Role Of Organic Ligands Research Articles

Tuning the structure of cerium-based metal-organic frameworks for efficient removal of arsenic species: The role of organic ligands.

The ability of organic ligands to change the structure of metal-organic frameworks (MOFs) in nature and influence their adsorption efficiency for arsenic species is enormous. The current work was designed to investigate the adsorption performance of cerium-based MOFs with tunable structures through the use of organic ligands (Ce-MOF-66 and Ce-MOF-808) towards arsenic species from water. The structural features of Ce-MOF-66 and Ce-MOF-808 with varying crystallinity, morphology, particle size, and surface area are considerably altered by organic ligands tuning, resulting in clearly distinct arsenate (As (V)) and arsenite (As (III)) adsorption capabilities. The experimental results showed that the Langmuir adsorption capacities of As (V) by Ce-MOF-66 and Ce-MOF-808 reached 355.67 and 217.80mg/g, respectively, while for As (III) were 5.52 and 402.10mg/g for Ce-MOF-66 and Ce-MOF-808, respectively. Except for the impact of PO43- on As (V), co-existing ions had no significant influence on adsorption, illustrating the high selectivity. Furthermore, to understand the structure and adsorption mechanism, two adsorbents were characterized by powder X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, specific surface area, Fourier transform infrared and X-ray photoelectron spectroscopy, in which identified that unsaturated sites and ligand exchange were the main adsorption mechanisms of As (V) and As (III). Overall, this research presents a novel approach for developing high-performance Ce-derived MOFs adsorbents to capture arsenic species.

On the carbonation of brucite: Effects of Mg-acetate on the precipitation of hydrated magnesium carbonates in aqueous environment

The role of organic ligands on the formation of hydrated magnesium carbonates (HMCs) has been remaining unclear. This work reports insights into the effects of Mg-acetate on the carbonation of brucite including the kinetics of reaction, the precipitation of different HMCs, and reaction mechanisms. We found that the organic ligand increases the kinetics of brucite's carbonation and alter the formation and conversion of HMCs. A relatively unknown phase (i.e., giorgiosite) precipitates in the presence of Mg-acetate with nanowire morphology. With the presence of acetate ligand, nucleation sites formed after the breakdown of Mg-acetate complexes and be replaced by the Mg–CO3 bonds. These sites act as a sink for Mg2+ to grow crystals and prevent the passivation layer of HMCs on brucite's surface. Findings reported here can enable an approach to steer pore solution chemistry in the HMC-based binder for better reaction degree, durability, and mechanical properties.

Roles of Organic Fragments in Redirecting Crystal/Molecular Structures of Inorganic-Organic Hybrids Based on Lacunary Keggin-Type Polyoxometalates.

Lacunary polyoxometalates (LPOMs) are key precursors for the synthesis of functional POMs. To date, reviews dedicated to behavioral studies of LPOMs often comprise the role of metal ions, including transition metal (TM) and rare earth (RE) ions, in extending and stability of high-nuclearity clusters. In contrast, the role of organic ligands in the structures and properties of lacunary-based hybrids has remained less explored. In this review, we focus on the role of organic fragments in the self-assembling process of POM-based architectures and discuss relationships between the nature and structure of organic ligand and properties such as the topology of hybrid inorganic–organic material in RE and TM-RE heterometallic derivatives of lacunary Keggin-type POMs. The effects of organic fragment in mixed ligand hybrids are also briefly reviewed.

