Mao Guangtao, Zhou Qian, Wang Bin, Xiong Yuan, Zheng Xingqun, Ma Jun, Fu Lin, Luo Leqing, Wang Qingmei
Guizhou University Key Laboratory of Green Chemical and Clean Energy Technology, Guizhou University Engineering Research Center of Efficient Utilization for Industrial Waste, School of Chemistry and Chemical Engineering, Guizhou University, Institute of Dual-carbon and New Energy Technology Innovation and Development of Guizhou Province, Guiyang, Guizhou 550025, China.
College of Safety Engineering, Chongqing University of Science & Technology, Chongqing 401331, China.
J Colloid Interface Sci. 2025 Jan;677(Pt B):657-665. doi: 10.1016/j.jcis.2024.08.033. Epub 2024 Aug 8.
Coordinating the interfacial interaction between Pt-based nanoparticles (NPs) and supports is a significant strategy for the modulation of d-orbital electronic configuration and the adsorption behaviors of intermediates, which is of critical importance for boosting electrocatalytic performance. Herein, we demonstrated a specific synergy effect between the ordered PtFe intermetallic and neighboring oxygen vacancies (Ov), which provides an "ensemble reaction pool" to balance the barriers of both the activity, stability, and CO poisoning issues for the methanol oxidation reaction (MOR). In our proposed "ensemble reaction pool", the deprotonation of methanol occurs on the Pt site to form the intermediate *CO, where the strain derived from the PtFe intermetallic could alter the d-orbital electronic configuration of Pt, intrinsically weakening the *CO adsorption energy, and Ov in CeO promote hydroxyl species (*OH) adsorption, which will react with *CO, facilitating the dissociative adsorption of *CO, thus cooperatively enhancing the performance of MOR. The X-ray absorption fine structure (XAFS) analyses reveal the electron transfer in CeO and then convert Ce to Ce. The density functional theory (DFT) calculations revealed that introducing Fe induces strain could modify the d-band center of Pt, and thus lower the energy barrier of the potential-determining step. Meanwhile, the introduction of CeO can favor the *OH adsorption, speeding up the oxidation and removal of *CO blocked at the Pt site. Furthermore, the determined atomic arrangement and surface composition of PtFe intermetallic further guarantee the stability of MOR by suppressing less-noble metal into the electrolyte.
协调铂基纳米颗粒（NPs）与载体之间的界面相互作用是调节d轨道电子构型和中间体吸附行为的重要策略，这对于提高电催化性能至关重要。在此，我们展示了有序PtFe金属间化合物与相邻氧空位（Ov）之间的特定协同效应，它提供了一个“整体反应池”，以平衡甲醇氧化反应（MOR）的活性、稳定性和CO中毒问题的障碍。在我们提出的“整体反应池”中，甲醇的去质子化发生在Pt位点上形成中间体CO，其中来自PtFe金属间化合物的应变可以改变Pt的d轨道电子构型，本质上削弱CO的吸附能，而CeO中的Ov促进羟基物种（OH）的吸附，OH将与CO反应，促进CO的解离吸附，从而协同提高MOR的性能。X射线吸收精细结构（XAFS）分析揭示了CeO中的电子转移，然后将Ce转化为Ce。密度泛函理论（DFT）计算表明，引入Fe引起的应变可以改变Pt的d带中心，从而降低决速步骤的能垒。同时，引入CeO有利于OH的吸附，加速在Pt位点上被阻断的CO的氧化和去除。此外，确定的PtFe金属间化合物的原子排列和表面组成通过抑制较不活泼的金属进入电解质进一步保证了MOR的稳定性。
