Ce projet concerne la synthèse et caractérisation de nouveaux matériaux composites à base de nanoclusteurs de thiolates d’or Au25(SR)18 (tGNCs), supportés sur divers polymères de coordination (MOFs), ainsi que sur ZrO2. L’activité catalytique de ces matériaux a été évaluée sur la transformation de différents substrats. Les tGNCs sont des matériaux atomiquement bien définis et connus pour être actifs dans des réactions d’oxydation. Les nanoparticules de MOFs sont des matériaux pouvant servir de support pour des tGNCs avec de bonnes dispersions. Certains MOFs sont connus pour avoir des propriétés acides et peuvent être actifs en catalyse. Parmi eux, MIL-101 (Cr), UiO-66 (Zr) et ZIF-8 (Zn) on été choisis en raison de leur propriétés acides et/ou de stabilité thermique. La synergie entre les tGNCs et les MOFs a été évaluée à travers la conversion catalytique de différents substrats tels le glucose, le fructose, l’alcool benzylique et le furfural, impliquant des étapes nécessitant un caractère acide et/ou oxydant. Globalement, il n’a pas été observé d’impact de la présence d’or sur la réactivité de ces substrats, et les tendences catalytiques sont celles obtenues avec les MOFs seuls. Cela est certainement dû à la stabilité thermique non suffisante des MOFs qui prévient une calcination efficace des tNGCs. Lorsque ces clusters sont déposés sur ZrO2, il a été possible de les calciner à différentes températures pour étudier l’effet du ligand et de la taille de particules, pour des réactions d’oxydation en phase liquide. Ainsi, il a été montré par exemple que la température de calcination a un impact significatif sur le comportement catalytique de ces composites, qui ont donné de bonnes activités pour l’oxydation de l’alcool benzylique en benzaldéhyde dans le toluène et en conditions douces, et pour l’esterification oxydante du furfural en furoate de méthyle / This research project reports the synthesis and characterization of new composite materials based on Au25(SR)18 thiolate gold nanoclusters (tGNCs), supported over a range of metal organic frameworks (MOFs), and ZrO2. The synthesized composite materials were tested for catalytic transformations of various substrates. tGNCs are atomically well defined materials known to be active in oxidation reactions. MOFs nanoparticles are materials suitable for high dispersion of tGNCs. Some MOFs are known to have acidity and can be active as catalysts. Among them, MIL-101 (Cr), UiO-66 (Zr) and ZIF-8 (Zn) were chosen due to their acidic and/or thermal stability properties. The synergy between tGNCs and MOFs has been tested through catalytic conversions of different substrates like glucose, fructose, benzylalcohol and furfural, involving steps requiring acidic and oxidative features. Globally, no impact of the presence of Au clusters was observed, and the composite materials showed the same catalytic trends as those obtained with the MOFs alone. This is mainly due to the not sufficient thermal stability of the MOFs that prevents efficient calcination of the tGNCs. In contrast, when deposited on ZrO2 it was possible to calcine Au25(SG)18 nanoclusters at different temperatures to study the ligand and particle size effects in liquid phase oxidation reactions. For example, the calcination temperature had a significant impact on the catalytic behaviour of this composite materials, which showed good activity for the oxidation of benzyl alcohol into benzaldehyde in toluene under mild conditions, and of furfural oxidative esterification into methyl-2-furoate

In this dissertation, density functional theory calculations are performed to calculate the thermodynamic and electrochemical properties of metal coordinated frameworks for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Gibb's free energy, overpotential, charge transfer and ligands effect are evaluated. The charge transfer analysis shows the positive charges on the metal coordinated frameworks play an essential role in improving the electrochemical properties of the metal coordinated frameworks. Based on the calculations, design principles are introduced to rationally design and predict the electrochemical properties of metal coordinated frameworks as efficient catalysts for ORR and OER. An intrinsic descriptor is discovered for the first time, which can be used as a materials parameter for rational design of the metal coordinated frameworks for energy storage and conversion. The success of the design principles provides a better understanding of the mechanism behind ORR and OER and a screening approach for the best catalyst for energy storage and conversion.

