Project description:Electrochemical reduction of nitrate into ammonia has lately been identified as one among the promising solutions to address the challenges triggered by the growing global energy demand. Exploring newer electrocatalyst materials is vital to make this process effective and feasible. Recently, metal-organic framework (MOF)-based catalysts are being well investigated for electrocatalytic ammonia synthesis, accounting for their enhanced structural and compositional integrity during catalytic reduction reactions. In this study, we investigate the ability of the PCN-250-Fe3 MOF toward ammonia production in its pristine and activated forms. The activated MOF catalyst delivered a faradaic efficiency of about 90% at -1 V vs RHE and a yield rate of 2.5 × 10-4 mol cm-2 h-1, while the pristine catalyst delivered a 60% faradaic efficiency at the same potential. Theoretical studies further provide insights into the nitrate reduction reaction mechanism catalyzed by the PCN-250-Fe3 MOF catalyst. In short, simpler and cost-effective strategies such as pretreatment of electrocatalysts have an upper hand in aggravating the intrinsic material properties, for catalytic applications, when compared to conventional material modification approaches.
Project description:To remove arsenite (As(iii)) from wastewater effectively, the catalytic oxidation of As(iii) to arsenate (As(v)) and As(v) precipitation with iron ions (Fe(iii)) was investigated. The Pt/SiO2 catalyst functioned as a reaction site for As(iii) with oxygen in the atmosphere. The combination of the Pt/SiO2 catalyst and Fe(iii) precipitant improved the removal of As(iii) in the precipitate; Pt/SiO2 worked as both an As(iii) oxidation site and precipitation site with Fe(iii) precipitant.
Project description:The preparation of a functional device based on a functionalized MIL-100(Fe) metal-organic framework for the solid-phase extraction of heavy metals is reported. By a simple and easy straightforward grafting procedure, a thiol-functionalized MIL-100(Fe) material (MIL-100(Fe)-SH) with a S/Fe ratio of 0.80 and a surface area of 840 m2 g-1 was obtained. MIL-100(Fe)-SH exhibited a higher Hg(II) extraction (96 ± 5%) than that of MIL-100(Fe) (78 ± 4%) due to the interaction between thiol groups and Hg(II) ions. For practical applications, the obtained MIL-100(Fe)-SH was integrated by a simple method to a 3D printed support based on a matrix of interconnected cubes using poly(vinylidene fluoride) as binder, obtaining a functional device that simultaneously acts as stirrer and sorbent. The developed device showed high efficiency for the removal of Hg(II), good reusability, and excellent performance for the simultaneous preconcentration and further detection and quantification of Hg(II), Pb(II), and As(V) in tap, well, and lake water samples.
Project description:Methods to remove dye pollutants with natural enzyme, like horseradish peroxidase (HRP), are still limited due to high costs and low stability levels. The development of such a method with similar enzymatic activity is important and could be helpful in wastewater disposal. A metal organic framework material, Fe-loaded MOF-545 (Fe), was synthesized in our study as a new way to remove dyes due to its peroxidase-like activity. The structural characterizations of Fe-loaded MOF-545(Fe) was investigated using scanning electron microscopy (SEM), UV-Vis absorption spectra, and X-ray diffraction (XRD). The peroxidase-like (POD-like) activity of Fe-loaded MOF-545(Fe) was investigated under different pH and temperature conditions. Because of the Fe added into the MOF-545 structure, the absorption of Fe-loaded MOF-545(Fe) for acid (anionic) dyes (methyl orange (MO)) was better than for basic (cationic) dyes (methylene blue (MB)). The Fe-loaded MOF-545(Fe) could give a significant color fading for MO and MB over a short time (about two hours) with peroxidase-like activity. The remarkable capacity of Fe-loaded MOF-545(Fe) to remove the MO or MB is due to not only physical adsorption, but also degradation of the MO and MB with POD-like activity. Therefore, Fe-loaded MOF-545(Fe) has significant potential regarding dye removal from wastewater.
