Xiao-qin Li

Lehigh University, Bethlehem, PA, United States

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Publications (11)31.01 Total impact

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    ABSTRACT: Palladized zero-valent iron nanoparticles have been frequently employed to achieve enhanced treatment of halogenated organic compounds; however, no detailed study has been published on their structures, especially the location and distribution of palladium within the nanoparticles. In this work, the structural evolution of palladized nanoscale iron particles (Pd-nZVI, with 1.5 wt % Pd) was examined using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and X-ray energy dispersive spectroscopy (XEDS) techniques. The STEM-XEDS technique enables direct visualization of the nanoscale structural and compositional changes of the bimetallic particles. For a freshly made Pd-nZVI sample, the particles consist of a metallic iron core and a thin amorphous oxide shell, and Pd is observed to form 2-5 nm islands decorating the outer surface of the nanoparticles. Upon exposure to water, Pd-nZVI undergoes substantial morphological and structural changes. STEM-XEDS elemental maps show that Pd infiltrates through the oxide layer to the metallic iron interface, which is accompanied by oxidation and outward diffusion of the iron species. Within a 24 h period, Pd is completely buried underneath an extensive iron oxide matrix, and a fraction of the nanoparticles exhibits a hollowed-out morphology with no metallic iron remaining. The microstructural variations observed concur with the reactivity data, which shows that the aged bimetallic particles display an 80% decrease in dechlorination rate of trichloroethene (TCE) compared to that of the fresh particles. These findings shed new light on the function of palladium in hydrodechlorination reactions, nZVI aging and deactivation, and the longevity of Pd-nZVI nanoparticles for in situ remediation.
    Environmental Science and Technology 06/2010; 44(11):4288-94. · 5.48 Impact Factor
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    ABSTRACT: Increasing evidence suggests that nanoscale zerovalent iron (nZVI) is effective for the removal of arsenic from contaminated water, but the immobilization mechanism is unclear. In particular, the existence of As(0) on the nanoparticle surface has been proposed but not substantiated in prior studies. By using high-resolution X-ray photoelectron spectroscopy (HR-XPS), we report clear evidence of As(0) species on nZVI surfaces after reactions with As(III) or As(V) species in solutions. These results prove that reduction to elemental arsenic by nZVI is an important mechanism for arsenic immobilization. Furthermore, reactions of nZVI with As(III) generated As(0), As(III), and As(V) on the nanoparticle surfaces, indicating both reduction and oxidation of As(III) take place with nZVI treatment. The dual redox functions exhibited by nZVI are enabled by its core−shell structure containing a metallic core with a highly reducing characteristic and a thin amorphous iron (oxy)hydroxide layer promoting As(III) coordination and oxidation. Results demonstrated here shed light on the underlying mechanisms of arsenic reactions with nZVI and suggest nZVI as a potential multifaceted agent for arsenic remediation.
    Journal of Physical Chemistry C - J PHYS CHEM C. 08/2009; 113(33).
  • Industrial & Engineering Chemistry Research - IND ENG CHEM RES. 02/2009; 47(7).
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    ABSTRACT: Zerovalent iron (nZVI) nanoparticles have long been used in the electronic and chemical industries due to their magnetic and catalytic properties. Increasingly, applications of nZVI have also been reported in environmental engineering because of their ability to degrade a wide variety of toxic pollutants in soil and water. It is generally assumed that nZVI has a core-shell morphology with zerovalent iron as the core and iron oxide/hydroxide in the shell. This study presents a detailed characterization of the nZVI shell thickness using three independent methods. High-resolution transmission electron microscopy analysis provides direct evidence of the core-shell structure and indicates that the shell thickness of fresh nZVI was predominantly in the range of 2-4 nm. The shell thickness was also determined from high-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis through comparison of the relative integrated intensities of metallic and oxidized iron with a geometric correction applied to account for the curved overlayer. The XPS analysis yielded an average shell thickness in the range of 2.3-2.8 nm. Finally, complete oxidation reaction of the nZVI particles by Cu(II) was used as an indication of the zerovalent iron content of the particles, and these observations further correlate the chemical reactivity of the particles and their shell thicknesses. The three methods yielded remarkably similar results, providing a reliable determination of the shell thickness, which fills an essential gap in our knowledge about the nZVI structure. The methods presented in this work can also be applied to the study of the aging process of nZVI and may also prove useful for the measurement and characterization of other metallic nanoparticles.