A straightforward means to include explicit hydrogen bonds within the Universal Force Field (UFF) is presented. Instead of treating hydrogen bonds as non-bonded interaction subjected to electrostatic and Lennard-Jones potentials, we introduce an explicit bond with a negligible bond order, thus maintaining the structural integrity of the H-bonded complexes and avoiding the necessity to assign arbitrary charges to the system. The explicit hydrogen bond changes the coordination number of the acceptor site and the approach is thus most suitable for systems with under-coordinated atoms, such as many metalorganic frameworks; however, it also shows an excellent performance for other systems involving a hydrogen-bonded framework. In particular, it is an excellent means for creating starting structures for molecular dynamics and for investigations employing more sophisticated methods. The approach is validated for the hydrogen bonded complexes in the S22 dataset and then employed for a set of metal-organic frameworks from the Computation-Ready Experimental database and several hydrogen bonded crystals including water ice and clathrates. We show that the direct inclusion of hydrogen bonds reduces the maximum error in predicted cell parameters from 66% to only 14%, and the mean unsigned error is similarly reduced from 14% to only 4%. We posit that with the inclusion of hydrogen bonding, the solvent-mediated breathing of frameworks such as MIL-53 is nowaccessible to rapid UFF calculations, which will further the aim of rapid computational scanning of metal-organic frameworks while providing better starting points for electronic structure calculations.

This thesis explores the use of computational chemistry and machine learning techniques to aid in the design of Metal-Organic Frameworks (MOFs) for use in postcombustion carbon capture and storage (PoC-CCS). PoC-CCS is an ongoing field of research which aims to selectively remove carbon dioxide, an important greenhouse gas, from the exhaust of fossil-fuel burning powerplants. By using a suite of advanced simulation techniques, high-throughput screenings were performed on thousands of MOFs to study their behaviour in a pressure swing adsorption (PSA) system. To develop a comprehensive picture of a material’s performance, the behaviour of individual gas molecules within the pores of the crystal structures to the material’s performance in industrial scale PSA columns was evaluated. To study the behaviour of individual gas molecules within the pores of a MOF, a new algorithm which can accurately determine the locations of gas binding sites was developed. This algorithm, which relies on probability distributions generated through grand canonical Monte Carlo simulations (GCMC), was optimized for CO2 with the goal of use in high-throughput screening. By tuning the user-controlled parameters for a desired gas, this algorithm, which was named the Guest Atom Localization Algorithm (GALA), was shown to accurately reproduce experimentally determined binding sites while being run in a high-throughput manner with no user intervention. Studying MOFs at the pore or crystal scale in this manner provides valuable insights into the behaviour of gases within the materials. A major shortcoming, however, is the lack of direct insight into the material’s behaviour in industrial systems. Materials scientists and MOF chemists have historically focused on a set of performance metrics measured at this scale; however, no clear connection can be made between such metrics and the performance of that sorbent material in a PSA column. To bridge this gap between MOF chemists and the process engineers studying the PSA systems, a large-scale screening of MOFs was performed using a sophisticated PSA simulator designed to reproduce the performance of an 80 kg PSA column. By supplying isotherms obtained using GCMC simulations to be used as inputs into the PSA simulator, a multi-scale high-throughput screening of MOFs for PoC-CCS was performed for the first time under coal-fired powerplant conditions. This multi-scale screening provided the ideal conditions to study the materials science performance metrics and their relationships to industrial PSA performance. To study this relationship, a series of machine learning and artificial intelligence techniques were employed. The primary goal was to extract important relationships between the materials science and industrial PSA performance metrics, with a secondary goal of developing a predictive model which could be used to accelerate the pace of materials discovery. Through the use of machine learning, several metrics were identified which could be used to predict whether a material could meet the minimum target of 95 % purity of captured CO2, and 90 % removal (or recovery) of CO2 from the flue gas stream. Among them was the isotherm parameters for N2, the most abundant species in the flue gas. This finding was significant as to date the focus among MOF chemists studying the PoC-CCS system was placed primarily on the CO2 metrics, with N2 only implicitly considered when calculating the CO2/N2 selectivity. Although several metrics were identified which could predict the purity and recovery targets, none of the conventional metrics tested could be used to estimate the energetic cost of capture or the size of the capture plant, both important considerations in evaluating the cost of capture. The relationship between N2 binding within the pores of the MOF and its ability to meet the purity-recovery targets was explored using GALA. Using a Tanimoto similarity metric and the ratio of single component and competitive loadings, the CO2 and N2 binding environments were studied. It was determined that when the N2 binding environment was significantly altered by the presence of CO2, the material was more likely to meet the purity-recovery targets. Further analysis found that this change in binding environments was correlated to a reduced N2 uptake in the presence of CO2, implying that the competition for binding sites within the pores of the MOF is an important indicator for the material’s ability to meet the purity-recovery target. For the first time, a direct relationship between the behaviour of individual gas molecules to industrial PSA performance can be reported. Although the PSA simulator used throughout this work has proven to be a powerful tool for materials discovery, several shortcomings still exist. The first is the method used by the simulator to predict the loadings at various points within the column. This method relies on single component isotherm data despite the ability of GCMC to simulate multi-component isotherms. An alternative method to using single component isotherms was proposed which relies on multi-component isotherm data and a linear interpolation model. The existing method was compared to the new proposed interpolation method, and it was found that the loadings predicted using the interpolation method were more accurate. The second shortcoming of the PSA simulator is the computational expense associated with the optimizations. Using the PSA simulator, a single material may take up to a week to be fully optimized on a high-performance computing cluster. To increase the pace of materials discovery, a surrogate model was developed using the data accumulated over the course of the work presented in this thesis. Using artificial neural networks, a suite of models was developed which reproduces the outputs of the PSA simulator and is able to optimize a single MOF in a matter of minutes. This suite of models, known as the Fossil Fuel Combustion for Carbon Capture and Storage (FoCAS) was used to perform a screening of over 4,000 materials.

