Zhaoyi Xu

Amino-functionalized Fe3O4@SiO2 core–shell magnetic nanomaterial as a novel adsorbent for aqueous heavy metals removal

A novel amino-functionalized Fe(3)O(4)@SiO(2) magnetic nanomaterial with a core-shell structure was developed, aiming to remove heavy metal ions from aqueous media. The structural, surface, and magnetic characteristics of the nanosized adsorbent were investigated by elemental analysis, FTIR, N(2) adsorption-desorption, transmission electron microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, and zeta-potential measurement. The amino-functionalized Fe(3)O(4)@SiO(2) nanoadsorbent exhibited high adsorption affinity for aqueous Cu(II), Pb(II), and Cd(II) ions, resulting from complexation of the metal ions by surface amino groups. Moreover, the adsorption affinity for heavy metal ions was not much impacted by the presence of a cosolute of humic acid (10.6mg/L) or alkali/earth metal ions (Na(+), K(+), Mg(2+)) (0.025-0.30mmol/L). The metal-loaded Fe(3)O(4)@SiO(2)-NH(2) nanoparticles could be recovered readily from aqueous solution by magnetic separation and regenerated easily by acid treatment. Findings of the present work highlight the potential for using amino-functionalized Fe(3)O(4)@SiO(2) magnetic nanoparticles as an effective and recyclable adsorbent for the removal of heavy metal ions in water and wastewater treatment.

Adsorption of Sulfonamide Antibiotics to Multiwalled Carbon Nanotubes

The presence of sulfonamide antibiotics in aquatic environments has been recognized as an issue warranting consideration. In this study, we evaluated multiwalled carbon nanotubes (MWNT) as a potential effective adsorbent for removal of two sulfonamide antibiotics, sulfapyridine and sulfamethoxazole, from aqueous solutions. Nonporous, functionality-free graphite was included as a comparative adsorbent. Despite the very low hydrophobicity, the two sulfonamides adsorbed strongly to MWNT and graphite, a fact attributed to pi-pi electron coupling with the graphene surface of the adsorbent. For both sulfonamide antibiotics, similar patterns of pH-dependent adsorption were observed between MWNT and graphite, implying the predominance of graphene structures for the adsorption to MWNT. Moreover, the observed pH effects on adsorption indicate that the protonated neutral form of sulfonamide adsorbs much more strongly than the deprotonated anionic counterpart does. The effects of ionic strength (NaCl and CaCl2) and the presence of a dissolved soil humic acid on adsorption of the two antibiotics to MWNT and graphite were also assessed. Ring current-induced 1H NMR upfield chemical shifts further verified face-to-face complex formation between neutral sulfamethoxazole and model pi-electron donor compounds (naphthalene, phenanthrene, and pyrene) in solution.

Adsorption of Pharmaceutical Antibiotics on Template-Synthesized Ordered Micro- and Mesoporous Carbons

The presence of pharmaceutical antibiotics in aquatic environments poses potential human health and ecological risks. We synthesized ordered micro- and mesoporous carbons, and further conducted batch experiments to systematically examine their adsorption properties toward three antibiotics, sulfamethoxazole, tetracycline, and tylosin, in aqueous solution. In comparison, nonporous graphite, single-walled carbon nanotubes, and two commercial microporous activated carbons were included as additional adsorbents. Adsorption of low-sized sulfamethoxazole was stronger on the activated carbons than on other carbonaceous adsorbents resulting from the pore-filling effect; in contrast, due to the size-exclusion effect adsorption of bulky tetracycline and tylosin was much lower on the activated carbons, especially for the more microporous one, than on the synthesized carbons. After normalizing for adsorbent surface area, adsorption of tetracycline and tylosin on the synthesized carbons was similar to that on nonporous graphite, reflecting complete accessibility of the adsorbent surface area in adsorption. Additionally, compared with other porous adsorbents the synthesized carbons showed faster adsorption kinetics of tetracycline and tylosin, which was attributed to their regular-shaped, open and interconnected three-dimensional pore structure. The findings indicate that template-synthesized micro- and mesoporous carbons are promising adsorbents for the removal of antibiotics, particularly, the bulky and flexible-structured compounds, from aqueous solution.

Adsorption of monoaromatic compounds and pharmaceutical antibiotics on carbon nanotubes activated by KOH etching.

