Electrode Surface Research Articles

Portable Amperometric Biosensor Enhanced with Enzyme-Ternary Nanocomposites for Prostate Cancer Biomarker Detection

Enzyme-based portable amperometric biosensors are precise and low-cost medical devices used for rapid cancer biomarker screening. Sarcosine (Sar) is an ideal biomarker for prostate cancer (PCa). Because human serum and urine contain complex interfering substances that can directly oxidize at the electrode surface, rapid Sar screening biosensors are relatively challenging and have rarely been reported. Therefore, highly sensitive and selective amperometric biosensors that enable real-time measurements within <1.0 min are needed. To achieve this, a chitosan–polyaniline polymer nanocomposite (CS–PANI NC), a carrier for dispersing mesoporous carbon (MC), was synthesized and modified on a screen-printed carbon electrode (SPCE) to detect hydrogen peroxide (H2O2). The sarcosine oxidase (SOx) enzyme-immobilized CS–PANI–MC-2 ternary NCs were referred to as supramolecular architectures (SMAs). The excellent electron transfer ability of the SMA-modified SPCE (SMA/SPCE) sensor enabled highly sensitive H2O2 detection for immediate trace Sar biomarker detection. Therefore, the system included an SMA/SPCE coupled to a portable potentiostat linked to a smartphone for data acquisition. The high catalytic activity, porous architecture, and sufficient biocompatibility of CS–PANI–MC ternary NCs enabled bioactivity retention and immobilized SOx stability. The fabricated biosensor exhibited a detection limit of 0.077 μM and sensitivity of 8.09 μA mM−1 cm−2 toward Sar, demonstrating great potential for use in rapid PCa screening.

Pilot Study on the Relationship Between Different Lower Limb Raising Velocities and Trunk Muscle Contraction in Active Straight Leg Raise

Background/Objectives: The active straight leg raise requires intricate coordination between the hip, knee, pelvis, and spine. Despite its complexity, limited research has explored the relationship between lower limb raising velocity and trunk muscle motor control during an active straight leg raise in healthy individuals. This study aimed to explore the potential effects of increased lower limb raising velocity on core muscle contractions during active straight leg raises. Methods: Six healthy adult men (mean age: 24.5 ± 2.5 years) participated in this study. Electromyography signals were recorded using surface electrodes placed on the rectus abdominis, external oblique, and internal oblique/transverse abdominis muscles. The participants performed active straight leg raises at three different velocities: 3 s, 2 s, and as fast as possible (max). The electromyography data were analyzed from 250 ms before to 1000 ms after movement initiation, with muscle activity expressed as a percentage of the maximal voluntary isometric contraction. Statistical analyses were conducted using non-parametric tests, including the Friedman test for overall differences, followed by pairwise Wilcoxon signed-rank tests with Bonferroni correction for multiple comparisons (p < 0.05). Results: During the 250 ms before movement initiation, the internal oblique/transverse abdominis, external oblique, and rectus abdominis muscles showed greater activity in the max condition compared to the 3 s and 2 s conditions (Friedman test, p < 0.05), but no significant differences were found in pairwise comparisons (Wilcoxon test, p > 0.05). Similarly, during the 500 ms after movement initiation, internal oblique/transverse abdominis activity was higher in the max condition, with no significant pairwise differences observed. Conclusions: Faster lower limb raising velocities during active straight leg raise may enhance core stability by activating anticipatory and sustained internal oblique/transverse abdominis, external oblique, and rectus abdominis activity on the raised limb side. Training to promote this activation could improve dynamic stability in rapid or asymmetric movements.

Investigation of Host–Guest Interactions in 2-Ureido-4-ferrocenylpyrimidine Derivatives

In the present study, synthesis, conformational behavior, host–guest complex formation, and electrochemical properties of novel 6-substituted-2-ureido-4-ferrocenylpyrimidines were explored. A comprehensive NMR spectroscopic investigation was carried out to confirm the structure and conformational equilibrium of the ureidopyrimidines through studying the temperature- and concentration dependence of NMR spectra. Low-temperature NMR measurements were used to clarify structural changes inflicted by a 2,6-diaminopyridine guest. Association constant (Kassoc) values of host–guest complexes were calculated based on low-temperature titrations. It was shown that the introduction of a pyridin-2-yl substituent in the pyrimidine ring in host 10 induced a considerable change not only in the conformational equilibrium of the host itself but also in that of the host–guest complex. Geometries and relative stabilities of the conformers of host 10 as well as its host–guest complexes were determined by quantum chemical calculations. Electrochemical behavior of ureidopyrimidine hosts and host–guest complexes was investigated by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) measurements. Two ureidopyrimidine derivatives were immobilized on the surface of spectral graphite electrodes, and their electrochemical response on the addition of 2,6-diaminopyridine was compared. These results also supported the importance of the pyridin-2-yl substituent in the efficient sensing of the guest.