Indiana University-Purdue University Indianapolis (IUPUI) / Metal-organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands in porous structure forms. MOFs have been proposed in use for gas adsorption, purification, and separation applications. This work combines MOFs with 3D printing technologies, in which 3D printed plastics serve as a mechanical structural support for MOFs powder, in order to realize a component design for gas adsorption. The objective of the thesis is to understand the gas adsorption behavior of MIL-101 (Cr) MOF coated on 3D printed PETG, a glycol modified version of polyethylene terephthalate, through a combined experimental and modeling study. The specific goals are: (1) synthesis of MIL-101 (Cr) MOFs; (2) nitrogen gas adsorption measurements and microstructure and phase characterization of the MOFs; (3) design and 3D printing of porous PETG substrate structures; (4) deposition of MOFs coating on the PETG substrates; and (5) Monte Carlo (MC) modeling of sorption isotherms of nitrogen and carbon dioxide in the MOFs. The results show that pure MIL-101 (Cr) MOFs were successfully synthesized, as confirmed by the scanning electron microscopy (SEM) images and X-ray diffraction (XRD), which are consistent with literature data. The Brunauer-Emmett-Teller (BET) surface area measurement shows that the MOFs samples have a high cover- age of nitrogen. The specific surface area of a typical MIL-101 (Cr) MOFs sample is 2716.83 m2/g. MIL-101 (Cr) also shows good uptake at low pressures in experimental tests for nitrogen adsorption. For the PETG substrate, disk-shape plastic samples with a controlled pore morphology were designed and fabricated using the fused deposition modeling (FDM) process. MOFs were coated on the PETG substrates using a layer-by-layer (LbL) assembly approach, up to 30 layers. The MOFs coating layer thicknesses increase with the number of deposition layers. The computational model illustrates that the MOFs show increased outputs in adsorption of nitrogen as pressure increases, similar to the trend observed in the adsorption experiment. The model also shows promising results for carbon dioxide uptake at low pressures, and hence the developed MOFs based components would serve as a viable candidate in gas adsorption applications.

No description available.

Metal-organic frameworks (MOFs) are an emerging class of materials exhibiting desirable properties and functionalities for a variety of applications, including catalysis, molecular separation, gas storage, and mechanical reinforcement. However, the majority of MOFs exist as particulate powders, limiting their transportability and applicability in practical fields. Polymers, on the other hand, are one of the most widely used materials in the world owing to their facile processability and low production cost. Combining MOFs and polymers to form MOF-polymer composites can potentially maintain the merits of both materials while overcoming drawbacks of each individual component. Specifically, MOFs are promising candidates as mechanical reinforcers for polymers because of their low density, high specific modulus, and controllable dimensions. Herein, we aim to provide a comprehensive investigation into the chemistry and mechanical properties of MOF-polymer composites. Various governing parameters, including particle aspect ratio (AR), MOF-particle interface, and intrinsic mechanical properties of MOFs, were thoroughly studied to construct an optimal pathway for fabricating mechanically reinforced MOF-polymer composites. Chapter 1 presents an introduction to MOFs, polymer composites, and mechanical properties and characterizations of polymeric materials. It serves as a foundation of this dissertation and outlines essential concepts for the scientific background. The primary factors that impact the mechanical properties of polymer composite are highlighted, leading to the following three research chapters. Comprehensive background on various characterization