Fabrication of Surfactant-Free Mixed-Metal Nanocatalyst–Carbon Fiber Paper Composites via Pulsed Laser Grafting

We present a novel methodology for fabricating surfactant-free mixed-metal nanocatalyst-carbon fiber paper composites, demonstrating significant improvements in impedance, electrocatalytic activity, and long-term stability over laser synthesized drop cast analogues on carbon fiber paper or highly ordered pyrolytic graphite. Our innovative pulsed laser grafting technique is a versatile, one-step aqueous process that integrates nanoparticle generation with surface attachment on macroscopic solid supports, such as sheets, rather than being limited to powders, particulate supports, or organic solvents as in prior methods. It effectively addresses longstanding challenges with nanoparticle adhesion and electrical contact between nanoparticles and macroscopic electrodes, and it alleviates environmental concerns associated with organic solvents. Laser grafting eliminates laborious synthesis, separation, purification, and postsynthesis attachment steps, thus significantly reducing composite preparation time. We fabricated [NiFe]-(OH)₂-hydrophilic carbon fiber paper composites using aqueous nickel-iron nitrate solution. Low-fluence 532 nm nanosecond laser pulses minimized surface damage and facilitated effective metal ion excitation for nanoparticle assembly. SEM, EDX and XPS data revealed surface [NiFe]-(OH)₂ without carbon encapsulation and prominent Ni-C interactions. The pulsed laser grafted composites showed enhanced electrocatalytic performance for alkaline water oxidation and decreased material charge transfer resistance, compared to drop cast analogues, leading to improved electrical conductivity and mass activity. Additionally, they demonstrated exceptional long-term stability, overcoming common adhesion issues in conventional nanoparticle-support systems, marking a significant advancement in the manufacturing of multimetallic nanoparticle-support composites, with promising implications for electrochemistry and electrocatalysis technologies.