Electronic Effects Research Articles

Synthesis of NaLTA zeolite confined CuO catalysts and superior catalytic properties for alkene epoxidation with H2O2 as oxidant

The NaLTA zeolite confined CuO catalyst CuO@NaLTA was prepared via the method of ligand protected in situ with Cu2+-glycine complex as Cu source, and characterized by multiple characteristic techniques. The results revealed that CuO nanoparticles were highly dispersed on NaLTA zeolite, and the catalytic properties of CuO@NaLTA were investigated in the alkene epoxidation with H2O2 as oxidant in dioxane. For styrene oxidation, catalyst CuO@NaLTA exhibited excellent catalytic activities with 83 % conversion and 63 % selectivity to styrene epoxide, and could be easily recycled several times without obvious activity loss. The excellent catalytic activities could be attributed to the highly dispersed active CuO species. Besides, multiple electronic effects and coordinative interactions exited in Cu ion and the Si-Al zeolite skeleton framework played a key role in the catalytic recyclability.

Efficient Organic Light-Emitting Diodes Obtained by Introducing Gadolinium (Gd) Complexes Based on Pyrazolone Derivative Ligands as Hole Trappers.

The utilization of lanthanide (Ln) complexes in the realm of organic light-emitting diodes (OLEDs) has garnered extensive interest, particularly in their role as luminescent materials or electron trappers. A series of gadolinium (Gd) complexes with energy levels of high HOMO/LUMO and different triplet state energies were designed and synthesized by introducing substituents with different electronic effects onto the pyrazolone derivative ligands. Subsequently, these complexes were precisely purified by vacuum sublimation and codoped into the light-emitting layer (EML) of the OLEDs. This process was facilitated through the well-matched HOMO/LUMO levels and triplet energies among various functional materials. Consequently, the maximum external quantum efficiencies of blue, red, and green OLEDs were simultaneously enhanced with the ratios of 119%, 28%, and 71%, respectively. This improvement can be credited to the introduction of Gd(III) complex molecules within EMLs, which helps to capture excess holes and improve carriers' balance.

An Acceptor-Substituted N-Heterocyclic ortho-Quinodimethane: Pushing the Boundaries of Polarization in Donor-Acceptor-Substituted Polyenes.

We report the synthesis, isolation, and characterization of a stable donor-acceptor substituted ortho-quinodimethane (oQDM). This system with an imidazolidine scaffold as the donor can also be referred to as acceptor-substituted ortho-N-heterocyclic quinodimethane (oNHQ). We have examined the extent of polarization of the conjugated π-system using single-crystal X-ray diffraction, NMR and UV/vis spectroscopy, cyclic voltammetry, and DFT computations. The bond lengths in the phenyl linker do not exhibit the alternation typical of oQDMs. In addition, the 13C and 15N NMR shifts suggest significant charge separation, an interpretation supported by the diatropic ring current determined by NICSZZ(r) computations, which is characteristic of aromatic compounds. DFT calculations show that polarization is an electronic effect that is amplified by steric influences. More strikingly, the oxidation and reduction potentials of the push-pull substituted oQDM are virtually identical to those of authenticated anionic and cationic derivatives. The results therefore indicate that an aromatic zwitterionic structure represents the electronic structure more accurately than a neutral quinoidal Lewis structure, which indicates that the acceptor-substituted oNHQ is a rare example of an organic zwitterion in which the centers of charge are in conjugation. The ambiphilic reactivity of the acceptor-substituted oNHQ, which is evidenced by the dehydrogenation of ammonia borane and the addition of phenylacetylene via heterolytic C-H bond cleavage, further supports its notation as an organic zwitterion and is reminiscent of frustrated Lewis pairs (FLPs). Thus, the acceptor-substituted oNHQ can be considered to be an intramolecular carbogenic FLP in terms of its reactivity.

Modulating the band structure of two-dimensional black phosphorus via electronic effects of organic functional groups for enhanced hydrogen production activity.

