Shi Xiaoyu, Yang Yang, Liu Xu, Wang Jingwen, Jin Fangming
State Key Laboratory of Green Papermaking and Resource Recycling, School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China.
ACS Appl Mater Interfaces. 2025 Oct 1;17(39):54711-54720. doi: 10.1021/acsami.5c10611. Epub 2025 Sep 19.
The current carbon capture and utilization (CCU) technologies suffer from energy-intensive processes due to conventional alkaline-based capture methods requiring significant energy input for regeneration and material cycling. In Earth's carbonate weathering process within Karst systems, CO is sequestered and transformed through interaction with CaCO. Inspired by this natural process, here, we propose an integrated CO capture-conversion strategy using geologically abundant carbonates as low-cost absorbents. We demonstrate that CO absorbed by carbonates can be efficiently hydrogenated in situ to formate in a one-pot system at 140 °C using a nonprecious cobalt-copper (CoCu) catalyst, achieving 21% yield of formate with diluted CO emissions (as low as 50 000 ppm, representative of typical industrial exhaust). Co facilitates the formation of a Cu/Cu interfacial structure, leading to an enhancement of the hydrogenation efficiency. Density functional theory calculations show that the Cu/Cu interface serves as the primary active site for H adsorption and activation to H*, which then promotes the reduction of bicarbonate (HCO) to formate. Furthermore, the interface between Co and Cu lowers the energy barrier for HCO adsorption, leading to its enhanced reduction by H*. This work offers a new pathway for simultaneous CO capture and catalytic conversion, advancing sustainable and energy-efficient CCU technologies.
当前的碳捕获与利用（CCU）技术由于传统的基于碱性的捕获方法需要大量能量用于再生和物质循环，因而存在能源密集型过程。在喀斯特系统的地球碳酸盐岩风化过程中，二氧化碳通过与碳酸钙的相互作用被封存和转化。受此自然过程启发，在此我们提出一种利用地质上丰富的碳酸盐作为低成本吸收剂的集成式二氧化碳捕获-转化策略。我们证明，在140°C下使用非贵金属钴-铜（CoCu）催化剂，在一锅法体系中，被碳酸盐吸收的二氧化碳能够原位高效加氢生成甲酸盐，在稀释的二氧化碳排放（低至50000 ppm，代表典型工业废气）情况下实现了21%的甲酸盐产率。钴促进了Cu/Cu界面结构的形成，从而提高了加氢效率。密度泛函理论计算表明，Cu/Cu界面是氢吸附并活化为H的主要活性位点，进而促进碳酸氢根（HCO₃⁻）还原为甲酸盐。此外，Co与Cu之间的界面降低了HCO₃⁻吸附的能垒，导致其被H还原的能力增强。这项工作为同时进行二氧化碳捕获和催化转化提供了一条新途径，推动了可持续且节能的CCU技术发展。
