Electrochemical Research Articles

Metal‐Phthalocyanine‐Based Two‐Dimensional Conjugated Metal‐Organic Frameworks for Electrochemical Glycerol Oxidation Reaction

Electrochemical glycerol oxidation reaction (GOR) is a promising candidate to couple with cathodic reaction, like hydrogen evolution reaction, to produce high‐value product with less energy consumption. Two‐dimensional conjugated metal‐organic frameworks (2D c‐MOFs), comprising square‐planar metal‐coordination motifs (e.g., MO4, M(NH)4, MS4), are notable for their programable active sites, intrinsic charge transport, and excellent stability, making them promising catalyst candidates for GOR. Here, we introduce a novel class of 2D c‐MOFs electrocatalysts, M2[NiPcS8] (M=Co/Ni/Cu), which are synthesized via coordination of octathiolphthalocyaninato nickel (NiPc(SH)8) with various metal centers. Due to a fast kinetic and high activity of CoS4 sites for GOR, the electrocatalytic tests demonstrate that Co2[NiPcS8] supported on carbon paper displays a low GOR potential of 1.35 V vs. RHE at 10 mA cm‐2, significantly reducing the overall water‐electrolysis‐voltage reduction by 0.27 V from oxygen evolution reaction to GOR, thereby outperforming Ni2[NiPcS8] and Cu2[NiPcS8]. Additionally, we have determined that the GOR activity of CoX4 linkage sites varies with different heteroatoms, following an experimentally and theoretically confirmed activity order of CoS4>CoO4>Co(NH)4. The GOR performance of Co2[NiPcS8] not only demonstrate superior performance among non‐noble metal complex, but also provides critical insights on designing high‐performance MOF electrocatalysts upon optimizing the electronic environment of active sites.

Metal‐Phthalocyanine‐Based Two‐Dimensional Conjugated Metal‐Organic Frameworks for Electrochemical Glycerol Oxidation Reaction

Electrochemical glycerol oxidation reaction (GOR) is a promising candidate to couple with cathodic reaction, like hydrogen evolution reaction, to produce high‐value product with less energy consumption. Two‐dimensional conjugated metal‐organic frameworks (2D c‐MOFs), comprising square‐planar metal‐coordination motifs (e.g., MO4, M(NH)4, MS4), are notable for their programable active sites, intrinsic charge transport, and excellent stability, making them promising catalyst candidates for GOR. Here, we introduce a novel class of 2D c‐MOFs electrocatalysts, M2[NiPcS8] (M=Co/Ni/Cu), which are synthesized via coordination of octathiolphthalocyaninato nickel (NiPc(SH)8) with various metal centers. Due to a fast kinetic and high activity of CoS4 sites for GOR, the electrocatalytic tests demonstrate that Co2[NiPcS8] supported on carbon paper displays a low GOR potential of 1.35 V vs. RHE at 10 mA cm‐2, significantly reducing the overall water‐electrolysis‐voltage reduction by 0.27 V from oxygen evolution reaction to GOR, thereby outperforming Ni2[NiPcS8] and Cu2[NiPcS8]. Additionally, we have determined that the GOR activity of CoX4 linkage sites varies with different heteroatoms, following an experimentally and theoretically confirmed activity order of CoS4>CoO4>Co(NH)4. The GOR performance of Co2[NiPcS8] not only demonstrate superior performance among non‐noble metal complex, but also provides critical insights on designing high‐performance MOF electrocatalysts upon optimizing the electronic environment of active sites.

Fabrication of Ultrahigh-Loading Dual Copper Sites in Nitrogen-Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral Conditions.

Synthesis of high-loading atomic-level dispersed catalysts for highly efficient electrochemical CO2 reduction reaction (eCO2RR) to ethylene(C2H4) in neutral electrolyte remain challenging tasks. To address common aggregation issues, a host-guest strategy is employed, by using a metal-azolate framework (MAF-4) with nanocages as the host and a dinuclear Cu(I) complex as the guest, to form precursors for pyrolysis into a series of nitrogen-doped porous carbons (NPCs) with varying loadings of dual copper sites, namely NPCMAF-4-Cu2-21 (21.2 wt%), NPCMAF-4-Cu2-11 (10.6 wt%), and NPCMAF-4-Cu2-7 (6.9 wt%). Interestingly, as the loading of dual copper sites increased from 6.9 to 21.2 wt%, the partial current density for eCO2RR to yield C2H4 also gradually increased from 38.7 to 93.6 mA cm-2. In a 0.1 m KHCO3 electrolyte, at -1.4 V versus reversible hydrogen electrode (vs. RHE), NPCMAF-4-Cu2-21 exhibits the excellent performance with a Faradaic efficiency of 52% and a current density of 180 mA cm-2. Such performance can be attributed to the presence of ultrahigh-loading dual copper sites, which promotes C─C coupling and the formation of C2 products. The findings demonstrate the confinement effect of MAF-4 with nanocages is conducive to the preparation of high-loading atomic-level catalysts.

