Exploring the insights and benefits of biomass-derived sulfuric acid activated carbon for selective recovery of gold from simulated waste streams.

The surging affluent in society, concomitant with increasing global demand for electrical and electronic devices, has led to a sharp rise in e-waste generation. E-wastes contain significant amounts of precious metals, such as gold, which can be recovered and reused, thus reducing the environmental impact of mining new metals. Selective recovery using sustainable and cost-effective materials and methods is therefore vital. This study undertook a detailed evaluation of low-cost biomass-derived activated carbon (AC) for selective recovery of Au from simulated e-waste streams. Utilizing high-performance synthesized H2SO4-AC, the adsorption mechanisms were explicated through a combination of characterization techniques, i.e., FE-SEM, BET, TGA, XRD, FTIR, XPS, and DFT simulations to conceptualize the atomic and molecular level interactions. Optimization of coordination geometries between model H2SO4-AC and anionic complexes revealed the most stable coordination for AuCl4- (binding energy, Eb = -4064.15 eV). The Au selectivity was further enhanced by reduction of Au(III) to Au(0), as determined by XRD and XPS. The adsorption reaction was relatively fast (∼5h), and maximum Au uptake reached 1679.74 ± 37.66 mg/g (among highest), achieved through adsorption isotherm experiments. Furthermore, a mixture of 0.5 M thiourea/1 M HCl could effectively elute the loaded Au and regenerate the spent AC. This study presents radical attempts to examine in detail, the synergistic effects of H2SO4 activation on biomass-derived ACs for selective recovery of Au from complex mixtures. The paper therefore describes a novel approach for the selective recovery of Au from e-wastes using multifunctional biomass-derived H2SO4-AC.

Adsorption of organic micropollutants on yeast: Batch experiment and modeling.

Yeast is ubiquitous and may act as a solid phase in natural aquatic systems, which may affect the distribution of organic micropollutants (OMs). Therefore, it is important to understand the adsorption of OMs on yeast. Therefore, in this study, a predictive model for the adsorption values of OMs on the yeast was developed. For that, an isotherm experiment was performed to estimate the adsorption affinity of OMs on yeast (i.e., Saccharomyces cerevisiae). Afterwards, quantitative structure-activity relationship (QSAR) modeling was performed for the purpose of developing a prediction model and explaining the adsorption mechanism. For the modeling, empirical and in silico linear free energy relationship (LFER) descriptors were applied. The isotherm results showed that yeast adsorbs a wide range of OMs, but the magnitude of Kd strongly depends on the types of OMs. The measured log Kd values of the tested OMs ranged from -1.91 to 1.1. Additionally, it was confirmed that the Kd measured in distilled water is comparable to that measured in real anaerobic or aerobic wastewater (R2 = 0.79). In QSAR modeling, the Kd value could be predicted by the LFER concept with an R2 of 0.867 by empirical descriptors and an R2 of 0.796 by in silico descriptors. The adsorption mechanisms of yeast for OMs were identified in individual correlations between log Kd and each descriptor: Dispersive interaction, hydrophobicity, hydrogen-bond donor, and cationic Coulombic interaction of OMs attract the adsorption, while the hydrogen-bond acceptor and anionic Coulombic interaction of OMs act as repulsive forces. The developed model can be used as an efficient method to estimate OM adsorption to yeast at a low level of concentration.

Adsorption modeling of microcrystalline cellulose for pharmaceutical-based micropollutants.

Cellulose can be considered as a raw material for the production of filters and adsorbents for the removal of micropollutants, particularly in pharmaceutical-based products. To study its applications, it is important to estimate the adsorptive interaction of cellulose with the targeted chemicals, and develop predictive models for the expandable estimation into various types of micropollutants. Therefore, the adsorption affinity between cellulose and micropollutants was measured through isotherm experiments, and a quantitative structure-adsorption relationship model was developed using the linear free energy relationship (LFER) equation. The results indicate that microcrystalline cellulose has a remarkably high adsorption affinity with cationic micropollutants. Moreover, it has interactions with neutral and anionic micropollutants, although they have relatively lower affinities than those of cations. Through a modeling study, an LFER model - comprising of excess molar refraction, polar interaction, molecular volume, and charge-related terms - was developed, which could be used to predict the adsorption affinity values with an R2 of 0.895. To verify the robustness and predictability of the model, internal and external validation studies were performed. The results proved that the model was reasonable and acceptable, with an SE = 0.207 log unit.

Polyethyleneimine impregnated alginate capsule as a high capacity sorbent for the recovery of monovalent and trivalent gold.

