Carboxylic Research Articles

Photocurable Thiol-Ene/Nanocellulose Elastomeric Composites for Bioinspired and Fluorine-Free Superhydrophobic Surfaces.

Artificially prepared superhydrophobic surfaces toward a self-cleaning "lotus effect" and anticontamination performance have become critically important in the past few years. However, most approaches to create the required topology with a hierarchical roughness comprise several manufacturing steps of varying practicality. Moreover, the desired low surface energy is in most cases achieved with fluorinated moieties that are currently criticized due to biological and environmental hazards. In this work, rapidly photocuring but weak thiol-ene resins were reinforced with cellulose nanofibrils (CNFs) to replicate lotus leaves via one-step UV nanoimprint lithography. The CNFs were surface-modified using countercation exchange of carboxyl groups and grafting of thiol and methacrylate functionalities. The formulation methodology resulted in free-flowing, shear-thinning composite resins without surfactants or dispersants. The rheological and photo-cross-linking behavior of the resins, the thermal stability, the mechanical performance, and the hydrophobicity of the cured composites were characterized. Notably, the surface modifications increased the as received fibril diameter (1.9 ± 0.6 nm) by 1.6-2.3 nm and raised the fibril-resin compatibility. The resins underwent rapid polymerization and the high thermal stability of thiol-enes was retained. The methacrylated nanofibrils (10 vol %) significantly strengthened the rubbery network, outperforming the neat thiol-ene polymer in terms of hardness (3.4×), reduced modulus (5.8×), and wear resistance (>100×). Moreover, the surface of lotus-texturized composites was superhydrophobic with a water contact angle of 155°, higher than that of the neat polymer (147°), and was self-cleaning. These CNF composite resins are compatible with fast-cure processes such as 3D printing and roll-to-roll processing, are exempt of fluorine or any other hydrophobization treatment, and are extremely wear-resistant.

Functionalization of Titania Nanoparticles with Carboxyl Groups for Improved Mechanical Performance of Hydroxyl Terminated Polybutadiene (HTPB) Composites

Functionalization of Titania Nanoparticles with Carboxyl Groups for Improved Mechanical Performance of Hydroxyl Terminated Polybutadiene (HTPB) Composites

Boosting uranium extraction from Seawater by micro-redox reactors anchored in a seaweed-like adsorbent

Efficient extraction of uranium from seawater is expected to provide virtually infinite fuel sources to power nuclear reactors and thus enable sustainable development of nuclear energy. The extraction efficiency for uranium greatly depends on the availability of active adsorption sites on the adsorbents. Maximization of the utilization rate of the binding sites in the adsorbent is vital for improving adsorption capacity. Herein, micro-redox reactors functioned by Cu(I)/Cu(II) conversion are constructed internally in an adsorbent bearing both amidoxime and carboxyl groups to induce active regeneration of the inactivated binding sites to enhance uranium capture. This adsorbent has high adsorption capacity (962.40 mg-U/g-Ads), superior anti-fouling ability as well as excellent uranium uptake (14.62 mg-U/g-Ads) in natural seawater after 56 days, placing it at the top of high-performance sorbent materials for uranium harvest from seawater.

Greenness assessment of a molecularly imprinted polymeric sensor based on a bio-inspired polymer

Methyldopa, a synthesized dopamine substitute with phenolic, amine, and carboxylic groups, was used to create a selective molecular imprinted polymer (MIP) for detecting formoterol fumarate dihydrate (FFD), a long-acting beta2-agonist for asthma and COPD. The bio-inspired polymer (MD) was electro-grafted onto a pencil graphite electrode (PGE) using cyclic voltammetry in a phosphate buffer (pH 6.5). An indirect method involving a redox probe (ferrocyanide/ferricyanide) and differential pulse voltammetry measured FFD binding to the MIP’s 3D cavities. The sensor showed a linear response range from 1 × 10⁻⁹ M to 2 × 10⁻¹⁰ M, with a detection limit of 1.7 × 10⁻¹¹ M. The polymethyldopa (PMD) and FFD interaction was assessed by UV spectroscopy, and the method was validated per ICH guidelines. Green analytical approaches, including RGB and GAPI, were also implemented. The goal was to use advances in molecularly imprinted polymers to develop a more precise and selective electrochemical sensor for FFD quantification.

