The operational efficiency of membrane electrode assemblies in direct liquid fuel cells is critically dependent on the fuel purity in the anode compartment. To address the inherent challenge of fuel mixing problem in alcohol systems, we propose a rational catalyst design strategy focusing on morphological and compositional optimization. Sodium borohydride-derived PtCuMo alloy aerogels (AA) exhibit abundant grain boundary defects, while solvothermally prepared nanowire arrays (NA) maintain excellent single-crystalline characteristics. Density functional theory calculations demonstrate that engineered grain boundaries can effectively broaden the adsorption energy window for key reaction intermediates, enabling superior adaptability to diverse catalytic pathways. By precisely controlling Cu content, we identified Pt₃Cu₃Mo_0.5 AA as the optimal catalyst configuration, demonstrating 150% enhancement in methanol oxidation reaction activity compared to Pt₃Cu₆Mo_0.5 NA (1.5 vs. 0.6 A·mg_Pt⁻¹) and 17% improvement in ethanol oxidation reaction performance versus Pt₃Cu₁Mo_0.5 NA (0.82 vs. 0.70 A·mg_Pt⁻¹). Practical application testing using gas diffusion electrodes (anode loading: 0.85 mg_Pt·cm⁻²) achieved a mass-specific power density of 14.14 W·g_Pt⁻¹ in 1:1 methanol/ethanol blends, representing a 3.5-fold improvement over commercial Pt/C benchmarks. This work establishes a fundamental framework for developing high-performance, broad-spectrum electrocatalysts in advanced fuel cell systems.

The rational design of advanced methanol oxidation reaction (MOR) electrocatalysts can significantly enhance the catalytic activity and performance of direct methanol fuel cells (DMFCs). Herein, the electrocatalysis informatics-assisted design electrocatalysts for MOR is firstly conducted by combining machine learning based on 616 experimental data points with first-principles calculations. Guided by this theoretical insight, a highly disordered PtRuPd alloy aerogel is prepared via a facile one-pot synthetic strategy. The obtained electrocatalyst demonstrates excellent mass activity of 2.42 A·mg_Pt⁻¹ and specific activity of 7.13 mA·cm⁻² for MOR, which is considerably higher than that of most Pt-based catalysts. The self-supported ultrathin anode catalyst layer (~6.3 μm) integrated into a membrane electrode assembly exhibits the mass-specific power density of 92.9 W·g_Pt⁻¹ at 65 °C for DMFC operation, surpassing that of recently reported Pt-based catalysts. This work offers a promising approach to exploring a digitalization and intelligent cross-scale design route for MOR electrocatalysts.