Electronic effects of organic functional groups play a fundamental role in determining the rate and/or direction of organic chemical reactions. The implementation of this concept in selective organic catalysis is achieved by tuning the electronic effects of organic functional groups to alter the corresponding reactivity. However, this approach has hardly been applied to modulate the band structure of inorganic materials. Here, we show that modulating the electronic band structure of two-dimensional black phosphorus (BP) is possible via the electronic effects of organic functional groups covalently modified on its surface. Organic functional group can either donate or withdraw charge density from BP surface, which will alter the bonding/anti-binding orbitals occupancy and thus shift the band-edge positions of functionalized BP downward/upward. Therefore, the valence-band maxima and the conduction-band minima of functionalized BP can be continuously tuned by changing the binding group with different Hammett parameters. Finally, unexpectedly high hydrogen evolution reaction rates under visible light are achieved using functionalized BP heterojunctions as photocatalysts. This work underscores the significant role of electronic effects in chemically controlling BP's band structure, offering greater flexibility and affordability beyond physical method limits.

Modulating the band structure of two‐dimensional black phosphorus via electronic effects of organic functional groups for enhanced hydrogen production activity

Electronic effects of organic functional groups play a fundamental role in determining the rate and/or direction of organic chemical reactions. The implementation of this concept in selective organic catalysis is achieved by tuning the electronic effects of organic functional groups to alter the corresponding reactivity. However, this approach has hardly been applied to modulate the band structure of inorganic materials. Here, we show that modulating the electronic band structure of two‐dimensional black phosphorus (BP) is possible via the electronic effects of organic functional groups covalently modified on its surface. Organic functional group can either donate or withdraw charge density from BP surface, which will alter the bonding/anti‐binding orbitals occupancy and thus shift the band‐edge positions of functionalized BP downward/upward. Therefore, the valence‐band maxima and the conduction‐band minima of functionalized BP can be continuously tuned by changing the binding group with different Hammett parameters. Finally, unexpectedly high hydrogen evolution reaction rates under visible light are achieved using functionalized BP heterojunctions as photocatalysts. This work underscores the significant role of electronic effects in chemically controlling BP’s band structure, offering greater flexibility and affordability beyond physical method limits.

Twenty Years of Graphene: From Pristine to Chemically Engineered Nano-Sized Flakes.

It is a celebratory moment for graphene! This year marks the 20th anniversary of the discovery of this amazing material by Geim and Novoselov. Curiously, it coincides with the century mark of graphite's layered structure discovery. Since the discovery of graphene with the promise that its outstanding properties would change the world, society often wonders where is graphene? In this context, their discoverers said in 2005, "despite the reigning optimism about graphene-based electronics, "graphenium" microprocessors are unlikely to appear for the next 20 years". Today, possibilities for graphene are endless! It can be used in electronics, photonics, fuel cells, energy storage, artificial intelligence, biomedicine, and even cultural heritage or sports. Additionally, the electronic properties of this material have been modified in fascinating ways. Bilayer graphene sheets have been found to be superconductive when twisted at a "magic angle", leading to a new and exciting field of research known as "moiré quantum materials" or "twistronics". Additionally, small graphene fragments with nanometer sizes undergo a quantum confinement effect of electrons, affording semiconductive materials with applications in optoelectronics. Organic synthesis allows the preparation of molecules with a graphene-like pattern with total control of the shape and size, exhibiting a big catalog of chiroptical and optoelectronic properties. This Perspective shows some of the fascinating milestones raised in the field of graphene-like materials from a chemical point of view, including functionalization strategies employed to chemically modify the topology and the properties of pristine graphene as well as the rising molecular graphenes.

Fluorination Affects the Force Sensitivity and Nonequilibrium Dynamics of the Mechanochemical Unzipping of Ladderanes.

When multiple reaction steps occur before thermal equilibration, kinetic energy from one reaction step can influence overall product distributions in ways that are not well predicted by transition state theory. An understanding of how the structural features of mechanophores, such as substitutions, affect reactivity, product distribution, and the extent of dynamic effects in the mechanochemical manifolds is necessary for designing chemical reactions and responsive materials. We synthesized two tetrafluorinated [4]-ladderanes with fluorination on different rungs and found that the fluorination pattern influenced the force sensitivity and stereochemical distribution of products in the mechanochemistry of these fluorinated ladderanes. The threshold forces for mechanochemical unzipping of ladderane were decreased by α-fluorination and increased by γ-fluorination; these changes correlated to the different stabilizing or destabilizing effects of fluorination patterns on the first transition state. Using ab initio steered molecular dynamics (AISMD), we compared the product distributions of synthesized and hypothetical ladderanes with different substitution patterns. These calculations suggest that fluorination on the first two bonds of ladderane gives rise to a larger fraction of dynamic trajectories and a larger fraction of E-alkene product through a mechanism resulting from larger momentum because of the greater atomic mass of fluorine. Fluorination on the third and fourth rungs instead gives a larger fraction of E-alkene product primarily due to electronic effects. These combined experimental and computational studies of the mechanochemical unzipping of fluorinated ladderanes provide an example of how relatively simple substituents can affect the extent of nonstatistical dynamics and, thus, mechanochemical outcomes.