The relatively low surface area and micropore volume of carbon nanotubes limit their potential application as effective adsorbents for hydrophobic organic contaminants. In this study, KOH dry etching was explored to prepare activated single-walled carbon nanotubes (SWNT) and multiwalled carbon nanotubes (MWNT) for adsorption of model monoaromatic compounds (phenol and nitrobenzene) and pharmaceutical antibiotics (sulfamethoxazole, tetracycline, and tylosin) in aqueous solutions. With activation, the specific surface area was increased from 410.7 m(2)/g to 652.8 m(2)/g for SWNT and from 157.3 m(2)/g to 422.6 m(2)/g for MWNT, and substantial pore volumes were created for the activated samples. Consistently, adsorption of the test solutes was enhanced 2-3 times on SWNT and 3-8 times on MWNT. Moreover, the activated carbon nanotubes showed improved adsorption reversibility for the selected monoaromatics, as compared with the pristine counterparts, which was attributed to the more interconnected pore structure and less pore deformation of the activated adsorbents. This is the first study on the adsorption/desorption of aqueous organic contaminants by KOH-activated carbon nanotubes. The findings indicate that KOH etching is a useful activation method to improve the adsorption affinity and adsorption reversibility of organic contaminants on carbon nanotubes.

Adsorption of tetracycline on single-walled and multi-walled carbon nanotubes as affected by aqueous solution chemistry.

Carbon nanotubes have shown great potential as effective adsorbents for hydrophobic organic contaminants in water treatment. The present study investigated the influence of aqueous solution chemistry on the adsorption of tetracycline to carbon nanotubes. Specifically, the effects of ionic strength (NaCl and CaCl(2) ) and presence of Cu(2+) ion (7.5 mg/L) or dissolved soil or coal humic acids (50 mg/L) on adsorption of tetracycline to single-walled carbon nanotubes (SWNT), multi-walled carbon nanotubes (MWNT), and nonporous pure graphite as a model of the graphite surface were systematically estimated. The presence of humic acids suppressed tetracycline adsorption on graphite and MWNT prominently, with stronger effects observed on graphite, but only slightly affected tetracycline adsorption on SWNT. The relatively large humic acid components could not readily access the small interstitial spaces of SWNT and thus were less competitive with tetracycline adsorption. The presence of Cu(2+) ion increased tetracycline adsorption to both SWNT and MWNT through the mechanism of cation bridging, with much larger effects observed on MWNT. This was probably because when compared with the Cu(2+) ions complexed on the surface of SWNT, those on the surface of MWNT having larger mesoporous interstices were more accessible to the relatively bulky tetracycline molecule. Increasing the ionic strength from 10 mM to 100 mM decreased tetracycline adsorption on both SWNT and MWNT, which was attributed to electronic shielding of the negatively charged surface sites. These results show that aqueous solution chemistry is important to tetracycline adsorption on carbon nanotubes.

On the photocatalytic properties of elongated TiO2 nanoparticles for phenol degradation and Cr(VI) reduction

Elongated TiO(2) nanoparticles with high aspect ratio have specific advantages in separation processes. In this study, TiO(2) nanofiber was prepared via a hydrothermal reaction, and TiO(2) nanoparticles with varied structural properties were obtained using hydrothermal and calcination post-treatments. Photocatalytic phenol degradation and Cr(VI) reduction over these catalysts was investigated. Results showed that hydrothermally prepared TiO(2) nanofiber consisted of titanate with high aspect ratio. Calcining the as-prepared TiO(2) nanofiber at 400 and 600 degrees C led to the crystalline phase transformation from titanate to TiO(2)-B and to the presence of mixed crystalline phases composed of TiO(2)-B and anatase. In contrast, hydrothermal post-treatment results in the generation of pure anatase TiO(2) nanoparticles. For photocatalytic phenol degradation, calcining the as-prepared TiO(2) nanofiber resulted in an enhanced catalytic activity, whereas TiO(2) nanoparticles obtained by calcination post-treatment showed lower catalytic activities for photocatalytic Cr(VI) reduction compared to as-prepared TiO(2) nanofiber. TiO(2) nanofiber modified using the hydrothermal post-treatment, however, exhibited the highest catalytic activity among TiO(2) nanoparticles examined for both photocatalytic phenol degradation and Cr(VI) reduction. Furthermore, TiO(2) nanoparticles obtained by hydrothermal post-treatment showed the best sedimentation efficiency, highlighting its prominent potential as a readily separable and recoverable photocatalyst.

Graphene nanosheets and graphite oxide as promising adsorbents for removal of organic contaminants from aqueous solution.

