电化学性能测试在H型电解池中进行，以0.1 mol/L CO2饱和的KHCO3溶液为电解液，采用三电极体系评估催化剂的CO2RR活性。线性扫描伏安法（LSV）和恒电流法测试显示，pre-ZrP-1.5Pd在–0.8 V vs RHE时乙醇法拉第效率达到87.6%，而pre-ZrP-2.5Pd在相同电位下的乙醇选择性更高，峰值法拉第效率达92.1%，电流密度为0.82 mA/cm2。值得注意的是，随着电位负移至–1.0 V vs RHE，析氢反应（HER）的竞争加剧，导致CO2RR法拉第效率下降。与铜基催化剂相比，该钯基催化剂的电流密度仍较低，但选择性已达到或超过部分优化的铜基体系。
本研究制备了负载于磷酸锆上的超小钯纳米颗粒催化剂，通过调控金属-载体相互作用实现了高效CO2RR制乙醇。该催化剂在–0.8 V vs. RHE下乙醇的法拉第效率达92.1%，性能优于多数铜基和非铜基催化剂。机理研究表明，磷酸锆载体的氧空位为钯提供了稳定的锚定位点，而强金属-载体相互作用通过d带中心上移增强*CO的吸附，促进了C-C的耦合。尽管电流密度仍低于铜基催化剂，但该研究为设计高选择性非铜基CO2RR催化剂提供了新思路，有望推动碳中性燃料合成技术的发展。
原文信息
Ultrasmall palladium nanoparticles supported on zirconium phosphate for electrochemical CO2 reduction to ethanol
1. College of Chemistry, Fuzhou University, Fuzhou 350108, China
2. College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, China
Abstract：
The electrochemical CO2 reduction reaction (CO2RR) provides a promising approach to mitigate the global greenhouse effect by converting CO2 into high-value chemicals or fuels. Noble metal-based nanomaterials are widely regarded as efficient catalysts for CO2RR due to their high catalytic activity and excellent stability. However, these catalysts typically favor the formation of C1 products, which have relatively low economic value. Moreover, the high cost and limited availability of noble materials necessitate strategies to reduce their usage, often by dispersing them on suitable support materials to enhance catalytic performance. In this study, a novel metal-based support, zirconium phosphate Zr3(PO4)4, was used to anchor ultrasmall palladium nanoparticles (pre-ZrP-Pd). Compared to the reversible hydrogen electrode, the pre-ZrP-Pd achieved a maximum Faradaic efficiency (FE) of 92.1% for ethanol at –0.8 V versus RHE, along with a peak ethanol current density of 0.82 mA/cm2. Density functional theory (DFT) calculations revealed that the strong metal-support interactions between the ZrP support and Pd nanoparticles lead to an upward shift of the Pd d-band center, enhancing the adsorption of CO* and promoting the coupling of CO and CO to produce ethanol.
Keywords:
electrochemical CO2 reduction reaction (CO2RR); noble metal-based nanocatalysts; zirconium phosphate (Zr3(PO4)4) support; ethanol selectivity; density functional theory (DFT) calculations
Cite this article:
Bowen Zhong, Chengwei Hu, Kaian Sun, Wei Yan, Jiujun Zhang, Zailai Xie. Ultrasmall palladium nanoparticles supported on zirconium phosphate for electrochemical CO2reduction to ethanol. Front. Energy, https://doi.org/10.1007/s11708-025-1025-1
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