Photocatalytic Hydrogen Evolution From Self-Assembled Stacks of Pd–TCPP and Pt–TCPP

Kim JH, Zdrazil L, Zhou X, Schmuki P (2026)

Publication Type: Journal article

Publication year: 2026

Journal

Small Wiley-VCH Verlag

DOI: 10.1002/smll.74115

Abstract

The present work demonstrates that surfactant-free precipitation of Pd– and Pt–TCPP in MeOH/H2O yields well-defined supramolecular architectures (µm-long nanorods) whose photocatalytic function tracks their metal-dependent photophysics and stacking. Among all tested M–TCPPs (M = Pd, Pt, Zn, Au, and Co), only Pd–TCPP and Pt–TCPP assemble to nanorods that are intrinsically active for H2 evolution without any Pt cocatalyst, with Pd–TCPP outperforming Pt–TCPP robustly across the optimal aggregation window (pH ≈ 4–5). In fact, the cocatalyst-free Pd–TCPP nanorods surpass many other state-of-the-art porphyrin platforms, including Zn–TCPP assemblies operated with high-loaded Pt cocatalysts, as well as porphyrinic metal–organic frameworks (MOFs). The self-assemblies display J-type π–π stacking stabilized by carboxylate hydrogen bonding, producing broadened, red-shifted light absorption and efficient charge transport. Correlating XRD analysis, spectroscopy, and electrochemistry reveals that compared to Pt–TCPP, Pd–TCPP nanorods exhibit tighter π–π stacking, extended triplet-state lifetime, and lower charge-transfer resistance, consistent with more efficient charge separation and faster interfacial electron transfer. Importantly, the approach taken in this work allows for one-pot, surfactant-free, co-catalyst-free operation of Pd–TCPP nanorods that not only is of low synthetic complexity but also avoids surfactant residues while delivering a high and stable photocatalytic H2 production activity under visible illumination.

Authors with CRIS profile

Ji Hyeon Kim Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik) (LKO) Xin Zhou Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik) (LKO) Patrik Schmuki Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik) (LKO)

Involved external institutions

Technical University of Ostrava / Vysoká škola báňská - Technická univerzita Ostrava CZ Czech Republic (CZ)

How to cite

APA:

Kim, J.H., Zdrazil, L., Zhou, X., & Schmuki, P. (2026). Photocatalytic Hydrogen Evolution From Self-Assembled Stacks of Pd–TCPP and Pt–TCPP. Small. https://doi.org/10.1002/smll.74115

MLA:

Kim, Ji Hyeon, et al. "Photocatalytic Hydrogen Evolution From Self-Assembled Stacks of Pd–TCPP and Pt–TCPP." Small (2026).

BibTeX: Download