Improved electrochemical properties of lithium-ion batteries prepared using oxygen plasma-treated needle coke-based anode materials

High-rate capacities and specific capacities are important indicators for evaluating lithium-ion battery (LIB) anodes. To improve the electrochemical properties of needle coke-based anode materials, oxygen plasma treatment was used. Various analyses were performed to assess the impact of the oxygen plasma treatments on the chemical, structural, and morphological properties of the needle coke samples. The oxygen plasma treatment effectively introduced oxygen functional groups (hydroxyl, ether, carbonyl, and carboxyl groups) without significant structural changes to the needle coke samples, and the O/C ratio increased to 0.23 after the plasma treatment. The synergistic effect of the increased oxygen content and the defects formed on the surface by plasma treatment improved the electrochemical properties of the needle coke-based anodes. The discharge capacity of the oxygen plasma-treated needle coke-based LIBs increased to a maximum of 20.48 %, and the retention rate was 74.51 % at 5 C with respect to 0.1 C. The oxygen plasma-treated needle coke material prepared via a simple method could have an important role in improving the rate capacities and specific capacities of LIBs.

Excitation Dependent Multiemissive Behaviour of Triimidazole Carboxylic Acid anti‐Kasha Luminophore and its Mononuclear Metal Complexes

Materials based on small molecules characterized by multi‐component short and long‐lived emissive behaviour are extremely desirable for various applications. The derivative of cyclic triimidazole (TT) functionalized with a carboxylic group, namely TT‐COOH, is isolated, investigated and used as coordinative ligand to obtain a series of isomorphous mononuclear complexes of general formula [M(TT‐COO)2(H2O)2] (M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)). Crystals of TT‐COOH display aggregation induced enhanced emission (AIEE) comprising dual fluorescence and dual phosphorescence of molecular origin together with an aggregation induced long lived, low energy phosphorescence. Emissive features are retained in crystals of the Zn(II) and Cd(II) complexes, where the metal plays the role of an external heavy atom perturber, but strongly quenched in the others. The mechanisms involved in the photophysics of TT‐COOH and its metal complexes have been disclosed thanks to combined structural, spectroscopic and computational investigations which reveal the presence of anti‐Kasha emissions.

Deciphering Spectroscopic Signatures of Competing Ca2+ - Peptide Interactions.

Calcium-protein interactions are of paramount importance in biochemistry. They are a key element in a number of biological processes, such as neuronal signaling. Therefore, an understanding of the interaction at the molecular level is highly desirable. Here, we study the zwitterionic model peptide l-alanyl-l-alanine (2Ala), which has two distinct and competing binding sites for Ca2+: The carbonyl of the peptide bond and the C-terminus, the carboxylate group. We perform linear and two-dimensional IR spectroscopy experiments and find that the spectroscopic signatures of both moieties in the IR spectra change in amplitude and peak position upon the addition of CaCl2: A blueshift of the asymmetric carboxylate band and a redshift for the amide I mode. Ab initio molecular dynamics simulations confirm the direct interaction of the Ca2+ ion at both the carboxylate and the amide CO site leading to different spectral responses. The blueshift of the asymmetric carboxylate band is caused by a localization of the charge, leading to a decoupling of the CO stretching modes of the carboxylate group. The slight redshift of the amide I mode of 2Ala upon the addition of CaCl2 contrasts the blueshift that has been observed for isolated amide motifs, such as N-methylacetamide (NMA). This difference is caused by the smaller number of water molecules being replaced by the Ca2+ ion for 2Ala's amide compared to less sterically hindered, isolated amide carbonyls, in conjunction with vibrational Stark effects. Our results highlight the importance of considering potential competing binding sites, such as the amide CO backbone, the termini and residues, as well as the nature of the hydration of both peptide and ion, when exploring ions' interacting with small peptides and larger proteins.

Sorption thermodynamic and kinetic study of Cu(II) onto modified plant stem bark.

