Publication

To mark the occasion of Nature Chemistry turning 10 years old, we asked scientists working in different areas of chemistry to tell us what they thought the most exciting, interesting or challenging aspects related to the development of their main field of research will be — here is what they said.

While catalytic mechanisms on electrode surfaces have been proposed for decades, the pathways by which the product’s chemical bonds evolve from the initial charge-trapping intermediates have not been resolved in time.  Here, we discover a reactive intermediate population with states in the middle of a semiconductor’s band-gap to reveal the dynamics of two parallel transition state pathways for their decay.

The EDL guides electrode passivation in batteries, while in (super)capacitors, it determines charge storage capacity. Despite its importance, quantification of the nanometer-scale and potential-dependent EDL remains a challenging problem. Here, we directly probe changes in the EDL composition with potential using in-situ vibrational spectroscopy and molecular dynamics simulations for a Li-ion battery electrolyte (LiClO4 in dimethyl carbonate). 

Catalysis research has long been divided between homogeneous and heterogeneous catalysis. In this issue of ACS Central Science, the authors, building upon the previous breakthrough work, tether a dual-atom Ir molecular water oxidation catalyst to heterogeneous catalysts in various surface-bound geometries and demonstrate differences between these configurations.

During photocatalytic water oxidation, n-SrTiO3(100) demonstrated near 100% Faradaic efficiency for O2 evolution with nano- (30 ns) and femto- (150 fs) second pulsed laser excitation of the band gap, despite surface rearrangements attributed to the high peak power (300 MW cm−2).

The initial step of the electrochemically controlled water oxidation reaction on transition metal oxide surfaces localizes positive charge onto surface atoms, creating one-electron intermediates. For decades, the stability of this critical reaction intermediate has been used to predict catalytic activity, by a Sabatier analysis of the first bond (O–O) the intermediates catalyse within the O2 evolution cycle.

A prominent architecture for solar energy conversion layers diverse materials, such as traditional semiconductors (Si, III–V) and transition metal oxides (TMOs), into a monolithic device. The efficiency with which photoexcited carriers cross each layer is critical to device performance and dependent on the electronic properties of a heterojunction.

The initial step of photocatalytic water oxidation reaction at the metal oxide/aqueous interface involves intermediates formed by trapping photogenerated, valence band holes on different reactive sites of the oxide surface. In SrTiO3, these one-electron intermediates are radicals located in Ti–O• (oxyl) and Ti–O•–Ti (bridge) groups arranged perpendicular and parallel to the surface respectively, and form electronic states in the band gap of SrTiO3.

X-ray absorption studies of the geometric and electronic structure of primarily heterogeneous Co, Ni, and Mn based water oxidation catalysts are reviewed. The X-ray absorption near edge and extended X-ray absorption fine structure studies of the metal K-edge, characterize the metal oxidation state, metal–oxygen bond distance, metal–metal distance, and degree of disorder of the catalysts.

The Co 2p3/2 X-ray absorption spectroscopy and high-energy-resolution (∼0.09 eV fwhm) 2p3d resonant inelastic X-ray scattering (RIXS) spectra of the single-cobalt-centered polyoxometalate K5H[CoW12O40]·xH2O were measured. The low-energy dd transition features at 0.55 eV, unmeasurable with ultraviolet–visible (UV/vis) spectroscopy, were experimentally revealed in 2p3d RIXS spectra.