Atomically dispersed hexavalent iridium oxide from MnO2 reduction for oxygen evolution catalysis.

Hexavalent iridium (IrVI) oxide is predicted to be more active and stable than any other iridium oxide for the oxygen evolution reaction in acid; however, its experimental realization remains challenging. In this work, we report the synthesis, characterization, and application of atomically dispersed IrVI oxide (IrVI-ado) for proton exchange membrane (PEM) water electrolysis. The IrVI-ado was synthesized by oxidatively substituting the ligands of potassium hexachloroiridate(IV) (K2IrCl6) with manganese oxide (MnO2). The mass-specific activity (1.7 × 105 amperes per gram of iridium) and turnover number (1.5 × 108) exceeded those of benchmark iridium oxides, and in situ x-ray analysis during PEM operations manifested the durability of IrVI at current densities up to 2.3 amperes per square centimeter. The high activity and stability of IrVI-ado showcase its promise as an anode material for PEM electrolysis.

Rationalizing the Influence of the Binding Affinity on the Activity of Phosphoserine Phosphatases.

The Sabatier principle states that catalytic activity can be maximized when the substrate binding affinity is neither too strong nor too weak. Recent studies have shown that the activity of several hydrolases is maximized at intermediate values of the binding affinity (Michaelis-Menten constant: Km ). However, it remains unclear whether this concept of artificial catalysis is applicable to enzymes in general, especially for those which have evolved under different reaction environments. Herein, we show that the activity of phosphoserine phosphatase is also enhanced at an intermediate Km value of approximately 0.5 mM. Within our dataset, the variation of Km by three orders of magnitude accounted for a roughly 18-fold variation in the activity. Owing to the high phylogenetic and physiological diversity of our dataset, our results support the importance of optimizing Km for enzymes in general. On the other hand, a 77-fold variation in the activity was attributed to other physicochemical parameters, such as the Arrhenius prefactor of kcat , and could not be explained by the Sabatier principle. Therefore, while tuning the binding affinity according to the Sabatier principle is an important consideration, the Km value is only one of many physicochemical parameters which must be optimized to maximize enzymatic activity.

Thermodynamic principle to enhance enzymatic activity using the substrate affinity.

Understanding how to tune enzymatic activity is important not only for biotechnological applications, but also to elucidate the basic principles guiding the design and optimization of biological systems in nature. So far, the Michaelis-Menten equation has provided a fundamental framework of enzymatic activity. However, there is still no concrete guideline on how the parameters should be optimized towards higher activity. Here, we demonstrate that tuning the Michaelis-Menten constant ([Formula: see text]) to the substrate concentration ([Formula: see text]) enhances enzymatic activity. This guideline ([Formula: see text]) was obtained mathematically by assuming that thermodynamically favorable reactions have higher rate constants, and that the total driving force is fixed. Due to the generality of these thermodynamic considerations, we propose [Formula: see text] as a general concept to enhance enzymatic activity. Our bioinformatic analysis reveals that the [Formula: see text] and in vivo substrate concentrations are consistent across a dataset of approximately 1000 enzymes, suggesting that even natural selection follows the principle [Formula: see text].

In situ FTIR study of CO2 reduction on inorganic analogues of carbon monoxide dehydrogenase.

The CO2-to-CO reduction by carbon monoxide dehydrogenase (CODH) with a [NiFe4S4] cluster is considered to be the oldest pathway of biological carbon fixation and therefore may have been involved in the origin of life. Although previous studies have investigated CO2 reduction by Fe and Ni sulfides to identify the prebiotic origin of the [NiFe4S4] cluster, the reaction mechanism remains largely elusive. Herein, we applied in situ electrochemical ATR-FTIR spectroscopy to probe the reaction intermediates of greigite (Fe3S4) and violarite (FeNi2S4). Intermediate species assignable to surface-bound CO2 and formyl groups were found to be stabilized in the presence of Ni, lending insight into its role in enhancing the multistep CO2 reduction process.

Atomic-scale evidence for highly selective electrocatalytic N-N coupling on metallic MoS2.

