Cooperative Effects Drive Water Oxidation Catalysis in Cobalt Electrocatalysts through the Destabilization of Intermediates.

A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple overlapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (∼0.34 eV/monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O2 evolution onset coincide due to weaker binding and destabilization (∼0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

Role of Electrolyte pH on Water Oxidation for Iridium Oxides.

Understanding the effect of noncovalent interactions of intermediates at the polarized catalyst-electrolyte interface on water oxidation kinetics is key for designing more active and stable electrocatalysts. Here, we combine operando optical spectroscopy, X-ray absorption spectroscopy (XAS), and surface-enhanced infrared absorption spectroscopy (SEIRAS) to probe the effect of noncovalent interactions on the oxygen evolution reaction (OER) activity of IrOx in acidic and alkaline electrolytes. Our results suggest that the active species for the OER (Ir4.x+-*O) binds much stronger in alkaline compared with acid at low coverage, while the repulsive interactions between these species are higher in alkaline electrolytes. These differences are attributed to the larger fraction of water within the cation hydration shell at the interface in alkaline electrolytes compared to acidic electrolytes, which can stabilize oxygenated intermediates and facilitate long-range interactions between them. Quantitative analysis of the state energetics shows that although the *O intermediates bind more strongly than optimal in alkaline electrolytes, the larger repulsive interaction between them results in a significant weakening of *O binding with increasing coverage, leading to similar energetics of active states in acid and alkaline at OER-relevant potentials. By directly probing the electrochemical interface with complementary spectroscopic techniques, our work goes beyond conventional computational descriptors of the OER activity to explain the experimentally observed OER kinetics of IrOx in acidic and alkaline electrolytes.

Dynamically Adaptive Bubbling for Upgrading Oxygen Evolution Reaction Using Lamellar Fern-Like Alloy Aerogel Self-Standing Electrodes.

Adopting renewable electricity to produce "green" hydrogen has been a critical challenge because at a high current density the mass transfer capability of most catalytic electrodes deteriorates significantly. Herein, a unique lamellar fern-like alloy aerogel (LFA) electrode, showing a unique dynamically adaptive bubbling capability and can effectively avoid stress concentration caused by bubble aggregation is reported. The LFA electrode is intrinsically highly catalytic-active and shows a highly porous, resilient, hierarchically ordered, and well-percolated conductive network. It not only shows superior gas evacuation capability but also exhibits significantly improved stability at high current densities, showing the record lowest oxygen evolution reaction (OER) overpotential of 244 mV at 1000 mA cm-2 and stably over 6000 h. With the merits of mechanical robustness, excellent electron transport, and efficient bubble evacuation, LFA can be self-standing catalytic electrode and gas diffusion layers in anion-exchange-membrane water electrolysis (AEMWE), which can achieve 3000 mA cm-2 at a low voltage of 1.88 V and can sustain stable electrolysis at 2000 mA cm-2 for over 1300 h. This strategy can be extended to various gas evolution reactions as a general design rule for multiphase catalysis applications.

Highly Conductive and Mechanically Robust NiFe Alloy Aerogels: An Exceptionally Active and Durable Water Oxidation Catalyst.

Poor stability of nanostructured electrocatalysts at rigorous industrial conditions significantly inhibits their performances in practical electrolyzers. Although many substrate-supported nanostructured electrocatalysts present attractive performance at small currents, they cannot sustain industry-level high current densities for long-term operation. Herein, by chemically organizing nanoscale electrocatalysts into a macroscopic substrate-free metallic alloy aerogel, this NiFe-based nano-catalyst achieves 1000-h durability at industrial-level current densities, with exceptionally high activities of 500 mA at the overpotential of only 281 mV. This NiFe alloy aerogel is constructed by a magnetic-field assisted growth and assembly of ferromagnetic NiFe nanoparticles, in which nanowires are loosely crosslinked by metallic joints. This alloy aerogel shows a high electric conductivity of 500 S m-1 , structural stability for more than 1.5 years in alkaline electrolyte, and almost complete recovery after compression exceeding 50% strain for 1000 cycles. The excellent mechanical stability of this metallic aerogel behaves as the key contributor to the superior electrocatalytic stability under industrially relevant conditions. This work offers a paradigm for electrode design for the practical application of nano-catalysts in industrial alkaline water electrolysis.

Exploration of the form factors of turbulence kinetic energy transfer for shear exfoliation of graphene.

Mass production of defect-free and large-lateral-size 2D materials via cost-effective methods is very important. Recently, shear exfoliation has shown great promise for large-scale production due to its simple operation, environmental-benignity and wide adaptability. However, a long-standing challenge is that with the production of more nanosheets, a ceiling yield and shattered products are encountered, which significantly limits their wider application. The method and efficiency of energy transfer in fluid is undoubtedly the key point in determining exfoliation efficiency, yet its in-depth mechanism has not yet been described. Thus, a thorough investigation of turbulence energy transfer is critically necessary. Herein, we identify two main factors that critically determine the exfoliation yield and provide a statistical analysis of the relationship between these factors and the exfoliation yield. In the initial shearing process, the coexistence of the 2D nanosheets and raw particles is the dominant factor; as time passes, the dimensional change of raw materials gradually has a greater influence on the energy transfer. These factors together lead to attenuated efficiency and a power function relationship between yield and exfoliation time. This investigation gives a statistical explanation of shear exfoliation technology for 2D material preparation and provides valuable insights for mechanical exfoliating high-quality 2D materials.

Tip-Enhanced Electric Field: A New Mechanism Promoting Mass Transfer in Oxygen Evolution Reactions.

The slow kinetics of oxygen evolution reaction (OER) causes high power consumption for electrochemical water splitting. Various strategies have been attempted to accelerate the OER rate, but there are few studies on regulating the transport of reactants especially under large current densities when the mass transfer factor dominates the evolution reactions. Herein, Nix Fe1- x alloy nanocones arrays (with ≈2 nm surface NiO/NiFe(OH)2 layer) are adopted to boost the transport of reactants. Finite element analysis suggests that the high-curvature tips can enhance the local electric field, which induces an order of magnitude higher concentration of hydroxide ions (OH- ) at the active sites and promotes intrinsic OER activity by 67% at 1.5 V. Experimental results show that a fabricated NiFe nanocone array electrode, with optimized alloy composition, has a small overpotential of 190 mV at 10 mA cm-2 and 255 mV at 500 mA cm-2 . When calibrated by electrochemical surface area, the nanocones electrode outperforms the state-of-the-art OER electrocatalysts. The positive effect of the tip-enhanced local electric field in promoting mass transfer is also confirmed by comparing samples with different tip curvature radii. It is suggested that this local field enhanced OER kinetics is a generic effect to other OER catalysts.

Template-free synthesis of highly porous V2O5 cuboids with enhanced performance for lithium ion batteries.

Highly porous hierarchical V2O5 cuboids have been synthesized by a template-free PVP-assisted polyxol method and the formation mechanism is studied. The cuboids are assembled from numerous mesoporous nanoplates and the preferred orientation of each single nanoplate exposes the 〈110〉 facets, facilitating lithium-ion diffusion by offering a prior channel. This material exhibits a high capacity of 143 mA h g(-1), high rate capacity of 10 C and long life cycling performance up to 1000 cycles. The excellent electrochemical performance of V2O5 cuboid electrodes is due to its unique porous cuboid morphology and optimized structural stability upon cycling. This research provides an effective route to the construction of complex porous architectures assembled from nanocrystals through a surfactant-assisted synthesis method.