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. As a proof-of-concept, this platform autonomously identifies and investigates an EC mechanism, an interfacial electron transfer (E step) followed by a solution reaction (C step), for cobalt tetraphenylporphyrin exposed to a library of organohalide electrophiles. The generally applicable workflow accurately discerns the EC mechanism's presence amid negative controls and outliers, adaptively designs desired experimental conditions, and quantitatively extracts kinetic information of the C step spanning over 7 orders of magnitude, from which mechanistic insights into oxidative addition pathways are gained. This work opens opportunities for autonomous mechanistic discoveries in self-driving electrochemistry laboratories without manual intervention.

Pairing of Aqueous and Nonaqueous Electrosynthetic Reactions Enabled by a Redox Reservoir Electrode.

Paired electrolysis methods are appealing for chemical synthesis because they generate valuable products at both electrodes; however, development of such reactions is complicated by the need for both half-reactions to proceed under mutually compatible conditions. Here, a modular electrochemical synthesis (ModES) strategy bypasses these constraints using a "redox reservoir" (RR) to pair electrochemical half-reactions across aqueous and nonaqueous solvents. Electrochemical oxidation reactions in organic solvents, the conversion of 4-t-butyltoluene to benzylic dimethyl acetal and aldehyde in methanol or the oxidative C-H amination of naphthalene in acetonitrile, and the reduction of oxygen to hydrogen peroxide in water were paired using nickel hexacyanoferrate as an RR that can selectively store and release protons (and electrons) while serving as the counter electrode for these reactions. Selective proton transport through the RR is optimized and confirmed to enable the ion balance, and thus the successful pairing, between redox half-reactions that proceed with different rates, on different scales, and in different solvents (methanol, acetonitrile, and water).

Operando Elucidation of Electrocatalytic and Redox Mechanisms on a 2D Metal Organic Framework Catalyst for Efficient Electrosynthesis of Hydrogen Peroxide in Neutral Media.

The practical electrosynthesis of hydrogen peroxide (H2O2) is hindered by the lack of inexpensive and efficient catalysts for the two-electron oxygen reduction reaction (2e- ORR) in neutral electrolytes. Here, we show that Ni3HAB2 (HAB = hexaaminobenzene), a two-dimensional metal organic framework (MOF), is a selective and active 2e- ORR catalyst in buffered neutral electrolytes with a linker-based redox feature that dynamically affects the ORR behaviors. Rotating ring-disk electrode measurements reveal that Ni3HAB2 has high selectivity for 2e- ORR (>80% at 0.6 V vs RHE) but lower Faradaic efficiency due to this linker redox process. Operando X-ray absorption spectroscopy measurements reveal that under argon gas the charging of the organic linkers causes a dynamic Ni oxidation state, but in O2-saturated conditions, the electronic and physical structures of Ni3HAB2 change little and oxygen-containing species strongly adsorb at potentials more cathodic than the reduction potential of the organic linker (Eredox ∼ 0.3 V vs RHE). We hypothesize that a primary 2e- ORR mechanism occurs directly on the organic linkers (rather than the Ni) when E > Eredox, but when E < Eredox, H2O2 production can also occur through Ni-mediated linker discharge. By operating the bulk electrosynthesis at a low overpotential (0.4 V vs RHE), up to 662 ppm of H2O2 can be produced in a buffered neutral solution in an H-cell due to minimized strong adsorption of oxygenates. This work demonstrates the potential of conductive MOF catalysts for 2e- ORR and the importance of understanding catalytic active sites under electrochemical operation.

Sustainable Coproduction of Two Disinfectants via Hydroxide-Balanced Modular Electrochemical Synthesis Using a Redox Reservoir.

Challenges posed by the sacrificial auxiliary reactions and expensive ion-exchange membranes in conventional electrosynthesis necessitate developing new electrochemical processes to enable efficient and sustainable distributed electrochemical manufacturing. Modular electrochemical synthesis (ModES) using a redox reservoir (RR) offers a promising membrane-free approach to improve energy efficiency and reduce waste through the pairing of multiple independent oxidative and reductive half-reactions; however, undesired ion-imbalance and induced pH changes in the existing ModES process limit sustained production. Here we present Ni(OH)2 as a heterogeneous RR that can selectively store and transport the hydroxide ions involved in the target half-reactions by reversible conversion with NiOOH to enable an ion-balanced ModES of two common disinfectants, hydrogen peroxide (H2O2) and sodium hypochlorite (NaClO). This hydroxide-balanced ModES realizes stable operation without appreciable pH swing to accumulate practically useful concentrations of H2O2 and NaClO up to 251 and 481 ppm, respectively. These results illustrate additional design principles for electrosynthesis without sacrificial auxiliary reactions and the need for ion-selective RRs for modular electrochemical manufacturing.

Torsion strained iridium oxide for efficient acidic water oxidation in proton exchange membrane electrolyzers.

Acidic oxygen evolution reaction is crucial for practical proton exchange membrane water splitting electrolysers, which have been hindered by the high catalytic overpotential and high loading of noble metal catalysts. Here we present a torsion-strained Ta0.1Tm0.1Ir0.8O2-δ nanocatalyst with numerous grain boundaries that exhibit a low overpotential of 198 mV at 10 mA cm-2 towards oxygen evolution reaction in 0.5 M H2SO4. Microstructural analyses, X-ray absorption spectroscopy and theoretical calculations reveal that the synergistic effects between grain boundaries that result in torsion-strained Ir-O bonds and the doping induced ligand effect collectively tune the adsorption energy of oxygen intermediates, thus enhancing the catalytic activity. A proton exchange membrane electrolyser using a Ta0.1Tm0.1Ir0.8O2-δ nanocatalyst with a low mass loading of 0.2 mg cm-2 can operate stably at 1.5 A cm-2 for 500 hours with an estimated cost of US$1 per kilogram of H2, which is much lower than the target (US$2 per kg of H2) set by the US Department of Energy.

