Configurational entropy-driven electronic reconstruction in five-component phthalocyanine frameworks: A transferable modulation route for sacrificial-agent-free solar-to-chemical H2O2 production

In this work, we synthesize an unprecedented five-component high-entropy phthalocyanine framework (HE-MPcF), a new molecular framework fundamentally distinct from conventional monometallic or simple polymetallic phthalocyanines. We unambiguously validate that the prominent configurational entropy effect, rather than trivial metal synergism widely reported in ordinary multi-metal phthalocyanines, acts as the core driving force to modulate the intrinsic electronic and catalytic properties of the framework. The entropy-triggered disordered spatial distribution of five types of metal centers constructs continuous gradient electronic states and extensive built-in electric fields throughout the skeleton, which enables ultrafast charge separation and drastically inhibits unfavorable electron-hole recombination. Benefiting from this unique entropy-mediated structural and electronic regulation, the optimized two-electron oxygen reduction pathway is achieved, delivering efficient and highly selective photocatalytic H 2 O 2 evolution in pure water without sacrificial agents. Under visible-light irradiation, the HE-MPcF exhibits an outstanding H 2 O 2 production rate of 4183µmol g −1 h −1 together with a selectivity of 78%. Multiple in situ spectroscopic measurements, synchrotron characterizations, and density functional theory theoretical calculations jointly corroborate the entropy-dominated catalytic mechanism. This work establishes an entropy-engineering strategy for designing phthalocyanine framework photocatalysts, provides a platform to explore high-entropy effects in molecular catalysis, and offers guidance for developing sustainable photocatalysts for environmental energy conversion. By revealing why entropy engineering is essential for overcoming the intrinsic limitations of conventional phthalocyanine photocatalysts, how high-entropy molecular frameworks regulate charge dynamics and reaction pathways, and what new design principles they offer for selective H 2 O 2 photosynthesis, this work advances the fundamental understanding and practical development of molecular photocatalysis. A high-entropy phthalocyanine framework with multi-metal M–N 4 sites enables efficient sacrificial-agent-free photocatalytic H 2 O 2 production in pure water via synergistic 2e − oxygen reduction reaction (ORR) and 2e − water oxidation reaction (WOR) pathways. Download: Download high-res image (199KB) Download: Download full-size image