Harnessing the Reactivity of Nitroarene Radical Anions to Create Quinoline N‐Oxides by Electrochemical Reductive Cyclization

AbstractElectrochemical reduction of 2‐allyl‐substituted nitroarenes using a simple, undivided electrochemical cell with non‐precious electrodes to generate nitroarene radical anions was developed. The nitroarene radical anion intermediates participate in 1,5‐hydrogen atom transfer reactions to construct quinoline N‐oxides bearing aryl‐, heteroaryl‐, alkenyl‐, benzyl‐, sulfonyl‐, or carboxyl groups.

Metal Organic Framework‐Derived Anionic P‐Substitution toward CoNiSe‐P with Excellent Electrochemical Stability for Supercapacitor

AbstractThe regulation of nanostructures and composition can significantly enhance the electrochemical activity and accelerate electrochemical reaction kinetics of electrode material. Herein, metal organic framework(MOF) is used as self‐sacrificing templates to prepare CoNiSe‐P by hydrothermal with following selenylation and phosphorization treatment. Due to the hollow porous structure, rich electrochemical active sites and elements synergistic influence, the obtained CoNiSe‐P electrode shows a high capacity of 838 C g−1, which is much higher than CoNiSe (322 C g−1) and CoNiP (616 C g−1). Furthermore, CoNiSe‐P electrode shows excellent rate characteristic (685 C g−1 at 20 A g−1) and ultrahigh electrochemical stability with capacity retention of 99.6% after 10 000 cycles. More importantly, an asymmetric supercapacitor is assembled with CoNiSe‐P as the positive electrode and nitrogen‐doped porous carbon as the negative electrode delivers an energy density of 42.4 Wh kg−1 at 266.6 W kg−1 and maintains a specific capacitance of 96.8% after 10 000 cycles. Significantly, the asymmetric supercapacitor shows a high energy density up to 21.3 Wh kg−1 at a very high power density of 21.3 kW kg−1, higher than those of previously reported asymmetric supercapacitors.

A MXene Modulator Enabled High‐Loading Iodine Composite Cathode for Stable and High‐Energy‐Density Zn‐I2 Battery

AbstractAchieving both high iodine loading cathode and high Zn anode depth of discharge (DOD) is pivotal to unlocking the full potential of energy‐dense Zn‐I2 batteries. However, this combination exacerbates the detrimental shuttle effect of polyiodide intermediates, significantly impairing the battery's reversibility and stability. Herein, this study reports an advanced high‐loading iodine cathode (denoted as MX‐AB@I) enabled by a multifunctional Ti3C2Tx MXene modulator, which presents high stability and energy density in Zn‐I2 batteries. Through comprehensive experimental and theoretical analyses, the intrinsic regulating mechanisms are elucidated by which the MXene modulator effectively suppresses polyiodide shuttling, enhances iodine conversion kinetics, and dramatically improves Zn anode reversibility. With the aid of the MXene modulator, the MX‐AB@I composite cathode achieves a high iodine mass loading of 23 mg cm−2 and realizes a practically high areal capacity of 4.0 mAh cm−2. When paired with a thin Zn anode (10 µm), this configuration realizes a high Zn DOD of 78.7% and a high energy density of 171.3 Wh kg−1, surpassing the majority of Zn‐I2 battery systems reported in the literature. This study presents an effective approach to designing high‐loading iodine cathodes for Zn‐I2 batteries by leveraging MXene modulators to regulate critical electrochemical reaction processes.

