Acid-base Interactions Research Articles

Constructing Atomic Tungsten-Based Solid Frustrated-Lewis-Pair Sites with d-p Interactions for Selective CO2 Photoreduction.

Solid frustrated Lewis pair (FLP) shows remarkable advantages in the activation of small molecules such as CO2, owing to the strong orbital interactions between FLP sites and reactant molecules. However, most of the currently constructed FLP sites are randomly distributed and easily reunited on the surface of catalysts, resulting in a low utilization rate of FLP sites. Herein, atomic tungsten-based FLP (N···WSA FLP) sites are constructed for photocatalytic CO2 conversion through introducing W single-atoms into polymeric carbon nitride. In the atomically dispersed N···WSA FLP, the electron-deficient W single-atom acts as the Lewis acid (LA), and the adjacent electron-rich N atom acts as the Lewis base. Through the combination of various characterizations, including pyridine-IR, in situ diffuse reflectance infrared Fourier transform spectroscopy, CO2-temperature programmed desorption, and theoretical calculations, the positive effects of N···WSA FLP on photocatalytic CO2 reduction are well revealed. The N···WSA FLP can effectively adsorb CO2 to form an unusual W-O-C-N structure with significant d-p orbital interactions, which leads to an interesting "push-push" electron transfer effect. The π back-donation from W 5d to the antibonding orbital (2π) of CO2 realizes reverse electron transfer from the W single-atom to the O site, while the electrons are transferred from the electron-rich N site to the electropositive C site via Lewis acid-base interactions, therefore effectively breaking the C═O bond to activate CO2 molecules and boost CO2-to-CO performance. This work provides a brand new route for the research on high-efficiency activation of small molecules based on single-atom-based FLP catalysts.

Hierarchical micro-meso-macroporous xAIL@HP UIO-66-NH2 catalysts used for efficient biodiesel production from low-grade acidic oils

The utilization of hierarchical porous supports to fabricate an efficient solid catalyst is a feasible strategy due to their remarkable merit in ameliorating the diffusion of reactants on the catalyst surface and increasing the exposure of active species in particular for the bulky molecule-involving reactions. In this research, to abatement the mass transfer resistance of large triglycerides, the hierarchical porous solid catalyst (xAIL@HP UIO-66-NH2) was prepared by grafting acidic ionic liquid (AIL) with double acidic sites of -SO3H and HSO4- onto micro-meso-macroporous metal-organic gels (HP UIO-66-NH2) through acid-base interactions between -NH2 moiety of HP UIO-66-NH2 and acidic moiety of AILs. The catalyst characterization results showed that the xAIL@HP UIO-66-NH2 catalyst owned the hierarchical porous structure and double Brønsted-Lewis acid centers with large BET surface area and pore volume. This catalyst was adopted for efficient biodiesel production from low-grade acidic oils, exhibiting high catalytic activities for triglyceride transesterification and free fatty acid (FFA) esterification reactions. By using acidic oils as feedstocks, the oil transesterification conversion could reach 91.3 % and the FFAs were completely converted to biodiesel under the conditions of 130 °C for 8 h at methanol-to-oil molar ratio of 35: 1 and catalyst dosage of 8 wt%. Based on the kinetic study, the activation energy Ea of this catalyst was 56.6 kJ/ mol, and the reaction complied with pseudo-first-order kinetics. This solid catalyst demonstrated satisfactory acid and water resistance, with good reusable performance, posing great potential in the efficient biodiesel preparation by the one-pot method using the low-grade acidic oils.

