Atom transfer radical polymerization is a versatile technique for exerting precise control over polymer molecular weights, molecular weight distributions, and complex architectures. Here, we show that an externally applied electrochemical potential can reversibly activate the copper catalyst for this process by a one-electron reduction of an initially added air-stable cupric species (Cu(II)/Ligand). Modulation of polymerization kinetics is thereby tunable in real time by varying the magnitude of applied potential. Application of multistep intermittent potentials successfully triggers initiation of polymerization and subsequently toggles the polymerization between dormant and active states in a living manner. Catalyst concentrations down to 50 parts per million are demonstrated to maintain polymerization control manifested in linear first-order kinetics, a linear increase in polymer molecular weight with monomer conversion, and narrow polymer molecular weight distributions over a range of applied potentials.

The electrochemical instability of semiconductors in aqueous electrolytes has impeded the development of robust sunlight-driven water-splitting systems. We review the use of protective thin films to improve the electrochemical stability of otherwise unstable semiconductor photoelectrodes (e.g., Si and GaAs). We first discuss the origins of instability and various strategies for achieving stable and functional photoelectrosynthetic interfaces. We then focus specifically on the use of thin protective films on photoanodes and photocathodes for photosynthetic reactions that include oxygen evolution, halide oxidation, and hydrogen evolution. Finally, we provide an outlook for the future development of thinlayer protection strategies to enable semiconductor-based solar-driven fuel production.

Photoelectrochemical (PEC) water splitting has received growing attention as a potential pathway to replace fossil fuels and produce a clean, renewable, and sustainable source of fuel. To achieve overall water splitting and the associated production of solar fuels, complex devices are needed to efficiently capture light from the sun, separate photogenerated charges, and catalyze reduction and oxidation reactions. To date, the highest performing solar fuels devices rely on multi-component systems, which introduce interfaces that can be associated with further performance loss due to thermodynamic and kinetic considerations. In this review, we identify several of the most important interfaces used in PEC water splitting, summarize methods to characterize them, and highlight approaches to mitigating associated loss mechanisms.

A. Calculation of the effective solution potential, E eff (A/AThe concentration corrections for the A/A -redox species performed herein have followed conditions previously outlined. 5 Figure S1 highlights the effect of this concentration correction for an ntype semiconductor-liquid junction photoelectrochemical cell. Point A denotes an experimentallyobtained V oc value at solution redox potential E(A/A -) at which the concentrations of oxidized species

Figure S1. XP spectra of the Si 2p region of MnO|Si photoelectrodes with 100 cycles (~10 nm) of MnO (filled circles and blue line) and 25 cycles (~2.5 nm) of MnO (open circles).