Partitioning of sodium into calcium carbonates synthesized at 10–40 °C: Influence of organic ligands and temperature

Calcium carbonates (calcite and aragonite) were synthesized at 10–40 °C to understand the partitioning behavior of sodium during the mineralization of marine organisms. The role of organic ligands (acetic acid) in sodium partitioning into calcium carbonates was also investigated. The partitioning coefficient of sodium, defined as Kd = (Na/Ca)CaCO3/(Na/Ca)solvent, was higher for aragonite than for calcite. The Kd values associated with organic-free solvents decreased with increasing temperature. In contrast, for solvents containing acetic acid, Kd increased with increasing temperature. The K-edge X-ray absorption near edge structure (XANES) measurement of Na suggests that Na substitutes the Ca sites in CaCO3 crystals, regardless of the solvent containing organic ligands. The partitioning behavior associated with the solvent containing acetic acid seems to represent the natural mineralization process in the calcification fluid, which contains a substantial amount of carboxylate. The temperature dependence of Kd was especially clear for aragonite produced from the solvent containing acetic acid. Our findings may help to understand the selection and regulation of crystal polymorphs by marine species in different localities and in different geological era.

Promotion of Microbial Oxidation of Structural Fe(II) in Nontronite by Oxalate and NTA.

Iron redox cycling occurs extensively in soils and sediments. Previous research has focused on microbially mediated redox cycling of aqueous Fe. At circumneutral pH, most Fe occurs in solid phase, where Fe and organic ligands interact closely. However, the role of organic ligands in microbial oxidation of solid-phase Fe(II) is not well understood. Here, we incubated reduced nontronite NAu-2 (rNAu-2) with an iron-oxidizing bacterium and in the presence of oxalate and nitrilotriacetic acid. These ligands significantly enhanced the rate and extent of microbial oxidation of structural Fe(II) in rNAu-2. Aqueous and solid-phase analyses, coupled with biogeochemical modeling, revealed a pathway for ligand-enhanced bio-oxidation of solid-phase Fe(II): (1) dissolution of rNAu-2 to form aqueous Fe(II)-ligand complex; (2) bio-oxidation to Fe(III)-ligand complex; (3) rapid reduction of Fe(III)-ligand complex to Fe(II)-ligand complex by structural Fe(II) in rNAu-2. In this process, the Fe(II)-ligand and Fe(III)-ligand complexes effectively serve as electron shuttle to expand the bioavailable pool of solid-phase Fe(II). These results have important implications for a better understanding of the bioavailability and reactivity of solid-phase Fe pool in the environment.

Dendrimer Ligand Directed Nanoplate Assembly.

Many studies on nanocrystal (NC) self-assembly into ordered superlattices have focused mainly on attractive forces between the NCs, whereas the role of organic ligands on anisotropic NCs is only in its infancy. Herein, we report the use of a series of dendrimer ligands to direct the assembly of nanoplates into 2D and 3D geometries. It was found that the dendrimer-nanoplates consistently form a directionally offset architecture in 3D films. We present a theory to predict ligand surface distribution and Monte Carlo simulation results that characterize the ligand shell around the nanoplates. Bulky dendrimer ligands create a nontrivial corona around the plates that changes with ligand architecture. When this organic-inorganic effective shape is used in conjunction with thermodynamic perturbation theory to predict both lattice morphology and equilibrium relative orientations between NCs, a lock-and-key type of mechanism is found for the 3D assembly. We observe excellent agreement between our experimental results and theoretical model for 2D and 3D geometries, including the percent of offset between the layers of NCs. Such level of theoretical understanding and modeling will help guide future design frameworks to achieve targeted assemblies of NCs.

Amorphous hybrid TiO2 thin films: The role of organic ligands and UV irradiation

The development of a simple, economic and low-temperature synthesis procedure for titanium oxide thin films is an important challenge, due to their diffusion and to the limitations imposed by high temperature annealing. The knowledge on the properties of amorphous TiO2 films, as well as on the effect of their functionalization by organic compounds, is still inadequate. Here we describe a hydrolytic sol-gel procedure to prepare TiO2-based hybrid (inorganic-organic) thin films containing four different complexing agents in their structure (acetylacetone, dibenzoylmethane, citric acid and diethanolamine). The process variables were explored in order to attain stable sols and to tune the features of the amorphous films resulting by drying at 80 °C. Their structural, morphological, optical and electrical properties were studied by SEM, AFM, XRD, ellipsometry, FT-IR and UV–vis-NIR spectroscopy and resistivity measurements. The effect of the organic component, precursors concentration, deposition parameters and annealing temperature was considered. Moreover, the modifications induced by the exposure of the hybrid films to UV light were deeply investigated. A short UV treatment has a strong impact on the microstructure and wettability of the films and promotes a striking increase in their electrical conductivity.

