CeO_(2)表面工程与PtBi纳米板间p-d轨道杂化的协同效应在甲醇电氧化中的应用

Synergistic effects of p-d orbital hybridization and CeO_(2) surface engineering on PtBi nanoplates for methanol electro-oxidation

调控铂(Pt)电子结构是增强Pt基电催化剂活性和耐久性的关键策略.本研究开发了CeO_(2)/PtBi金属间纳米板(NPs),这种结构通过Pt和Bi之间的强p-d轨道杂化,显著提高了催化剂在甲醇电氧化反应(MOR)中的活性和稳定性.CeO_(2)的表面沉积不仅进一步优化了Pt的电子结构,还提供了额外的羟基吸附位点.特别是,在酸性和碱性环境下,CeO_(2)/PtBi NPs展现出超越商业Pt/C的甲醇电氧化质量活性,分别提高了1.62和7.65倍.在经历了1000次耐久性测试后,CeO_(2)/PtBi NPs在酸碱环境下的活性仅分别下降了20.1%和39.8%,相比之下,商业Pt/C的活性在相同条件下分别下降了55.4%和78.5%.CeO_(2)/PtBi NPs的这一卓越性能得益于Pt与Bi之间的p-d轨道杂化以及CeO_(2)表面工程对催化剂电子结构的有效调节.本研究为Pt基电催化剂设计提供了新的电子结构调控策略和深入见解.

Modulating the electronic structure of Pt is an effective strategy for enhancing the activity and durability of Pt-based electrocatalysts.Herein,we reported a type of in-termetallic CeO_(2)/PtBi nanoplates(NPs),which possessed en-hanced activity and durability for methanol electro-oxidation reaction(MOR)through strong p-d hybridization between the Pt and Bi.The surface-deposited CeO_(2) can further optimize the electronic structure of Pt,while providing more hydroxyl adsorption sites.Specifically,the CeO_(2)/PtBi NPs exhibited excellent mass activity for MOR in both acidic and alkaline environments,which were 1.62 and 7.65 times higher than those of commercial Pt/C,respectively.After 1000 durability tests in acidic and alkaline environments,the activities of CeO_(2)/PtBi NPs only decreased by 20.1%and 39.8%,respec-tively,while the activities of commercial Pt/C decreased by 55.4%and 78.5%,respectively.The excellent activity and durability can be attributed to the modulation of the elec-tronic structure through p-d orbital hybridization between Pt,Bi and the surface-deposited CeO_(2).This study provides new insights into the electronic structure regulation of Pt-based electrocatalysts.