Graphenes are an emerging class of carbon nanomaterials whose adsorption properties toward organic compounds have not been well understood. In the present study, graphene nanosheets were prepared by reoxidation and abrupt heating of graphite oxide, which was prepared by sequential chemical oxidation of commercial nonporous graphite powder. Adsorption properties of three aromatic compounds (naphthalene, 2-naphthol, and 1-naphthylamine) and one pharmaceutical compound (tylosin) on graphene nanosheets and graphite oxide were examined to explore the potential of these two adsorbents for the removal of organic contaminants from aqueous solutions. Compared with the literature data of adsorption on carbon nanotubes, adsorption of bulky, flexible tylosin on graphene nanosheets exhibited markedly faster adsorption kinetics, which can be attributed to their opened-up layer structure. Graphene nanosheets and graphite oxide showed similar sequences of adsorption affinity: 1-naphthylamine > 2-naphthol > tylosin > naphthalene (with much larger differences observed on graphite oxide). It was proposed that the strong adsorption of the three aromatic compounds was mainly due to π-π electron donor-acceptor interactions with the graphitic surfaces of adsorbents. Additionally, Lewis acid-base interaction was likely an important factor contributing to the strong adsorption of 1-naphthylamine and tylosin, especially for the O-functionality-abundant graphite oxide. After being normalized on the basis of adsorbent surface area, adsorption affinities of all four tested adsorbates on graphene nanosheets were very close to those on nonporous graphite powder, reflecting complete accessibility of the adsorbent surface area in adsorption.

Adsorption of sulfonamides to demineralized pine wood biochars prepared under different thermochemical conditions

The main objective of this study was to understand the key factors and mechanisms controlling adsorption of sulfonamides to biochars. Batch adsorption experiments were performed for sulfamethoxazole and sulfapyridine to three pine-wood biochars prepared under different thermochemical conditions: pyrolysis at 400 °C (C400) and 500 °C (C500), and pyrolysis at 500 °C followed with hydrogenation (C500-H). For both sulfonamides, the adsorbent surface area-normalized adsorption was stronger to C500 than to C400. This is attributable to the enhanced π-π electron-donor-acceptor interaction with the carbon surface of C500 due to the higher degree of graphitization. Despite the relatively large difference in surface O-functionality content between C500 (12.2%) and C500-H (6.6%), the two biochars exhibited nearly identical adsorbent surface area-normalized adsorption, indicating negligible role of surface O-functionalities in the adsorption to these adsorbents. Effects of solution chemistry conditions (pH, Cu(2+), and dissolved soil humic acid) on adsorption were examined.

Adsorption of methyl tert-butyl ether (MTBE) from aqueous solution by porous polymeric adsorbents

MTBE has emerged as an important water pollutant because of its high mobility, persistence, and toxicity. In this study, a postcrosslinked polymeric adsorbent was prepared by postcrosslinking of a commercial chloromethylated polymer, and a nonpolar porous polymer with comparable surface area and micropore volume to the postcrosslinked polymer was prepared by suspended polymerization. The postcrosslinked polymer, nonpolar porous polymer and chloromethylated polymer were characterized by N2 adsorption, FTIR and XPS analysis. Results showed that postcrosslinking reaction led to the generation of a microporous postcrosslinked polymer with BET surface area 782m2g(-1), average pore width 3.0nm and micropore volume 0.33cm3g(-1). FTIR and XPS analysis indicated the formation of surface oxygen-containing groups on the postcrosslinked polymer. The three polymers were used as adsorbents to remove aqueous methyl tert-butyl ether (MTBE). Adsorption of MTBE over the postcrosslinked polymeric adsorbent was found to follow the linear adsorption isotherm, whereas MTBE adsorption onto the nonpolar porous polymer and chloromethylated polymer followed Langmuir adsorption model. Comparison of adsorption capacities of the postcrosslinked polymer, chloromethylated polymer and nonpolar porous polymer revealed that the adsorption of MTBE from aqueous solution is dependent on both pore structure and surface chemistry of polymeric adsorbents, and the high adsorption efficiency of the postcrosslinked polymer towards MTBE is attributed to its high surface area, large micropore volume and moderate hydrophility. The process of MTBE adsorption onto the adsorbents can be well described by pseudo-second-order kinetics, and the rate of adsorption decreased at higher MTBE initial concentration.

TiO2 supported Pd@Ag as highly selective catalysts for hydrogenation of acetylene in excess ethylene

A novel TiO2 supported core-shell (Pd@Ag) bimetallic catalyst was fabricated via the sequential photodeposition method. The Ag shell effectively blocks the high coordination sites on the Pd core, and therefore pronouncedly enhances the ethylene selectivity for the catalytic hydrogenation of acetylene in excess ethylene.