Mohammad Jafarzadeh

   In recent years, microbial fuel cells (MFCs) have attracted considerable attention as promising technologies for simultaneous wastewater treatment and bioelectricity generation. However, the performance of proton exchange membranes (PEMs), as one of the key components of MFC systems, is still limited by challenges such as oxygen crossover, low proton conductivity, and high internal resistance. In the present study, eucalyptus plant extract was utilized as an environmentally friendly bio-based additive for the modification of sulfonated polyether sulfone (SPES) membranes in order to improve their physicochemical and electrochemical performance in MFCs. For this purpose, SPES membranes containing different concentrations of eucalyptus extract (EE) including 0.5, 1, and 1.5 wt% were fabricated and compared with the bare membrane. Various characterization techniques including FTIR, ATR-FTIR, SEM, water uptake (WU), cation exchange capacity (CEC), water contact angle (WCA), dissolved oxygen (DO) analysis were employed to investigate membrane properties. Furthermore, electrochemical performance was evaluated using polarization curves, power density (PD), current density (CD), COD removal, and coulombic efficiency (CE). FTIR and ATR-FTIR analyses confirmed the successful incorporation of EE into the membrane structure. SEM images revealed that the modified membranes exhibited more compact and homogeneous morphologies compared to the bare membrane. In addition, incorporation of EE enhanced membrane hydrophilicity, improved CEC, and reduced oxygen crossover. Among all fabricated membranes, the membrane containing 1 wt% EE exhibited the best overall performance. This membrane achieved the highest PD of 193.4 mW m?² and maximum CD of 716.2 mA m?². Moreover, the highest COD removal (89.16%) and CE (76.11%) were also obtained for this membrane. The enhanced performance can be attributed to improved hydrophilicity, enhanced proton tra  ort capability, higher CEC, and lower oxygen permeability. Overall, the obtained results demonstrated that EE can effectively improve the performance of SPES membranes for MFC applications and provides a promising approach for the development of sustainable and environmentally friendly PEMs.   

  Abstracts??UiO-66-NH?@WCl?/H?O? as a Robust MOF-Based Catalyst for Chemo-Selective Oxidation of Sulfides to Sulfoxides and Sulfones under Green and Sustainable Conditions

   Abstract: Pollution of water resources from industrial wastewater containing persistent organic compounds has become a serious environmental challenge. Conventional treatment methods and common polymer membranes such as polyether sulfone (PES) face problems such as fouling and limited efficiency in removing persistent pollutants. This research aimed to prepare a novel photocatalytic membrane through surface modification with superior performance and self-cleaning properties. In this regard, the surface of polyether sulfone membranes was coated using TiO?-chlorophyll photocatalytic nanoclay to overcome the limitation of TiO? activity in the ultraviolet region and to use visible sunlight for its activation. In this study, TiO?-chlorophyll nanoclay was first synthesized chemically. Then, the surface of PES-based membranes was modified using aqueous suspensions containing different proportions (0.01 to 0.03 wt%) of this nanoclay through coating. The characterization of the nanocomposite and modified membranes was performed using Fourier transform infrared (FTIR), emission reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The performance of the membranes was evaluated in terms of pure water flux, pollutant removal efficiency (direct dye), fouling resistance, and reusability. The results showed that surface modification with nanoclay caused a shift in the optical absorption band of TiO? from 380 to about 480 nm and a significant increase in the hydrophilicity of the membrane surface (a decrease in the contact angle from 74 to 54 degrees). The optimized membrane (M-0.02) with 0.02 wt% nanoclay increased the pure water flux from 17.7 to 50.8 L/m²·h, and the direct dye removal efficiency under visible light reached 93%, while this efficiency was only 64% in the dark. This difference indicates a significant contribution of photocatalysis to the removal process. The membrane also showed a flux recovery ratio (FRR) of over 85%, indicating its excellent self-cleaning property. The results of stability tests also indicated the stable performance of the photocatalytic layer in successive use cycles. Overall, the results of this study indicate that the surface modification of PES membrane with TiO?-chlorophyll nanoclay is a sustainable, biocompatible and efficient solution for the effective treatment of industrial wastewater, especially dye-bearing wastewater.   

