team from Shenyang University of Chemical Technology (SYUCT) collaborated with Academician Noritaka Tsubaki’s team from the University of Toyama, Japan, to conduct a series of studies. Through three core strategies—spatial regulation of active sites, optimization of interfacial electronic structure, and synergistic design of supports/zeolites—they published 4 research papers in international journals such as Nature Communications, Applied Catalysis B: Environment and Energy, and ACS Catalysis. These studies successively achieved selective switching of CO₂ to light olefins/LPG, efficient synthesis of aromatics, and methanol-mediated directional conversion of LPG, ultimately constructing an Fe-Al bimetal-zeolite tandem system that set a new record for LPG conversion efficiency. The series of achievements form a complete research chain of “site regulation → product expansion → efficiency optimization,” providing multiple innovative solutions to the challenges of selectivity, conversion rate, and stability in CO₂ conversion. Academically, the results enrich the synergistic theories of bimetallic catalysis, support engineering, and zeolite sieving; practically, they offer implementable catalyst systems and process parameters for industrial-scale technologies such as CO₂ hydrogenation to LPG and aromatics.

Series Research Progress 1: Graphene Fence-Regulated Fe-Co Bimetallic Sites—Selective Switching Between Light Olefins and LPG

Adjusting the distribution of CO₂ hydrogenation products to obtain high-selectivity target products is of great significance. However, due to the insufficient precision in regulating chain growth and hydrogenation reactions, the directional synthesis of a single product remains highly challenging. Herein, this paper reports a method for controlling multiple active sites through graphene fence engineering, which enables the direct conversion of CO₂/H₂ mixtures into different types of hydrocarbons. The Fe-Co active sites on the surface of graphene fences exhibit a selectivity of 50.1% for light olefins (C₂-C₄⁼), while the isolated Fe-Co nanoparticles separated by graphene fences can produce 43.6% liquefied petroleum gas (LPG). With the assistance of graphene fences, iron carbides and metallic cobalt can effectively regulate C-C bond growth and olefin secondary hydrogenation, thereby achieving product selectivity switching between light olefins and LPG. Furthermore, this work pioneers the direct hydrogenation of CO₂ to LPG via the Fischer-Tropsch route, with a space-time yield (STY) much higher than that of other reported composite catalysts. Published in Nature Communications in January 2024, this study lists Professor Liang Bing from SYUCT and Academician Noritaka Tsubaki from the University of Toyama as co-corresponding authors, and Liang Jiaming (Ph.D. candidate at the University of Toyama) and Liu Jiangtao (Master’s candidate from the School of Materials Science and Engineering, SYUCT) as co-first authors.

Paper link: https://doi.org/10.1038/s41467-024-44763-9

Series Research Progress 2: Interlayer Ternary System—Breaking the ASF Limit for Efficient Aromatic Synthesis

Improving the selectivity of light olefin intermediates is crucial for the efficient synthesis of aromatics via CO₂ hydrogenation. However, due to the constraint of the ASF product distribution law, the directional synthesis of light olefins using iron-based catalysts is highly challenging. Herein, this paper innovatively inserts Y zeolite between the Fe-based catalyst and ZSM-5 zeolite to form an interlayer structure. The excellent cracking function of the interlayer Y zeolite concentrates the products into light unsaturated hydrocarbons before aromatization, thereby achieving high aromatic selectivity in the subsequent aromatization process. With the assistance of Y zeolite, the light olefin selectivity of the K-Fe catalyst increases from 30.8% to 40.3% compared to the bifunctional catalyst without Y zeolite. Further combination with ZSM-5 zeolite enhances the aromatic selectivity of the ternary system from 27.6% to 51.5%. This study provides valuable guidance for the rational use of multifunctional zeolites in the direct synthesis of target products. Published in Applied Catalysis B: Environment and Energy in November 2024, this work designates Professor Liang Bing from SYUCT and Academician Noritaka Tsubaki from the University of Toyama as co-corresponding authors, and Liang Jiaming (Researcher at the University of Toyama) and Liu Hengyang (Master’s candidate from the School of Materials Science and Engineering, SYUCT) as co-first authors.

Paper link: https://doi.org/10.1016/j.apcatb.2024.124305

Series Research Progress 3: Zn-Cr Interface Oxygen Vacancy Regulation—Methanol-Mediated Directional Conversion of LPG

Understanding the influence of oxygen vacancies is significant for revealing molecular adsorption and rational catalyst design. However, for catalysts with multiple active phases, the properties of oxygen vacancies at different active sites and their intrinsic catalytic mechanisms have not been fully studied. Herein, this paper synthesizes Zn-Cr catalysts with varying oxygen vacancy distributions and contents across different active phases via co-precipitation for CO₂ hydrogenation. Characterizations and density functional theory (DFT) calculations indicate that although oxygen vacancies are less likely to form at the adjacent interface between ZnO and ZnCr₂O₄ compared to spinel or metal oxide phases, the interfacial oxygen vacancy sites at ZnO/ZnCr₂O₄−Ov reduce the formation energy barriers of key intermediates (HCOO* and H₃CO*) during methanol synthesis, thereby promoting methanol production. Consequently, with uniformly distributed interfacial oxygen vacancies, the 3Zn1Cr catalyst exhibits the highest methanol selectivity (80.5%) and CO₂ conversion rate (19.2%) among all Zn-Cr catalyst ratios. Additionally, further combination of 3Zn1Cr with modified β zeolite endows the composite catalyst with superior LPG selectivity—achieving 84.0% LPG selectivity at a CO₂ conversion rate of 30.2%. The strategy proposed in this paper provides new insights for designing efficient composite catalysts for C1 chemical reactions via methanol-mediated pathways. Published in ACS Catalysis in April 2025, this study lists Professor Liang Bing from SYUCT and Academician Noritaka Tsubaki from the University of Toyama as co-corresponding authors, and Liang Jiaming (Researcher at the University of Toyama) and Jiang Lei (Master’s candidate from the School of Materials Science and Engineering, SYUCT) as co-first authors.

Paper link: https://pubs.acs.org/doi/10.1021/acscatal.5c00766

Series Research Progress 4: Synergy Between Fe-Al Bimetals and SSZ-13 Zeolite—A New Exploration of LPG Conversion Efficiency

Improving the selecticvity of target products is critical for CO₂ hydrogenation. However, iron-based catalysts still face challenges in this regard due to the ASF distribution limit. Herein, this study constructs a tandem catalyst composed of Fe-Al bimetals and modified SSZ-13 zeolite to achieve the efficient conversion of CO₂ to LPG. By balancing CO₂ adsorption and Fe carburization, K-2FeAl with an Fe/Al molar ratio of 2 exhibits the highest CO₂ conversion rate and light olefin selectivity. Further mixing with HSSZ-13 zeolite induces cracking and hydrogenation of the generated olefins, concentrating the products primarily in propane and butane. Thus, the optimized system achieves 51.7% LPG selectivity at a CO₂ conversion rate of 47.3%, with a space-time yield (STY) of 141.1 g kgcat⁻¹ h⁻¹—surpassing previously reported catalysts for traditional methanol-mediated pathways. This work provides guidance for combining high reaction rates with high product selectivity in iron-based catalysts. Published in ACS Catalysis in October 2025, this paper designates SYUCT as the first affiliated unit. Professor Liang Bing from SYUCT, Liang Jiaming (Researcher at the University of Toyama), and Academician Noritaka Tsubaki serve as co-corresponding authors, with Meng Bowei (Master’s candidate from the School of Materials Science and Engineering, SYUCT) as the first author.

Paper link: https://pubs.acs.org/doi/10.1021/acscatal.5c02333