Defect-regulated and amino-functionalized UiO-67 for efficient removal of tetracycline hydrochloride from aqueous solutions

There is notable interest in the development of the efficient removal technologies for antibiotic contaminants in aqueous environments. In this study, L-cysteine was introduced into a UiO-67 precursor solution, and the defective amino-functionalized adsorbent UiO-67-HAc-NH2 was synthesized via a hydrothermal method. This adsorbent was used for the adsorption of tetracycline hydrochloride (TCH) from aqueous solutions. The characterization results confirmed the successful incorporation of amino groups into the adsorbent through L-cysteine and indicated that the defective structure, resulting from competitive interactions with organic ligands, significantly increased the specific surface area. UiO-67-HAc-NH2 demonstrated a maximum adsorption capacity of 605 mg/g for TCH and a notable enhancement in the specific surface area from 704.1 m2/g for pristine UiO-67–2858.7 m2/g. The adsorption mechanism was governed by the synergistic interplay of coordination, acid-base interactions, π–π conjugation, and weak noncovalent interactions. Recycling and regeneration experiments indicated that UiO-67-HAc-NH2 retained a regeneration recovery rate exceeding 90 %, highlighting its excellent reusability as an adsorbent. This result indicates the significant potential of defective amino-functionalized metal-organic framework (MOFs) materials for antibiotic adsorption applications.

Semi-interpenetrating polybenzimidazole membrane containing polymeric ionic liquid with high power density and enhanced proton conductivity for fuel cells

In phosphoric acid (PA)-doped polybenzimidazole (PBI) membranes designed for high-temperature proton exchange membranes (HT-PEMs), increasing the PA doping is essential. Yet, excessive PA doping causes a decline in mechanical strength, which in turn affects the cell performance. We utilize a strategy that integrates elevated PA absorption, increased mechanical strength, and enhanced PA retention. An azide-type ionic liquid (IL) containing double bonds was synthesized and crosslinked with PBI via free radical polymerization reaction. In addition, the IL can also self-polymerize to form long-chain polymeric ionic liquid (PIL). Together, the two structures together form a semi-interpenetrating polymer network (sIPN) system, which has good mechanical properties. The synthesized alkaline ionic liquid can absorb and retain a large amount of PA through acid-base interactions and inter-ionic interactions. Consequently, the proton conductivity of the amino-type polybenzimidazole (AmPBI)-polymeric ionic liquid (PIL)-30 (where 30 stands for the wt% of IL) membrane in an anhydrous environment at 180 °C reached 138.2 mS cm−1. After PA retention test at 160 °C/0 % relative humidity (RH) for 240 h, the proton conductivity reached 99.4 mS cm−1 at 180 °C. The AmPBI-PIL-10 membrane exhibited a significant power density of 635.4 mW cm−2 at 160 °C. The AmPBI-PIL-X composite membranes exhibited exceptional performance.

Shielding Fluoride Ion Basicity through Diurea Coordination for Nonaqueous Fluoride Shuttle Batteries.

The strong basicity of fluoride ions leads to detrimental nucleophilic attack on organic components in the electrolytes, such as β-hydrogen elimination reactions with organic cations and solvents, converting "naked" F- into corrosive and unstable bifluoride (HF2-) ions. These reactions significantly constrain the choice of suitable solvents and salts to develop electro(chemical) stable fluoride ion electrolytes. In this work, we replaced the triple water ligands typically present in industrialorganic fluoride salts with dual 1,3-diphenylurea (DPU) coordination via hydrogen bonding interaction. This modification successfully suppressed the Lewis basicity of fluoride ions, providing long-term chemical stability (over 1000 hours) acrossa wide range of aprotic solvents, a broadened electrochemical stability window (-2.5 ~ 0.9 V vs. Ag+/Ag) and high ionic conductivity (1.7 mS cm-1) at room temperature. Additionally, the weaker hydrogen bonding in F--DPU coordination, compared to the conventional boron-based anion acceptor (AA) strategy that relies on intensive Lewis acid-base interactions, facilitates faster (de)fluorination kineticsat the electrode. The proposed room temperature fluoride ion batteries sustain improved electrochemical performance by pairing with the Pb-PbF2 anode and BiF3 or Ag cathode.