In this study, four types of "Juá" stem barks (Ziziphus joazeiro) were investigated for the removal of Cu(II) from aqueous solutions. The tested samples included natural coarse barks, and barks washed with water, ethanol-water, and NaOH solutions. The solvent-modified materials simulated the waste of the industrial extraction of saponins from bark. The valorization of these processing residues as sorbents was evaluated. The NaOH-washed sorbent exhibited the highest sorption capacity for Cu(II) (maximum sorption capacity 32mgg-1). Ion exchange process between copper and exchangeable surface cations and electrostatic attraction of copper with carboxylate and phenolate groups were identified as the primary sorption mechanisms. Desorption tests revealed that a large portion of the metal sorbed (80%) was easily released from the sorbent thus suggesting, in line with the proposed mechanisms, the existence of weak sorbate-sorbent interactions. The sorptive process was found to be exothermic (∆H° = - 48.1 ± 13.5kJ.mol-1) and thermodynamically favorable at lower temperatures.

Understanding CO adsorption in MOFs combining atomic simulations and machine learning

This study introduces a computational method integrating molecular simulations and machine learning (ML) to assess the CO adsorption capacities of synthesized and hypothetical metal–organic frameworks (MOFs) at various pressures. After extracting structural, chemical, and energy-based features of the synthesized and hypothetical MOFs (hMOFs), we conducted molecular simulations to compute CO adsorption in synthesized MOFs and used these simulation results to train ML models for predicting CO adsorption in hMOFs. Results showed that CO uptakes of synthesized MOFs and hMOFs are between 0.02–2.28 mol/kg and 0.45–3.06 mol/kg, respectively, at 1 bar, 298 K. At low pressures (0.1 and 1 bar), Henry’s constant of CO is the most dominant feature, whereas structural properties such as surface area and porosity are more influential for determining the CO uptakes of MOFs at high pressure (10 bar). Structural and chemical analyses revealed that MOFs with narrow pores (4.4–7.3 Å), aromatic ring-containing linkers and carboxylic acid groups, along with metal nodes such as Co, Zn, Ni achieve high CO uptakes at 1 bar. Our approach evaluated the CO uptakes of ~ 100,000 MOFs, the most extensive and diverse set studied for CO capture thus far, as a robust alternative to computationally demanding molecular simulations and iterative experiments.

A Comparative Study of Structural Contribution to Biocidability via Immobilization of Fluorinated and Nonfluorinated Quaternary Ammonium Salts on Top Surfaces.

Higher biocidability of fluorinated quaternary ammonium salt (QAS) is usually contributed to its preferential segregation to the surface to better contact with and kill bacteria. However, whether its structure also elicits better performance is still unclear. Herein, the same amount of a fluorinated QAS and its nonfluorinated counterpart are both immobilized on the top surface to eliminate the effect of concentration distribution to only study their structure-biocidability relationship. Briefly, the fluorinated and nonfluorinated QASs were synthesized by quaternization of N,N-dimethylethanolamine with 2-(perfluorooctyl)ethyl bromide that was prepared by bromination of 2-(perfluorooctyl)ethanol and 1-bromodecane, respectively. Polystyrene (PS) and diblock copolymer poly(styrene)-b-poly(tert-butyl acrylate) (PS-PtBA) were successively spin coated on SiO2 wafers at different concentrations to form bilayer structures that have a PS base layer and a PtBA top layer. The tert-butyl acrylate groups of the PtBA layer of 0.9 nm were converted to carboxylic acid groups with trifluoroacetic acid for respective esterification with the two hydroxy-containing QASs. It was observed that the fluorinated and nonfluorinated surfaces fabricated at the maximum comparable esterification yield of 63.5% fully eradicated ∼104 CFU of Staphylococcus aureus and Escherichia coli in 120 and 150 min, respectively, indicating that the fluorocarbon chain is more biocidal through better interpenetration into bacterial membranes. Immobilization of a functionality on top surface provides a universal strategy to study its structural contribution to activity without interference of the concentration distribution.

Construction of a Fluorescence/Phase-Change Dual-Mode Sensor Based on Carbon Dots/Poly(acrylic acid) for Highly Selective and Sensitive Detection of Ferric Ions.