DFT studies on storage and adsorption capacities of gases on MOFs

Abstract Metal-organic frameworks (MOFs) are highly porous crystalline materials, consisting of metal ions linked together with organic bridging ligands, exhibiting high surface areas. Lately, they have been utilized for gas sorption, storage, sensing, drug delivery, etc. The chemistry of MOFs is expanding with an extraordinary speed, constituting both theoretical and experimental research, and MOFs have proved to be promising candidates so far. In this work, we have reviewed the density functional theory studies of MOFs in the adsorption and separation of the greenhouse gas, CO2, as well as the storage efficiencies for fuel gases like H2, CH4 and C2H2. The role of organic ligands, doping with other metal ions and functional groups, open metal sites and hybrid MOFs have been reviewed in brief.

The role of organic ligands in iron cycling and primary productivity in the Antarctic Peninsula: A modeling study

Iron (Fe) is the limiting nutrient for primary productivity in the Southern Ocean, with much of the dissolved iron (dFe) bound to organic ligands or colloids. A Fe model for the Southern Ocean (SOFe) is developed to understand the role of bacteria and organic ligands in controlling Fe cycling and productivity. The model resolves the classical food web and microbial loop, including three types of nutrients (N, Si, Fe) and two types of Fe ligands. Simulations of the zero-dimensional (0-D) model are calibrated with detailed results of shipboard grow-out incubation experiments conducted with Antarctic Peninsula phytoplankton communities during winter 2006 to provide the best estimate of key biological parameters. Then a one-dimensional (1-D) model is developed by coupling the biological model with the Regional Oceanic Modeling System (ROMS) for a site on the Antarctic Peninsula shelf, and the model parameters are further calibrated with data collected from two surveys (summer 2004 and winter 2006) in the area. The results of the numerical simulations agree reasonably well with observations. An analysis of the 1-D model results suggests that bacteria and organic ligands may play an important role in Fe cycling, which can be categorized into a relatively fast mode within the euphotic zone dominated by photo-reactions (summer d Fe residence time about 600 days) and complexation and a slow mode below with most of the dFe biologically complexed (summer dFe residence time >10 years). The dFe removal from the euphotic zone is dominated by colloidal formation and further aggregations with additional contribution from biological uptake, and an increase of organic ligands would reduce Fe export. The decrease of Fe removal rate over depth is due to the continuous dissolution and remineralization of particulate Fe. A number of sensitivity experiments are carried out for both 0-D and 1-D models to understand the importance of photo-reactive processes in primary productivity, bacterial activity, Fe speciation, and dFe residence time within the euphotic zone. The bio-availability of ligand-bound Fe (FeL) is critical to modeled high primary productivity, which is consistent with both shipboard measurements and field observations. In addition, model productivity is sensitive to photoreaction rates if FeL is not directly available for phytoplankton uptake.

The role of organic ligands in ferrous-induced photochemical degradation of 2,4-dichlorophenoxyacetic acid