Methanol tolerable ultrathin proton exchange membrane fabricated via in-situ ionic self-crosslinking strategy for high-performance DMFCs

Proton exchange membranes (PEMs) with high proton conductivity, mechanical stability, and methanol barrier capability is urgently needed for direct methanol fuel cell (DMFCs). In response, a series of highly sulfonated polybenzimidazoles (SPBI) were synthesized, followed by the creation of a unique in-situ ionic self-crosslinking mechanism via acid-base pair interactions between –SO3- and protonated N within the imidazolium rings of SPBI in an acidic milieu. The in-situ ionic self-crosslinking not only significantly enhances the mechanical stability of the prepared membrane, but also constructs a microstructure with a free volume radius smaller than the molecular dimensions of methanol, subsequently imparting unparalleled resistance to methanol permeation. After being reduced to an ultrathin thickness of 15 μm, the optimal SPBI-SO3H-200 % membrane obtains remarkable high specific proton conductivity of 33.48 S cm−2. Furthermore, the assembled DMFC demonstrates an exceptionally low methanol crossover current density of 188.25 mA/cm2 alongside high power density of 109.92 mW cm−2 within 2 M methanol fuel, significantly outperforming the methanol crossover current density of 386.06 mA/cm2 and power density of 87.13 mW cm−2 achieved by a single cell assembled with Nafion 115 membrane.

Antimicrobial and acaricide sanitizer tablets produced by wet granulation of spray-dried soap and clove oil-loaded microemulsion.

A novel sanitizer tablet containing clove essential oil (CO) microemulsion was developed. A preformulation study using nuclear magnetic resonance and thermal analyses showed component compatibility. The main components of the samples remained intact despite a color change, probably due to a strong acid-base interaction between eugenol and diethanolamine. The CO microemulsion showed acaricidal and larvicidal activities superior to the commercial product, with product efficacy of 99.9% and larvae mortality of 94%. Optimal spray-drying conditions were achieved with inlet and outlet temperatures of 50°C and 40°C, respectively, an aspiration rate of 1 m3 min⁻1, and a 0.25 L h⁻1 injection flow. The feed suspension comprised 50% (v/v) liquid soap, 37.5% (v/v) water, 12.5% (v/v) ethanol, and 5.0% (w/v) silica. This formulation and processing parameters allowed for successful free-flow powder formation, providing a suitable matrix for incorporating the CO microemulsion via wet granulation without heating. Finally, sanitizer tablets produced from such granules resulted in a uniform product with low weight variation (coefficient of variation of 0.15%), eugenol content of 95.5% ± 3.3, and friability of 0.58%. Furthermore, the tablets showed rapid aqueous dispersion, forming a colloidal system with particle sizes of 221 nm and a zeta potential of -17.2 mV. Antimicrobial activity tests demonstrated the effectiveness of the sanitizer tablet against bacteria and fungi, exhibiting comparable antimicrobial potency to isolated CO. Hence, the sanitizer tablet developed represents a promising candidate as a practical and efficient solution for pest control, offering strong antimicrobial and acaricidal activity.

Proton Pool for the Mitigation of Salt Precipitate Enhancing CO2 Electroreduction in a Flow Cell

Flow cells featuring a gas diffusion electrode (GDE) have emerged as an attractive platform for electrochemical CO2 reduction, offering high current densities (~300 mA·cm−2) and low energy consumption. However, the formation of salt precipitates, particularly carbonate and bicarbonate, poses a significant deficiency by reducing the cell’s operational longevity. In this study, we present a novel approach to mitigate salt precipitates in real-time through acid–base interaction. Recovery efficiency and partial current density of the cell were used to evaluate the capability of removing salt precipitates and the maintenance of CO2 reduction reactions (CO2RRs). It was suggested that the direct treatment of intermittent acid rinse recovers the performance of CO2RRs to a large extent (>97%), and the modification of the proton exchange resin reduces the reduction rate of partial current densities to 1/15 than that of the unmodified. This improvement enhances the cell’s catalytic performance, enabling the stability test for catalysts within the GDE-based flow cell.