Electronic Effects and Steric Effects for the Design of N-Sulfonate Ester Phthalimide Photoacid Generators with High Acid Production Efficiency and Thermal Stability

Electronic Effects and Steric Effects for the Design of N-Sulfonate Ester Phthalimide Photoacid Generators with High Acid Production Efficiency and Thermal Stability

FeN4S1 Single-Atom Sites Anchored on Three-Dimensional Porous Carbon for Highly Efficient and Durable Oxygen Electrocatalysis.

Precisely designing asymmetric active centers and exploring their electronic regulation effects to prepare efficient bifunctional single-atom catalysts (SACs) is important for boosting the practical applications of zinc-air batteries (ZABs). Herein, an effective strategy has been developed by introducing an axial S atom to the FeN4 active center, simultaneously assisted by pyrolyzing the graphene oxide (GO) sheathed zeolitic-imidazolate framework-8 (ZIF8) composite and constructing a three-dimensional (3D) porous framework with abundant FeN4S1 moieties. This structure can accelerate the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics owing to the modulated electronic redistribution and d-band center with a reduced energy barrier. The optimal S-Fe-NC/rGO showcases a lower voltage gap (ΔE) of 0.64 V between both the ORR and OER half-wave potentials at 10 mA cm-2, highlighting the excellent bifunctional activities. The assembled S-Fe-NC/rGO rechargeable liquid ZABs deliver a power density of 154.05 mW·cm-2 and a desirable durability of >900 h. More importantly, the corresponding flexible solid-state ZABs exhibit considerable foldability.

Tuning the selectivity of Pd-based catalysts for CO oxidative esterification: Regulating Pd's electronic effect

CO oxidative esterification is crucial in converting inorganic CO into organic oxygenated compounds within C1 chemistry and technology. However, understanding the structure-activity relationship underlying this reaction remains limited, primarily due to the entanglement of the Pd's geometric and electronic structures, which complicates selectivity control in practical applications. In this work, we design four Pd-based catalysts using the Al(111) motif to investigate their catalytic performance in CO oxidative esterification through density functional theory (DFT) calculations. Firstly, the larger lattice parameter of Al weakens horizontal Pd–Pd interactions while enhancing the vertical stability of Pd. Secondly, the electronic structure of Pd is locally regulated via charge transfer between subsurface and surface Pd, driven by their differences in work function. Our results indicate that the relative activity between CC coupling for dimethyl oxalate (DMO) and CO coupling for dimethyl carbonate (DMC) is primarily influenced by Pd's electronic effects, as revealed by energy barrier decomposition analysis. Thus, focusing on the regulation of Pd's electronic effects may offer a new strategy for controlling the selective oxidation esterification of CO.

Symmetry Breaking in Inorganic Nanostructures: Chirality vs. Optical Activity or Structural vs. Electronic Effects

AbstractThis essay presents the viewpoint of the author on the topic of chirality and optical activity in nanostructures. It particularly focuses on the interaction of chiral molecules with plasmonic and excitonic nanocrystals and on induction of circular dichroism in such achiral nanocrystals. It discusses recent developments in the shape symmetry breaking of achiral metal nanostructures using photochemical processes induced by asymmetric localized plasmonic hot spots excited through circularly polarized light illumination. Finally, it addresses symmetry breaking in intrinsically chiral inorganic nanocrystals using chiral ligands during their formation, leading to 100 % enantiomeric excess in the nanocrystals of TbPO4⋅H2O. These nanocrystals exhibit an interesting nucleation mechanism, which leads to very high chiral amplification (secondary nucleation).

