Autonomous closed-loop mechanistic investigation of molecular electrochemistry via automation.

Electrochemical research often requires stringent combinations of experimental parameters that are demanding to manually locate. Recent advances in automated instrumentation and machine-learning algorithms unlock the possibility for accelerated studies of electrochemical fundamentals via high-throughput, online decision-making. Here we report an autonomous electrochemical platform that implements an adaptive, closed-loop workflow for mechanistic investigation of molecular electrochemistry.

Bisulfate as a redox-active ligand in vanadium-based electrocatalysis for CH functionalization.

The roles of unforgiving HSO solvent in CH activation with molecular catalysts have not been experimentally well-illustrated despite computational predictions. Here, we provide experimental evidence that metal-bound bisulfate ligand introduced by HSO solvent is redox-active in vanadium-based electrocatalytic CH activation discovered recently. Replacing one of the two terminal bisulfate ligands with redox-inert dihydrogen phosphate in the pre-catalyst vanadium (V)-oxo dimer completely quenches its activity towards CH, which may inspire environmentally benign catalysis with minimal use of HSO.

Ag -Mediated Electrocatalytic Ambient CH Functionalization Inspired by HSAB Theory.

Although most class (b) transition metals have been studied in regard to CH activation, divalent silver (Ag ), possibly owing to its reactive nature, is the only class (b) high-valent transition metal center that is not yet reported to exhibit reactivities towards CH activation. We now report that electrochemically generated Ag metalloradical readily functionalizes CH into methyl bisulfate (CH OSO H) at ambient conditions in 98 % H SO . Mechanistic investigation experimentally unveils a low activation energy of 13.

Expanding nanoparticle multifunctionality: size-selected cargo release and multiple logic operations.

Physically stimulated nanoparticles that deliver size-selected cargo and function as logic gates are reported. To achieve this goal the particle requires multiple components, and we recognized early on that the components, not just the released cargo, could be used to demonstrate logic operations (OR and AND logic). For stimuli, we chose two non-invasive types, red light and alternating magnetic fields (AMF), because they both have potential biological relevance.

Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer.

The abundant yet widely distributed methane resources require efficient conversion of methane into liquid chemicals, whereas an ambient selective process with minimal infrastructure support remains to be demonstrated. Here we report selective electrochemical oxidation of CH to methyl bisulfate (CHOSOH) at ambient pressure and room temperature with a molecular catalyst of vanadium (V)-oxo dimer. This water-tolerant, earth-abundant catalyst possesses a low activation energy (10.