π-Conjugated Porous Polymer Nanosheets for Explosive Sensing: Investigation on the Role of H-Bonding.

Nitroaromatic explosive sensing plays a critical role in ensuring public security and environmental protection. Herein, we report 2-pyridyl-thiazolothiazole (pyTTz) integrated blue-fluorescent π-conjugated porous polymer nanosheets, NTzCMP and TzCMP for selective sensing of picric acid (PA) among nitrophenol explosives. Acid-base interactions between PA and pyTTz of CMP lead to H-bonding interactions, where the hydroxy group of PA engaged in weak H-bonding interactions with pyridine and TTz of pyTTz moiety. This led to a strong fluorescence quenching of CMPs-such formation of ground state complex was supported by linear Stern-Volmer quenching plots, unaltered excited state lifetimes, and detailed FTIR analysis of PA exposed CMPs. Interestingly, both CMPs exhibited an excellent response to smaller analytes such as o-nitrotoluene compared to 2,4-dinitrotoluene. Both NTzCMP and TzCMP CMPs exhibited high KSV values of 9×103 and 2.1×103 M-1 for PA and the corresponding limit of detection values were found to be 0.46 and 1.6 ppm, respectively.

Engineering Molecule‐Designed In Situ Polymerization on Al‐Doped Molecular‐Sieve Framework Enables Robust Quasi‐Solid‐State Lithium Batteries

AbstractAchieving fast Li+ transport kinetics and stable electrode/electrolyte interfaces is of paramount importance, yet extremely challenging for the practical success of solid‐state lithium metal batteries, which requires the rational design of the structure and composition of solid‐state electrolytes. Herein, a composite quasi‐solid‐state electrolyte is fabricated through in situ polymerization of a molecule‐designed polymer chain within the functionalized molecular sieve framework (Al‐MCM41). In this design, the robust Brønsted/Lewis acid–base interactions between Al‐MCM41 and TFSI− facilitate the dissociation of lithium salt, leading to a Li+ transference number as high as 0.81. Meanwhile, the well‐ordered mesopores of Al‐MCM41 act as the “reservoir” of the polymer chain, creating continuous ionic migration pathways to offer an excellent Li+ conductivity of 1.09 × 10−3 S cm−1 at 30 °C. Furthermore, the polymer with fluorinated and nitrided functional groups guarantees a dual‐reinforced anode and cathode interface. Such an integrated electrolyte with simultaneous unimpeded Li+ transport and robust interfaces delivers extraordinary capacity retention of 84.6% over 600 cycles at 5 C when coupled with LiFePO4 cathode and remarkable reversible capacity of 129.0 mAh g−1 after 200 cycles with high‐voltage NCM622 cathode. This work provides a significant avenue for enhancing the practical feasibility of solid‐state lithium metal batteries.

Polymeric ionic liquids and piperidinium synergistically improve proton conductivity and acid retention of polybenzimidazole-based proton exchange membranes

Amino-type polybenzimidazole is prepared, then ionic liquid with three nitrogen positive sites ([CTDTr]Br3) is polymerized into polymeric ionic liquids (PILs) by in-situ radical polymerization, and AmPBI-CTDTr-Px membranes were prepared by piperidinium (PPd) and [CTDTr]Br3 combination to cross-linked with AmPBI. Following treatment with KOH and phosphoric acid (PA), the ion pairs (N+ - H2PO4-) generated in the composite membrane system can enhance proton conductivity and facilitate proton transport. The AmPBI-CTDTr-Px membranes shown exceptional PA retention as a result of the alkaline properties of both [CTDTr]Br3 and PPd, which can engage in acid-base interactions with phosphoric acid. Specifically, the proton conductivity of AmPBI-CTDTr-P5 at 180 °C is 129.7 mS cm-1, which is 2.52 times that of pure membranes. Acid retention of AmPBI-CTDTr-P5 at 80 °C/40% RH and 160 °C are 64.4% and 84%.