Embedding Plate‐Like Pyrochlore in Perovskite Phase to Enhance Energy Storage Performance of BNT‐Based Ceramic Capacitors

AbstractNext‐generation electrical and electronic systems rely on the development of efficient energy‐storage dielectric ceramic capacitors. However, achieving a synergistic enhancement in the polarization and in the breakdown field strength (Eb) presents a considerable challenge. Herein, a heterogeneous combination strategy involving embedding a high Eb plate‐like pyrochlore phase in a high‐polarization perovskite phase is proposed. The embedded plate‐like pyrochlore increases the breakdown field strength and promotes the dynamic polarization response. Meanwhile, the strong spin–orbit coupling effect of the 5d electrons is conducive to the maintenance of the high polarization value of the perovskite. Consequently, the prepared multilayer ceramic capacitor (MLCC) exhibits an ultrahigh Eb and a high polarization. More specifically, an energy storage density (Wrec) of 14.9 J cm−3 with an efficiency of up to 93.4% is achieved for the optimized pyrochlore/perovskite phase. Furthermore, the MLCCs also exhibits an Wrec of ≈ 7.7 J cm−3 ± 4.5% in the temperature range of −50–180 °C. Therefore, this heterogeneous combination strategy therefore provides a simple and effective method for improving the energy‐storage performances of dielectric ceramic capacitors.

Unconventional Hexagonal Close-Packed High-Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution.

Accelerating the alkaline hydrogen evolution reaction (HER), which involves the slow cleavage of HO-H bonds and the adsorption/desorption of hydrogen (H*) and hydroxyl (OH*) intermediates, requires developing catalysts with optimal binding strengths for these intermediates. Here, the unconventional hexagonal close-packed (HCP) high-entropy alloy (HEA) atomic layers are prepared composed of five platinum-group metals to enhance the alkaline HER synergistically. The breakthrough is made by layer-by-layer heteroepitaxial deposition of subnanometer RuRhPdPtIr HEA layers on the HCP Ru seeds, despite the thermodynamic stability of Rh, Pd, Pt, and Ir in a face-centered cubic (FCC) structure except for Ru. The synchrotron X-ray absorption spectroscopy (XAS) confirms the atomic mixing and coordination environment of HCP RuRhPdPtIr HEA. Most importantly, they exhibit notable improvements in both electrocatalytic activity and durability for the HER in an alkaline environment, as compared to their FCC RuRhPdPtIr counterparts. Electrochemical measurements, operando XAS analysis, and density functional theory unveil that the binding strengths of H* and OH* intermediates on the active Pt and Ir sites can be weakened and strengthened to a moderate level, respectively, by mixing non-active Ru, Rh, and Pd atoms with Pt and Ir atoms within the HCP HEA with strong synergistic electronic effects.

Organoiodine Catalysed Intramolecular C−N Bond Oxidative Coupling for the Synthesis of 3‐Monosubstituted Oxindoles

AbstractAn efficient organoiodine‐catalysed intramolecular direct C−N bond oxidative coupling reaction is presented. Structurally diverse 3‐(mono)substituted oxindoles were rapidly obtained in a complex oxidative system in up to 87 % yield. Various N‐alkoxy‐2‐phenylpropanamides were well‐tolerated. This study showed that the electronic effects on the aromatic ring of reactants have a crucial effect on the selectivity (C−N/C−O) of cyclisation products. In addition, gram‐scale synthesis and late‐stage modification of 3‐(mono)substituted oxindole derivatives revealed the practical application of this transformation.

Construction of 2D/2D Pd Metallene/COFs System with Strong Internal Electric Field for Outstanding Solar Energy Photocatalysis.

Due to the severe recombination of charge carriers, the photocatalytic activity of covalent organic frameworks (COFs) materials is limited. Herein, through simple ultrasound and stirring processes, the Pd metallene (Pde) is successfully combined with 2D COFs to form Pde/TpPa-1-COF (Pde/TPC) composites. Obviously, a strong internal electric field (IEF) is successfully formed in Pde/TPC hybrid materials, which significantly boosts the separation of photogenerated charges. In addition, the matched 2D structure of the two materials can also lead to electronic coupling effects, plentiful active sites, and shortened carrier migration paths. Thus, the Pde/TPC hybrid materials own extraordinary carrier separation ability with a longer carriers lifetime (3.3 ns for Pde/TPC and 2.7 ns for TPC), which can be proved series of photoelectrochemical and spectroscopic tests. Benefiting from the formation of IEF and the matched 2D structure, the 8% Pde/TPC demonstrates the highest photocatalytic H2 evolution efficiency, with H2 production rate reaching up to 5.85 mmolg-1h-1, which is over 25 times greater than that of pristine COFs, also exceeding that of many reported COFs-based photocatalysts. This research provides new perspectives and innovative approaches to further research on enhancing the internal electric field of COFs to promote their photocatalytic performance.