Molybdenum sulfide (MoS2) is the most widely studied transition-metal dichalcogenide (TMDs) and phase engineering can markedly improve its electrocatalytic activity. However, the selectivity toward desired products remains poorly explored, limiting its application in complex chemical reactions. Here we report how phase engineering of MoS2 significantly improves the selectivity for nitrite reduction to nitrous oxide, a critical process in biological denitrification, using continuous-wave and pulsed electron paramagnetic resonance spectroscopy. We reveal that metallic 1T-MoS2 has a protonation site with a pKa of ∼5.5, where the proton is located ∼3.26 Šfrom redox-active Mo site. This protonation site is unique to 1T-MoS2 and induces sequential proton-electron transfer which inhibits ammonium formation while promoting nitrous oxide production, as confirmed by the pH-dependent selectivity and deuterium kinetic isotope effect. This is atomic-scale evidence of phase-dependent selectivity on MoS2, expanding the application of TMDs to selective electrocatalysis.

Enzyme Mimetic Active Intermediates for Nitrate Reduction in Neutral Aqueous Media.

Nitrate is a pervasive aquatic contaminant of global environmental concern. In nature, the most effective nitrate reduction reaction (NRR) is catalyzed by nitrate reductase enzymes at neutral pH, using a highly-conserved Mo center ligated mainly by oxo and thiolate groups. Mo-based NRR catalysts mostly function in organic solvents with a low water stability. Recently, an oxo-containing molybdenum sulfide nanoparticle that serves as an NRR catalyst at neutral pH was first reported. Herein, in a nanoparticle-catalyzed NRR system a pentavalent MoV (=O)S4 species, an enzyme mimetic, served as an active intermediate for the NRR. Potentiometric titration analysis revealed that a redox synergy among MoV -S, S radicals, and MoV (=O)S4 likely play a key role in stabilizing MoV (=O)S4 , showing the importance of secondary interactions in facilitating NRR. The first identification and characterization of an oxo- and thiolate-ligated Mo intermediates pave the way to the molecular design of efficient enzyme mimetic NRR catalysts in aqueous solution.

Shift of the Optimum Binding Energy at Higher Rates of Catalysis.

The binding energy between the catalyst and the reactant is considered to be the primary descriptor of catalytic activity. Therefore, identifying the optimum binding energy that would yield maximum activity is fundamentally important for the development of efficient catalysts. Here, we show analytically how the binding energy that maximizes the activity at large reaction rates, i.e., the operating conditions of catalysis, may deviate from the traditional understanding obtained near equilibrium. This shift can be on the order of 0.5 eV, which is easily sufficient for the optimum material to change. This binding energy shift is consistent with experimental observations in the literature, suggesting that a reinvestigation of materials previously considered to be inactive may be necessary.

Stable Potential Windows for Long-Term Electrocatalysis by Manganese Oxides Under Acidic Conditions.

Efficient, earth-abundant, and acid-stable catalysts for the oxygen evolution reaction (OER) are missing pieces for the production of hydrogen via water electrolysis. Here, we report how the limitations on the stability of 3d-metal materials can be overcome by the spectroscopic identification of stable potential windows in which the OER can be catalyzed efficiently while simultaneously suppressing deactivation pathways. We demonstrate the benefits of this approach using gamma manganese oxide (γ-MnO2 ), which shows no signs of deactivation even after 8000 h of electrolysis at a pH of 2. This stability is vastly superior to existing acid-stable 3d-metal OER catalysts, but cannot be realized if there is a deviation as small as 50-mV from the stable potential window. A stable voltage efficiency of over 70 % in a polymer-electrolyte membrane (PEM) electrolyzer further verifies the availability of this approach and showcases how materials previously perceived to be unstable may have potential application for water electrolysis in an acidic environment.

Design Strategy of Multi-electron Transfer Catalysts Based on a Bioinformatic Analysis of Oxygen Evolution and Reduction Enzymes.

Understanding the design strategy of photosynthetic and respiratory enzymes is important to develop efficient artificial catalysts for oxygen evolution and reduction reactions. Here, based on a bioinformatic analysis of cyanobacterial oxygen evolution and reduction enzymes (photosystem II: PS II and cytochrome c oxidase: COX, respectively), the gene encoding the catalytic D1 subunit of PS II was found to be expressed individually across 38 phylogenetically diverse strains, which is in contrast to the operon structure of the genes encoding major COX subunits. Selective synthesis of the D1 subunit minimizes the repair cost of PS II, which allows compensation for its instability by lowering the turnover number required to generate a net positive energy yield. The different bioenergetics observed between PS II and COX suggest that in addition to the catalytic activity rationalized by the Sabatier principle, stability factors have also provided a major influence on the design strategy of biological multi-electron transfer enzymes.

Selective Electrocatalytic Reduction of Nitrite to Dinitrogen Based on Decoupled Proton-Electron Transfer.