techniques that aim at mechanical properties is covered in detail. Chapter 2 focuses on the role of MOF AR on the mechanical properties of MOF-polymer composites. PCN-222, a Zr-MOF with porphyrin linkers, was synthesized with AR ranging from 3.4 to 54. The crystallinity and chemical structure of the MOFs remained consistent for different ARs, ensuring that the AR was the only variable in determining the mechanical reinforcement. Fabricated through the doctor-blade technique, the MOF-PMMA composite films showed homogeneous MOF distribution and alignment. Tensile tests revealed that Young's modulus of the composites increased with MOF AR, exhibiting a good agreement with a modified Halpin-Tsai model. Both storage and loss moduli were also enhanced following increased MOF AR. In addition, the thermal stability was also improved with the addition of MOF particles. In Chapter 3, the authors extend the understanding of mechanical properties of MOF-polymer composites to the interfacial properties between the two materials. Pristine MOFs often lack strong interactions with a polymer matrix due to the difference in chemical/physical properties. The authors developed a three-step synthetic route to grow PMMA on the surface of PCN-222. Owing to an efficient surface-initiated polymerization technique, the PMMA was successfully grafted with high molecular weight and grafting density. The molecular weight of PMMA could be controlled by simply varying polymerization time. The PMMA-grafted PCN-222 was manufactured along with PMMA matrix to form composite films. Mechanical analysis proved that the mechanical reinforcement was improved with increasing grafted molecular weight. Chapter 4 presents an experimental approach to unveil the structure-mechanical property of MOF single crystals, which provides insights on designing MOFs with desired mechanical strength. Zeolitic imidazolate frameworks (ZIFs), a subdivision of MOFs, were chosen as the template owing to their facile synthesis, structural diversity, and high crystallinity. Two types of micron-sized ZIFs, ZIF-8 with Zn2+ node and ZIF-67 with Co2+ node, were synthesized to compare the effect of metal-linker bond. Moreover, the linker composition was varied to examine the difference in crystal structure and defect level. The mechanical properties of these ZIF samples were revealed by nanoindentation on single particles. Overall, the stronger metal-linker bond and high crystallinity were able to yield the highest elastic modulus and hardness. Finally, Chapter 5 offers a comprehensive review on polymer-grafted MOF particles regarding the synthesis and applications associated with surface-anchored polymers. Various polymerization techniques were summarized, and their adjustment and limitations with respect to MOFs were highlighted. The novel and unique applications arisen from polymer-grafted MOFs and Mixed Matrix Membranes were thoroughly discussed. / Doctor of Philosophy / Polymer composites, a combination of polymer matrix and particle fillers, have shown great applicability in nearly every aspect of our daily lives. For example, rubber tires, composed of synthetic polymeric rubber and inorganic particle fillers (e.g., carbon black and glass fiber), have been a great booster for modern society owing to their durability and mechanical strength. Aircraft are also made of roughly 50% composite materials, because of their lightweight and high mechanical strength. Herein, we present a novel type of polymer composite using metal-organic frameworks (MOFs) as mechanical reinforcers. Thanks to the low density, high modulus, and tunable geometry, MOFs can be ideal candidates for mechanically reinforced polymer composites. In this dissertation, several fundamental parameters that impact the mechanical properties of MOF-polymer composites are discussed. The intent of this work is to provide mechanistic insights on the development of outstanding lightweight composites with efficient mechanical reinforcement.