Advanced Electrode Materials for Low‐Temperature Na Storage

AbstractSodium‐ion batteries have drawn worldwide attention as ideal candidates for the upcoming generation of large‐scale electrical energy storage devices due to the low cost and abundance of sodium. Due to its unique electrochemical and chemical properties, sodium‐ion batteries hold the promise of breaking geographical and environmental constraints, achieving efficient sodium storage under low‐temperature conditions. However, low‐temperature sodium‐ion batteries, especially for their electrode materials, still face numerous challenges, such as the sluggish electrochemical reaction kinetics, poor material stability, significant volume changes leading to the pulverization of materials and the rapid degradation of battery performance. Here, it is focused on the modification methods for electrode materials, the research progress on cathode and anode materials of low‐temperature sodium‐ion batteries is summarized systematically and the other components of the electrodes are discussed briefly, and the shortcomings of the current research and possible future research directions are discussed thoroughly.

Electrochemical Reactions Affected by Electric Double Layer Overlap in Conducting Nanopores.

When a potential is applied to an electrode immersed in an electrolyte solution, ions with opposite charges accumulate around the electrode, forming an electrical double layer (EDL). Unlike flat electrodes, nanoporous electrodes with pore sizes comparable to the EDL thickness experience overlapping EDLs, altering the electrochemically effective surface area. Although previous research has primarily examined the ion charging dynamics and EDL formation in nanoporous electrodes, the impact of EDL overlap on Faraday reactions remains underexplored. In this study, we examined the influence of EDL overlap on electrochemical reactions within nanoporous electrodes using chronoamperometry and DC and AC voltammetry. We used the electrolyte concentration, measurement duration, overpotential, and electrode material as variables to determine the relationship between the extent of EDL overlap and the electrochemical reaction. The electrolyte concentration-dependent electrochemical reaction due to the EDL overlap was more pronounced for electrodes with faster potential changes, shorter measurement times, lower overpotentials, and slower catalytic activity. This is a unique nanoporous electrochemical phenomenon that is not observed on flat electrodes. These findings provide insight into the utilization of nanoporous electrodes in catalytic and sensor applications.

Non-Innocent Role of Sacrificial Anodes in Electrochemical Nickel-Catalyzed C(sp2)-C(sp3) Cross-Electrophile Coupling.

Sacrificial anodes composed of inexpensive metals such as Zn, Fe, and Mg are widely used to support electrochemical nickel-catalyzed cross-electrophile coupling (XEC) reactions, in addition to other reductive electrochemical transformations. Such anodes are appealing because they provide a stable counter-electrode potential and typically avoid interference with the reductive chemistry. The present study outlines the development of an electrochemical Ni-catalyzed XEC reaction that streamlines access to a key pharmaceutical intermediate. Metal ions derived from sacrificial anode oxidation, however, directly contribute to homocoupling and proto-dehalogenation side products that are commonly formed in chemical and electrochemical Ni-catalyzed XEC reactions. Use of a divided cell limits interference by the anode-derived metal ions and supports a high product yield with negligible side product formation, introducing a strategy to overcome one of the main limitations of Ni-catalyzed XEC.

Dual-Sliding-Surface Robust Control for the PEMFC Air-Feeding System Based on Terminal Sliding Mode Algorithm

The proton exchange membrane fuel cell (PEMFC) is the most widely used fuel cell, but it also has some limitations. One of the research pain points is controlling the oxygen content in PEMFCs. A moderate excess of oxygen boosts electrochemical reaction efficiency, while an appropriate oxygen content ensures system stability. In this paper, a fourth-order nonlinear mathematical model of a PEMFC stack air supply system is established to solve the problem of optimal oxygen excess ratio (OER) control under dynamic load conditions. Based on the model, a nonsingular terminal sliding mode controller (NTSMC) based on a sliding mode observer (SMO) is proposed. The NTSM exhibits superior robustness and performance compared to other sliding mode structures. Meanwhile, the SMO accurately predicts system states, facilitating precise control actions. Additionally, the dual sliding mode surfaces enhance system stability against parameter uncertainties and external disturbances. Our results demonstrate that the proposed controller outperforms traditional ones in terms of robustness and performance, which significantly enhances PEMFC system efficiency and stability.

Sulfate Oxyanion Steered d-Orbital Electronic State of Nickel-Iron Nanoalloy for Boosting Electrocatalytic Performance.