  This study explores

Polymeric nanofiltration membranes have shown significant efficacy in rejecting heavy metals from wastewater. However, fouling remains a key challenge, leading to a decline in the performance of these membranes. This research is dedicated to the modification of polyacrylonitrile (PAN) nanofiltration membranes using the deep eutectic solvent L-menthol:ethylene glycol with the aim of reducing fouling and increasing the membrane’s permeate flux. The presence of hydrophilic functional groups was confirmed using Fourier-Transform Infrared Spectroscopy (FT-IR) analysis of the Deep Eutectic Solvent (DES) and the resulting modified membranes. Scanning Electron Microscopy (SEM) imaging and Energy-Dispersive X-ray Spectroscopy (EDX) were employed to investigate the morphology, porosity, pore size distribution, and water contact angle. The modified membranes exhibited a lower water droplet contact angle compared to the pristine membrane due to the hydrophilicity imparted by the nanoparticles, decreasing from 87.6 degree for the pristine membrane to 69.2 degree for the modified membrane containing 0.3% nanoparticles. Furthermore, the pore size in these membranes significantly increased, which consequently led to an improvement in membrane flux. The PAN/DES0.3 membrane modified with 0.3% w/w of the Deep Eutectic Solvent (DES) demonstrated the highest flux, recovery rate, and lowest fouling propensity. The modified PAN membrane showed the highest heavy metal ion rejection rates, achieving 98.11% for Pb2+ and 96.43% for Mn2+. Conversely, the lowest rejection rates for the same metals were observed in the unmodified PAN/DES0.3 membrane, measuring 38.82% and 36.1% for Pb2+ and Mn2+ , respectively. Consequently, the modified PAN membranes demonstrated heavy metal rejection exceeding 96%   

      Although airlift bioreactors have recently achieved success in the simultaneous removal of carbon (C) and nutrients (N and P) from various wastewaters, their focus has largely been on conventional mechanisms such as simultaneous nitrification and denitrification (SND) and enhanced biological phosphorus removal (EBPR). Building on this, the present study aimed to establish diverse mechanisms for synchronous CNP removal in a hybrid dual internal circulation airlift A2O (DCAL-A2O) bioreactor by implementing specific operating conditions. The influence of nitrogenous species, particularly NH4+-N/(NH4+-N + NO3--N) ratio (0.5-1.0), and hydraulic retention time (HRT; 8-12h) on the bioreactor's performance was investigated. The synergistic effect of various biological mechanisms played a significant role in achieving simultaneous CNP removal in a single-stage bioreactor. Under optimal conditions, achieved at an NH4+-N/(NH4+-N + NO3--N) ratio of 0.55 and an HRT of 10.5 h, the bioreactor demonstrated exceptional performance, with removal efficiencies of 95.4 % for total chemical oxygen demand (TCOD) (inlet: 1500 mg/L), 86 % for total nitrogen (TN) (inlet: 210 mg/L), and 66 % for total phosphorus (TP) (inlet: 45 mg/L), along with an effluent turbidity of 9 NTU. Furthermore, the hybrid DCAL-A2O bioreactor exhibited outstanding nitrate removal efficiency of 98 % when treating high-strength nitrate wastewater (262.5 mg/L). In conclusion, the hybrid DCAL-A2O bioreactor proved to be highly effective for simultaneous CNP removal and demonstrated superior performance in nitrate removal from high-strength nitrate wastewater.

I sincerely thank God, Merciful and Almighty, for the divine guidance and i  iration that enabled me to pursue this path and reach this academic level. I sincerely thank my supervisors, Prof Ali Akbar Zinatizadeh, and Dr. Sirus Zinadini, as well as my advisers, Dr. Sara Ivani, and Dr. Mehdi Khiadani, for their invaluable support and insightful recommendations throughout this project, which significantly contributed to its success. I sincerely thank the referees for their thorough review of this thesis and my supportive friends and colleagues for the enjoyable moments we shared. It is worth mentioning that the completion of this thesis owes to the knowledge, patience, and extraordinary attention of these magnanimous professors, and I once again thank them. And I am thanking God for putting these magnanimous professors on the path to completion of this project. And in the end, I sincerely appreciate my parents for their massive support at all stages of life.      