    Langmuir 05/2008; 24(8):4329-34. · 4.38 Impact Factor
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    ABSTRACT: Remediation of chromium-contaminated sites presents both technological and economic challenges as conventional methods are often too expensive in removing chromium in the soil matrix such as chromium ore process residue (COPR). In this work, reduction and precipitation of hexavalent chromium [Cr(VI)] by nanoscale zerovalent iron (nZVI) are evaluated. Cr(VI) is rapidly reduced and immobilized on the iron nanoparticle surface. In the pH range of 4 to 8, the nZVI has a chromium removal capacity ranging from 180 to 50 mg Cr/g nZVI. Under similar conditions, microscale iron particles (100 mesh) typically have a capacity of less than 4 mg Cr/g Fe. Characterizations with high-resolution X-ray photoelectron spectroscopy (HR-XPS) indicate that Cr(VI) is reduced to Cr(III), which is subsequently incorporated into the iron oxyhydroxide shell of nZVI and form alloy-like Cr−Fe hydroxides with a representative formula approximating (Cr0.67Fe0.33)(OH)3 or Cr0.67Fe0.33OOH. The Cr−Fe hydroxide shell is relatively stable and serves as a sink for Cr(VI). Because of the fast reaction kinetics and high chromium removal capacity, nZVI has the potential to become an effective remedial agent for in situ immobilization of chromium-contaminated soil and groundwater.
    03/2008;
  • Xiao-qin Li, Wei-xian Zhang
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    ABSTRACT: Applications of nanoscale zerovalent iron (nZVI) for removal of metal cations in water are investigated with the result that nZVI has much larger capacity than conventional materials for the sequestration of Zn(II), Cd(II), Pb(II), Ni(II), Cu(II), and Ag(I). Characterizations with high-resolution X-ray photoelectron spectroscopy (HR-XPS) confirm that the iron nanoparticles have a core−shell structure, which leads to exceptional properties for concurrent sorption and reductive precipitation of metal ions. For metal ions such as Zn(II) and Cd(II) with standard potential E0 very close to or more negative than that of iron (−0.41 V), the removal mechanism is sorption/ surface complex formation. For metals with E0 greatly more positive than iron, for instance Cu(II), Ag(I), and Hg(II), the removal mechanism is predominantly reduction. Meanwhile, metals with E0 slightly more positive than iron for example Ni(II) and Pb(II) can be immobilized at the nanoparticle surface by both sorption and reduction. The dual sorption and reduction mechanisms on top of the large surface of nanosized particles produce rapid reaction and high removal efficiency, and offer nZVI as an efficient material for treatment and immobilization of toxic heavy metals.
    04/2007;
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    ABSTRACT: Biosolids are the treated organic residuals, also known as sludge, that are generated from domestic wastewater treatment plants. According to the USEPA, over 7millions tons (dry weight) of biosolids are generated every year in the US by more than the 16,000 wastewater treatment plants and a large portion of these biosolids is disposed on land. Nuisance odors, the potential of pathogen transmission, and presence of toxic and persistent organic chemicals and metals in biosolids have for the most part limited the use of land applications. This paper presents zero-valent iron nanoparticles (1–100nm) for the treatment and stabilization of biosolids. Iron nanoparticles have been shown to form stable and nonvolatile surface complexes with malodorous sulfur compounds such as hydrogen sulfide and methyl sulfides, degrade persistent organic pollutants such as PCBs and chlorinated pesticides, and sequestrate toxic metal ions such as mercury and lead. The end products from the nanoparticle reactions are iron oxides and oxyhydroxides, similar to the ubiquitous iron minerals in the environment. Due to the large surface area and high surface reactivity, only a relatively low dose (<0.1%wt) of iron nanoparticles is needed for effective biosolids stabilization. The iron nanoparticle technology may thus offer an economically and environmentally sustainable and unique solution to one of the most vexing environmental problems.