Chitosan/platinum nanocubes/Mn(TPDCA)2-modified glassy carbon electrodes for the electrochemical quantification of amlodipine in unprocessed plasma samples

A novel electrochemical probe is developed to detect amlodipine (AMD) in unprocessed plasma samples. The fabrication process involves the synthesis of platinum nanocubes (Pt NCs) and Mn(TPDCA)2 complexes, which are then immobilized them onto the glassy carbon electrode (GCE) surface. The developed electrochemical probe demonstrates exceptional detection performance, with a wide dynamic range, outstanding selectivity, and commendable reproducibility. The linear range and lower limit of detection of the developed method are 53 nM-3.5 µM and 53 nM, respectively. Electrochemical experiments have been conducted to study the kinetics of electrooxidation on the modified electrode, revealing that the process is diffusion-controlled. Furthermore, method validation studies are performed to assess the accuracy, precision, and selectivity of the sensor, demonstrating excellent performance in all these aspects. Consequently, it can be concluded that the sensor is highly suitable for practical applications in drug analysis.

Novel Methodology of General Scaling-Approach Normalization of Impedance Parameters of Insertion Battery Electrodes – Case Study on Ni-Rich NMC Cathode: Part II. Detailed Analysis Using a Transmission Line Model

Abstract Here, we extend the general approach shown in PART-1 to a detailed analysis of the measured data using our previously published physics-based transmission line model (TLM). We construct general relationships between the TLM parameters and the electrode mass. We then systematically check the scaling properties of all model parameters by fitting the measured impedance responses of 8 NMC-NMC cells with different masses (thicknesses) of NMC cathodes ranging from 2.3 to 58.5 mg per 2 cm2 of geometric electrode surface. We consider in detail all deviations of the measured spectra from the idealized spectra predicted by the model. Among other things, we discuss the high-frequency inductive effects, the ambiguities in the analysis of the low-frequency diffusion phenomena, and the effects of non-ideal capacitive properties (the so-called constant-phase elements) on the shape of the measured spectra. We also report an unexpected additional feature observed in measurements on thin (light) electrodes: a diffusion arc due to the diffusion of lithium in the electrolyte in the micropores of the NMC aggregates in the material used. Finally, we present a detailed dependence of all model parameters on the mass (thickness) of the electrode and discuss the potential practical significance of such an analysis.

MXene Nanoconfinement of SAM-Modified Molecularly Imprinted Electrochemical Biosensor for Point-of-Care Monitoring of Carcinoembryonic Antigen.

The high rate of cancer worldwide and the heavy costs imposed on governments and humanity have always motivated researchers to develop point-of-care (POC) biosensors for easy diagnosis and monitoring of cancer treatment. Herein, we report on a label-free impedimetric biosensor based on Ti3C2Tx MXene and imprinted ortho-phenylenediamine (o-PD) for the detection of carcinoembryonic antigen (CEA), a biomarker for various cancers surveillance, especially colorectal cancer (CRC). Accordingly, MXene was drop-casted on the surface of a disposable silver electrode to increase the sensitivity and create high-energy nanoareas on the surface, which are usable for protein immobilization and detection. A self-assembled monolayer (SAM) was exploited for oriented CEA immobilization on the MXene-modified electrode. The monomer-protein interaction and successful protein removal were confirmed by molecular docking and atomic force microscopy (AFM) investigations to evaluate the quality of the fabricated molecularly imprinted polymer (MIP). Also, the role of MXene in increasing the electrical field inside the nanoareas was simulated using COMSOL Multiphysics software. A suitable limit of detection (9.41 ng/mL), an appropriate linear range of detection (10 to 100 ng/mL) in human serum, and a short detection time (10 min) resulted from the use of SAM/MIP next to MXene. This biosensor presented outstanding repeatability (97.60%) and reproducibility (98.61%). Moreover, acceptable accuracy (between 93.04 and 116.04%) in clinical serum samples was obtained compared with immunoassay results, indicating the high potential of our biosensor for real sample analysis. This biomimetic and disposable sensor provides a cost-effective method for facile and POC monitoring of cancer patients during treatment.