   حذف همزمان كربن و مواد مغذي (CNP) در يك بيوراكتور واحد از نظر حجم راكتور و مصرف انرژي از اهميت بالايي برخوردار است.از اين رو، در اين مطالعه، دو راكتور زيستي لجن فعال (AS) و لجن فعال با رشد چسبيده ثابت (IFAS) با پيكر­بندي تقسيم بندي شده، جهت حذف همزمان كربن و مواد مغذي از پساب سنتزي رب گوجه فرنگي و در نهايت مقايسه عملكرد دو راكتور مذكور به كار گرفته شد. در اين مطالعه تأثير دو متغير مستقل بر عملكرد بيوراكتورها مورد بررسي قرار گرفت. براي ارزيابي عملكرد فرآيند هشت پاسخ مختلف در طول 13 اجرا در شرايط آزمايشي مختلف طراحي شده توسط نرم افزار Design Expert Software ارزيابي شد. تأثير دو متغير مستقل شامل زمان ماند هيدروليك   (HRT)، سرعت جريان هوا (AFR) بر عملكرد بيوراكتور از نظر حذف اكسيژن محلول شيميايي (COD)، حذف نيتروژن كل (TN)، پساب   -NO3، حذف N-NH4 و كدورت پساب بررسي شد. HRT هاي 4، 8, 12 ساعت و AFR هاي 2، 3 و 4 ليتر در دقيقه براي مدل­سازي عملكرد بيوراكتور مورد بررسي قرار گرفت. بازده حذف PO4،   COD، TN وN-NH   در شرايط بهينه با HRT 12ساعت و AFR 3 ليتر در دقيقه براي راكتور AS به ترتيب17.89 و   92.94 و 50.069 و 50.423درصد بود كه اين بازده حذف در راكتور IFAS به ترتيب88.91 و98.85 و40.75 و30.97 درصد بود. براي بررسي پايداري عملكرد دو راكتور مذكور تحت شرايط بهينه به‌دست ‌آمده هر دو راكتور به مدت يك ماه مورد بررسي قرار گرفتند، كه بيوراكتورها عملكرد تقريباً پايداري از خود نشان دادند. نتايج نشان داد كه راندمان حذف COD در هردو راكتور به دليل ساختار منحصر به فرد راكتور مورد استفاده بالاي 90 درصد بود، در حالي كه حذف مواد مغذي تابع شرايط آزمايش بود. با بررسي كلي نتايج به دست آمده مي­توان نتيجه گرفت كه اولا ساختار منحصر به فرد راكتور مورد استفاده نقطه قوت اصلي اين مطالعه است كه سبب بالا بردن كارايي هردو حالت راكتور شد. ثانيا از مقايسه كلي داده­ها نتيجه گرفت كه علاوه بر ثابت بودن شرايط حاكم بر هردو راكتور و كارايي بالاي هردو، مي­توان با اختلافي چشمگير به برتري نسبي راكتور IFAS اذعان داشت.   

   On the basis of the energy storage, importance of chemical energies and the charge transfer, the objective of this research is study on Homo-Cubane and 1-Azahomocubane (C9H10 and C9H10N, respectively; as the high energetic with high stress molecules) and their molecular deformation by stepwise reduction and oxidation states (i.e. C9H10n and C9H10Nn; n=0 & ?1 to ?4 and n=0 & +1 to +4, respectively). In this study, the molecules of homocubane and 1-azahomocubane were optimized to obtain the minimized molecular geometry and the electronic structure by the density functional theory (DFT, B3LYP) using 6-31+G* basis set. Some important properties such as bond order changes, electron densities, frontier orbital (HOMO and LUMO) energies and characters,computed IR spectrum and structural deformation parameters were calculated and investigated for C9H10n and C9H10Nn (n=0 & ?1 to ?4 and n=0 & +1 to +4). The results of the DFT investigations revealed that this compound exhibit excellent performance in the charge changes processes in its reduced and oxidized forms.

  Electrochemical water-splitting technology for producing “green hydrogen” has attracted increasing attention to the global mission to replace fossil fuel-based energy sources and reduce CO2 emissions. Briefly, an introduction to water electrolysis and a review of effective catalysts are presented in chapter 1. In Chapter 2, we adopted zeolitic imidazolate frameworks-8 (ZIF-8) as the precursor to fabricate ZnS-MOF via facile sulfidation processes. The ZnS-MOF nanostructures were anchored on the surface of the nickel nanowire (denoted as Ni NW@ZnS-MOF nanohybrids) and their catalytic activity for HER, OER, and overall water splitting were studied. The prepared Ni NW@ZnS-MOF revealed a low overpotentials value of 90 and 260 mV at 10 mA cm?2 for HER and OER in 1.0 M KOH solution, respectively. The alkaline electrolyzer assembled by Ni NW@ZnS-MOF provides a low cell voltage of 1.61 V at 10 mA cm?2 current density to boost the overall water splitting and robust stability for 15 h. The superior electrocatalytic activity of Ni NW@ZnS-MOF is due to the facile and effective electron transfer of Ni NW, accessible active sites of ZnS-MOF, and as well as the synergistic effect of the hybrid structures. This finding provides a synthesis strategy to fabricate an efficient free-noble metal catalyst for energy conversion and storage. Achieving the rational design of nanostructures for efficient oxygen evolution reaction (OER) is crucial for green energy utilization. Chapter 3 synthesized the ZnxFe3-xS4 hollow spheres derived from ZnFe-zeolitic imidazolate frameworks (ZnFe-ZIFs) through solvothermal sulfidation with superior OER activity and stability. The ZnxFe3-xS4 electrocatalyst delivers superior OER activity: it requires only low overpotentials of 235 and 285 mV to achieve current densities of 10 and 50 mA cm?2, respectively, as well as a small Tafel slope of 72 mV dec?1. In an alkaline solution, the hollow ZnxFe3-xS4 nanospheres exhibit exceptional durability in the multi-step chronoamperometry test for 20 h. This work offers a blueprint for the design and synthesis of stateof- the-art sulfide-based OER catalysts.

