scholarly journals Cu(II) Ion Adsorption by Aniline Grafted Chitosan and Its Responsive Fluorescence Properties

Molecules ◽  
2020 ◽  
Vol 25 (5) ◽  
pp. 1052 ◽  
Author(s):  
Bahareh Vafakish ◽  
Lee D. Wilson

The detection and removal of heavy metal species in aquatic environments is of continued interest to address ongoing efforts in water security. This study was focused on the preparation and characterization of aniline grafted chitosan (CS-Ac-An), and evaluation of its adsorption properties with Cu(II) under variable conditions. Materials characterization provides support for the grafting of aniline onto chitosan, where the kinetic and thermodynamic adsorption properties reveal a notably greater uptake (>20-fold) of Cu(II) relative to chitosan, where the adsorption capacity (Qm) of CS-Ac-An was 106.6 mg/g. Adsorbent regeneration was demonstrated over multiple adsorption-desorption cycles with good uptake efficiency. CS-Ac-An has a strong fluorescence emission that undergoes prominent quenching at part per billion levels in aqueous solution. The quenching process displays a linear response over variable Cu(II) concentration (0.05–5 mM) that affords reliable detection of low level Cu(II) levels by an in situ “turn-off” process. The tweezer-like chelation properties of CS-Ac-An with Cu(II) was characterized by complementary spectroscopic methods: IR, NMR, X-ray photoelectron (XPS), and scanning electron microscopy (SEM). The role of synergistic effects are inferred among two types of active adsorption sites: electron rich arene rings and amine groups of chitosan with Cu(II) species to afford a tweezer-like binding modality.

2020 ◽  
Vol 4 (3) ◽  
pp. 95
Author(s):  
Dexu Kong ◽  
Lee D. Wilson

To address the need to develop improved hybrid biopolymer composites, we report on the preparation of composites that contain chitosan and pectin biopolymers with tunable adsorption properties. Binary biopolymer composites were prepared at variable pectin–chitosan composition in a solvent directed synthesis, dimethyl sulfoxide (DMSO) versus water. The materials were characterized using complementary methods (infrared spectroscopy, thermal gravimetric analysis, pH at the point-of-zero charge, and dye-based adsorption isotherms). Pectin and chitosan composites prepared in DMSO yielded a covalent biopolymer framework (CBF), whereas a polyelectrolyte complex (PEC) was formed in water. The materials characterization provided support that cross-linking occurs between amine groups of chitosan and the –COOH groups of pectin. CBF-based composites had a greater uptake of methylene blue (MB) dye over the PEC-based composites. Composites prepared in DMSO were inferred to have secondary adsorption sites for enhanced MB uptake, as evidenced by a monolayer uptake capacity that exceeded the pectin–chitosan PECs by 1.5-fold. This work provides insight on the role of solvent-dependent cross-linking of pectin and chitosan biopolymers. Sonication-assisted reactions in DMSO favor CBFs, while cross-linking in water yields PECs. Herein, composites with tunable structures and variable physicochemical properties are demonstrated by their unique dye adsorption properties in aqueous media.


2020 ◽  
Vol 7 (2) ◽  
pp. 38
Author(s):  
Leila Dehabadi ◽  
Abdalla H. Karoyo ◽  
Majid Soleimani ◽  
Wahab O. Alabi ◽  
Carey J. Simonson ◽  
...  

The role of chemical modification of pristine linen fiber (LF) on its physicochemical and adsorption properties is reported in this contribution. The surface and textural properties of the pristine LF and its peroxyacetic acid- (PAF) and chlorite-treated (CF) fiber forms were characterized by several complementary methods: spectroscopy (SEM, TEM, FT-IR, and XPS), thermal analysis (DSC and TGA), gas/water adsorption isotherms, and zeta potential (ξ). The results obtained reveal that the surface charge and textural properties (surface area and pore structure) of the LF material was modified upon chemical treatment, as indicated by changes in the biomass composition, morphology, ξ-values, and water/dye uptake properties of the fiber samples. Particularly, the pristine LF sample displays preferential removal efficiency (ER) of methylene blue (MB) dye with ER ~3-fold greater (ER~62%) as compared to the modified materials (CF or PAF; ER~21%), due to the role of surface charge of pectins and lignins present in pristine LF. At higher MB concentration, the relative ER values for LF (~19%) relative to CF or PAF (~16%) reveal the greater role of micropore adsorption sites due to the contributing effect of the textural porosity observed for the modified flax biomass at these conditions. Similar trends occur for the adsorption of water in the liquid vs. vapour phases. The chemical treatment of LF alters the polarity/charge of the surface functional groups, and pore structure properties of the chemically treated fibers, according to the variable hydration properties. The surface and textural properties of LF are altered upon chemical modification, according to the variable adsorption properties with liquid water (l) vs. water vapor (g) due to the role of surface- vs. pore-sites. This study contributes to an understanding of the structure-adsorption properties for pristine and oxidized flax fiber biomass. The chemical conversion of such biomass yields biomaterials with tunable surface and textural properties, as evidenced by the unique adsorption properties observed for pristine LF and its modified forms (CF and PAF). This study addresses knowledge gaps in the field by contributing insight on the relationship between structure and adsorption properties of such LF biomass in its pristine and chemically modified forms.


