reaxFF Reactive Force Field for Disulfide Mechanochemistry, Fitted to Multireference ab Initio Data

Mechanochemistry, in particular in the form of single-molecule atomic force microscopy experiments, is difficult to model theoretically, for two reasons: Covalent bond breaking is not captured accurately by single-determinant, single-reference quantum chemistry methods, and experimental times of milliseconds or longer are hard to simulate with any approach. Reactive force fields have the potential to alleviate both problems, as demonstrated in this work: Using nondeterministic global parameter optimization by evolutionary algorithms, we have fitted a reaxFF force field to high-level multireference ab initio data for disulfides. The resulting force field can be used to reliably model large, multifunctional mechanochemistry units with disulfide bonds as designed breaking points. Explorative calculations show that a significant part of the time scale gap between AFM experiments and dynamical simulations can be bridged with this approach

Black TiO₂ Nanotubes: Cocatalyst-Free Open-Circuit Hydrogen Generation

Here we report that TiO₂ nanotube (NT) arrays, converted by a high pressure H₂ treatment to anatase-like “black titania”, show a high open-circuit photocatalytic hydrogen production rate without the presence of a cocatalyst. Tubes converted to black titania using classic reduction treatments (e.g., atmospheric pressure H₂/Ar annealing) do not show this effect. The main difference caused by the high H₂ pressure annealing is the resulting room-temperature stable, isolated Ti³⁺ defect-structure created in the anatase nanotubes, as evident from electron spin resonance (ESR) investigations. This feature, absent for conventional reduction, seems thus to be responsible for activating intrinsic, cocatalytic centers that enable the observed high open-circuit hydrogen generation

Forming a Highly Active, Homogeneously Alloyed AuPt Co-catalyst Decoration on TiO₂ Nanotubes Directly During Anodic Growth

Au and Pt do not form homogeneous bulk alloys as they are thermodynamically not miscible. However, we show that anodic TiO₂ nanotubes (NTs) can in situ be uniformly decorated with homogeneous AuPt alloy nanoparticles (NPs) during their anodic growth. For this, a metallic Ti substrate containing low amounts of dissolved Au (0.1 atom %) and Pt (0.1 atom %) is used for anodizing. The matrix metal (Ti) is converted to oxide, whereas at the oxide/metal interface direct noble metal particle formation and alloying of Au and Pt takes place; continuously these particles are then picked up by the growing nanotube wall. In our experiments, the AuPt alloy NPs have an average size of 4.2 nm, and at the end of the anodic process, these are regularly dispersed over the TiO₂ nanotubes. These alloyed AuPt particles act as excellent co-catalyst in photocatalytic H₂ generation, with a H₂ production rate of 12.04 μL h^–1 under solar light. This represents a strongly enhanced activity as compared to TiO₂ NTs decorated with monometallic particles of Au (7 μL h^–1) or Pt (9.96 μL h^–1)