  The main goalof this thesis is to modify the surface of kappa-carrageenan (?-Car)-basedpolysaccharide using acidic and basic functional groups as efficient catalystsin organic reaction synthesis.   In this regard, in the first study, theacid-basic catalyst was synthesized in three steps. Due to the availablehydroxyl (-OH) groups on the surface of ?-Car, it can be easily modified.Initially, the hydroxyl groups were converted into appropriate leaving groupsusing 4-toluene sulfonyl chloride. Next, metformin was integrated into itssurface via a nucleophilic substitution mechanism. Finally, its surface wasmagnetized by Fe3O4 nanoparticles (M  ). The introducednanocomposite was characterized by various techniques, such as FT-IR, VSM,FE-SEM/EDS, TGA, and XRD. The resulting nanocatalyst showed significant activityin multicomponent reaction for the synthesis of dihydropyrano[2,3-c]pyrazolewith an efficiency of 94%.In the secondstudy, the Fe3O4@Carr-PGly-SO3H catalyst was prepared and identified by theabove techniques. The performance of the prepared nanocatalyst has been examinedin synthesis of 1-amido alkyl-2-naphthols derivatives and the conversion offructose to 5-hydroxymethylfurfural.Interestingly,as-prepared catalytic systems can be easily separated by an external magnet and used five times without a significant decrease in theiractivities. Also, due to the presence of sulfur groups onthe surface of the second catalyst, it showed significant activity againstGram-positive (Staphylococcus aureus) and Gram-negative (Escherichiacoli) strains.

  The main goal of this thesis is to modify iron-basedmetal-organic frameworks (MOF), MIL-101-NH2, with metalnanoparticles (  ) as efficient catalysts in organic syntheses. In thisregard, the metal    were synthesized in two steps including the preparationof bimetallic    in core-shell form. The as-synthesized CuO@Ag    areencapsulated inside the pores of the MOF and characterized by various techniquessuch as FTIR, XRD, FE-SEM/EDS, TGA, and DRS. The photocatalyst(CuO@Ag/MIL-101-NH2) showed appropriate performance for thesynthesis of benzimidazoles and biaryls under visible light. The catalyticsystem was recycled and reused several times without a significant decrease inactivity.

The photocatalysts containing bimetallic CuNi nanoparticles (  ) were successfully synthesized by in-situ reduction of Cu2+ and Ni2+ salts inside the highly porous and photoactive Ti-based metal-organic framework (MOF), NH2-MIL-125, via impregnation method.   The resulting composite, CuNi@NH2-MIL-125, was characterized by various techniques such as Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TGA), UV-vis diffuse reflectance spectroscopy (DRS), Brunauer-Emmet-Teller (BET) surface area, and X-ray photoelectron spectroscopy (XPS). The one-pot synthesis of 1,4-dihydropyridines (1,4-DHPs) was investigated utilizing the composite photocatalyst via pseudo four-component (4-CR) reaction between aromatic aldehydes, ethyl acetoacetate, and ammonium acetate promoted under visible light irradiation in mild conditions. Products were selectively formed in good-to-high yields. Moreover, the work discloses, for the first time, a simple and environmentally friendly approach for the direct synthesis of ?-acetamido ketones via one-pot thermo-photocatalytic approach using a photoactive CuNi@NH2-MIL-125 in the absence of any chemical additive.

In line with the goals of green chemistry, in this project we used chitosan as an environmentally-friendly substrate. The catalyst was prepared in three steps. Due to the presence of amino groups at the surface of chitosan, it can be easily modified. Therefore, we modified its surface using 1,3-di-bromopropane so that the desired nucleophile could be attached. In the next step, we attached the 2-aminopyridine compound to its surface. The binding of this compound will be through pyridine nitrogen. Finally, we magnetized its surface by immobilizing Fe3O4 nanoparticles. This method has advantages such as environmental compatibility, economical, simple preparation and ease of catalyst recovery. Finally, we used nanocatalysts prepared for the synthesis of 1,4-dihydropyridine and polyhydroquinoline as well as for the synthesis of pyrazole compounds. Using an environmentally-friendly support, easy separation capability, mild reaction conditions, and catalyst activity after several catalytic cycles can be considered as advantages.   

