The splitting of water photoelectrochemically into hydrogen and oxygen represents a promising technology for converting solar energy to fuel. The main challenge is to ensure that photogenerated holes efficiently oxidize water, which generally requires modification of the photoanode with an oxygen evolution catalyst (OEC) to increase the photocurrent and reduce the onset potential. However, because excess OEC material can hinder light absorption and decrease photoanode performance, its deposition needs to be carefully controlled--yet it is unclear which semiconductor surface sites give optimal improvement if targeted for OEC deposition, and whether sites catalysing water oxidation also contribute to competing charge-carrier recombination with photogenerated electrons. Surface heterogeneity exacerbates these uncertainties, especially for nanostructured photoanodes benefiting from small charge-carrier transport distances. Here we use super-resolution imaging, operated in a charge-carrier-selective manner and with a spatiotemporal resolution of approximately 30 nanometres and 15 milliseconds, to map both the electron- and hole-driven photoelectrocatalytic activities on single titanium oxide nanorods. We then map, with sub-particle resolution (about 390 nanometres), the photocurrent associated with water oxidation, and find that the most active sites for water oxidation are also the most important sites for charge-carrier recombination. Site-selective deposition of an OEC, guided by the activity maps, improves the overall performance of a given nanorod--even though more improvement in photocurrent efficiency correlates with less reduction in onset potential (and vice versa) at the sub-particle level. Moreover, the optimal catalyst deposition sites for photocurrent enhancement are the lower-activity sites, and for onset potential reduction the optimal sites are the sites with more positive onset potential, contrary to what is obtainable under typical deposition conditions. These findings allow us to suggest an activity-based strategy for rationally engineering catalyst-improved photoelectrodes, which should be widely applicable because our measurements can be performed for many different semiconductor and catalyst materials.

Nitromethane (NM), a flammable liquid, has been a model system for the shock-to-detonation transition in homogeneous condensed-phase explosives for over 50 years, but we do not understand the fast processes at the molecular scale in the detonation front at the molecular scale. That is largely because prior studies triggered detonations in bomb-sized charges with input shock durations and times-to detonation that were typically microseconds, which made it impossible to observe the faster processes in real time. We studied NM shocked with 4 ns duration input pulses using a tabletop apparatus with laser-launched flyer plates and arrays of tiny disposable optical cuvettes, where the pressure and temperature were probed in real time (1 ns) with photon Doppler velocimetry, optical pyrometry, and high-speed video. Using a 4 ns shock with an input pressure close to the von Neumann spike pressure of 19 GPa, we achieved the minimum time-to-detonation, about 12 ns, where the time-to-detonation is controlled by fundamental molecular processes. We demonstrated the reproducibility of our detonations and showed that they had the same properties as in bomb-sized charges: our detonation velocity, von Neumann spike and Chapman-Jouguet pressures, temperatures, and reaction zone lengths were the same as in bomb-sized charges. Being able to trigger realistic reproducible detonations from a short pulse makes it possible to investigate molecular and fluid dynamics in the detonation by measuring transient responses in real time. We found that it took 6 ns for the temperature to reach 3430 K. The high pressure was observed at about 8 ns, when there was a volume explosion to nearly twice the von Neumann spike pressure before settling down to a steady detonation.

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Quasi-isentropic compression of liquid water beyond 5 GPa rapidly creates ice VII on 1–10 ns time scales. The onset of this phase transition can be modified by changing the initial temperature of the liquid sample and/or the compression rate. These effects were studied using the Sandia Thor-64 pulsed power machine. Increasing the initial temperature pushes freezing above the previously reported 7 GPa metastable limit. Slower compression allows freezing to occur below the metastable limit, though the compression rate has a greater effect at an elevated temperature than at room temperature.

We describe studies of shock initiation and shock‐to‐detonation transitions in energetic materials using a tabletop shock compression microscope with nanosecond time resolution and micrometer spatial resolution. Planar input shocks with durations of 4–20 ns are produced using 0–4.5 km/s laser‐launched flyer plates. Emphasis is on measurements of temperature, velocities, pressure, and microstructure using photon Doppler velocimetry (PDV), optical pyrometry and high‐speed videography. Techniques are discussed for fabricating disposable shock target arrays of tiny plastic‐bonded explosives (PBX), liquid and powder explosives, and single‐crystal explosives for high‐throughput studies. Optical temperature measurements of shocked triaminotrinitrobenzene (TATB) are discussed. Since TATB is yellow, we developed methods to correct for the blue absorption to obtain more accurate temperatures. Hot spots in shocked polymer‐encased HMX (octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine) crystals are observed in real‐time, showing a hot spot produced in a collapsing void that ignites a deflagration. Despite the small dimensions of our explosive charges (typically 1 mm diameter and 250 μm length), we produced reproducible detonation states in solid and liquid explosives using short‐duration shocks near the von Neumann spike (VNS) pressure. We show the VNS pressure is associated with a transition to high‐efficiency gas production from the explosives. In studies of NM, prior to detonation, we see reaction originating at hot spots which coalesce to form a superdetonation.

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Adding amines to liquid nitromethane (NM) is known to lower the threshold for the shock-to-detonation transition because amines catalyze proton transfer reactions that are the initial steps in the energy release process. We studied NM with 1 wt % ethylenediamine (NM/EDA) with 4 ns input shocks using time and space resolved diagnostics: photon Doppler velocimetry (PDV), optical pyrometry, and nanosecond video imaging. The 4 ns shocks are fast enough to time-resolve the reaction kinetics and the shock-to-detonation transition. We find that it is possible to shock ignite the NM/EDA without producing a detonation, so there is more to amine sensitization of the shock-to-detonation process than simply lowering the barrier to initial reactions. We find that although 1 wt % EDA has little effect on the ambient properties of NM, it dramatically alters the Hugoniot. The shock speed in NM/EDA is reduced, indicating that shocked NM/EDA is significantly more compressible than NM. Higher compressibility is associated with greater adiabatic heating, so EDA both lowers the barrier to proton transfer reactions and increases shock energy absorption. To explain the enhanced compressibility, we propose that shocking NM/EDA produces a reactive flow that has a much higher ionic strength than in NM. The sudden transformation from a molecular liquid to an ionic liquid with stronger intermolecular interactions is responsible for enhanced compressibility and shock heating.

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