For the first time, a polyethyleneimine-impregnated alginate capsule (PEIIAC) with a high adsorption capacity is developed for the recovery of monovalent and trivalent gold from an acidic solution. The strategy results in a new type of adsorbent, polyethyleneimine impregnated alginate capsule (PEIIAC) with a core-shell structure having a large number of amine groups as cationic binding site, facilitating maximum uptake of anionic auric chloride. The maximum uptake of PEIIAC was 3078 and 929 mg/g for Au (III) and Au (I), respectively, are recordable compared to other reported adsorbents to date. The as-prepared material was executed to check the sorption efficacy for Au (III) and Au (I) in the pH range of 1-12. With an increment in pH, the uptake capacity for Au (III) increased, while the uptake capacity for Au (I) decreased. The FTIR, XRD, and XPS studies revealed that the gold adsorption mechanism includes ionic interactions and reduction, wherein the amine, hydroxyl, and carboxyl groups are involved. The capsule showed a higher adsorption efficiency than other reported sorbents, making the material applicable in acidic solutions for the recovery of Au (I) and Au (III).

Self-coagulating polyelectrolyte complexes for target-tunable adsorption and separation of metal ions.

Metal-containing wastes in aquatic environments lead to public health hazards and valuable resource lose. Metal-bearing wastewater must be treated to remove heavy metals or recover precious metals. To achieve these, target-tunable adsorbents that bind cationic and anionic metal species were developed through facile polyelectrolyte complexation using polyethylenimine (PEI) and polyacrylic acid (PAA). Utilizing the properties of the two polyelectrolytes and pKa variabilities, stable tunable adsorbents were fabricated in water without additional solvents. The homogenous complex adsorbents were strategically synthesized via dissolution in 0.1 M NaOH and drop-wise addition of 1 M HCl, followed by crosslinking with glutaraldehyde. Consequently, the adsorbents in alternating weight ratios of 4:1 and 1:4 (PEI:PAA) exhibited good tunability and adsorption properties. The maximum single metal adsorption capacities were 1609.7 ± 49.6 and 558.6 ± 9.67 mg/g for gold and cadmium, respectively. The pseudo-second-order model fitted the kinetics data more appropriately and was recognized as the rate controlling step. In a binary mixture, gold selectivity was observed to be influenced by adsorption-reduction mechanism, which was elucidated by XRD and XPS. Moreover, the adsorbents demonstrated NO3- sequestration properties, a feat deemed important for environmental remediation of nitrate ions. Finally, sequential separation was achieved with ethylenediaminetetraacetic acid (EDTA) and acidified thiourea.

Highly efficient and acid-resistant metal-organic frameworks of MIL-101(Cr)-NH2 for Pd(II) and Pt(IV) recovery from acidic solutions: Adsorption experiments, spectroscopic analyses, and theoretical computations.

Cr-based metal-organic frameworks (MOFs) of MIL-101(Cr)-NH2 was post-synthesized from nitro-functionalized MIL-101(Cr) (MIL-101(Cr)-NO2) through a reduction process. Adsorption behaviors and interactions of MIL-101(Cr)-NH2 and MIL-101(Cr)-NO2 with platinum group metal (PGM) anions of Pd(II) (PdCl42-) and Pt(IV) (PtCl62-), were investigated through batch adsorption experiments, spectroscopic analyses, and theoretical computations. According to adsorption kinetics and isotherms, the uptakes of Pd(II) and Pt(IV) by in MIL-101(Cr)-NH2 were found to be much higher than their uptakes by MIL-101(Cr)-NO2. The abundant protonated amine groups (BDC-NH3+) in MIL-101(Cr)-NH2 were verified to be the main adsorptive binding sites by XPS and FTIR spectroscopy, and FE-SEM imageries. Additionally, BDC-NH3+ shows extremely high affinities (b value) and binding energies (Ebind) for PdCl42- and PtCl62- through electrostatic attraction, resulting in much higher adsorption capacities of MIL-101(Cr)-NH2 for these PGMs as compared to those of MIL-101(Cr)-NO2. Moreover, the MOFs' Cr nodes without terminal -OH indicated positive electrostatic potentials, and certain values of Ebind for PGM anions. Thus, the few-amount cationic Cr sites could also make little contributions to the adsorption of PGM anions in MIL-101(Cr)-NH2 or MIL-101(Cr)-NO2. Furthermore, the perfect regeneration and reusability of MIL-101(Cr)-NH2 over five of adsorption-desorption cycles, suggesting its potential in practical applications.