Covalent organic frameworks (COFs) have emerged as promising materials for energy-related applications, where precise control over charge and mass transport is critical, such as in electrocatalysis an...

Understanding the structural response of framework materials to external stimuli has been of great interest. However, little is known about the stimuli responsiveness of titanium-based metal–organic f...

Thio-lithium superionic conductors (thio-LISICONs) are a family of promising solid electrolyte materials for potential applications in solid-state batteries. The orthorhombic polymorph of the thio-LIS...

Polycrystalline single-phase bulk Hydrogrossulars (Ca3Al2(SiO4)3-x(OH)4x (0 ≤ x ≤ 3)) of various compositions were synthesized for the first time utilizing hydrothermal treatment at 200 °C of the phyl...

Hybrid organic–inorganic (HOI) antimony and bismuth halides exhibit diverse structural features and have been studied intensely for their promising electronic and optical properties. There are well-ex...

All-solid-state batteries (ASSBs) promise higher energy and power densities and improved safety over lithium-ion batteries (LIBs) by using non-flammable solid electrolytes (SEs), with thiophosphate-ba...

Covalent organic frameworks (COFs) have emerged as promising semiconducting materials for photocatalytic applications due to their large surface area, high crystallinity, and vast synthetic tunability. This is especially noticeable in the context of photocatalytic water splitting, where many COFs have been employed for the hydrogen evolution half-reaction. There, sacrificial reagents typically replace the kinetically demanding oxygen evolution half-reaction. On the contrary, only few reports focus on (sacrificial) water oxidation with COF photocatalysts. In most of these cases, cobalt species are employed as oxygen evolution cocatalyst, often with limited insight into their structure and detailed role in the catalysis. Herein, we use heterogenization of a molecularly defined iridium half-sandwich complex onto a bipyridine-based COF (Ir@TAPB-BPY COF) and provide detailed structural insights ensuring the integrity of the targeted cocatalyst. First, we demonstrate the retained catalytic activity of the anchored Cp*Ir(III) motifs in chemical water oxidation experiments. In contrast, subsequent photocatalytic and electrocatalytic tests indicate that Ir@TAPB-BPY COF does not evolve oxygen and that careful control experiments have to be conducted in order to avoid false positive results, caused for example by the sacrificial electron acceptor. Using computational methods, we trace back the missing performance to thermodynamic and kinetic limitations of the employed systems. This work demonstrates the pitfalls associated with low-performing oxygen evolution photocatalysts as well as the indispensability of control experiments and their careful evaluation.

Dr. Bibhuti Bhusan Rath, postdoc at the Max Planck Institute for Solid State Research, demonstrates the long-term storage of the stabilized charges in the organic scaffold compounds for use in solar b...