Fe3+ is one of the crucial metal ions in biological systems, and its excess or deficiency in the body can trigger various diseases, posing a serious threat to human health. Moreover, improper handling or disposal of Fe3+ can lead to water pollution, thereby harming the environment. Therefore, the development of highly selective and sensitive Fe3+ detection probes is particularly urgent. In this paper, a dual-mode sensor based on sol-gel and fluorescence signal responses was developed for the visual detection of Fe3+. The visual sensing method based on the simultaneous response of Fe3+-triggered dual signals can minimize the interference from false-positive signals and enhance detection accuracy. The dual-mode sensor, denoted as PAA@CDs, was constructed by incorporating high-brightness (high fluorescence emission intensity) green-yellow carbon dots (CDs) into poly(acrylic acid) (PAA), which possesses a large number of carboxyl functional groups. Based on the interaction of Fe3+ with the surface functional groups of CDs, nonfluorescent complexes are formed, leading to nonradiative electron transfer, which induces fluorescence quenching and produces a fluorescence signal visible to the naked eye. Additionally, the interaction of Fe3+ with the carboxyl groups of PAA triggers the cross-linking of PAA, causing a sol-gel phase change signal. Consequently, the PAA@CDs exhibit a dual-response signal in Fe3+ detection. Based on the fluorescence method, the linear detection range of PAA@CDs for Fe3+ is 0.05-2.60 mM with a limit of detection (LOD) of 5.14 μM. Meanwhile, using the sol-gel method, the linear detection range is 0.02-2.20 mM, and the LOD is 42.5 μM. Furthermore, the PAA@CDs probes can be successfully applied to the detection of Fe3+ in real water samples, demonstrating their potential value in the analysis of real samples containing multiple ions.

Conversion of waste polystyrene into porous adsorbents for efficient removal of hazardous pollutants: Adsorption properties and adsorption mechanism

Herein, the porous adsorbent material (PS-SAS) was prepared by introducing a large number of carboxyl groups on the benzene ring of waste polystyrene (WPS) by Friedel-Crafts acylation reaction using succinic anhydride as the modifying group, followed by further alkaline modification, and was used for the removal of hazardous dye and heavy metal ion. The chemical structure and surface morphology of the prepared adsorbent were assessed via Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), optical microscope (OM), Brunauer–Emmett–Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The prepared adsorbent gave highly efficient separation performance towards malachite green (MG) and Cu2+ with corresponding maximum sorption capacities of 2231 mg/g and 156 mg/g at 298 K. The experimental data indicated that the sorption process followed the Langmuir adsorption isotherm and the pseudo-second-order kinetic model. Moreover, thermodynamic studies also demonstrated that the sorption process occurred spontaneously. The adsorption mechanisms of the adsorbent for MG include hydrogen bonding, electrostatic attraction, n-π interactions, and π-π interactions, while for Cu2+ via electrostatic attraction, ion exchange, and complexation. Furthermore, the selective adsorption, regeneration, dynamic sorption, and simulated wastewater experiment demonstrated that the adsorbent is a promising adsorbent. And phytotoxicity test proved that the prepared adsorbent can effectively reduce the toxicity of dye and metal ions. In summary, the transformation of waste polystyrene into an adsorbent represents a promising solution for water purification.

Construction of cellulose 3D network composite membrane supported by hydroxylated boron nitride with high surface charge density to achieve high-efficiency osmotic energy harvesting

Ion selectivity and mechanical persistence are critical properties of membranes to harvest osmotic energy. Two-dimensional nanofluidic membranes have been studied to enhance those properties, whereas they are usually constrained due to unsatisfactory mass transfer performances. Herein, a ternary three-dimensional membrane (T-CNF/PVDF/BN-OH composite membrane, abbreviated as CPBN) with distinct mechanical strength and high surface charge density (−2.65 mC·m−2) for sustainable osmotic energy harvesting is designed. In CPBN, negatively charged TEMPO-oxidized cellulose acts as a scaffold and constructs a 3D network structure together with the hydroxylated boron nitride (BN-OH) via a self-assembly process. The affluent nano-constrained ion channels effectively enhance the controllability and effectiveness of ion transport. The abundant ionized carboxyl groups extremely facilitate the selective transportation of the cations, while the BN-OH also assist this process, promoting the one-way transmission of cations in the channel. Additionally, the participation of PVDF polymer forms a network interlock structure, which significantly improves mechanical performances and stability in water. The membrane demonstrates a high power density (10.6 W/m2), measured in minimal testing areas, and an average power density around 1 W/m2 in larger areas, with an energy conversion efficiency of up to 30.7 %. This study provides a promising exploration of replacing traditional two-dimensional layered structure with three-dimensional network structure of cellulose for osmotic energy harvesting.