Recent studies have shown that hydrogen peroxide is generated in a ferrioxalate-induced photoreductive reaction, but information about the effect of organic ligands on the photochemical behaviour of ferrous species is limited. The degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by a ferrous-catalyzed oxidation in the presence of various ligands such as formate, citrate, malelate, oxalate, and ethylenediaminetetra-acetic acid (EDTA) was studied. The experiments were conducted under either dark or irradiated (350n m) conditions. Forty-two percent and 34% of 2,4-D were removed by the Fe(2+)/oxalate/UV and Fe(2+)/citrate/UV processes, respectively, after 30 min of reaction and oxidative intermediates were obtained in both cases. The presence of hydroxylated intermediates suggests that 2,4-D may be attacked by hydroxyl radicals, which are the products of the photo-Fenton-like reaction. As such, hydrogen peroxide was produced by the photolysis of ferrous oxalate or ferrous citrate, referred to hereafter as photogenerated H(2)O(2). As expected, the total removal percentage of 2,4-D jumped to 97% when 1mM of hydrogen peroxide (so-called spiked H(2)O(2)) was externally added to the reaction vessel to initiate the Fe(2+)/oxalate/UV process. Therefore, the treatment of 2,4-D by the Fe(2+)/oxalate/H(2)O(2)/UV system can be operated in two steps: the photolysis of ferrous oxalate first, followed by adding the spiked H(2)O(2) sometime after the commencement of the reaction. A two-phase model has been developed to describe this tandem ferrous-catalyzed photooxidation, which would help to achieve the mineralization of 2,4-D.

Tight-binding studies of surface effects on electronic structure of CdSe nanocrystals: the role of organic ligands, surface reconstruction, and inorganic capping shells

We utilize a tight-binding model to study the effects of surface structure on electronic properties of CdSe clusters. The model takes into account experimental information about structure and shape of the nanocrystals, as well as the nature and distribution of capping ligands. The effects of both organic capping ligands and inorganic capping shells on the densities of states (DOS) and on the single-particle absorption spectra of the clusters are calculated for various cluster shapes and sizes, and are compared to results for clusters with truncated surfaces. For organic capping ligands, the effect of ligand hybridization is investigated and a simple model of surface reconstruction is developed. Both ligand hybridization and surface reconstruction are seen to have a major influence on the band edge electronic and optical properties. Inorganic capping shells give rise to differential localization of valence and conduction band edge states, with the hole primarily confined to the core region and the electron more evenly distributed over both core and shell.

Effect of total cadmium and organic complexing on the uptake of cadmium by the brine shrimp, Artemia franciscana

The effect of total cadmium and organic complexing on the rate of cadmium uptake by the brine shrimp, Artemia franciscana has been studied in chemically defined saltwater solutions. The uptake of cadmium from solution by the laboratory-reared brine shrimp displays saturable uptake kinetics. Uptake of cadmium is linear in time up to a total cadmium concentration of 200 μmoll-1 and saturates above 800 μmoll-1. Complexation of cadmium with organic ligands decreases the uptake of the metal by the brine shrimp. This is in agreement with the view that the availability of cadmium to aquatic organisms is related to the activity of the free cadmium ion in the solution. There is no evidence that the direct uptake of cadmium complexes is important in determining uptake of cadmium. Cadmium uptake is not, however, a mere function of the free cadmium ion activity in the solution, i.e., cadmium uptake rates may differ by an order of magnitude for the same free cadmium ion activity depending on the complexation conditions. In addition to controlling the free cadmium ion activity, the role of organic ligands in metal ion buffering and metal ion masking appear important factors in determining the availability of the metal to the organism.

Importance of heavy metal-organic matter interactions in natural waters

The role of organic ligands in metal complexing in natural waters has received little attention because of uncertainties regarding both the abundance and nature of dissolved organic carbon compounds. Recent data show that the bulk of dissolved organic matter in natural waters consists of highly oxidized and chemically and biologically stable polymeric compounds closely resembling soil humic substances. Average molar concentrations of these aquatic humics in major U.S. rivers range from 5 × 10 −6 to 3 × 10 −5 moles 1 −1. Fractional elution of soil organic matter by meteoric waters may be considered to be the main process contributing to the presence of humic matter in rivers. The aquatic humic polymers participate in complex formation through ionizable functional groups with a range of differential acidities. The stabilities of metal-humic complexes in natural waters are higher than those of the corresponding inorganic metal complexes. Quantitative evaluation of the metal-organic interactions can be approached by applying variable equilibrium functions which take into account the differential physico-chemical characteristics of the active complexing sites on the polymer molecule. Assuming an average humic concentration of 10 mg 1 −1, complexation of trace metals can be significant even in the presence of excess concentrations of major cations.