Effective removal of tetracycline antibiotics from water by in-situ nitrogen-doped porous biochar derived from waste antibiotic fermentation residues

This study explored the utilization of waste oxytetracycline fermentation residue (OFR), abundant in nitrogen and organic matter, to prepare in-situ nitrogen-doped porous biochar (activated OFR derived biochar, AOBC) through a coupled pyrolysis process, and investigated the removal of tetracycline antibiotics (TCs) from water with the prepared AOBCs. The physicochemical characterization results showed the characterizations of abundant nitrogen functional groups, high specific surface area (1960.38 m2/g), and the high microporosity (61.6 %) for AOBCs. At 25 ℃, the maximum adsorption capacity calculated by Langmuir model of AOBC-3–600 for tetracycline hydrochloride (TC), chlortetracycline hydrochloride (CTC), oxytetracycline hydrochloride (OTC), and doxycycline hydrochloride (DOC) reached 473.00, 293.28, 220.61, and 282.72 mg/g, respectively. The superior fit of the pseudo-second-order and Langmuir models indicated that the adsorption mechanism involved both the physical effect (pore filling) and chemical interactions (electrostatic attraction, hydrogen bonding, π-π interaction, and Lewis acid-base interaction). Environmental risk assessments substantiated the absence of residual oxytetracycline and antibiotic resistance genes in the prepared biochar, indicating its application safety. This research provides a sustainable route to simultaneously treat the antibiotic contamination in water and rationally utilize antibiotic fermentation residues.

Relationship of CO2 adsorption performance and physicochemical property of biochar prepared by different types of biomass waste

The physicochemical property of biochar prepared by biomass waste is crucial for CO2 adsorption performance. However, the quantified relationship between the physicochemical property and CO2 adsorption capacity for biochar is still unclear. In this study, biochar samples with different physicochemical properties were prepared from six representative biomass of sewage sludge, chicken manure, apple and prickly ash branch, corn and rice straw. The quantitative investigation was conducted and the relationship between the physicochemical properties and CO2 adsorption capacity of biochar was analysed using Pearson correlation analysis method. The results showed that the biochar prepared from prickly ash branch at 800 °C pyrolysis exhibited a better CO2 adsorption capacity of 154.44 mg/g and larger specific surface area of 160.83 m2/g, compared with other biochars. According to the quantitative data about physicochemical properties of twenty-four kinds of biochar samples, the correlations between CO2 adsorption capacity and microcrystalline structure, surface functional groups, nitrogen content and specific surface area were obtained. The CO2 adsorption capacity showed a significant positive correlation with the specific surface area (SBET), stacking height of aromatic layers (Lc), number of aromatic layers (N) and nitrogen content, and the correlation order was SBET >N >Lc = nitrogen content. Moreover, the CO2 adsorption capacity showed a negative correlation with diameter of aromatic planes (La), CO, O-H and index of aromaticity (Aal/Aar), and the order of correlation was CO > O-H >La >Aal/Aar. The effect mechanism of physicochemical properties on CO2 adsorption of biochar was that microcrystalline structure had an influence on CO2 adsorption by van der Waals force, and nitrogen, oxygen-containing functional groups, and so on by Lewis acid-base interaction and hydrogen bonding.

3D Conductive Nanostructure with the Lewis Acid–Base Interaction for High-Performance Lithium–Sulfur Batteries

3D Conductive Nanostructure with the Lewis Acid–Base Interaction for High-Performance Lithium–Sulfur Batteries

Interface Synergy of Exposed Oxygen Vacancy and Pd Lewis Acid Sites Enabling Superior Cooperative Photoredox Synthesis.