Project description:According to the World Health Organization, more than two billion people in our world use drinking water sources which are not free from pathogens and heavy metal contamination. Unsafe drinking water is responsible for the death of several millions in the 21st century. To find facile and cost-effective routes for developing multifunctional materials, which has the capability to resolve many of the challenges associated with drinking water problem, here, we report the novel design of multifunctional fluorescence-magnetic biochar with the capability for highly efficient separation, identification, and removal of pathogenic superbugs and toxic metals from environmental water samples. Details of synthesis and characterization of multifunctional biochar that exhibits very good magnetic properties and emits bright blue light owing to the quantum confinement effect are reported. In our design, biochar, a carbon-rich low-cost byproduct of naturally abundant biomass, which exhibits heterogeneous surface chemistry and strong binding affinity via oxygen-containing group on the surface, has been used to capture pathogens and toxic metals. Biochar dots (BCDs) of an average of 4 nm size with very bright photoluminescence have been developed for the identification of pathogens and toxic metals. In the current design, magnetic nanoparticles have been incorporated with BCDs which allow pathogens and toxic metals to be completely removed from water after separation by an external magnetic field. Reported results show that owing to the formation of strong complex between multifunctional biochar and cobalt(II), multifunctional biochar can be used for the selective capture and removal of Co(II) from environmental samples. Experimental data demonstrate that multifunctional biochar can be used for the highly efficient removal of methicillin-resistant Staphylococcus aureus (MRSA) from environmental samples. Reported results also show that melittin, an antimicrobial peptide-attached multifunctional biochar, has the capability to completely disinfect MRSA superbugs after magnetic separation. A possible mechanism for the selective separation of Co(II), as well as separation and killing of MRSA, has been discussed.
Project description:Biochars were produced from long-root Eichhornia crassipes at four temperatures: 200, 300, 400 and 500°C, referred to as LEC200, LEC300, LEC400 and LEC500, respectively. The sorption ability of lead, zinc, copper and cadmium from aqueous solutions by four kinds of biochars was investigated. All the biochars had lower values of CEC and higher values of pH. LEC500 was the best one to bind toxic metals which can be reflected in the results of SEM, BET and elemental analyser. It was also found that alkyl, carboxyl, phosphate and cyano groups in the biochars can play a role in binding metals. In addition, the sorption processes of four metals by the biochars in different metal concentration were all excellently represented by the pseudo-second-order model with all correlation coefficients R 2 > 0.95. And the sorption processes of four metals in different temperatures could be described satisfactorily by the Langmuir isotherms. According to calculated results by the Langmuir equation, the maximum removal capacities of Pb(II), Zn(II), Cu(II) and Cd(II) at 298 K were 39.09 mg g-1, 45.40 mg g-1, 48.20 mg g-1 and 44.04 mg g-1, respectively. The positive value of the ΔH 0 confirmed the adsorption process was endothermic and the negative value of ΔG 0 confirmed the adsorption process was spontaneous. The sorption capacities were compared with several other lignocellulosic materials which implied the potential of long-root Eichhornia crassipes waste as an economic and excellent biosorbent for eliminating metal ions from contaminated waters.
Project description:Enzymatic heme and non-heme Fe(iv)-O species usually play an important role in hydrogen abstraction of biocatalytic reactions, yet duplicating the reactivity in biomimicry remains a great challenge. Based on Xiao et al.'s experimental work [Nat. Chem., 2014, 6(7), 590], we theoretically found that in the presence of the oxidant N2O, the enzyme-like metal organic framework, i.e., magnesium-diluted Fe-MOF-74 [Fe/(Mg)-MOF-74] can activate the C-H bonds of 1,4-cyclohexadiene (CHD) into benzene with a two-step hydrogen abstraction mechanism based on the density functional theory (DFT) level. It is shown that the first transition state about the cleavage of the N-O bond of N2O to form the Fe(iv)-O species is the rate-determining step with activation enthalpy of 19.4 kcal mol-1 and the complete reaction is exothermic by 62.8 kcal mol-1 on quintet rather than on triplet PES. In addition, we proposed a rebound mechanism of cyclic cyclohexane (CHA) hydroxylation to cyclohexanol which has not been studied experimentally. Note that the activation enthalpies on the first hydrogen abstraction for both cyclic CHD and cyclohexane are just 8.1 and 3.5 kcal mol-1, respectively, which are less than that of 13.9 kcal mol-1 for chained ethane. Most importantly, for the hydrogen abstraction of methane catalyzed by M/(Mg)-MOF-74 (M = Cu, Ni, Fe, and Co), we found that the activation enthalpies versus the C-H bond length of methane of TSs, NPA charge of the reacting oxyl atom have linear relationships with different slopes, i.e., shorter C-H bond and less absolute value of NPA charge of oxyl atom are associated with lower activation enthalpy; while for the activation of methane, ethane, propane and CHD catalyzed by Fe/(Mg)-MOF-74, there also exists positive correlations between activation enthalpies, bond dissociation energies (BDEs) and C-H bond lengths in TSs, respectively. We hope the present theoretical study may provide the guideline to predict the performance of MOFs in C-H bond activation reactions.
