A triad [FeFe] hydrogenase system for light-driven hydrogen evolution

A novel molecular triad [FeFe]-H(2)ase 1, and its model complexes 2 and 3 have been successfully constructed. The multistep PET and long-lived Fe(i)Fe(0) species were found to be responsible for the better performance of triad 1 than that of 2 with 3 for light-driven H(2) evolution.     

Quantifying the Contribution of Hot Electrons in Photothermal Catalysis: A Case Study of Ammonia Synthesis over Carbon-supported Ru Catalyst

Photothermal catalysis is one of the most promising green catalytic technologies, while distinguishing the effects of hot electrons and local heating remains challenging. Herein, we reported that the actual reaction temperature of photothermal ammonia synthesis over carbon-supported Ru catalyst can be measured based on Le Chatelier′s principle, enabling the hot-electron contribution to be quantified. By excluding local heating effects, we established that the activation energy via photothermal catalysis was much lower than that of thermocatalysis (54.9 vs. 126.0 kJ mol⁻¹), stemming from hot-electron injection lowering the energy barriers for both N₂ dissociation and intermediates hydrogenation. Furthermore, hot-electron injection acted to suppress carbon support methanation, giving the catalyst outstanding operational stability over 1000 h. This work provides new insights into the hot-electron effects in ammonia synthesis, guiding the design of high-performance photothermal catalysts.     

Photoinduced triplet-triplet energy transfer via the 2-ureido-4[1H]-pyrimidinone self-complementary quadruple hydrogen-bonded module

Phosphorescence quenching and flash photolysis experiments demonstrate that photoinduced intra-assembly triplet-triplet energy transfer can take place via a 2-ureido-4[1H]-pyrimidinone-bridged benzophenone-naphthalene assembly I with a rate constant of 3.0 x 106 s-1 and an efficiency of 95% in CH2Cl2. This new finding suggests that with high binding strength and directionality, the 2-ureido-4[1H]-pyrimidinone hydrogen-bonded module may serve as a new model to illustrate the fundamental principles governing the triplet-triplet energy-transfer process through hydrogen bonds.     

Photooxidation of olefins under oxygen in platinum(II) complex-loaded mesoporous molecular sieves

Cyclometalated platinum(II) complex has been successfully incorporated into the (3-aminopropyl) triethoxysilane-modified channels of ordered mesoporous silica SBA-15 that has large pore hexagonal channels. Studies on the (1)O(2) generation conclusively demonstrates that the olefins in the nano-channels of SBA-15 can be enriched 8 times higher than those in the homogeneous solution as the diffusion quantum yield of singlet oxygen ((1)O(2)) is assumed to be unit. The platinum(II) complex loaded in the channel of SBA-15 is stable, and the photosensitized oxidation occurs efficiently. No obvious degradation and leaching of photosensitizers is observed even after 10 runs. Only a simple filtration is needed for the recycled use of the expensive noble metal catalysts. This versatile system is a good example of photochemical reactions occurring in the mesoporous silica molecular sieve. SBA-15 not only provides a support for the photosensitizer, but also acts as a nano-reactor to facilitate the photooxidation.     

First fluorescent sensor for fluoride based on 2-ureido-4[1H]-pyrimidinone quadruple hydrogen-bonded AADD supramolecular assembly

A simple, highly selective, neutral, fluorescent sensor for fluoride anions is reported. It is based on 2-ureido-4[1H]-pyrimidinone quadruple hydrogen-bonded AADD supramolecular assembly, and its assembling and disassembling processes are also able to respond to external stimuli reversibly.