Morphofunctional Features of Glomeruli and Nephrons After Exposure to Electrons at Different Doses: Oxidative Stress, Inflammation, Apoptosis

Kidney disease has emerged as a significant global health issue, projected to become the fifth-leading cause of years of life lost by 2040. The kidneys, being highly radiosensitive, are vulnerable to damage from various forms of radiation, including gamma (γ) and X-rays. However, the effects of electron radiation on renal tissues remain poorly understood. Given the localized energy deposition of electron beams, this study seeks to investigate the dose-dependent morphological and molecular changes in the kidneys following electron irradiation, aiming to address the gap in knowledge regarding its impact on renal structures. The primary aim of this study is to conduct a detailed morphological and molecular analysis of the kidneys following localized electron irradiation at different doses, to better understand the dose-dependent effects on renal tissue structure and function in an experimental model. Male Wistar rats (n = 75) were divided into five groups, including a control group and four experimental groups receiving 2, 4, 6, or 8 Gray (Gy) of localized electron irradiation to the kidneys. Biochemical markers of inflammation (interleukin-1 beta [IL-1β], interleukin-6 [IL-6], interleukin-10 [IL-10], tumor necrosis factor-alpha [TNF-α]) and oxidative stress (malondialdehyde [MDA], superoxide dismutase [SOD], glutathione [GSH]) were measured, and morphological changes were assessed using histological and immunohistochemical techniques (TUNEL assay, caspase-3). The study revealed a significant dose-dependent increase in oxidative stress, inflammation, and renal tissue damage. Higher doses of irradiation resulted in increased apoptosis, early stages of fibrosis (at high doses), and morphological changes in renal tissue. This study highlights the dose-dependent effects of electrons on renal structures, emphasizing the need for careful consideration of the dosage in clinical use to minimize adverse effects on renal function.

Electronic Synergistic Effects on the Stability and Oxygen Evolution Reaction Efficiency of the Mesoporous LiMn2-xMxO4 (M = Mn, Fe, Co, Ni, and Cu) Electrodes.

Stable porous manganese oxide-based electrodes are essential for clean energy generation and storage because of their high natural abundance and health safety. This investigation focuses on mesoporous LiMn2-xMxO4 (where M is Fe, Co, Ni, and Cu and x is 0, 0.1, 0.3, 0.5, and 0.67) electrodes and thin/thick films. The mesoporous electrodes and films are fabricated by coating clear and homogeneous ethanol solutions of the salts (LiNO3, [Mn(OH2)4](NO3)2, and [M(OH2)x](NO3)2) and surfactants (P123 and CTAB) and calcining at elevated temperature (denoted as F-LiMn2-xMxO4, G-LiMn2-xMxO4, and meso-LiMn2-xMxO4, respectively). The electrochemical properties, stability, and oxygen evolution reaction (OER) performance of the F/G-LiMn2-xMxO4 electrodes are investigated in alkaline media using a three electrode setup. The F-LiMn1.33M0.67O4 electrodes (where M is Mn, Fe, Co, and Ni) exhibit low Tafel slopes of 60, 43, 44, and 32 mV/dec, respectively. While all the Mn-rich and F-LiMn2-xFexO4 electrodes degrade via Mn(VI) disproportionation reaction, the 33% Co electrode shows high stability during the OER. The nickel-based electrodes are stable with as little as 15% Ni and display excellent OER performance over 25% Ni, albeit undergoing a transformation that accumulates Ni(OH)2 species on the electrode surface. Copper in the F-LiMn2-xCuxO4 electrodes is homogeneous at low Cu percentages but forms a CuO phase above 15% Cu, undergoes degradation, and displays a weak OER performance. In short, Co and Ni stabilize the F-LiMn1.33Co0.67O4 and F-LiMn1.7Ni0.3O4 electrodes, which display excellent OER performance.