Exploring the relationship between lignin structure and antioxidant property using lignin model compounds

Lignin has a natural polyphenol structure that is expected to replace chemically synthesized antioxidants as a native antioxidant with biodegradable and convenient source characteristics. However, the improvement of the antioxidant property of lignin and its application as an antioxidant are still somewhat limited due to the lack of understanding of the relationship between specific lignin structures and antioxidant property. Therefore, the study of the relationship between lignin structure and antioxidant property is crucial to realize the high-quality application of lignin. In this experiment, the scavenging ability of free 1,1-diphenyl-2-picrylhydrazyl (DPPH·) radicals was determined for different grades of acetylated tannins, typical lignin model compounds and different structural units of milled wood lignin to investigate the relationship between lignin structure and antioxidant property. Based on the experimental results, some structure-activity relationships were proposed and the mechanism of the antioxidant property of lignin was discussed. The number of phenolic hydroxyl groups was linearly and positively correlated with antioxidant property, and the scavenging of DPPH radicals increased significantly with the increase in the number of methoxy groups in the model compounds. Moreover, aldehyde and carboxyl groups had a negative effect on the antioxidant property of lignin, while methoxy, alkyl and alcohol hydroxyl groups played a positive role. The guaiacyl (G) and syringyl (S) units favored the antioxidant property, so the difference in the content of structural units in lignin under certain conditions of phenolic hydroxyl content also affected the antioxidant property. Therefore, the antioxidant property of aspen milled lignin was higher than that of other milled lignin from different wood species. Finally, the mechanism of DPPH free radical scavenging by lignin was revealed to better understand the relationship between lignin structure and antioxidant property.

Key biochar properties linked to denitrification products in a calcareous soil

Meta-analyses show an overall decrease in soil N2O emissions after biochar (BC) amendment. Nonetheless, N2O mitigation with BC cannot be extrapolated to every BC-soil combination, inasmuch as an increase in soil N2O release has been occasionally reported. We hypothesized that BC characteristics are key, and performed two microcosm experiments to advance in the understanding of the properties associated. We first investigated how 22 well-characterized BCs affect N2O emissions in a calcareous soil under denitrification conditions. Whereas most BCs decreased N2O emissions, some substantially increased N2O emissions. In a second experiment, we selected and further characterized eight of the 22 previous BCs. We applied the 15N-gas-flux method to study how these BCs affect denitrification products (N2O and N2) in the same soil. Results indicate that the interaction between BC and the denitrification process depends on the temperature of pyrolysis. Whereas BCs produced at 400 °C tended to increase total denitrification (N2O+N2) by an average of 28%, BCs produced at 600 °C significantly reduced total denitrification by 53%. Nevertheless, this decline in overall denitrification did not result in a decrease of N2O emissions, as there was a strong shift in the N2O/(N2+N2O) ratio favoring N2O. A redundancy analysis revealed a direct correlation between carboxylic groups on BCs surface and N2O emissions. This research enhances our understanding of the interaction of BC with denitrification, particularly concerning the relevance of the temperature of pyrolysis, and opens up new paths for investigation, crucial for optimizing the application of BCs in different soil environments.Graphical

Andrographolide Encapsulation in Metal‐organic Frameworks (MOFs) via Solvent‐free Process at High Pressure

