山东大学张进涛团队报了热驱动的铋纳米颗粒在碳基体中的分散用于高效的二氧化碳还原。相关研究成果于2024年4月26日发表在《德国应用化学》。

在二氧化碳（CO₂）的电催化转化中，由于苛刻的还原条件，金属电催化剂的电催化稳定性差和快速失活总是存在的。

该文中，研究人员展示了仅是通过热驱动的扩散过程，超细铋纳米颗粒在中空碳壳(Bi@C-700-4)中可控的分散。氮掺杂碳基体的限制效应能够降低铋纳米颗粒的表面能，以对抗热处理中常见的易聚集现象。基于纳米铋与碳基体之间的协同作用和约束作用，高度分散的活性位点使二氧化碳还原为甲酸盐的电催化活性和稳定性明显提高。

还原过程的原位实验观察和理论计算表明，纳米铋与氮掺杂碳基体的结合将促进CO₂的活化和关键中间体（*OCHO）的容易形成，从而导致电催化活性的增强，甲酸盐的法拉第效率（FE）约为94.8%，且具有长期稳定性。此外，太阳能驱动系统中5-羟甲基糠醛氧化反应（HMFOR）阳极的耦合，使2，5-呋喃二羧酸（FDCA）的产率高达81.2%，表现出令人印象深刻的太阳能到燃料的转化率。

附：英文原文

Title: Thermal-driven Dispersion of Bismuth Nanoparticles among Carbon Matrix for Efficient Carbon Dioxide Reduction

Author: Weijian Guo, Xueying Cao, Dongxing Tan, Bari Wulan, Jizhen Ma, Jintao Zhang

Issue&Volume: 2024-04-26

Abstract: The poor electrocatalytic stability and rapid deactivation of metal electrocatalysts are always present in the electrocatalytic conversion of carbon dioxide (CO2) due to the harsh reduction condition. Herein, we demonstrate the controllable dispersion of ultrafine bismuth nanoparticles among the hollow carbon shell (Bi@C-700-4) simply by a thermal-driven diffusion process. The confinement effect of nitrogen-doped carbon matrix is able to low the surface energy of bismuth nanoparticles against the easy aggregation commonly observed for the thermal treatment. On the basis of the synergistic effect and confinement effect between bismuth nanoparticles and carbon matrix, the highly dispersed active sites render the obviously improved electrocatalytic activity and stability for carbon dioxide reduction into formate. The in-situ experimental observation on the reduction process and theoretical calculations reveal that the incorporation of bismuth nanoparticles with nitrogen-doped carbon matrix would promote the activation of CO2 and the easy formation of key intermediate (*OCHO), thus leading the enhanced electrocatalytic activity, with a Faradaic Efficiency (FE) of formate about 94.8% and the long-time stability. Furthermore, the coupling of an anode for 5-hydroxymethylfurfural oxidation reaction (HMFOR) in solar-driven system renders the high 2,5-furandicarboxylic acid (FDCA) yield of 81.2%, presenting the impressive solar-to-fuel conversion.

DOI: 10.1002/anie.202401333

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202401333