Iron Oxide-Carbon Black Promotional Effect on Palladium Nanoparticles Toward Ethylene Glycol Oxidation in Alkaline Medium: Experimental and Computational Studies
Iron Oxide-Carbon Black Promotional Effect on Palladium Nanoparticles Toward Ethylene Glycol Oxidation in Alkaline Medium: Experimental and Computational Studies
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DOI：
10.1002/ente.202300856
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发表时间：
2023-12-14
影响因子：
3.8
通讯作者：
Maxakato，Nobanathi W.
中科院分区：
文献类型：
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作者：
Chabalala，Makhaokane P.;Matthews，Thabo;Maxakato，Nobanathi W.
直接醇燃料电池由于其高功率密度而成为未来的下一代能源。钯电催化剂在碱性介质中促进醇氧化方面具有很好的应用前景，但较高的成本和对CO中毒的敏感性限制了其应用和商业化。因此，需要通过利用双负载体系来改善Pd电催化剂的性能。采用微波辅助多元醇法合成了负载在氧化铁-炭黑材料上的钯纳米粒子（Pd/Fe 2 O3-CB）。对所获得的电催化剂材料进行物理化学和电化学表征，以研究所合成的电催化剂的形态和电化学行为。Pd/Fe 2 O3-CB由于Fe 2 O3和CB的掺入而显示出更高的动力学，其通过58.7 mA cm−2的更高电流密度、稳定性和耐久性而得到证实。密度泛函理论（DFT）证明来自CO的C与表面Pd具有更强的相互作用，从而解释Pd的更强的C-O结合性质。轨道分析表明Pd的3d轨道参与了与C和O的2 p轨道的杂化。因此，C2 p和Pd 3d/Fe 3d轨道之间的重叠显着加宽，导致CO在Pd/Fe 2 O3上的固体吸附。
Direct alcohol fuel cells are the next‐generation energy sources of the future due to their high power density. Palladium electrocatalysts are promising prospects for enhancing alcohol oxidation in alkaline media, but the higher cost and susceptibility to CO poisoning limit their application and commercialization. Thus, there is a need to improve the performance of the Pd electrocatalysts by utilizing a double supporting system. A microwave‐assisted polyol method is used to synthesize the palladium nanoparticles supported on iron oxide‐carbon black material (Pd/Fe2O3‐CB). Physiochemical and electrochemical characterization of the obtained electrocatalysts materials is conducted to study morphology and the electrochemical behaviour of the as‐synthesized electrocatalysts. The Pd/Fe2O3‐CB displayed higher kinetics approved by a higher current density of 58.7 mA cm−2, stability, and durability, owing to Fe2O3,and CB incorporation. Density functional theory (DFT) proves that C from CO has more robust interactions with surface Pd, thereby explaining the stronger C‐O binding property of Pd. The orbital analysis revealed that 3d orbitals of Pd participate in the hybridization with 2p orbitals of C and O. As a result, the overlap between C2p and Pd3d/Fe3d orbitals significantly broadened, leading to solid adsorption of CO over Pd/Fe2O3.