Carborane-based BODIPY dyes: synthesis, structural analysis, photophysics and applications

Icosahedral boron clusters-based BODIPY dyes represent a cutting-edge class of compounds that merge the unique properties of boron clusters with the exceptional fluorescence characteristics of BODIPY dyes. These kinds of molecules have garnered substantial interest due to their potential applications across various fields, mainly including optoelectronics, bioimaging, and potential use as boron carriers for Boron Neutron Capture Therapy (BNCT). Carborane clusters are known for their exceptional stability, rigid geometry, and 3D-aromaticity, while BODIPY dyes are renowned for their strong absorption, high fluorescence quantum yields, and photostability. The integration of carborane into BODIPY structures leverages the stability and versatility of carboranes while enhancing the photophysical properties of BODIPY-based fluorophores. This review explores the synthesis and structural diversity of boron clusters-based BODIPY dyes, highlighting how carborane incorporation can lead to significant changes in the electronic and optical properties of the dyes. We discuss the enhanced photophysical characteristics, such as red-shifted absorption and emission poperties, charge and electronic transfer effects, and improved cellular uptake, resulting from carborane substitution. The review also delves into the diverse applications of these compounds. In bioimaging, carborane-BODIPY dyes offer superior fluorescence properties and cellular internalization, making them ideal for cell tracking. In photodynamic therapy, (PDT) these dyes can act as potent photosensitizers capable of generating reactive oxygen species (ROS) for targeted cancer treatment making them excellent candidates for PDT. Additionally, their unique electronic properties make them suitable candidates for optoelectronic applications, including organic light-emitting diodes (OLEDs) and sensors. Overall, carborane-BODIPY dyes represent a versatile and promising class of materials with significant potential for innovation in scientific and technological applications. This review aims to provide a comprehensive overview of the current state of research on carborane-BODIPY dyes, highlighting their synthesis, properties, and broad application spectrum.

Cascade Reactions of Alkynyl Ketones and Amides to Generate Unsaturated Oxacycles and Aromatic Carbocycles.

We describe novel amine-mediated transformation of alkynyl ketones and amides to generate 2-methylene-2H-pyrans, substituted 3-hydroxy-9H-fluoren-9-ones, and amine-incorporated arenes. These cascade processes are initiated by conjugate addition of secondary amine followed by hydrolysis of the enamine/vinylogous amide intermediates. The product distribution is highly sensitive to the steric and electronic effects of the substituents on both the alkyne moieties, the tether structure connecting them, and the nature of the amine. Alkynyl amide participates in the Alder-ene reaction favorably to generate more reactive allene amide that reacts with amine to generate amine-incorporated arene products. These metal-free cascade reactions are a useful synthetic method that can be exploited for the construction of various hetero- and carbocyclic systems.

Engineering multiple nano-twinned high entropy alloy electrocatalysts toward efficient water electrolysis

Inducing defects in high entropy alloys (HEAs) has been recognized as a promising approach for tuning surface energetics and catalytic activities. However, the comprehensive understanding and facile synthetic methods for defect-rich HEAs remain challenging. Herein, we present an interstitial-atom engineering strategy that involves interstitial atom doping to synthesize B-doped FeCoNiCuMoB HEA films containing abundant multiple nano-twin boundaries. The resulting fivefold-twinned FeCoNiCuMoB catalyst exhibits exceptional performance in alkaline hydrogen evolution reaction (HER, 26mV at -10 mA cm-2) and oxygen evolution reaction (OER, 201mV at 10mAcm-2). Notably, the two-electrode electrolyzer composed of the FeCoNiCuMoB film electrodes achieved the 10mAcm-2 at an ultralow cell voltage (1.48V) for water electrolysis, simultaneously maintaining long-term durability. Through in-situ Raman spectroscopy, X-ray absorption spectroscopy (XAS), electrochemical analyses, and density functional theory (DFT) calculations, we elucidate that the unique twin boundaries play a crucial role in tailoring surficial electronic structures. Moreover, election-rich B atoms display optimized atomic configurations, synergistically contributing to a thermodynamically favourable HER/OER pathway. This work provides a platform via interstitial-atom engineering for designing exceptional HEA catalysts, integrating planar defects and electronic effects, to enhance the efficiencies in water electrolysis applications.