2021 ◽  
Author(s):  
Inhak Song ◽  
Konstantin Khivantsev ◽  
Yong Wang ◽  
Janos Szanyi

Pd ion exchanged zeolites emerged as promising materials for the adsorption and oxidation of air pollutants. For low-temperature vehicle exhaust, dispersed Pd ions are able to adsorb NOx even in H2O-rich exhaust in the presence of carbon monoxide. In order to understand this phenomenon, changes in Pd ligand environment have to be monitored in-situ. Herein, we directly observe the activation of hydrated Pd ion shielded by H2O into a carbonyl-nitrosyl complex Pd2+(NO)(CO) in SSZ-13 zeolite. The subsequent thermal desorption of ligands on Pd2+(NO)(CO) complex proceeds to nitrosyl Pd2+ rather than to carbonyl Pd2+ under various conditions. Thus, CO molecules act as additional ligands to provide alternative pathway through Pd2+(NO)(CO) complex with lower energy barrier for accelerating NO adsorption on hydrated Pd2+ ion, which is kinetically limited in the absence of CO. We further demonstrate that hydration of Pd ions in the zeolite is a prerequisite for CO-induced reduction of Pd ions to metallic Pd. The reduction of Pd ions by CO is limited under dry conditions even at a high temperature of 500°C, while water makes it possible at near RT. However, the primary NO adsorption sites are Pd2+ ions even in gases containing CO and water. These findings clarify additional mechanistic aspects of the passive NOx adsorption (PNA) process and will help extend the NOx adsorption chemistry in zeolite-based adsorbers to practical applications.


1997 ◽  
Vol 62 (4) ◽  
pp. 575-580 ◽  
Author(s):  
Tomas Jirsak ◽  
Vladimír Nikolajenko ◽  
Zlatko Knor

Room temperature adsorption-desorption properties of Pd overlayers of various thicknesses were studied by thermal desorption spectroscopy of carbon monoxide. Pd overlayers were deposited on clean and oxidized Nb foil (NbOx/Nb). Adsorption properties of Pd overlayers deposited on clean Nb at temperature 350-400 K were not influenced by annealing in the temperature range 400 K to 600 K. Annealing above this temperature caused the decrease in the area of the Pd surface. It became probably smoother, exhibiting lower number of adsorption sites for CO. Non-annealed Pd overlayers deposited on the oxide carrier (NbOx/Nb) at temperatures between 350 and 400 K possessed the same adsorption capability as Pd deposited directly on Nb. Pd atoms thus neither massively penetrated into the oxide layer nor were encapsulated by NbOx.


Nanomaterials ◽  
2021 ◽  
Vol 11 (11) ◽  
pp. 2831
Author(s):  
Martin Ravutsov ◽  
Yavor Mitrev ◽  
Pavletta Shestakova ◽  
Hristina Lazarova ◽  
Svilen Simeonov ◽  
...  

The post-synthesis procedure for cyclic amine (morpholine and 1-methylpiperazine) modified mesoporous MCM-48 and SBA-15 silicas was developed. The procedure for preparation of the modified mesoporous materials does not affect the structural characteristics of the initial mesoporous silicas strongly. The initial and modified materials were characterized by XRD, N2 physisorption, thermal analysis, and solid-state NMR. The CO2 adsorption of the obtained materials was tested under dynamic and equilibrium conditions. The NMR data revealed the formation of different CO2 adsorbed forms. The materials exhibited high CO2 absorption capacity lying above the benchmark value of 2 mmol/g and stretching out to the outstanding 4.4 mmol/g in the case of 1-methylpiperazin modified MCM-48. The materials are reusable, and their CO2 adsorption capacities are slightly lower in three adsorption/desorption cycles.