   AbstractIn wastewater treatment, a variety of efficient issues such as theeco-friendly and cost-effective nanomaterials have been developed to have theunique functionalities for the potential decontamination of industrial effluents,surface water, ground water and drinking water. Amongorganic contaminants, the dyes are considered to be the serious pollutants dueto their toxicity. Conventional water treatment processes are very diverse andinclude physical decolorization techniques (such as, sedimentation, filtration,adsorption, and reverse osmosis), chemical decolorization techniques (such as,neutralization, recovery, chemical oxidation and ion exchange methods), andbiological decolorization techniques.Among the various kind of photocatalytic semiconductors, the metaltungstates have grabbed the considerable attention. In this research, the binary nanocomposite of cobalttungstate/reduced graphene oxide hasbeen synthesized by the hydrothermal method. One of the problems that limited the use of thesenanoparticles in the photocatalyst process is the rapid recombination ofelectrons and hole. Therefore, present research has focused on the modification of cobalt tungstate/reduced graphene oxideby adding nickelhydroxide. The results showed that the structure of the Co/Ni/RGO had asuitable photocatalytic activity in the destruction of the direct red 16(DR16). The maximum photodegradation efficiency of DR16 were obtained at concentration of 5 ppm, pH of solution,catalyst loading 2 g/L and irradiationtime 60 minutesconditions.   The catalyst was foundto be reusable, even after several runs and its catalytic activity was almostthe same as that of freshly used catalyst. The amount of the recovered catalyst(wt.%) was measured after each run. The results showed that weight losses ofthe catalyst during the operation was negligible. The synthesized photocatalystwas characterized by using the Fourier transform infrared, scanning electronmicroscopy, X-ray diffraction, Transmission electronmicroscopy, X-ray photoelectron spectroscop, electron dispersive X-ray, diffuse reflectance spectra, andphotoluminescence.

Design and preparation of a novel photocatalyst, based on polymethylhydrosiloxane (PMHS) was reported. To investigate the straightforward preparation of PMHS-PEG-xT-PW, different characterization methods including FTIR, XRD, FESEM, UV-Vis DRS, EDX, PL, and EIS were utilized. The prepared photocatalyst was used for the photocatalytic degradation of Rhodamin B (RhB) under incident visible light irradiation and also efficiency of the catalyst was examined under sun light irradiation. To study the efficiency of this research for the photodegradation of RhB, the effect of different crucial parameters such as time of illumination, catalyst loading, RhB concentration, pH of the solution, reusability function of the catalyst and scavenger experiments were checked. Trapping tests showed that the photogenerated O2•- and 1O2 are the main active species involved in the photocatalytic process. Photoactivity of glass coated PMHS-PEG-xT-PW were also investigated in photodegradation of the RhB which showed about 90% dye removal after 4 h. Thus introduced photocatalyst showed excellent activity in suspension and fix bed reactor. This inorganic based polymer can not only extend the absorption wavelength range of TiO2 but also consequently increase life-time of excited electron and hole with an appropriate viscosity for casting, which improve the photocatalytic efficiency of the photocatalyst in fix bed reactor too. Stability and reproducibility of coated film were also evaluated. The charge transfer resistance was also decreased compare with bare TiO2 which was proved by Nyquist and Bode plots.

An efficient supported ionic liquid catalyst is designed for the condensation reaction of aldehydes and dimedone. The Zr-based metal-organic framework (MOF), UiO-66-NH2, was initially functionalized with 1-(4-bromobutyl)-1H-imidazole and then 1,4-butane sultone to form a supported ionic-liquid (SIL). Next, HSO4– was exchanged with tetrafluoroborate, the catalyst exhibits excellent performance for the synthesis of derivative xanthenes. The UiO-66-NH2-ILBF4–-SO3H showed a synergistic effect on the efficiency of the reaction. The supported catalyst system was recycled simply by filtration and reused five times without a significant decrease in its activity. The catalyst was characterized with PXRD, FTIR, TGA, BET, FE-SEM, EDS, and elemental mapping.   

  In this research, in-situ modification of the three-dimensional Zr-based metal-organic framework, NH2-UiO-66(Zr) [Zr6O4(OH)4(O2C–C6H4–CO2-NH2)6], (UiO = University of Oslo), with different temperatures of Zn and Ti was carried out via a cation exchange approach. The prepared samples including NH2-UiO-66(Zr/Ti 70 ?C), NH2-UiO-66(Zr/Ti 80 ?C), NH2-UiO-66(Zr/Ti 90 ?C), NH2-UiO-66(Zr/Ti 100 ?C), NH2-UiO-66(Zr/Ti 110 ?C), NH2-UiO-66(Zr/Zn 70 ?C), NH2-UiO-66(Zr/Zn 80 ?C), NH2-UiO-66(Zr/Zn 90 ?C), NH2-UiO-66(Zr/Zn 100 ?C), NH2-UiO-66(Zr/Zn 110 ?C) exhibited a red shift in the visible light region. Accroding to the reduction of bandgap in some samples particulary in Ti samples, we can conclude that, modified MOFs (metal-organic frameworks) can be exhibited potential photocatalytic application. The resulting characterized with powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM) and energy-dispersive X-ray spectroscopy or EDS elemental analysis and mapping, diffuse reflectance UV-Vis spectroscopy (DRS UV-Vis , Photoluminescence spectroscopy (PL) , Brunauer-Emmett-Teller (BET) porosimetry )and total reflection infrared (ATR-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS).