Identification of the Active-Layer Structures for Acidic Oxygen Evolution from 9R-BaIrO3 Electrocatalyst with Enhanced Iridium Mass Activity.

Iridium-based perovskites show promising catalytic activity for oxygen evolution reaction (OER) in acid media, but the iridium mass activity remains low and the active-layer structures have not been identified. Here, we report highly active 1 nm IrOx particles anchored on 9R-BaIrO3 (IrOx/9R-BaIrO3) that are directly synthesized by solution calcination followed by strong acid treatment for the first time. The developed IrOx/9R-BaIrO3 catalyst delivers a high iridium mass activity (168 A gIr-1), about 16 times higher than that of the benchmark acidic OER electrocatalyst IrO2 (10 A gIr-1), and only requires a low overpotential of 230 mV to reach a catalytic current density of 10 mA cm-2geo. Careful scanning transmission electron microscopy, synchrotron radiation-based X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analyses reveal that, during the electrocatalytic process, the initial 1 nm IrOx nanoparticles/9R-BaIrO3 evolve into amorphous Ir4+OxHy/IrO6 octahedrons and then to amorphous Ir5+Ox/IrO6 octahedrons on the surface. Such high relative content of amorphous Ir5+Ox species derived from trimers of face-sharing IrO6 octahedrons in 9R-BaIrO3 and the enhanced metallic conductivity of the Ir5+Ox/9R-BaIrO3 catalyst are responsible for the excellent acidic OER activity. Our results provide new insights into the surface active-layer structure evolution in perovskite electrocatalysts and demonstrate new approaches for engineering highly active acidic OER nanocatalysts.

Defect-mediated ferromagnetism in correlated two-dimensional transition metal phosphorus trisulfides.

Controlling the magnetic spin states of two-dimensional (2D) van der Waals (vdW) materials with strong electronic or magnetic correlation is important for spintronic applications but challenging. Crystal defects that are often present in 2D materials such as transition metal phosphorus trisulfides (MPS3) could influence their physical properties. Here, we report the effect of sulfur vacancies on the magnetic exchange interactions and spin ordering of few-layered vdW magnetic Ni1−xCoxPS3 nanosheets. Magnetic and structural characterization in corroboration with theoretical calculations reveal that sulfur vacancies effectively suppress the strong intralayer antiferromagnetic correlation, giving rise to a weak ferromagnetic ground state in Ni1−xCoxPS3 nanosheets. Notably, the magnetic field required to tune this ferromagnetic state (<300 Oe) is much lower than the value needed to tune a typical vdW antiferromagnet (> several thousand oersted). These findings provide a previously unexplored route for controlling competing correlated states and magnetic ordering by defect engineering in vdW materials.

Modifying redox properties and local bonding of Co3O4 by CeO2 enhances oxygen evolution catalysis in acid.

Developing efficient and stable earth-abundant electrocatalysts for acidic oxygen evolution reaction is the bottleneck for water splitting using proton exchange membrane electrolyzers. Here, we show that nanocrystalline CeO2 in a Co3O4/CeO2 nanocomposite can modify the redox properties of Co3O4 and enhances its intrinsic oxygen evolution reaction activity, and combine electrochemical and structural characterizations including kinetic isotope effect, pH- and temperature-dependence, in situ Raman and ex situ X-ray absorption spectroscopy analyses to understand the origin. The local bonding environment of Co3O4 can be modified after the introduction of nanocrystalline CeO2, which allows the CoIII species to be easily oxidized into catalytically active CoIV species, bypassing the potential-determining surface reconstruction process. Co3O4/CeO2 displays a comparable stability to Co3O4 thus breaks the activity/stability tradeoff. This work not only establishes an efficient earth-abundant catalysts for acidic oxygen evolution reaction, but also provides strategies for designing more active catalysts for other reactions.

Stable Tetrasubstituted Quinone Redox Reservoir for Enhancing Decoupled Hydrogen and Oxygen Evolution.

Redox reservoirs (RRs) may be used to decouple the two half-reactions of water electrolysis, enabling spatial and temporal separation of hydrogen and oxygen evolution. Organic RRs are appealing candidates for this application; however, their instability limits their utility. Here, we show that a tetrathioether-substituted quinone, tetramercaptopropanesulfonate quinone (TMQ), exhibits significantly enhanced stability relative to anthraquinone-2,7-disulfonate (AQDS), the most effective organic RR reported previously. The enhanced stability, confirmed by symmetric flow battery experiments under relevant conditions, enables stable electrochemical production of H2 and O2 in a continuous flow electrolysis cell. The reduced RR, tetramercaptopropanesulfonate hydroquinone (TMHQ), is not susceptible to decomposition, while the oxidized state, TMQ, undergoes slow decomposition, evident only after sustained operation (>60 h). Analysis of the byproducts provides that basis for a decomposition mechanism, establishing a foundation for the design of new organic RRs with even better performance.