Oxyanion groups recently offer an innovative avenue for improving the sluggish kinetics of electrochemical reactions benefitting from their particular polyanion configurations and large electronegativity. Nevertheless, the exact structure design and deep regulating mechanism of oxyanion species remain poorly understood. Herein, a fresh architecture of the sulfate oxyanion coordinated nickel-iron nanoalloy on nitrogen and sulfur co-doped carbon nanotube (SO4 2--NiFe/NSCT) is newly proposed to study the activity increment effect and mechanism. The SO4 2--NiFe/NSCT displays hierarchical nanostructure with robust-wrinkled surface and highly efficient active sites. Importantly, the SO4 2- group, as a significant manipulation factor, is first evidenced to promote the oxygen reduction reaction (ORR) activity for NiFe nanoalloy under the reductive condition, showcasing outstanding bifunctional properties toward ORR and oxygen evolution reaction (OER), as well as the exceptional performance in non-aqueous Li-O2 battery. Both experimental and theoretical results elucidate that, as an electron bridge, the introduction of SO4 2- downshifts the d-band center of SO4 2--NiFe/NSCT and gives the electron transfer passageway between the H atom in OH* intermediate and the O atom in SO4 2- group, greatly optimizing the metal-intermediate interaction with weaker bond energy. This work provides a deep insight into the activity enhancement mechanism by the sulfate oxyanion.

Highly Active and Stable Cu-Cd Bimetallic Oxides for Enhanced Electrochemical CO2 Reduction.

Electrochemical reduction of carbon dioxide (CO2) can produce value-added chemicals such as carbon monoxide (CO) and multicarbon(C2+). However, the complex reaction pathways of CO2electro-reduction reaction (CO2RR) greatly limit the product selectivity and conversion efficiency. Herein, the Cu-Cd bimetallic oxides catalyst was designed and applied for the CO2RR. The optimized 4.73%Cd-CuO exhibits remarkable electrocatalytic CO2RR activity for selective CO production in H-cell using 0.5 M 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6)/MeCN as electrolyte. The Faradaic efficiency of CO (FE(CO)) can be maintained above 90% over a wide potential range of -2.0 to -2.4 V vs. Ag/Ag+. Particularly, the catalyst achieves an impressive FE(CO) of 96.3% with a current density of 60.7 mA cm-2at -2.2 V vs. Ag/Ag+. Furthermore, scaling up the 4.73%Cd-CuO catalyst into a flow cell can reach 56.64% FE of C2+products (ethylene, ethanol and n-propanol) with a current density as high as 600 mA cm-2steadily.The excellent CO2RR performance of the as-synthesized 4.73%Cd-CuOcan be mainly attributed to the introduction of CdO to improve the ability of CuO to activate CO2, the electronic interactions between Cu and Cd can boostactivation and conversionkey intermediates of CO2RR and ensure the continuous stability of4.73%Cd-CuOin electrolysis process.

Transition Metals Doped into g-C3N4 via N,O Coordination as Efficient Electrocatalysts for the Carbon Dioxide Reduction Reaction.

The electrochemical carbon dioxide reduction reaction (CO2RR) is a potential and efficient method that can directly convert CO2 into high-value-added chemicals under mild conditions. Owing to the exceptionally high activation barriers of CO2, catalysts play a pivotal role in CO2RR. In this study, the transition metal (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) is doped into g-C3N4 with a unique N,O-coordination environment, namely, TM-N1O2/g-C3N4. Herein, the catalytic performance and reaction mechanism for the CO2RR on TM-N1O2/g-C3N4 are systematically investigated by density functional theory methods. Especially, through the calculation of ΔG*H and ΔG*COOH/ΔG*OCHO, the catalysts with preference for the CO2RR over the hydrogen evolution reaction (HER) are selected for further study. Furthermore, Gibbs free energy computation results of each elementary step for the CO2RR on these catalysts indicate that Ti-N1O2/g-C3N4 has significant catalytic activity and selectivity for reducing CO2 to methanol (CH3OH) with the limiting potential (UL) of -0.55 V. Finally, through frontier molecular orbital theory and charge transfer analyses, the introduction of the O atoms illustrates that it is instrumental in regulating the electron distribution of the catalytic active site, thereby improving the catalytic performance. This work provides insight into the design of single-atom catalysts with unique coordination structures for the CO2RR.

Site-Specific Stochastic Rates and Energetics of Ag Nucleation on Highly Ordered Pyrolytic Graphite.