Post-combustion CO2 capture is a promising approach for complementing other strategies to mitigate climate change. Liquid absorption is currently used to capture CO2 from post-combustion flue gases. However, the high energy cost required to regenerate the liquid absorbents is a major drawback for this process. As a result, solid sorbents have been investigated extensively in recent years as alternative media to capture CO2 from flue gases. For example, metal organic frameworks (MOFs) are nanoporous materials that have high surface areas, large pore volumes, and flexible designs. A large number of MOFs, however, suffer from 1) low CO2 adsorption capacity at low pressure, which is the typical condition for flue gases, 2) degradation upon exposure to water present in flue gases, and 3) low selectivity of CO2 when present in a mixture of gases. Zeolitic Imidazolate Frameworks (ZIFs) are heavily investigated MOFs for CO2 sorption applications because they have better selectivity for CO2 compared to other MOFs and are resistant to degradation in water due to their hydrophobic nature. However, ZIFs (e.g., ZIF-8) investigated for CO2 sorption applications are typically produced using toxic solvents and their CO2 sorption capacity is drastically lower than other types of MOFs. Post-synthesis modifications with amine functional groups have been known to increase CO2 sorption capacity and selectivity within nanoporous materials. For ZIFs, previous research showed that sufficient loading with linear polyethyleneimine increased their CO2 sorption capacity. Therefore, the objectives of this research were to a) investigate the CO2 sorption capacity of ZIF-8 synthesized by solvothermal methods that use more eco-friendly solvents (e.g., methanol and water) and b) introduce post-synthetic modifications to ZIF-8 using branched polyethyleneimine (bPEI) to enhance its sorption capacity. A custom quartz crystal microbalance (QCM) system was assembled and used to measure the CO2 sorption capacity of unmodified and bPEI-modified ZIF-8 sorbent. The tests were conducted at 0.3 - 1 bar. The results showed that the unmodified ZIF-8 synthesized in methanol (ZIF-8-MeOH) had comparable crystal structure, thermal stability, surface area, and chemical properties to that of literature (Ta et.al 2018). ZIF-8-MeOH had a surface area of 1300 m2/g and a CO2 sorption capacity of 0.85 mmol CO2/g ZIF-8 @ 1 bar. This surface area and sorption capacity are comparable to those of ZIF-8 made in dimethylformamide (DMF). Therefore, ZIF-8-MeOH proved to be a worthy candidate MOF for replacing the ZIF-8 made in DMF for CO2 capture research. Water-based ZIF-8 was also synthesized in this study; however, its CO2 sorption capacity was not tested because it exhibited a significantly lower surface area (732 m2/g) compared to that of ZIF-8-MeOH. Modification of the ZIF-8-MeOH with bPEI resulted in a decrease in its CO2 sorption capacity. This undesired outcome is likely a result of insufficient bPEI load (mass attached), on ZIF-8-MeOH (~ 10% w/w) combined with the surface area lost (~ 770 m2/g) due to bPEI blocking some of the ZIF-8-MeOH pores. Therefore, the bPEI load attained in this study was not enough to compensate for the loss of surface area of the modified ZIF-8 and thus, the CO2 sorption capacity decreased. Future investigations should enhance the post-synthetic modification by increasing the loading of amine functional groups onto the eco-friendlier ZIF-8-MeOH used in this study.

Metal-organic frameworks (MOFs) have been intensely researched over the past 20 years. In this dissertation, metal-inorganic frameworks (MIFs), a new class of porous and nonporous materials using inorganic complexes as linkers, in lieu of traditional organic linkers in MOFs is reported. Besides novel MIF regimes, the previously described fluorous MOF "FMOF-1", is re-categorized herein as "F-MIF1". F-MIF-1 is comprised of [Ag4Tz6]2- (Tz = 3,5-bis-trifluoromethyl-1,2,4-triazolate) inorganic clusters connected by 3-coordinate Ag+ metal centers. Chapter 2 describes isosteric heat of adsorption studies of F-MIF1 for CO2 at near ambient temperatures, suggesting promise for carbon capture and storage. We then successfully exchanged some of these Ag(I) centers with Au(I) to form an isostructural Au/F-MIF1. Other, nonporous MIFs have been synthesized using Ag2Tz2 clusters with bridging diamine linkers 4,4'-bipyridine, pyrazine, and a Pt(II) complex containing two oppositely-situated non-coordinating pyridines. This strategy attained luminescent products better-positioned for photonic devices than porous materials due to greater exciton density. Chapter 3 overviews work using an entirely inorganic luminescent complex, [Pt2(P2O5)4]4- (a.k.a. "PtPOP") to form new carbon-free MIFs. PtPOP is highly luminescent in solution, but as a solid shows poor quantum yield (QY ~0.02) and poor stability under ambient conditions. By complexing PtPOP to various metals, we have shown a dramatic enhancement in its solid-state luminescence (by an order of magnitude) and stability (from day to year scale). One embodiment (MIF-1) demonstrates microporous character. Chapter 4 overviews the design and application of new MIF linkers. Pt complexes based upon (pyridyl)azolates, functionalized with carboxylic acid groups, have been synthesized. These complexes, and their esterized precursors, show strong luminescence on their own. They have been used to generate new luminescent MIFs. Such new MIFs may be useful toward future inorganic (LEDs) or organic (OLEDs) light-emitting diodes, respectively. The electronic communication along their infinite coordination structures is desirable for color tuning and enhanced conductivity functions, compared to the small molecules used in such technologies, which rely on intermolecular interactions for these functions.