2014 ◽  
Vol 70 (a1) ◽  
pp. C1261-C1261
Author(s):  
Jorge Sotelo ◽  
Scott McKellar ◽  
Stephen Moggach ◽  
John Mowat ◽  
Anna Warren ◽  
...  

In recent years the development of new methods of storing, trapping or separating light gases, such as CO2, CH4 and CO has become of utmost importance from an environmental and energetic point of view. Porous materials such as zeolites and porous organic polymers have long been considered good candidates for this purpose. More recently, the ample spectrum of existing metal organic frameworks (MOFs) together with their functional and mechanical properties have attracted even further interest. The porous channels found in these materials are ideal for the uptake of guests of different shapes and sizes, and with careful design they can show high selectivity. Adsorption properties of MOFs have been thoroughly studied, however obtaining in depth structural insight into the adsorption/desorption mechanism of these materials is challenging. For example, out of the hundreds of MOF structures published to date, there are less than 20 entries currently in the CSD in which the CO2 molecule can be located. Here we present our novel findings using the high-pressure gas cell at the Diamond Light Source on beamline I19, where we have studied the inclusion of CO2, CH4 and CO on the microporous scandium framework, Sc2BDC3 (BDC = benzene-1,4-dicarboxylate) and its amino-functionalised derivative, Sc2(BDC-NH2)3. Here, the different adsorption sites for CO2, CH4 and CO in both frameworks have been determined as a function of increasing gas pressure. These structures, coupled with Density Functional Theory calculations, have helped to elucidate the host-guest interactions governing the different levels of selectivity shown by both Sc2BDC3 and Sc2(BDC-NH2)3. Additionally, gas mixtures have also been studied; in particular CO2/CH4 mixtures of different compositions, explaining the selectivity of the frameworks for CO2 over other gases and showing the great potential of in situ structural experiments for investigation of the potential applications of MOFs.


Catalysts ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 916
Author(s):  
Xianwei Wang ◽  
Nobutaka Maeda ◽  
Daniel M. Meier

Bimetallic AuPd nanoparticles supported on TiO2 are known to catalyze the reduction of NO with CO. Here, we investigated the effects of the addition of lanthanum oxide to a AuPd/TiO2 catalyst with a AuPd particle size of 2.1–2.2 nm. The addition of La2O3 enhanced the catalytic activity; for example, at 250 °C, there was 40.9% NO conversion and 49.3% N2-selectivity for AuPd/TiO2, and 100% NO conversion and 100% N2-selectivity for AuPd-La (1:1)/TiO2. The temperature requiring 100% NO conversion dropped from 400 °C to 200 °C by the simple post-impregnation of La2O3 onto AuPd/TiO2. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) combined with modulation excitation spectroscopy (MES) demonstrated that CO adsorption occurs first on Au atoms and then, within 80 s, moves onto Pd atoms. This transformation between two adsorption sites was facilitated by the addition of La2O3.


2018 ◽  
Vol 69 (1) ◽  
pp. 38-44
Author(s):  
Nicoleta Mirela Marin ◽  
Olga Tiron ◽  
Luoana Florentina Pascu ◽  
Mihaela Costache ◽  
Mihai Nita Lazar ◽  
...  

This study investigates the synergistic effects of ion exchange and biodegradation methods to remove the Acid Blue 193 also called Gryfalan Navy Blue RL (GNB) dye from wastewater. Ion exchange studies were performed using a strongly basic anion exchange resin Amberlite IRA 400. The equilibrium was characterized by a kinetic and thermodynamic points of view, establishing that the sorption of the GNB dye was subject to the Freundlich isotherm model with R2 = 0.8710. Experimental results showed that the activated resin can removed up to 93.4% when the concentration of dye solution is 5.62�10-2 mM. The biodegradation of the GNB was induced by laccase, an enzyme isolated from white-rot fungus. It was also analyzed the role of pH and dye concentration on GNB biodegradation, so 5�10-2 mM dye had a maximum discoloration efficiency of 82.9% at pH of 4. The laccase showed a very fast and robust activity reaching in a few minutes a Km value of 2.2�10-1mM. In addition, increasing the GNB concentration up to 8�10-1 mM did not triggered a substrat inhibition effect on the laccase activity. Overall, in this study we proposed a mixt physicochemical and biological approach to enhance the GNB removal and biodegradability from the wastewaters and subsequently the environment.


2020 ◽  
Author(s):  
Nicolò Maria della Ventura ◽  
Szilvia Kalácska ◽  
Daniele Casari ◽  
Thomas Edward James Edwards ◽  
Johann Michler ◽  
...  

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