Lin Zijie, Sathishkumar Nadaraj, Xia Yu, Li Shenzhou, Liu Xuan, Mao Jialun, Shi Hao, Lu Gang, Wang Tanyuan, Wang Hsing-Lin, Huang Yunhui, Elbaz Lior, Li Qing
State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 430074, Wuhan, China.
Department of Physics and Astronomy, California State University Northridge, 91330, Northridge, CA, USA.
Angew Chem Int Ed Engl. 2024 Jun 21;63(26):e202400751. doi: 10.1002/anie.202400751. Epub 2024 May 24.
Developing efficient and anti-corrosive oxygen reduction reaction (ORR) catalysts is of great importance for the applications of proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel approach to prepare metal oxides supported intermetallic Pt alloy nanoparticles (NPs) via the reactive metal-support interaction (RMSI) as ORR catalysts, using Ni-doped cubic ZrO (Ni/ZrO) supported L1-PtNi NPs as a proof of concept. Benefiting from the Ni migration during RMSI, the oxygen vacancy concentrations in the support are increased, leading to an electron enrichment of Pt. The optimal L1-PtNi-Ni/ZrO-RMSI catalyst achieves remarkably low mass activity (MA) loss (17.8 %) after 400,000 accelerated durability test cycles in a half-cell and exceptional PEMFC performance (MA=0.76 A mg at 0.9 V, peak power density=1.52/0.92 W cm in H-O/-air, and 18.4 % MA decay after 30,000 cycles), representing the best reported Pt-based ORR catalysts without carbon supports. Density functional theory (DFT) calculations reveal that L1-PtNi-Ni/ZrO-RMSI requires a lower energetic barrier for ORR than L1-PtNi-Ni/ZrO (direct loading), which is ascribed to a decreased Bader charge transfer between Pt and *OH, and the improved stability of L1-PtNi-Ni/ZrO-RMSI compared to L1-PtNi-C can be contributed to the increased adhesion energy and Ni vacancy formation energy within the PtNi alloy.
开发高效且抗腐蚀的氧还原反应（ORR）催化剂对于质子交换膜燃料电池（PEMFC）的应用至关重要。在此，我们报告了一种通过反应性金属-载体相互作用（RMSI）制备金属氧化物负载的金属间Pt合金纳米颗粒（NPs）作为ORR催化剂的新方法，以掺杂Ni的立方ZrO（Ni/ZrO）负载的L1-PtNi NPs作为概念验证。受益于RMSI过程中的Ni迁移，载体中的氧空位浓度增加，导致Pt的电子富集。优化后的L1-PtNi-Ni/ZrO-RMSI催化剂在半电池中经过400,000次加速耐久性测试循环后，质量活性（MA）损失极低（17.8%），并且具有出色的PEMFC性能（在0.9 V时MA = 0.76 A mg，在H-O/-空气中峰值功率密度 = 1.52/0.92 W cm，30,000次循环后MA衰减18.4%），代表了报道的无碳载体的最佳Pt基ORR催化剂。密度泛函理论（DFT）计算表明，L1-PtNi-Ni/ZrO-RMSI的ORR能量势垒低于L1-PtNi-Ni/ZrO（直接负载），这归因于Pt与*OH之间的巴德电荷转移减少，并且与L1-PtNi-C相比，L1-PtNi-Ni/ZrO-RMSI稳定性的提高可归因于PtNi合金内粘附能和Ni空位形成能的增加。