:This thesis consists of two section Preparation and Charactrization of Fe3O4@  S@SiO2-SO3H as an Magnetic Heterogeneous Nonocatalyst and its Application for the Synthesis of 3,4-Dihydropyrimidinones Derivatives Fe3O4@  s@SiO2-SO3H as a magnetic heterogeneous nanocatalyst was synthesized during several steps. Fe3O4@  s@SiO2-SO3H wascharacterized using FT?IR spectroscopy, XRD, TEM, SEM, EDX, TGA, VSM and Mappin . Then, it was used as a new, efficient and stable nanocatalyst in synthes 3,4-dihydropyrimidinone derivatives via reaction of aromatic aldehydes with 1,3-dicarbonyl compounds and urea or thiourea .under solvent free conditions, at 80 °C with excellent yields Synthesis of 5-Substituted 1-H-Tetrazoles with Fe3O4@  s@SiO2-SO3H as an Magnetic Heterogeneous Nanocatalyst Fe3O4@  s@SiO2-SO3H was described as a effective and stable nanocatalyst for the synthesis of 5-substituted 1H-tetrazoles using aromatic aldehydes, sodium azide and malononitrile to help a [2+3] dipolar cycloaddition reaction-Knoevenagel condensation in solvent-free conditions at 80 °C. being eco-friendly, easy procurement method, use of cheap raw materials, high yields, short times, easy separation and recyclability of the catalyst are the benefits of this method   

  The preparation of carbon dots using the green method is used in many researches due toUniquq   roperties such as low toxicity, high water solubility, easy surface modification,Strong     rooting, good biocompatibility, easy and cost-effective preparation, and chemicalstability.   In ihis research, a green and simple carbon dots preparation method was presentedusing   apple as a natural source without the need for surface and oxidant inactivationagents or mineral salts. The formation of carbon dots with an average size of 8.64 nmwas confirmed by TEM (Electron Microscopy). FTIR spectrometer showed device presence ofcarbonyl, hydroxyl, carboxylic acid groups. and a double carbon bond on the carbon-surface.In the second work, a simple and cost effective method for spectrophotometric determinationof sulfide is proposed. The Bear law is followed at the wavelength of 427 nm and in aconcentration range of 0.99-9.8 ppm sulfide in the presence of silver nanoparticles.Thismethod   was used to determine sulfide in Qar-e-sou water samples and Mirage Ghanbar.RSD (relative standard deviation) and RE (relative error) were found to be less than 10% forDetermination of sulfide in real samples. In the third work, for the determination of dithionitein the presence of silvernanoparticles, a spectrophotometric method was introducedDetermination at a wavelength of 420 nm was carried out in a concentration range of 0.562-8.317 ppm of dithionite. This method was used for determination of dithionite in flour sampleRSD (relative standard deviation) and RE (relative error) were found to be less 10% fordetermination of dithionite in real samples.

Synthesis, Characterization and Application of GO-CPTMS-Melamine-CAN as a new Heterogeneous Nanocatalyst for the Preparation of 2-Substituted Benzoimidazoles and Benzothiazole  

In this research,post-synthesis modification of amino-functionalized Zr-based metal-organicframework NH2-Uio-66 (Zr) with different percentages of Zn and Tiwas performed via a cation exchange approach. The prepared samples including NH2-Uio-66(Zr-Ti 25%), NH2-Uio-66 (Zr-Ti 50%), NH2-Uio-66 (Zr-Ti75%), NH2-Uio-66 (Zr-Zn 25%), NH2-Uio-66 (Zr-Zn 50%), NH2-Uio-66(Zr-Zn 75%) and as well as in situ modified NH2-Uio-66 (Zr-Ti 50%)exhibited a red shift in the visible light region. Regarding the reduction ofbandgap, modified MOFs can be had potential photocatalytic application. The resultingsamples were characterized with powder X-ray diffraction (PXRD), field emissionscanning electron microscopy (FE-SEM) and EDS mapping, X-ray photoelectronspectroscopy (XPS), X-ray fluorescence (XRF), UV-Vis diffuse reflectancespectrum (UV-Vis DRS), Brunauer-Emmett-Teller (BET).  

In this research the three-dimensional Zr-based metal-organicframework UiO-66-NH2 was functionalized with ionic liquid (UiO-66-NH2-ILBr-),then Ureawas added to the ionic liquid and the supported ionic liquid phase was formed.Anion Brom was exchanged with tetrafluoro borate, then catalyst exhibited excellent activity for synthesis of oximes, the catalyst showed a good performance. In addition, the supported catalyst systems can be recycledsimply by filtration and reused for five times without significant decrease inactivity. The sample were characterizedwith powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy(FTIR), thermogravimetric analysis (TGA), Field Emission Scanning Electron Microscopy (FE-SEM), (EDS) spectroscopy, (  Mapping), (CHN) analysis, X-ray photoelectron spectroscopy (XPS).  