Nucleation is a fundamentally important step in electrochemical phase transition reactions, e.g., in electrodeposition, which is pertinent for emerging battery technology, nanoparticle synthesis, and many industrial processes. Surface defects have been suggested to enhance nucleation rates. However, directly quantifying the nucleation rates at specific surface sites is challenging due to the ensemble averaging effect in bulk measurements. Herein, we report the measurement of rates and energetics of electronucleation across the model surface of highly oriented pyrolytic graphite (HOPG). Specifically, scanning electrochemical cell microscopy (SECCM) is used to confine the nucleation spatially in the nanoscale cell, allowing one nucleation event to be measured at one time. The scanning capability further allows the mapping of Ag nucleation at the step edge vs basal plane. A stochastic model is developed to extract the nucleation rate and energetics from voltammetric experiments. We observed a ∼57 mV difference in the median nucleation overpotential between the step edge and basal plane, corresponding to a ∼12 kJ mol-1 difference in the nucleation energy barrier. The voltammetric method to measure the nucleation rate explored here can be extended to understand the heterogeneity of nucleation rates in other electrochemical nucleation systems, e.g., metal anode batteries.

Development of CuFe2O4 microspheres/carbon sheets composite materials as a sensitive electrochemical sensorfor determination of bisphenol A.

A composite material based on CuFe-ZIF-derived CuFe2O4 nano-microspheres grown in situ and well-ordered on carbon sheets (CS) was prepared and applied for highly effective determination of bisphenol A (BPA). The composite material possessed inherently high redox activity due to the presence of both Cu and Fe ions with various oxidation states (Cu²⁺/Cu⁺ and Fe³⁺/Fe²⁺), high specific surface area, uniform distribution of Cu and Fe ions, and a robust framework imparted by its precursor CuFe-ZIF. Thisled to increased active sites for electrochemical reactions, improved electron transfer efficiency, and structural integrity during electrochemical cycling. Furthermore, combining CS with CuFe2O4 not only provided a large surface area to support well-ordered CuFe₂O₄ nano-microspheres without aggregation, but also enhanced the conductivity and mechanical stability of the CuFe₂O₄/CS composite. This results in synergistic effects that enhanced the overall performance of the composite material. In addition, both copper and iron are relatively non-toxic and abundant, making CuFe₂O₄/CS safe and cost-effective for large-scale applications. Consequently, the CuFe2O4/CS-modified electrode shows highly efficient electrochemical sensing properties with a wider detection range of 0.009-168 µM and lower detection limit of 0.0027 µM (S/N = 3) compared withmost reported BPA sensors. It also hasanoptimized current at pH 7 which is convenient for real world applications. This CuFe2O4/CS modified electrode as a highly sensitive electrochemical platform can be applied to monitor BPA concentrations in bottled water with good recovery (97.2-102.2%).

Rational Strategies for Preparing Highly Efficient Tin-, Bismuth- or Indium-Based Electrocatalysts for Electrochemical CO2 Reduction to Formic acid/Formate.

Electrochemical carbon dioxide reduction reaction (CO2RR) is an environmentally friendly and economically viable approach to convert greenhouse gas CO2 into valuable chemical fuels and feedstocks. Among various products of CO2RR, formic acid/formate (HCOOH/HCOO-) is considered the most attractive one with its high energy density and ease of storage, thereby enabling widespread commercial applications in chemical, medicine, and energy-related industries. Nowadays, the development of efficient and financially feasible electrocatalysts with excellent selectivity and activity towards HCOOH/HCOO- is paramount for the industrial application of CO2RR technology, in which Tin (Sn), Bismuth (Bi), and Indium (In)-based electrocatalysts have drawn significant attention due to their high efficiency and various regulation strategies have been explored to design diverse advanced electrocatalysts. Herein, we comprehensively review the rational strategies to enhance electrocatalytic performances of these electrocatalysts for CO2RR to HCOOH/HCOO-. Specifically, the internal mechanism between the physicochemical properties of engineering materials and electrocatalytic performance is analyzed and discussed in details. Besides, the current challenges and future opportunities are proposed to provide inspiration for the development of more efficient electrocatalysts in this field.