A Signal-On Microelectrode Electrochemical Aptamer Sensor Based on AuNPs–MXene for Alpha-Fetoprotein Determination

As a crucial biomarker for the early warning and prognosis of liver cancer diseases, elevated levels of alpha-fetoprotein (AFP) are associated with hepatocellular carcinoma and germ cell tumors. Herein, we present a novel signal-on electrochemical aptamer sensor, utilizing AuNPs–MXene composite materials, for sensitive AFP quantitation. The AuNPs–MXene composite was synthesized through a simple one-step method and modified on portable microelectrodes. As signal molecules, AFP aptamers were conjugated with methylene blue (MB) and immobilized on the electrode surface. When interacting with AFP, conformational changes in the aptamer–target complex caused MB to approach the electrode, and the electrochemical signal was enhanced through signal-on mechanisms. The developed sensor demonstrated high sensitivity and selectivity for AFP, with a log-linear relationship defined as 1–300 ng/mL, and the LOD was 0.05 ng/mL (S/N = 3). The method was applied to laboratorial and real clinical samples and presented satisfactory selectivity, reproducibility, and long-term stability. The proposed high-performance sensor highlights the potential of electrochemical aptamer sensors in improving the warning capabilities in disease management.

3D Printing of Graphene Aerogel Microspheres to Architect High-Performance Electrodes for Hydrogen Evolution Reaction.

The hydrogen evolution reaction (HER) efficiency is highly dependent on the electrocatalysts microstructure and the macrostructure of the electrodes. Herein, the graphene aerogel microspheres loaded with well-dispersed ultrafine Ni/Co nanoparticles catalyst is prepared through electro-spraying, in-situ crosslinking, freeze-drying, and pyrolysis, and then is utilized to print the HER electrode via direct ink writing (DIW). The obtained graphene-based aerogel microspheres possess peculiar cabbage-like mesoporous structures which allow ready access of reaction species to active sites, optimal mass transfer, and proton diffusion within the microspheres. DIW 3D printing achieves the ordered control on the periodic lattice macro-geometry and thus facilitates the fast gas bubble evolution and release from the electrode surface. The as-fabricated 3D electrode possesses a low overpotential of 341 mV at 10 mA cm-2, a decrease by 31.5% compared to 3D printed electrode directly from 2D graphene, and a low Tafel slope of 119.1 mV dec-1, 40% lower than that of the electrodes fabricated via directly casting the aerogel microspheres. Furthermore, the 3D-printed electrode of aerogel microspheres displays good HER stability. This work provides a good approach for constructing high-performance HER electrodes through 3D printing of graphene aerogel microspheres.

Ultrasensitive Electrochemiluminescence Aptamer Sensor Based on Ru@ZIF-Pd Cathode for Acetamiprid Detection.

Ru(bpy)32+ is commonly used in electrochemiluminescence (ECL) as a conventional luminophore. However, Ru(bpy)32+ can leak off the electrode surface, resulting in a reduced ECL signal. In this work, a nanocube composite material Ru@ZIF was prepared by incorporating doping luminescent Ru(bpy)32+ into the skeleton of Zn(II) ions and 2-methylimidazole (2-MI), and the ECL probe Ru@ZIF-Pd was prepared by in situ growth of Pd nanoparticles (Pd NPs). Potassium persulfate (K2S2O8) was used as a coreactant to investigate the cathodic ECL behavior. The ZnCoCH@MXene-Au (ZC@T-Au) was used as a coreactant accelerator to promote the production of SO4•-, which effectively amplified the ECL intensity of Ru@ZIF-Pd. Under optimal experimental conditions, we successfully constructed an aptamer ECL sensor, which achieves an accurate detection of acetamiprid from 0.1 fM to 10 μM with a detection limit of 0.029 fM. It provides a potential idea for the detection of pesticide residues in food.