   In recent years, considerable attention has been paid in design and synthesis of a class of new crystalline porous materials known as metal–organic frameworks (MOFs). These porous materials have great potential for a wide range of applications like separation, ion exchange, conductivity, drug delivery, catalysis, gas storage and selective gas adsorption due to their large surface area, tailored pore volume and designable chemical environment. MOFs are typically constructed by connecting secondary building units (SBUs) consist of metal ions with organic connectors to produce various networks. They are completely regular, have high porosity, highly designable frameworks, and tunable functionalities. The samples were characterized with powder x-ray diffraction (PXRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), nitrogen adsorption and desorption isotherms (BET) analysis, thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS). The MOF containing NH2 groups have high capacity for catalytic reaction. In this work, UiO-66-NH2 was used for post-synthesis by melamine and ethylamine to provide higher content of primary amine for Knoevenagel reaction. The modified MOFs were characterized with powder x-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 adsorption-desorption isotherms (BET), thermogravimetric analysis (TGA), and x-ray photoelectron spectroscopy (XPS). The effective parameters in Knoevenagel reaction such as catalyst type and amount, and solvent type were investigated. The modified MOFs exhibited excellent catalyst activities in heterogeneous phase due to their large surface area and porosity, gigh number of active sites (-NH2) on the structures. The catalyst could be recyclable and reusable without losing its framework integrity and catalytic activity.

  In this thesis, we have designed the ZnO @ SiO2-TTIP nanocatalyst and studied its activity in the synthesis of 2-substituted benzimidazole, benzothiazole and benzoxazole derivatives as well as the synthesis of dihydropyrimidone and yielded quite good results in comparison with past wor

  Metal-organic frameworks or coordination polymers or MOFs are the latest class of ordered porous solids. Since their discovery many potential applications have been proposed in strategic domains such as catalysis, separation, magnetism or others. One of their key advantages compared to their organic (carbons) or inorganic counterparts (zeolites, silica), is the possibility to easily tune their composition through a change of the metal and/or the organic linker. Compared to zeolites, in addition to a wider chemical versatility, MOF structures exhibit a larger panel of pore sizes and shapes (tunnels, cages, etc), with sometimes a flexible porosity which allows to reversibly adapt the pore size to the adsorbate. Functionalization of the organic linker represents another advantage of MOFs with the possibility of grafting during or after the synthesis various organic functionalities (polar, apolar), changing thus the physicochemical properties of the solid. One of the major potential applications for MOFs is in drug delivery, considering their host–guest properties and facile modification via chemical synthesis. In this work, We have made three types of metal-organic frameworks based copper cationic structures, whose methods of making them have been based on ultrasonic, mechanical, and ultrasonic magnetic methods (U-CuBTC, S-CuBTC and M-CuBTC). In the third method, we were able to construct a completely new metal organic structure called M-CuBTC. The purpose of this thesis is to examine the framework including copper nuclei, in absorbing and liberating acriflavine. Acriflavine is one of the most interesting biological compounds used to treat bacterial, fungal or parasitic infections and infections in aquarium fish. In addition to bacteriostatic and antibacterial properties, it has antiviral ability against some viruses, binds DNA and RNA, and changes their physical form. Also, acriflavine Hydrochloride is known and used as an organic color. Magnetic nanoparticles are one of the most important and widely used types of nanomaterials, with their unique properties that make them more specific to other nanostructures. These particles can be used in different branches. Their role is particularly significant in the field of drug delivery and also as a catalyst for various reactions, since these materials are easily separated from the reaction solution by a magnet. It also facilitates targeting, which is essential for drug delivery.

