Water oxidation is the key step in natural and artificial photosynthesis for solar-energy conversion. As this process is thermodynamically unfavorable and is challenging from a kinetic point of view, the development of highly efficient catalysts with low energy cost is a subject of fundamental significance. Herein, we report on iron-based films as highly efficient water-oxidation catalysts. The films can be quickly deposited onto electrodes from Fe(II) ions in acetate buffer at pH 7.0 by simple cyclic voltammetry. The extremely low iron loading on the electrodes is critical for improved atom efficiency for catalysis. Our results showed that this film could catalyze water oxidation in neutral phosphate solution with a turnover frequency (TOF) of 756 h(-1) at an applied overpotential of 530 mV. The significance of this approach includes the use of earth-abundant iron, the fast and simple method for catalyst preparation, the low catalyst loading, and the large TOF for O2 evolution in neutral aqueous media.

An ultrathin Fe-based film was prepared by electrodeposition from an Fe(II) solution through a fast and simple cyclic voltammetry method. The extremely low Fe loading of 12.3 nmol cm(-2) on indium tin oxide electrodes is crucial for high atom efficiency and transparence of the resulted film. This Fe-based film was shown to be a very efficient electrocatalyst for oxygen evolution from neutral aqueous solution with remarkable activity and stability. In a 34 h controlled potential electrolysis at 1.45 V (vs NHE) and pH 7.0, impressive turnover number of 5.2 × 10(4) and turnover frequency of 1528 h(-1) were obtained. To the best of our knowledge, these values represent one of the highest among electrodeposited catalyst films for water oxidation under comparable conditions. The morphology and the composition of the catalyst film was determined by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray, and X-ray photoelectron spectroscopy, which all confirmed the deposition of Fe-based materials with Fe(III) oxidation state on the electrode. This study is significant because of the use of iron, the fast and simple cyclic voltammetry electrodeposition, the extremely low catalyst loading and thus the transparency of the catalyst film, the remarkable activity and stability, and the oxygen evolution in neutral aqueous media.

Pressure‐induced polymerization (PIP) of aromatics is a novel method for constructing sp3‐carbon frameworks, and nanothreads with diamond‐like structures were synthesized by compressing benzene and its derivatives. Here by compressing a benzene‐hexafluorobenzene cocrystal (CHCF), H‐F‐substituted graphane with a layered structure in the PIP product was identified. Based on the crystal structure determined from the in situ neutron diffraction and the intermediate products identified by gas chromatography‐mass spectrum, we found that at 20 GPa CHCF forms tilted columns with benzene and hexafluorobenzene stacked alternatively, and leads to a [4+2] polymer, which then transforms to short‐range ordered H‐F‐substituted graphane. The reaction process involves [4+2] Diels–Alder, retro‐Diels–Alder, and 1‐1′ coupling reactions, and the former is the key reaction in the PIP. These studies confirm the elemental reactions of PIP of CHCF for the first time, and provide insight into the PIP of aromatics.

Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure.

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