Preparation of Ionic Polymer–Metal Composites Using Copper Electrodes via Magnetron Sputtering

The effective treatment of the surface electrode is the core technology of an ionic polymer–metal composite (IPMC), and its preparation significantly affects the driving performance of the IPMC. Copper, which is inexpensive and has excellent electrical conductivity, was selected as the surface electrode material, and copper electrode IPMCs (Cu-IPMCs) were prepared via magnetron sputtering. Orthogonal experiments were performed to optimize the parameters of the preparation process. The indices of the deformation angle and surface resistance were used, and the sample electrodes’ surface morphology and elemental content were analyzed. The results showed that sputtering pressure was the major factor affecting two indices. The Cu-IPMC, prepared at a sputtering pressure of 0.9 Pa, sputtering time of 35 min, argon flow rate of 30 sccm, and sputtering power of 150 W, had a more minor surface resistance and a larger deformation angle under continuous direct current boosting. It required a sputtering time of 1.2 h, which was more than 10 times shorter than its chemically plated counterpart. It exhibited surface resistance in the 2–3 Ω/cm range, which was 23 times smaller than chemically plated platinum.

The Behaviors of Interfacial Nanobubbles on Flat or Rough Electrode Surfaces in Electrochemistry.

The existence of interfacial nanobubbles on electrode surfaces is thought to block the active area, leading to a considerable decrease in the energy conversion efficiency. Gaining insight into how bubbles form on electrodes will be beneficial for designing effective electrochemical cells and enhancing the electrolytic efficiency. In this article, molecular dynamics (MD) simulations are employed to make a systematic comparison of behaviors of interfacial nanobubbles on both flat and rough electrode surfaces in electrochemistry. On a flat electrode surface, bubble nucleation can be categorized into single-site and multisite nucleation, influenced by the electrode sizes and electrolytic rates. The various rates of gas production result in three different scenarios for single-site nucleation: "growth-growth," "growth-shrinking," and "growth-stabilization" behaviors. On a rough one, bubbles are pinned at an early stage. Either through cooperative release or self-release, the bubbles continue to grow until the influx and outflux gas of the bubble reach an equilibrium. In addition, the evolutionary mechanism of interface nanobubbles was discussed on a rough nanoelectrode surface. Based on the dynamic equilibrium mechanism, a theoretical relationship between contact angle and base diameter of equilibrium interfacial nanobubbles was developed. The theoretical model can qualitatively describe the simulation observation of how bubble's shape depends on the electrode surface morphology.

Solvation Environment and Interface Dynamics of Li2B12H12 and Li2B12F12 Electrolytes Uncovered by Theory and Operando Optical and FTIR Spectroelectrochemistry.

In this work, we evaluated two closo-borate salts (Li2B12H12 and Li2B12F12) in propylene carbonate from theoretical and experimental perspectives to understand how the coordination environment influences their spectroscopic and electrochemical properties. The coordination environments of the closo-borate salts were modeled via density functional theory (DFT) and molecular dynamics (MD). Vibrational spectra calculated from the predicted coordination environments are in agreement with experimentally measured steady-state FTIR data. This theoretical investigation also suggested that Li2B12F12 would possess a higher ionic conductivity than Li2B12H12, which was corroborated experimentally. Additionally, an electrochemical cell was designed and fabricated that enabled operando optical and FTIR spectroelectrochemical (OP-IR-SEC) measurements. This allowed for the simultaneous measurement of the relative changes of species at a lithium electrode-liquid electrolyte interface and the visualization of lithium plating at the electrode surface. This technique could provide new chemical insights and potentially link optical changes at the electrode-electrolyte interface to specific chemical species in similar electrochemical systems. The Li2B12F12 electrolyte was found to have a higher thermal stability, which may find utility in applications for batteries that are subject to high-temperature conditions.

Advanced characterization of confined electrochemical interfaces in electrochemical capacitors.

The advancement of high-performance fast-charging materials has significantly propelled progress in electrochemical capacitors (ECs). Electrochemical capacitors store charges at the nanoscale electrode material-electrolyte interface, where the charge storage and transport mechanisms are mediated by factors such as nanoconfinement, local electrode structure, surface properties and non-electrostatic ion-electrode interactions. This Review offers a comprehensive exploration of probing the confined electrochemical interface using advanced characterization techniques. Unlike classical two-dimensional (2D) planar interfaces, partial desolvation and image charges play crucial roles in effective charge storage under nanoconfinement in porous materials. This Review also highlights the potential of zero charge as a key design principle driving nanoscale ion fluxes and carbon-electrolyte interactions in materials such as 2D and three-dimensional (3D) porous carbons. These considerations are crucial for developing efficient and rapid energy storage solutions for a wide range of applications.

