Chen Jiadong, Mao Tingjie, Wang Juan, Wang Jichang, Wang Shun, Jin Huile
Key Lab of Advanced Energy Storage and Conversion, Zhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering, Wenzhou University Wenzhou, Zhejiang, 325035, China.
Zhejiang Engineering Research Center for Electrochemical Energy Materials and Devices, Institute of New Materials and Industrial Technologies, Zhejiang- Canada Joint Laboratory on Energy Storage and electrocatalysis, Wenzhou University, Wenzhou, Zhejiang, 325035, China.
Angew Chem Int Ed Engl. 2024 Oct 7;63(41):e202408849. doi: 10.1002/anie.202408849. Epub 2024 Sep 5.
The electrochemical CO reduction reaction (CORR) to generate chemical fuels such as formate presents a promising route to a carbon-neutral future. However, its practical application is hindered by the competing CO production and hydrogen evolution reaction (HER), as well as the lack of pH-universal catalysts. Here, Te-modified Bi nanorods (Te-Bi NRs) were synthesized through in situ reconstruction of BiTeO NRs under the CORR condition. Our study illustrates that the complex reconstruction process of BiTeO NRs during CORR could be decoupled into three distinct steps, i.e., the destruction of BiTeO, the formation of Te/Bi phases, and the dissolution of Te. The thus-obtained Te-Bi NRs exhibit remarkably high performance in CORR towards formate production, showing high activity, selectivity, and stability across all pH conditions (acidic, neutral, and alkaline). In a flow cell reactor under neutral, alkaline, or acidic conditions, the catalysts achieved HCOOH Faradaic efficiencies of up to 94.3 %, 96.4 %, and 91.0 %, respectively, at a high current density of 300 mA cm. Density functional theory calculations, along with operando spectral measurements, reveal that Te manipulates the Bi sites to an electron-deficient state, enhancing the adsorption strength of the *OCHO intermediate, and significantly suppressing the competing HER and CO production. This study highlights the substantial influence of catalyst reconstruction under operational conditions and offers insights into designing highly active and stable electrocatalysts towards CORR.
通过电化学一氧化碳还原反应（CORR）生成诸如甲酸盐等化学燃料，为实现碳中和未来提供了一条有前景的途径。然而，其实际应用受到竞争性的一氧化碳生成和析氢反应（HER）以及缺乏pH通用催化剂的阻碍。在此，通过在CORR条件下对BiTeO纳米棒进行原位重构合成了碲修饰的铋纳米棒（Te-Bi NRs）。我们的研究表明，CORR过程中BiTeO纳米棒的复杂重构过程可解耦为三个不同步骤，即BiTeO的破坏、Te/Bi相的形成以及Te的溶解。如此获得的Te-Bi NRs在CORR生成甲酸盐方面表现出极高的性能，在所有pH条件（酸性、中性和碱性）下均显示出高活性、选择性和稳定性。在中性、碱性或酸性条件下的流动池反应器中，该催化剂在300 mA cm的高电流密度下分别实现了高达94.3%、96.4%和91.0%的HCOOH法拉第效率。密度泛函理论计算以及原位光谱测量表明，碲将铋位点操纵到缺电子状态，增强了*OCHO中间体的吸附强度，并显著抑制了竞争性的HER和一氧化碳生成。这项研究突出了操作条件下催化剂重构的重大影响，并为设计用于CORR的高活性和稳定电催化剂提供了见解。