Ph. D. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / A major challenge for this generation is cleaning up heavy metal pollution disposed during industrial, domestic and agricultural activities. So, to obtain clean water resources, new treatment technologies are needed that can be applied to a broad range of highly toxic heavy metals in water. In this study, metal organic frameworks (MOFs) were synthesized from 1,2,4,5-tertabenzene carboxylic acid with metal salts of; cobalt, copper, iron, antimony, strontium and lanthanum through solvothermal method. The synthesized MOFs were reacted with polyvinyl alcohol (PVA) by electrospinning. To the best of our knowledge it is for the first time that such hybrid materials are synthesized and reported. PVA/MOF materials were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetry analyzer (TGA). The SEM micrographs of PVA/MOFs materials showed relatively uniform nanofibers that were non-beaded and entangled. Some formed patches, while others were partially cross linked. TGA analysis revealed that PVA/MOF nanofibers exhibited higher decomposition temperature than PVA nanofibres. Thus, it confirmed the interactive force between MOF and PVA nanofibres. FTIR plots also exhibited shifts in critical functional group positions, thus it confirmed that there was a given amount of MOFs embedded in the electrospun fibrous mat. PVA/MOFs materials were used in the adsorption of lead ions in solution to study the effects of temperature, time dependant studies and concentrations. The batch adsorption experiments were performed at five different Pb(II) ion concentrations (20, 40, 60, 80 and 100 mg/L), four different temperatures (25, 40, 60 and 80 oC), time dependent studies ranged from (5, 10, 30 and 60 min) and pH of all Pb(II) solutions were recorded to be 5.05. The results indicated that the uptake performance of PVA and PVA/MOFs nanofibers significantly changed with concentration, temperature and time. The PVA/MOFs nanofiber hybrids demonstrated greater adsorption percentage and adsorption capacity for Pb(II) ions than PVA nanofibers. PVA nanofibers showed moderate adsorption percentage and capacity performance of 25.5 % and 44.13 mg/g (meaning 44.13 mg of Pb(II) per gram of PVA nanofibers) while PVA/MOFs nanofibers showed improved percentage and capacity perfomance (PVA/Cu-MOFs 76.36 % and 152.72 mg/g), (PVA/Co-MOFs 59.41 % and 99.28 mg/g), (PVA/La-MOFs 92.27 % and 184.03 mg/g), (PVA/Cd-MOFs 83.19 % and 165.94 mg/g), (PVA/Sb-MOFs 50.66 % - 91.57 mg/g), (PVA/Sr-MOFs 58.85 % - 124.82 mg/g) and (PVA/Fe-MOFs 56.76 % - 108.82 mg/g). The adsorption data of Pb(II) ions on PVA and all PVA/MOFs nanofibers showed that a pseudo-second order kinetic model was more suitable than a pseudo first order kinetic model. The adsorption rate was much faster on PVA/MOFs nanofibers. This is marked by lower activation energy compared to PVA nanofibers activation energy. The Temkin model did not correlate well with all the adsorption data. On the contrary, Freundlich and Langmuir isotherm models described the adsorption data adequately. All PVA/MOFs nanofibers followed Langmuir isotherm model, only PVA nanofibers followed Freundlich isotherm model. The PVA and PVA/MOFs nanofibers gave negative values of enthalpy change (ΔHo) and negative values of Gibbs free energy change (ΔGo) showing the adsorption processes were exothermic and spontaneous. Moreover, obtained positive entropy changes (ΔSo) on PVA, PVA/Fe-MOF, PVA/Cu-MOF, PVA/Co-MOF and PVA/Sb-MOF nanofibers showed that the sorped Pb(II) ions were not restricted on the electrospun nanofibres and physisorption mechanism was dominant, while negative entropy changes (ΔSo) on PVA/Sr-MOF and PVA/La-MOF nanofibers indicated that chemisorption was more dominant. The influence of ubiquitous cations such as Ca(II) and Mg(II) on the adsorption of Pb(II) ions onto PVA and PVA/MOF nanofibers was also assessed. The results showed that the ubiquitous ions had no significant influence on the sorption of Pb(II) ions. Current investigation provides a method to develop novel PVA/MOFs nanofibers hybrid adsorbents for water purification system. The adsorption capacities and removal achieved with the PVA/MOFs nanofibers sorbent were higher than those for PVA sorbent. The electro spun nanofiber sorbents presents an efficient alternative for pre-treating lead ions in aqueous solutions. Results from this research demonstrated that higher performance novel nanofibers, which possessed higher adsorption percentages and capacity capabilities were obtsained far exceeding some of the commonly used adsorbents, were obtained.