 This thesis consists of five sections:·   Synthesis of Fe3O4@SiO2-ZnCl2 Nanocatalyst:A magnetic nanocatalyst of Fe3O4@SiO2-ZnCl2 was prepared by supporting ZnCl2 on silica?coated magnetic nanoparticles of Fe3O4 and prepared by chemical co-precipitation method. This recoverable catalyst was used for the different synthesis. The core?shell nanoparticles were stable and reusable, non?toxic and inexpensive heterogeneous nanocatalyst with great potential applications in organic syntheses.Synthesise of Benzimidazolesa simple, rapid and efficient method for the preparation of benzimidazoles from the condensation of o-phenylenediamines with aldehydes in the presence of Fe3O4@SiO2 supported ZnCl2 (Fe3O4@SiO2-ZnCl2) as catalyst in EtOH solvent at 50 °C.Synthesise of Qoumarinsa simple and an efficient synthesis of substituted coumarins via Pechmann condensations of phenols with ethyleacetoacetate using Fe3O4@SiO2-ZnCl2 catalyst under solvent-free conditions at 120 °C. This method offers some advantages in terms of simplicity of performance, low reaction times, good yields, solvent-free condition, and it follows along the line of green chemistry.·   Synthesise of benzo[b][1,4]oxazinesan efficient and ecofriendly process for the preparation of benzo[b][1,4]oxazines by the three-component condensation of 2-aminophenole, an aldehyde, and isocyanide using of Fe3O4@SiO2-ZnCl2 catalyst in ethanol and water (80% and 20%, respectively), in the presence and absence of a K2CO3 catalyst, at 70 ?C and 2-12h.·   Synthesise of DihydropyrimidinonesDihydropyrimidinones (DHPMS) were synthesized by a multicomponent condensation of a ?-keto ester, an aldehyde and urea, in ethanol at 80 °C using Fe3O4@SiO2-ZnCl2 as catalysts. The method is environmentally benign and offers operational advantages, such as clean reaction profiles and simple experimental/product isolation procedures.

  In this research the three-dimensional Zr-based metal-organic framework UiO-66-NH2 was functionalized with melamine (UiO-66-NH2-Mlm), then copper (II) acetate monohydrate successfully anchored by the surface of the amino-functionalized Zr-MOF. Copper ions were reduced with sodium borohydride to obtain nanoparticles of copper oxide, then catalyst exhibited excellent activity for Ullman reaction. Furthermore, the catalyst showed a good performance. The sample were characterized with powder x-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), Thermogravimetric analysis (TGA), Scanning electron microscopy (SEM), Scanning transmission electron microscopy (STEM), X-ray Photoelectron Spectroscopy (XPS), and Atomic Absorption spectroscopy (AA).

  Application of FM  -TA-SO3H as an Efficient Heterogeneous Acidic Nanocatalyst for the Synthesis of Tetrazole and Xanthene Derivatives

  Abstract   Metal-organic frameworks (MOFs) also known as porous coordination polymers (PCPs) have attracted the attention of chemists, physicists, and materials scientists because of interest in the creation of nanometer-sized spaces and the novel phenomena in them. There is also interest in their application in adsorption, separation, catalysis, magnetism, sensing, and drug delivery. MOFs are typically constructed by connecting secondary building units (SBUs) consist of metal ions with organic connectors to produce various networks. They are completely regular, have high porosity, highly designable frameworks, and tunable functionalities. These properties make MOFs suitable for various application especially in trap and adsorption affinities for dangerous material. In this research absorption and desorption of iodine molecules and their structural affects using three Zr-MOFs have studied. Absorption and desorption of these guests in highly stable three-dimensionlal (3D) porous coordination polymers UiO-66 (Zr-bdc=1, 4-benzenedicarboxylate), UiO-66-NH2 (Zr-NH2-bdc=2-amino-benzenedicarboxylic acid) and UiO-66-vac (UiO-66 with defects) was investigated. The samples were characterized with powder x-ray diffraction (PXRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), nitrogen adsorption and desorption isotherms (BET) analysis, thermogravimetric analysis (TGA), UV–vis spectroscopy, transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS).The MOF containing NH2 groups have high capacity for iodine capture because of having high porosity, creating charge-transfer complexes between NH2 and I2 molecules. It has also higher iodine adsorption rate more than two other MOFs.The TEM image after iodine incorporated into MOFs has shown some differences on the morphology of particles proving iodine adsorption either on surface or into pores of MOF.The amounts of guest adsorbed into these Zr-MOFs had comparable and the sorption rate, especially for UiO-66-NH2 had higher than those previously reported. In addition, the UiO-66 MOF has shown the lowest amount of iodine sorption which can be reffered to its lower surface area, having no defects in its structure and Shortage of functional groups proportion to Uio-66-NH2.It particularly have demonstrated the quick sorption process of I2 in diluted n-hexane in Zr-based MOFs, and the influence of porosity and functionalization to maximize the loading capacity.AbstractMetal organic frameworks (MOFs) also known as porous coordination polymers (PCPs) have attracted the attention of chemists, physicists, and materials scientists because of interest in the creation of nanometer-sized spaces and the novel phenomena in them. There is also interest in their application in adsorption, separation, catalysis, magnetism, sensing and drug delivery. MOFs are typically constructed by connecting secondary building units (SBUs) consist of metal ions with organic connectors to produce various networks. They are completely regular, have high porosity, highly designable frameworks and tunable functionalities. These properties make MOFs suitable for various application especially in trap and adsorption affinities for dangerous material. In this research absorption and desorption of iodine molecules, their structural affects and kinetic surveys using three Zr-MOFs have studied. Absorption and desorption of these guests in highly stable three-dimensionlal (3D) porous coordination polymers UiO-66, UiO-66-NH2