Microneedle Electrode Patch Modified with Graphene Oxide and Carbon Nanotubes for Continuous Uric Acid Monitoring and Diet Management in Hyperuricemia.

Hyperuricemia is a common disorder induced by purine metabolic abnormality, which will further cause chronic kidney disease, cardiovascular disease, and gout. Its main pathological characteristic is the high uric acid (UA) level in the blood, so that the detection of UA is highly important for hyperuricemia diagnosis and therapy. Herein, we report a biocompatible and minimally invasive microneedle electrode patch (MEP) for continuous UA monitoring and diet management in hyperuricemia. The composite of graphene oxide and carboxylated multiwalled carbon nanotubes was modified on the microneedle electrode surface to enhance its sensitivity, selectivity, and stability, thus realizing the continuous detection of UA in the interstitial fluid to accurately predict the UA level in the blood. This further allowed us to study the hypouricemic effect of anthocyanins on the hyperuricemia model mouse. It was found that anthocyanins extracted from blueberry can effectively inhibit the activity of xanthine oxidase to reduce the production of UA. The UA level of hyperuricemia model mice fed with anthocyanins is ∼1.7 fold lower than that of the control group. We believe that this MEP offers enormous promise for continuous UA monitoring and diet management in hyperuricemia.

Experimental analysis of a rotating cylinder electrode reactor: Hydrodynamics and mass transport

AbstractThis report deals with the hydrodynamic and mass transport characterization in an rotating cylinder electrode (RCE) in continuous and batch configuration employing relatively simple techniques like obtaining the mixing time, polarization, and residence time distribution (RTD) curves. For batch configuration, the limiting current and Sh values were higher than for continuous configuration, indicating that the mixing pattern is influenced by possible flow inhomogeneities during the operation as a continuous mixing stirrer. This could diminish the amount of electroactive reactant that reaches the electrode surface, due to the possible shrinking of recirculation zones during the rotation of the cylindrical stirrer, forming channeling and by‐pass flow zones. These results could evidence the existence of slight deviations from the ideal mixer and other non‐ideality flow zones associated with the width of curves upon analyzing age function through RTD curves, at the different flow rates employed in continuous configurations.

Hydride-Induced Reconstruction of Pd Electrode Surfaces: A Combined Computational and Experimental Study.

Designing electrocatalysts with optimal activity and selectivity relies on a thorough understanding of the surface structure under reaction conditions. In this study, experimental and computational approaches are combined to elucidate reconstruction processes on low-index Pd surfaces during H-insertion following proton electroreduction. While electrochemical scanning tunneling microscopy clearly reveals pronounced surface roughening and morphological changes on Pd(111), Pd(110), and Pd(100) surfaces during cyclic voltammetry, a complementary analysis using inductively coupled plasma mass spectrometry excludes Pd dissolution as the primary cause of the observed restructuring. Large-scale molecular dynamics simulations further show that these surface alterations are related to the creation and propagation of structural defects as well as phase transformations that take place during hydride formation.

Effect of High Voltage Electrode Material on Methanol Synthesis in a Pulsed Dielectric Barrier Discharge Plasma Reactor

Plasma methanol synthesis from captured CO2 and renewable H2 is one of the most promising technologies that can drastically lower the carbon footprint in methanol production, but the associated high energy costs make it less competitive. Herein, we investigated the impact of the high-voltage electrode configuration on methanol formation. The effect of electrode materials Cu, Al, and stainless steel (SS) SUS304 on CO2 hydrogenation to methanol using a temperature-controlled pulsed dielectric barrier discharge (DBD) plasma reactor was examined. The electrode surface area (ESA) was varied from 157 mm2 to 628 mm2 to determine the effect on discharge characteristics and the overall influence of plasma surface reactions on methanol production. The Cu electrode showed superior methanol synthesis performance (0.14 mmol/kWh) which was attributed to its catalytic activity function, while the Al electrode had the least production (0.08 mmol/kWh) ascribed to the excessive oxide coating on its surface, passivating its ability to promote methanol synthesis chemical reactions. In all electrode materials, the highest methanol production was achieved at 157 mm2 ESA at a constant applied voltage. Lastly, the plasma charge concentration per discharge volume was determined to be an important parameter in fine-tuning the DBD reactor to enhance methanol synthesis.