Parameter Analysis of Anion Exchange Membrane Water Electrolysis System by Numerical Simulation

Anion exchange membrane electrolysis, which combines the advantages of both alkaline electrolysis and proton-exchange membrane electrolysis, is a promising technology to reduce the cost of hydrogen production. The present work focused on the study of the electrochemical phenomena of AEM electrolysis and the investigation of the key factors of the AEM hydrogen production system. The numerical model is established according to electrochemical reactions, polarization phenomena, and the power consumption of the balance of plant components of the system. The effects of operation parameters, including the temperature and hydrogen pressure of the electrolyzer, electrolyte concentration, and hydrogen supply pressure on the energy efficiency are studied. The basic electrochemical phenomena of AEM water electrolysis cells are analyzed by simulations of reversible potential and activation, and ohmic and concentration polarizations. The results reveal that increasing the operating temperature and hydrogen production pressure of the AEM electrolyzer has positive effects on the system’s efficiency. By conducting an optimization analysis of the electrolyzer temperature—which uses the heat energy generated by the electrochemical reaction of the electrolyzer to minimize the power consumption of the electrolyte pump and heater—the AEM system with an electrolyzer operating at 328 K and 30 bar can deliver hydrogen of pressure up to 200 bar under an energy efficiency of 56.4%.

Hierarchically conductive electrodes unlock stable and scalable CO2 electrolysis.

Electrochemical CO2 reduction has emerged as a promising CO2 utilization technology, with Gas Diffusion Electrodes becoming the predominant architecture to maximize performance. Such electrodes must maintain robust hydrophobicity to prevent flooding, while also ensuring high conductivity to minimize ohmic losses. Intrinsic material tradeoffs have led to two main architectures: carbon paper is highly conductive but floods easily; while expanded Polytetrafluoroethylene is flooding resistant but non-conductive, limiting electrode sizes to just 5 cm2. Here we demonstrate a hierarchically conductive electrode architecture which overcomes these scaling limitations by employing inter-woven microscale conductors within a hydrophobic expanded Polytetrafluoroethylene membrane. We develop a model which captures the spatial variability in voltage and product distribution on electrodes due to ohmic losses and use it to rationally design the hierarchical architecture which can be applied independent of catalyst chemistry or morphology. We demonstrate C2+ Faradaic efficiencies of ~75% and reduce cell voltage by as much as 0.9 V for electrodes as large as 50 cm2 by employing our hierarchically conductive electrode architecture.

Promoting Water Activation via Molecular Engineering Enables Efficient Asymmetric C-C Coupling during CO2 Electroreduction.

Water activation plays a crucial role in CO2 reduction, but improving the electrocatalytic performance through controlled water activation presents a significant challenge. Herein, we achieved electrochemical CO2 reduction to ethene and ethanol with high selectivity by promoting water dissociation and asymmetric C-C coupling by engineering Cu surfaces with N-H-rich molecules. Direct spectroscopic evidence, coupled with density functional theory calculations, demonstrates that the N-H-rich molecules accelerate interfacial water dissociation via hydrogen-bond interactions, and the generated hydrogen species facilitate the conversion of *CO to *CHO. This enables the efficient asymmetric *CHO-*CO coupling to C2 products with a faradaic efficiency (FE) ∼ 30% higher than that of the unmodified catalyst. Moreover, by adjustment of the relative *CHO/*CO coverage via Cu surface facet regulation, the selectivity can be entirely switched between C2 products and CH4. These mechanistic insights further guided the development of a more efficient catalyst by directly modifying Cu2O nanocubes with the N-H-rich molecule, achieving remarkable C2 product (mainly ethene and ethanol) FEs of 85.7% at a current density of 800 mA cm-2 and excellent stability under nearing industrial conditions. This study advances our understanding of the CO2 reduction mechanisms and offers an effective and general strategy for enhancing electrocatalytic performance by accelerating water dissociation.

How Ir‐Rh Alloys Improve Electrochemical Ammonia Oxidation Activity Studied by Density Functional Theory

The electrochemical ammonia oxidation reaction (AOR) has applications in hydrogen storage and ammonia waste remediation. Using density functional theory, we investigate the mechanism of AOR on Ir, Rh, and their alloys at varied atomic ratios (Ir75Rh25, Ir50Rh50, and Ir25Rh75) towards N2(g), NO2–(aq), and NO3–(aq) formation. This work introduces a method for computational alloy design by considering both electronic energy and configurational entropy. The structures considered are selective to N2(g) formation and all favoured *N‐N coupling. An Ir50Rh50 alloy was found to reduce the theoretical onset potential for N2(g) formation relative to pure Ir while not exhibiting a downhill coupling step corresponding to catalyst poisoning by *N as shown for pure Rh, consistent with previous experimental work. The formation of NO2–(aq) and NO3–(aq) demand significantly higher potentials, typically limited by the final hydroxylation step before desorption.