    Journal of Nanoparticle Research 03/2007; 9(2):233-243. · 2.18 Impact Factor
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    ABSTRACT: Reported herein is a method for the synthesis of fully dispersed and reactive nanoscale particles of zero-valent iron. Polyvinyl alcohol-co-vinyl acetate-co-itaconic acid (PV3A), a nontoxic and biodegradable surfactant, is used in the synthesis of the nanoscale zero-valent iron (nZVI). The addition of PV3A effects three key surface-related changes, which lead to significant enhancements in surface chemistry, particle stability and subsurface mobility potential. These include (1) a reduction of the mean nZVI particle size from 105 nm to 15 nm, (2) a reduction of the zeta (ζ)-potential from +20 mV to −80 mV at neutral pH, and (3) a shift of the isoelectric point (IEP) from pH ≅ 8.1 to 4.5. X-ray photoelectron spectroscopy (XPS) indicates the sorption of PV3A on the nanoparticle surface and also the existence of zero-valent iron (Fe0) in the nZVI mass. Batch experiments further confirm that the PV3A-stabilized iron nanoparticles are capable of effectively reducing trichloroethene (TCE), as has been observed with previous nZVI materials. No sedimentation of the PV3A stabilized nZVI has been observed for over 6 months, suggesting the formation of stable nZVI dispersion. The appreciably smaller mean particle sizes and ability to remain in suspension should translate into improved subsurface mobility potential.
    Colloids and Surfaces A: Physicochemical and Engineering Aspects. 01/2007;
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    ABSTRACT: The iron nanoparticle technology has received considerable attention for its potential applications in groundwater treatment and site remediation. Recent studies have demonstrated the efficacy of zero-valent iron nanoparticles for the transformation of halogenated organic contaminants and heavy metals. In this work, we present a systematic characterization of the iron nanoparticles prepared with the method of ferric iron reduction by sodium borohydride. Particle size, size distribution and surface composition were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), high-resolution X-ray photoelectron spectroscopy (HR-XPS), X-ray absorption near edge structure (XANES) and acoustic/electroacoustic spectrometry. BET surface area, zeta (zeta) potential, iso-electric point (IEP), solution Eh and pH were also measured. Methods and results presented may foster better understanding, facilitate information exchange, and contribute to further research and development of iron nanoparticles for environmental and other applications.
    Advances in Colloid and Interface Science 07/2006; 120(1-3):47-56. · 8.64 Impact Factor
  • Xiao-qin Li, Wei-xian Zhang
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    ABSTRACT: It is demonstrated that iron nanoparticles function as a sorbent and a reductant for the sequestration of Ni(II) in water. A relatively high capacity of nickel removal is observed (0.13 g Ni/g Fe, or 4.43 mequiv Ni(II)/g), which is over 100% higher than the best inorganic sorbents available. High-resolution X-ray photoelectron spectroscopy (HR-XPS) confirms that the zerovalent iron nanoparticles have a core-shell structure and exhibit characteristics of both hydrous iron oxides (i.e., as a sorbent) and metallic iron (i.e., as a reductant). Ni(II) quickly forms a surface complex and is then reduced to metallic nickel on the nanoparticle surface. The dual properties of iron nanoparticles may offer efficient and unique solutions for the separation and transformation of metal ions and other environmental contaminants.
    Langmuir 06/2006; 22(10):4638-42. · 4.38 Impact Factor
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    ABSTRACT: Zero-valent iron nanoparticle technology is becoming an increasingly popular choice for treatment of hazardous and toxic wastes, and for remediation of contaminated sites. In the U.S. alone, more than 20 projects have been completed since 2001. More are planned or ongoing in North America, Europe, and Asia. The diminutive size of the iron nanoparticles helps to foster effective subsurface dispersion whereas their large specific surface area corresponds to enhanced reactivity for rapid contaminant transformation. Recent innovations in nanoparticle synthesis and production have resulted in substantial cost reductions and increased availability of nanoscale zero-valent iron (nZVI) for large scale applications. In this work, methods of nZVI synthesis and characterization are highlighted. Applications of nZVI for treatment of both organic and inorganic contaminants are reviewed. Key issues related to field applications such as fate/transport and potential environmental impact are also explored.
    Critical Reviews in Solid State and Material Sciences 01/2006; 31(4):111-122. · 5.95 Impact Factor