Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.

In this Letter, the photoinduced switching of the single nitrogen-vacancy (NV) center between two different charge states, negative (NV(-)) and neutral (NV(0)), is studied under resonant excitation at liquid helium temperature. We show that resonant conversion of NV(0) to NV(-) significantly improves spectral stability of the NV(-) defect and allows high fidelity initialization of the spin qubit. Based on density functional theory calculations a novel mechanism involving an Auger ionization of NV(-) and charge transfer of an electron from the valence band to NV(0) is discussed. This study provides further insight into the charge dynamics of the NV center, which is relevant for quantum information processing based on an NV(-) defect in diamond.

Doping of carbon nanoparticles with impurity atoms is central to their application. However, doping has proven elusive for very small carbon nanoparticles because of their limited availability and a lack of fundamental understanding of impurity stability in such nanostructures. Here, we show that isolated diamond nanoparticles as small as 1.6 nm, comprising only ∼400 carbon atoms, are capable of housing stable photoluminescent colour centres, namely the silicon vacancy (SiV). Surprisingly, fluorescence from SiVs is stable over time, and few or only single colour centres are found per nanocrystal. We also observe size-dependent SiV emission supported by quantum-chemical simulation of SiV energy levels in small nanodiamonds. Our work opens the way to investigating the physics and chemistry of molecular-sized cubic carbon clusters and promises the application of ultrasmall non-perturbative fluorescent nanoparticles as markers in microscopy and sensing.

NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni 2+ to Ni 3+ , followed by oxidation to a mixed Ni 3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fedoped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe 4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixedmetal oxidation states in heterogeneous catalysts.NiFe oxyhydroxide | oxygen evolution reaction | electrocatalysis | spectroelectrochemistry | density functional theory T he photoelectrochemical conversion of water into O 2 and H 2 is a major focus of energy storage and conversion efforts (1-4), with significant attention directed toward development of efficient catalysts for water oxidation and reduction. Such catalysts should operate at low overpotential, exhibit high selectivity, and be composed of earth-abundant materials. Commercial electrolyzers typically use transition-metal-oxide electrocatalysts for the oxygen evolution reaction (OER) (5, 6), and nickel, nickel-iron, and other mixed-metal oxides are especially effective under alkaline conditions (7,8). Despite the importance and potential future impact of these materials, many features of their catalytic mechanism are poorly understood.Nickel oxyhydroxide has long been associated with OER electrocatalysis (9, 10); however, much of the activity in this material has been shown to arise from the presence of Fe impurities (7, 11). This conclusion complements extensive independent studies demonstrating the effectiveness of NiFebased oxide and oxyhydroxide materials as OER electrocatalysts (12-14), including a survey of nearly 3,500 mixed-metal-oxide compositions, which drew attentio...