The development of denitrification catalysts which can reduce nitrate and nitrite to dinitrogen is critical for sustaining the nitrogen cycle. However, regulating the selectivity has proven to be a challenge, due to the difficulty of controlling complex multielectron/proton reactions. Here we report that utilizing sequential proton-electron transfer (SPET) pathways is a viable strategy to enhance the selectivity of electrochemical reactions. The selectivity of an oxo-molybdenum sulfide electrocatalyst toward nitrite reduction to dinitrogen exhibited a volcano-type pH dependence with a maximum at pH 5. The pH-dependent formation of the intermediate species (distorted Mo(V) oxo species) identified using operando electron paramagnetic resonance (EPR) and Raman spectroscopy was in accord with a mathematical prediction that the pKa of the reaction intermediates determines the pH-dependence of the SPET-derived product. By utilizing this acute pH dependence, we achieved a Faradaic efficiency of 13.5% for nitrite reduction to dinitrogen, which is the highest value reported to date under neutral conditions.

Element strategy of oxygen evolution electrocatalysis based on in situ spectroelectrochemistry.

Oxygen evolution electrocatalysis has received extensive attention due to its significance in biology, chemistry, and technology. However, it is still unclear how the abundant 3d-elements can be used to drive the four-electron oxidation of water as efficiently as in Nature. In this Feature Article, we will propose a design strategy concerning the optimization of the charge accumulation process based on our ongoing spectroelectrochemical study on Mn, Fe, and Ir oxygen evolution catalysts. Spectroscopic identification of the reaction intermediates showed that the activity of MnO2 and Fe2O3 was dictated by the generation of Mn3+ and Fe4+, whereas in the case of IrOx, the activity did not correlate with the valence change of Ir. The efficiency of charge accumulation through valence change is closely linked with the spin configuration of the metal center, because charge disproportionation, which was found to inhibit charge accumulation in the high-spin 3d metals, requires an electron in the eg orbital. In addition to directly increasing the overpotential through the generation of an unstable intermediate, charge disproportionation inhibits charge accumulation by dissipating the total oxidative energy of the system. A favorable charge accumulation process may also be beneficial for electrode kinetics due to the enhanced coupling between reaction rates and electrochemical driving force. The model proposed in this study may help explain why low-spin 4d/5d rare metals are often more active than the abundant high-spin 3d materials for multi-electron transfer reactions in general, and provides new insight into how active 3d-metal catalysts can be synthesized by optimizing the energetics of both bond formation and charge accumulation.

Competition between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media.

Understanding the competition between hydrogen evolution and CO2 reduction is of fundamental importance to increase the faradaic efficiency for electrocatalytic CO2 reduction in aqueous electrolytes. Here, by using a copper rotating disc electrode, we find that the major hydrogen evolution pathway competing with CO2 reduction is water reduction, even in a relatively acidic electrolyte (pH 2.5). The mass-transport-limited reduction of protons takes place at potentials for which there is no significant competition with CO2 reduction. This selective inhibitory effect of CO2 on water reduction, as well as the difference in onset potential even after correction for local pH changes, highlights the importance of differentiating between water reduction and proton reduction pathways for hydrogen evolution. In-situ FTIR spectroscopy indicates that the adsorbed CO formed during CO2 reduction is the primary intermediate responsible for inhibiting the water reduction process, which may be one of the main mechanisms by which copper maintains a high faradaic efficiency for CO2 reduction in neutral media.

Legitimate intermediates of oxygen evolution on iridium oxide revealed by in situ electrochemical evanescent wave spectroscopy.

Understanding how the four-electron oxidation of water to dioxygen proceeds in different materials is critical to the rational design of efficient catalysts towards artificial photosynthetic systems. Here, using in situ electrochemical evanescent wave spectroscopy under oxygen-evolving conditions, we report two intermediates of iridium oxide (IrOx), which is the most active and stable catalyst characterized to date in acidic medium. The observed potential dependence of the two intermediates indicated that they were associated with different surface sites, and intermediate scavenging experiments using H2O2 provided insight into their role during catalysis. Notably, an Ir(V) species with an absorption maximum at 450 nm was found to mediate the initial two-electron oxidation of water. Inhibition of the Ir(V) species by H2O2, combined with computational modeling, indicates that the accumulation and concurrent spin-state change of the Ir(V) species is a prerequisite for efficient water oxidation by IrOx electrodes.