Project description:This work reported the preparation of Mg-MOF, Fe-MOF and Fe-Mg MOF by a solvothermal technique and their characterization with FT-IR, XRD, SEM, EDS, TEM and S BET analyses. The nanoparticle diameter ranged from 3.1 to 10.9 nm. The acidity of the MOFs was measured by nonaqueous potentiometric titration of n-butylamine. It was observed that the formation of a bimetallic MOF sharply increases the surface acidity and the catalytic activity. The catalytic results of the Fe-Mg MOF catalyzing the synthesis of 14-aryl-14-H-dibenzo[a,j]xanthenes in comparison with those of parent MOFs showed a higher yield of the desired product in a lower time and among various Fe : Mg, the (0.6 : 1) Fe-Mg MOF showed the highest catalytic activity and acidity. Even after the 4th run, the Fe-Mg MOF catalyst still maintained nearly the initial catalytic activity. The adsorption performance of Mg-MOF, Fe-MOF and Fe-Mg MOF was evaluated by batch experiments. The effect of contact time, the solution pH, the adsorbent dose and the initial concentration of the heavy metal ions was discussed. It was found that the capacity of the bimetallic Fe-Mg MOF for Pb(ii), Cu(ii) and Cd(ii) adsorption was higher than that of the Mg-MOF and Fe-MOF, the kinetic data followed the pseudo-second-order kinetic model and the isothermal data obeyed the Langmuir isotherm model. The mechanism of the removal of the heavy metal ions was discussed.
Project description:Experimental trace element partitioning values are often used to model the chemical evolution of metallic phases in meteorites, but limited experimental data were previously available to constrain the partitioning behavior in the basic Fe-Ni system. In this study, we conducted experiments that produced equilibrium solid metal and liquid metal phases in the Fe-Ni system and measured the partition coefficients of 25 elements. The results are in good agreement with values modeled from IVB iron meteorites and with the limited previous experimental data. Additional experiments with low levels of S and P were also conducted, to help constrain the partitioning behaviors of elements as a function of these light elements. The new experimental results were used to derive a set of parameterization values for element solid metal-liquid metal partitioning behavior in the Fe-Ni-S, Fe-Ni-P, and Fe-Ni-C ternary systems at 0.1 MPa. The new parameterizations require that the partitioning behaviors in the light-element-free Fe-Ni system are those determined experimentally by this study, in contrast to previous parameterizations that allowed this value to be determined as a best-fit parameter. These new parameterizations, with self-consistent values for partitioning in the end-member Fe-Ni system, provide a valuable resource for future studies that model the chemical evolution of metallic phases in meteorites.
Project description:Green chemistry places an emphasis on safer chemicals, waste reduction, and efficiency. Processes should be optimized with green chemistry at the forefront of decision making, embedded into research at the earliest stage. To assist in this endeavor, we present a spreadsheet that can be used to interpret reaction kinetics via Variable Time Normalization Analysis (VTNA), understand solvent effects with linear solvation energy relationships (LSER), and calculate solvent greenness. With this information, new reaction conditions can be explored in silico, calculating product conversions and green chemistry metrics prior to experiments. The application of this tool was validated with literature case studies. Reaction performance was predicted and then confirmed experimentally for examples of aza-Michael addition, Michael addition, and an amidation. The combined analytical package presented herein permits a thorough examination of chemical reactions, so that the variables that control reaction chemistry can be understood, optimized, and made greener for research and education purposes.