Photo-driven cross-coupling of o-arylenediamines and alcohols has emerged as an alternative for the synthesis of bio-active benzimidazoles. However, tackling the key problem related to efficient adsorption and activation of both coupling partners over photocatalysts towards activity enhancement remains a challenge. Here, we demonstrate an efficient interface synergy strategy by coupling exposed oxygen vacancies (VO) and Pd Lewis acid sites for benzimidazole and hydrogen (H2) coproduction over Pd-loaded TiO2 nanospheres with the highest photoredox activity compared to previous works so far. The results show that the introduction of VO optimizes the energy band structure and supplies coordinatively unsaturated sites for adsorbing and activating ethanol molecules, affording acetaldehyde active intermediates. Pd acts as a Lewis acid site, enhancing the adsorption of alkaline amine molecules via Lewis acid-base pair interactions and driving the condensation process. Furthermore, VO and Pd synergistically promote interfacial charge transfer and separation. This work offers new insightful guidance for the rational design of semiconductor-based photocatalysts with interface synergy at the molecular level towards the high-performance coproduction of renewable fuels and value-added feedstocks.

2,2'-Bipyridyl-4,4'-Dicarboxylic Acid Modified Buried Interface of High-Performance Perovskite Solar Cells.

The regulation of interfaces remains a critical and challenging aspect in the pursuit of highly efficient and stable perovskite solar cells (PSCs). Here, 2,2'-bipyridyl-4,4'-dicarboxylic acid (HBPDC) is incorporated as an interfacial layer between SnO2 and perovskite layers in PSCs. The two carboxylic acid moieties on HBPDC bind to SnO2 through esterification, while its nitrogen atoms, possessing lone electron pairs, interact with uncoordinated lead (Pb2+) atoms through Lewis acid-base interactions. This dual functionality enables simultaneous passivation of surface defects on both the SnO2 and buried perovskite layers. In addition, the electron-deficient nature of HBPDC enhances interfacial energy band alignment and facilitates electron transfer from the perovskite to SnO2. Furthermore, the incorporation of HBPDC strengthens the interfacial adhesion, improving mechanical reliability. As a result, the PSCs exhibited an impressive power conversion efficiency (PCE) of 25.41 % under standard AM 1.5G conditions, along with remarkable environmental stability.

Targeted synergistic chemical bonding strategy for Efficient and stable CsPbI3-based perovskite solar cells

Regulating the crystallization process of perovskite film and suppressing iodine-related defects hold significant importance in improving the efficiency and stability of CsPbI3-based perovskite solar cells (PSCs), thereby endowing their more potential for commercial applications. Herein, we introduced 2-Aminoethyl methylsulfone hydrochloride (AMS) into the perovskite precursor solution to establish targeted synergistic chemical bonding involving Lewis acid-base interactions and hydrogen bonds with CsPbI3 perovskite. We emphasize the importance of the DMAPbI3 intermediate phase for the crystal quality of CsPbI3 perovskite, and reveal that diminishing the size of Pb-I framework colloids in precursor solution can facilitate the formation of DMAPbI3 and optimize the crystallization process of CsPbI3 perovskite. Simultaneously, we demonstrate the generation of high valence iodine defects due to the photoinduction, and prove that constructing N-H···I hydrogen bond can effectively passivate the iodine-related defects. Consequently, the CsPbI3-based PSCs display an impressive power conversion efficiency of 19.59% along with markedly improved stability. Our finding presents a feasible strategy for managing perovskite crystallization and mitigating the defects-induced perovskite degradation, thus promoting the commercialization of CsPbI3-based PSCs.

Influence of punch coating surface properties on sticking during the tableting process