Andrographolide (ADG) encapsulation was carried out on MOFs MIL‐53(Al) and ZIF‐8 by high‐pressure (0.3 GPa) contact. This methodology is not only environment‐friendly but also energy/time‐saving and gives rise to ADG‐MOFs with physical features equivalent to those of materials obtained by common liquid phase encapsulation. The loaded MOFs were characterized through TEM, SEM, XRD, TGA, FT‐IR, BET, and NMR. The observed decrease in the intensity of ADG XRD peaks is due to the adsorption of ADG into the MOFs. TGA showed the decomposition step of ADG in the range of 200‐300 °C in both loaded MOFs. FT‐IR also showed intense signals of the ADG in the synthesized materials. The dissolution profile of ADG in MIL‐53(Al) in PBS (pH = 7.4) was carried out showing that the drug was released up to 96% after 75 h. NMR confirmed the interactions between ADG molecules and ZIF‐8 groups and the formation of a hydrogen bond between the carboxylic group of ADG and the hydroxyl group of MIL‐53(Al). Coefficient partition studies determined that both MOFs did not improve the hydrophilicity of the ADG, due to the loading of the drug preferably occurring by interactions in the hydrophobic areas within the pores of the MOFs.

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

Electrochemical 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.

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

Electrochemical 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.

Positional Isomerism Toward Tunable Organic Afterglow and Reversible Photoactivation Behavior for Anti‐Counterfeiting and Encryption

AbstractAchieving amorphous polymers with ultralong room‐temperature phosphorescence (RTP), tunable organic afterglow, and reversible photoactivation behavior is highly desirable for practical applications but challenging. Herein, simple positional isomers with three carboxyl groups located in the ortho, meta, and para positions of the triphenylamine skeleton are designed and synthesized. By physically blending with the poly(vinyl alcohol) matrix, these isomers show ultralong RTP properties, among which the meta‐isomer has the longest RTP lifetime (620.1 ms). Theoretical calculations reveal that the more efficient intersystem crossing, the slower radiative decay rate of the lowest triplet excitons, and stronger intermolecular hydrogen‐bonding interactions should be responsible for the superior RTP property of meta‐isomer. Furthermore, the tunable organic afterglow is readily realized via a triplet‐to‐singlet energy transfer process. More impressively, the meta and para isomers exhibit reversible photoactivated ultralong RTP properties after embedding into the rigid poly(methyl methacrylate) matrix. Finally, amorphous and flexible polymer films prepared from these positional isomers show potential applications in advanced anti‐counterfeiting and multilevel encryption through subtly combining ultralong RTP lifetime, tunable organic afterglow, and reversible photoactivation behavior.

Strategically Modified Ligand Incorporating Mixed Phosphonate and Carboxylate Groups to Enhance Performance in All‐Iron Redox Flow Batteries

AbstractIron redox flow batteries (Fe‐RFBs) hold significant promise for achieving cost‐effectiveness and utilizing abundant materials for stationary energy storage applications. Here, a design of a novel Fe complex utilizing a nitrogenous phosphonate/carboxylate mixed ligand, N,N‐Bis(phosphonomethyl)glycine (BMPG), is presented to achieve high performance Fe anolyte. Compared to its all‐phosphonate form, nitrilotri(methylphosphonic acid) (NTMPA), the new complex Fe(BPMG)2 demonstrates a negatively shifted redox potential, resulting in ≈0.07 V (≈10%) increase in battery output voltage. Full battery testing paired with ferrocyanide catholyte demonstrates stable cycling (capacity degradation <0.0001%/cycle) over 730 consecutive charge/discharge cycles with Coulombic Efficiency of 100% at a current density of 20 mA cm−2 under near neutral pH (≈8). Of particular interest, density functional theory (DFT) studies and operando Raman measurements provide strong evidence supporting a molecular structure in BPMG, which reveals the mixed phosphonate/carboxylate groups in BPMG maintain the octahedral coordination of the Fe ion center with phosphonates exclusively, while leaving the carboxylate unbound for both Fe(II) and Fe(III) complexes. This structural similarity between BPMG‐based Fe(II) and Fe(III) complexes effectively mitigates the slow redox reaction kinetics observed in Fe(NTMPA)2 anolyte, where significant ligand reorientation occurs between Fe(II) and Fe(III) complexes.