Impedimetric Sensor for SARS-CoV-2 Spike Protein Detection: Performance Assessment with an ACE2 Peptide-Mimic/Graphite Interface

The COVID-19 pandemic has prompted the need for the development of new biosensors for SARS-CoV-2 detection. Particularly, systems with qualities such as sensitivity, fast detection, appropriate to large-scale analysis, and applicable in situ, avoiding using specific materials or personnel to undergo the test, are highly desirable. In this regard, developing an electrochemical biosensor based on peptides derived from the angiotensin-converting enzyme receptor 2 (ACE2) is a possible answer. To this end, an impedimetric detector was developed based on a graphite electrode surface modified with an ACE2 peptide-mimic. This sensor enables accurate quantification of recombinant 2019-nCoV spike RBD protein (used as a model analyte) within a linear detection range of 0.167–0.994 ng mL−1, providing a reliable method for detecting SARS-CoV-2. The observed sensitivity was further demonstrated by molecular dynamics that established the high affinity and specificity of the peptide to the protein. Unlike other impedimetric sensors, the herein presented system can detect impedance in a single frequency, allowing a measure as fast as 3 min to complete the analysis and achieving a detection limit of 45.08 pg mL−1. Thus, the proposed peptide-based electrochemical biosensor offers fast results with adequate sensitivity, opening a path to new developments concerning other viruses of interest.

Leveraging Interfacial Electric Field for Smart Modulation of Electrode Surface in Nitrate to Ammonia Conversion

AbstractThe efficiency of nitrate reduction reaction (NO3RR) at low nitrate concentration is predominantly hindered by the poor affinity of nitrate ions and competitive hydrogen evolution reaction (HER), particularly in neutral and acidic media. Here, an innovative strategy to leverage the interfacial electric field (IEF) is introduced to boost the NO3RR performance. By in situ constructing tannic acid‐metal ion (TA‐M2+) crosslinked structure on the electrode surface, the TA‐M2+‐CuO NW/Cu foam sample exhibits an exceptional Faraday efficiency of 99.4% at −0.2 V versus reversible hydrogen electrode (RHE) and 83.9% at 0.0 V versus RHE under neutral and acidic conditions, respectively. The computational studies unveil that the TA‐Cu2+ complex on the CuO (111) plane induces the increasing concentration of nitrate at the interface, accelerating NO3RR kinetics over HER via the IEF effect. This interfacial modulation strategy also contributes the enhanced ammonia production performance when it is employed on commercial electrode materials and flow reactors, exhibiting great potential in practical application. Overall, combined results illustrated multiple merits of the IEF effect, paving the way for future commercialization of NO3RR in the ammonia production industry.

An Interstitial Boron Inserted Metastable Hexagonal Rh Nanocrystal for Efficient Hydrogen Oxidation Electrocatalysis

AbstractConstructing metastable phase structure plays an important role in changing the physicochemical properties and improving the catalytic performance of nanocrystals. Unfortunately, the synthesis of metastable phase metallic nanocrystals is highly challenging, mainly due to the thermodynamically unstable ground‐state. Here, we report a synthesis of unconventional metastable hexagonal rhodium nanocrystal (Bint−Rhhcp/C) via interstitial boron insertion. The insertion of boron atoms into the interstitial sites of cubic Rh lattice not only induces the atomic arrangements from face‐centered cubic (fcc) to hexagonal close‐packed (hcp), but also stabilizes the metastable hexagonal Rh structure. Benefiting from the phase transition and interstitial boron doping, the Bint−Rhhcp/C catalyst exhibits remarkable catalytic performance toward hydrogen oxidation reaction (HOR) under alkaline media, with a mass activity of 1.413 mA μgPGM−1. Experimental measurements including in situ surface‐enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) calculations indicate that the strengthened adsorption of hydroxyl species on the electrode surface of Bint−Rhhcp/C is responsible for the reconstruction of interfacial water structure and increased water proportions in the gap region in the electric double layers. As a result, the increased water connectivity and hydrogen bond network facilitate high‐efficiency hydrogen transfer across the interface, thereby boost the alkaline HOR performance.