Introduction The present study evaluates the sticking propensity of Uncoated steel, and chromium nitride (CrN), zirconium nitride (ZrN), titanium nitride (TiN) and Ultracoat punch coatings during the tableting process of microcrystalline cellulose (MCC) conducted on a Manesty® F3 single station tableting press. Methods Surface properties including surface roughness, surface free energy (SFE) and its components, the atomic percentage of surface polar functional groups and oxides measured with X-ray photoelectron spectroscopy were used to characterize the surface propensity to sticking. Results After five hours of tablet pressing, MCC powder particles were found to adhere to the TiN coated and the uncoated steel punches. Surface analysis show that surface roughness of all the tested punches was similar. The Lewis base SFE component (LB-comp) was found to govern the acid-base interactions of the tested surfaces, and its value was higher for punch surfaces affected by sticking. The surfaces exhibiting higher LB-comp are more prone to strong acid-base interactions with water molecules that evaporate from the powder bed during compression. Therefore, these surfaces adsorbed water and allow sticking through capillary adhesion force. Conclusion The total atomic percentage of the surface polar functional groups (PFG) and oxides was also high for the surfaces that stick to MCC during tableting, suggesting that hydrophilic molecules on the punch surface favor sticking.

Leveraging Soft Acid-Base Interactions Alters the Pathway for Electrochemical Nitrogen Oxidation to Nitrate with High Faradaic Efficiency.

Electrocatalytic nitrogen oxidation reaction (N2OR) offers a sustainable alternative to the conventional methods such as the Haber-Bosch and Ostwald oxidation processes for converting nitrogen (N2) into high-value-added nitrate (NO3 -) under mild conditions. However, the concurrent oxygen evolution reaction (OER) and inefficient N2 absorption/activation led to slow N2OR kinetics, resulting in low Faradaic efficiencies and NO3 - yield rates. This study explored oxygen-vacancy induced tin oxide (SnO2-Ov) as an efficient N2OR electrocatalyst, achieving an impressive Faradaic efficiency (FE) of 54.2% and a notable NO3 - yield rate (22.05µg h-1 mgcat -1) at 1.7V versus reversible hydrogen electrode (RHE) in 0.1m Na2SO4. Experimental results indicate that SnO2-Ov possesses substantially more oxygen vacancies than SnO2, correlating with enhanced N2OR performance. Computational findings suggest that the superior performance of SnO2-Ov at a relatively low overpotential is due to reduced thermodynamic barrier for the oxidation of *N2 to *N2OH during the rate-determining step, making this step energetically favorable than the oxygen adsorption step for OER. This work demonstrates the feasibility of ambient nitrate synthesis on the soft acidic Sn active site and introduces a new approach for rational catalyst design.

Superior proton conductivity of amino acid-modified UiO-66-(COOH)2 embedded in chitosan: Mechanistic insights into the acid-base interactions

We focus on optimizing acid-base interactions and hydrogen bonding networks to achieve enhanced proton conductivity under low relative humidity (RH) and high temperature. By functionalizing UiO-66-(COOH)2 with glutamic acid (Glu) and lysine (Lys), we generate Glu-UiO-66-(COOH)2 and Lys-UiO-66-(COOH)2. These modified materials are subsequently incorporated into chitosan (CS) to produce the composites Glu-UiO-66-(COOH)2@CS and Lys-UiO-66-(COOH)2@CS. The successful incorporation of amino acids and cross-linking between -COOH and -NH2 groups in the composites, confirmed by FTIR and PXRD analyses, significantly enhances the structural integrity and durability by strengthening the network, and reducing polymer chain mobility. Proton conductivity assessments reveal that Lys-UiO-66-(COOH)2@CS-7 exhibits a remarkable conductivity of 0.022 S/cm at 100 % RH and 363 K, outperforming Glu-UiO-66-(COOH)2@CS-7. The lower activation energy (Ea) of 0.28 eV for Lys-UiO-66-(COOH)2@CS-7, compared to 0.336 eV for Glu-UiO-66-(COOH)2@CS-7, highlights the significant improvement in intramolecular acid-base interactions and hydrogen bonding. Furthermore, Lys-UiO-66-(COOH)2@CS-7 maintains notable proton conductivity at 43 % RH, with an Ea of 0.216 eV, demonstrating its efficacy in low-humidity conditions. These findings underscore the profound impact of amino acid modifications and cross-linking on proton conductivity by reinforcing acid-base interactions, hydrogen bonding networks, and proton transfer efficiency.