Enhanced photocatalytic activities of silicon nanowires/graphene oxide nanocomposite: Effect of etching parameters

Homogeneous and vertically aligned silicon nanowires (SiNWs) were successfully fabricated using silver assisted chemical etching technique. The prepared samples were characterized using scanning electron microscopy, transmission electron microscopy and atomic force microscopy. Photocatalytic degradation properties of graphene oxide (GO) modified SiNWs have been investigated. We found that the SiNWs morphology depends on etching time and etchant composition. The SiNWs length could be tuned from 1 to 42 µm, respectively when varying the etching time from 5 to 30 min. The etchant concentration was found to accelerate the etching process; doubling the concentrations increases the length of the SiNWs by a factor of two for fixed etching time. Changes in bundle morphology were also studied as function of etching parameters. The SiNWs diameter was found to be independent of etching time or etchant composition while the size of the SiNWs bundle increases with increasing etching time and etchant concentration. The addition of GO was found to improve significantly the photocatalytic activity of SiNWs. A strong correlation between etching parameters and photocatalysis efficiency has been observed, mainly for SiNWs prepared at optimum etching time and etchant concentrations of 10 min and 4:1:8. A degradation of 92% was obtained which further improved to 96% by addition of hydrogen peroxide. Only degradation efficiency of 16% and 31% has been observed for bare Si and GO/bare Si samples respectively. The obtained results demonstrate that the developed SiNWs/GO composite exhibits excellent photocatalytic performance and could be used as potential platform for the degradation of organic pollutants.     

The role of extracellular organic matter on the cyanobacteria ultrafiltration process

The membrane fouling caused by extracellular organic matter (EOM) and algal cells and organic matter removal of two typical cyanobacteria (M. aeruginosa and Pseudoanabaena sp.) during ultrafiltration (UF) process were studied in this work. The results showed that EOM had a broad molecular weight (Mw) distribution and the irreversible membrane fouling was basically caused by EOM. Moreover, humic acid and microbial metabolites were major components of EOM of two typical cyanobacteria. Since EOM could fill the voids of cake layers formed by the algal cells, EOM and algal cells played synergistic roles in membrane fouling. Fourier transform infrared spectroscopy analysis indicated that the CH₂ and CH₃ chemical bonds may play an important role in membrane fouling caused by EOM. Interestingly, the cake layer formed by the algal cells could trap the organic matter produced by algae and alleviate some irreversible membrane fouling. The results also showed that although the cake layer formed by the algal cells cause severe permeate flux decline, it could play a double interception role with UF membrane and increase organic matter removal efficiency. Therefore, when using UF to treat algae-laden water, the balance of membrane fouling and organic matter removal should be considered to meet the needs of practical applications.     

Ni(NH3)62+ more efficient than Ni(H2O)62+ and Ni(OH)2 for catalyzing water and phenol oxidation on illuminated Bi2MoO6 with visible light

Nickel (hydr)oxide (NiOH) is known to be good co-catalyst for the photoelectrochemical oxidation of water, and for the photocatalytic oxidation of organics on different semiconductors. Herein we report a greatly improved activity of Bi₂MoO₆ (BMO) by nickel hexammine perchlorate (NiNH). Under visible light, phenol oxidation on BMO was slow. After NiNH, NiOH, and Ni²⁺ loading, a maximum rate of phenol oxidation increased by factors of approximately 16, 8.8, and 4.7, respectively. With a BMO electrode, all catalysts inhibited O₂ reduction, enhanced water (photo-)oxidation, and facilitated the charge transfer at solid-liquid interface, respectively, the degree of which was always NiNH > NiOH > Ni²⁺. Solid emission spectra indicated that all catalysts improved the charge separation of BMO, the degree of which also varied as NiNH > NiOH > Ni²⁺. Furthermore, after a phenol-free aqueous suspension of NiNH/BMO was irradiated, there was a considerable Ni(III) species, but a negligible NH₂ radical. Accordingly, a plausible mechanism is proposed, involving the hole oxidation of Ni(II) into Ni(IV), which is reactive to phenol oxidation, and hence promotes O₂ reduction. Because NH₃ is a stronger ligand than H₂O, the Ni(II) oxidation is easier for Ni(NH₃)⁶⁺ than for Ni(H₂O)⁶⁺. This work shows a simple route how to improve BMO photocatalysis through a co-catalyst.     

Competitive role of nitrogen functionalities of N doped GO and sensitizing effect of Bi2O3 QDs on TiO2 for water remediation

The promising solar irradiated photocatalyst by pairing of bismuth oxide quantum dots (BQDs) doped TiO₂ with nitrogen doped graphene oxide (NGO) nanocomposite (NGO/BQDs-TiO₂) was fabricated. It was used for degradation of organic pollutants like 2,4-dichlorophenol (2,4-DCP) and stable dyes, i.e. Rhodamine B and Congo Red. X-ray diffraction (XRD) profile of NGO showed reduction in oxygenic functional groups and restoring of graphitic crystal structure. The characteristic diffraction peaks of TiO₂ and its composites showed crystalline anatase TiO₂. Morphological images represent spherical shaped TiO₂ evenly covered with BQDs spread on NGO sheet. The surface linkages of $\text{NO}?\mathrm{O}?\text{Ti}$, $\mathrm{C}?\mathrm{O}?\text{Ti}$, $\mathrm{B}\mathrm{i}?\mathrm{O}?\text{Ti}$ and vibrational modes are observed by Fourier transform infrared spectroscopy (FTIR) and Raman studies. BQDs and NGO modified TiO₂ results into red shifting in visible region as studied in diffused reflectance spectroscopy (DRS). NGO and BQDs in TiO₂ are linked with defect centers which reduced the recombination of free charge carriers by quenching of photoluminescence (PL) intensities. X-ray photoelectron spectroscopy (XPS) shows that no peak related to $\mathrm{C}?\mathrm{O}$ in NGO/BQDs-TiO₂ is observed. This indicated that doping of nitrogen into GO has reduced some oxygen functional groups. Nitrogen functionalities in NGO and photosensitizing effect of BQDs in ternary composite have improved photocatalytic activity against organic pollutants. Intermediate byproducts during photo degradation process of 2,4-DCP were studied through high performance liquid chromatography (HPLC). Study of radical scavengers indicated that ${\mathrm{O}}_2^{·?}$ has significant role for degradation of 2,4-DCP. Our investigations propose that fabricated nanohybrid architecture has potential for degradation of environmental pollutions.